CA1109757A - Low phosphate laundry detergent compositions - Google Patents

Abstract

LOW PHOSPHATE LAUNDRY DETERGENT COMPOSITIONS
Abstract of The Disclosure Laundry detergent compositions containing specific alcohol ethoxylate nonionic-surfactants together with selected di-long chain cationic surfactants, within a narrow range of nonionic: cationic ratios, and which are either free of phosphate materials and preferably polyethylene glycol di-esters, or contain only low levels of such materials, are disclosed. These compo-sitions are unusually effective in removing particulate soils from fabrics and, additionally, provide fabric softening, static control, color fidelity, and dye transfer inhibition benefits to fabrics laundered therewith. A process for laundering fabrics, using these compositions, is also disclosed.

Description

97~7 LOW PHOSPHATE LAUNDRY DETERGENT COMPOSITIONS
Technical Field This invention relates to laundry detergent compositions which exhibit surprisingly effective removal of particulate soils, as well as fabric softening, static control, color fidelity (i.e., the inhibition of the bleeding of fabric colors into the laundry solution), and dye transfer inhibition (i.e., the inhibition of the redeposition of dyes in the laundry solution onto fabrics) capabilities, even in the total absence of detergency builder materials. Specifically com-pletely unbuilt compositions of the present invention have demonstrated the ability to remove particulate soils from fabrics as well, and under some conditions better, than fully-built conventional laundry detergents. Other detergent compo-sitions which utilize mixtures of selected nonionic surfactantsand cationic surfactants are defined in Canadian Patent Appli-cation Serial No. 306,474, Murphy, filed June 29, 1978, and Canadian Patent Application Serial No. 306,456, Cockrell, filed June 29, 1978.
Background Art Nonionic surfactants are generally utilized in laundry detergent compositions for their ability to remove greasy and oily, rather than particulate, soils from fabrics. Some types of cationic surfactants have been included in detergent compo-sitions, primarily because they provide adjunct fabric care benefits, and not because they provide any cleaning advantage.
Thus, certain cationic surfactants have been included in detergent compositions for the purpose of yielding a germicidal ~' . ~ .

l~L~7~7 or sanitization benefit to washed surfaces; e.g., U.S. Patent No. 2,742,434, Kopp, issued April 17, 1956; U.S. Patent No.
3,539,520, Cantor et al, issued November 10, 1970; and U.S.
Patent No. 3,965,026, Lancz, issued June 22, 1976. Other cationic materials, particularly those of the di-long chain type, have been included in detergent conpositions for the purpose of providing a fabric softening benefit (see U.S.
Patent No. 3,607,763, Salmen et al, issued September 21, 1971, and U.S. Patent No. 3,644,203, Laberti et al, issued February 22, 1972), or a static control benefit (see U.S. Patent No.
3,951,879, Wixon, issued April 20, 1976, and U.S. Patent No.
3,959,157, Inamorato, issued May 25, 1976).
The relative insolubility of the di-long chain quaternary ammonium materials has led formulators of detergent composi-tions away from their inclusion for the purpose of yieldinga cleaning or whiteness maintenance benefit; this is particu-larly true in compositions, such as those described herein, where the relatively low nonionic:cationic ratios required preclude the use of large amounts of the nonionic surfactant to solubilize the cationic material. In fact, it is well known in the detergency art that the use of such di-long chain cationic materials actually causes fabrics laundered with them to become yellow and dingy. See U.S. Patent No. 3,644,203, Lamberti et al, issued February 22, 1972; U.S. Patent No.
3,360,470, Wixon, issued December 26, 1967; U.S. Patent No.
3,676,341, Gerecht and Wixon, issued July 11, 1972; and U.S.
Patent No. 3,904,359, Ramachandran, issued September 9, 1975, which teach ways of avoiding this yellowing problem caused by the di-long chain cationics. The teachings of patents such as these makes the whiteness maintenance properties of the present invention, which result from inhibiting the transfer of dyes in the wash solution, particularly surprising.
The compositions of the present invention have outstanding cleaning capabilities in terms of the removal of particulate soils. In laundry tests, these compositions, not containing any builder components, have been shown to remove particulate .
, iL1~9~7~7 soils (such as clay) as well, and in some cases dramatically better, than fully-built conventional laundry detergent compo-sitions. The compositions are relatively insensitive to water hardness conditions, performing 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, static control, fabric color fidelity, and dye transfer inhibition benefits to the laundered fabrics. This well-rounded cleaning and fabric care performance is the result of a heretofore unrecognized cleaning potential of the selected di-long chain cationic surfactants defined herein, when they are used in the presence of certain alcohol ethoxylate nonionic surfactants, within a narrow range of nonionic:cationic surfactant ratios.
It is, therefore, an object of this invention to provide law- or no-phosphate laundry detergent compositions which demonstrate outstanding particulate soil removal capabilities.
It is another object of this invention to provide laundry detergent compositions, yielding excellent particulate soil removal, which may conveniently be produced in a variety of physical forms, such as liquid, solid, paste, granular, powder, or in conjunction with a carrier, such as a substrate.
It is a further object of this invention to provide a single composition which provides outstanding cleaning perform-ance together with fabric softening, static control, colorfidelity, and dye transfer inhibition benefits.
It is yet another object of this invention to provide a process for laundering fabrics which yields exceptional particulate soil removal, over a range of water hardness conditions, using cationic and nonionic surfactant-containing detergent compositions.
Summary of the Invention The present invention relates to low- or no-phosphate laundry detergent compositions, especially beneficial for the removal of particulate soils from fabrics, having a pH in the laundry solution of greater than about 7, containing no more than about 15~ phosphate and no more than about 10% silicate ,, materials, and being substantially free of ethoxylated cationic surfactants containing more than an average of about 10 moles of ethylene oxide per mole of surfactant, which comprise from about 5% to about 100%, by weight, of a sur-factant mixture consisting essentially of:
(a) a nonionic surfactant having the formula R(OC2H4) 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, and having an HLB of from 5 to about 14, or a mixture of such surfactants: and (b) 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 surfactants;
the ratio of said nonionic surfactant to said cationic sur-factant being in the range of from about 2:1 to about 9:1.
Disclosure of the Invehtion The compositions of the present invention comprise, by weight, from about 5 to about 100%, preferably from about 15 to about 90%, and most preferably from about 20 to about 80%, of a mixture of particularly defined nonionic and cationic surfactants in the ratios stated herein. Preferred composi-tions contain at least about 15% of the nonionic/cationic surfactant mixture and at least about.l% of the cationic component, itself, in order to assure the presence of a suffi-cient amount of both the cationic surfactant and the nonionic/
cationic mixture to provide the desired cleaning and fabric conditioning benefits.
The compositions of the present invention contain the nonionic and cationic surfactants, defined hereinafter, within ratios of nonionic to cationic surfactant of from about 2:1 to about 9:1, preferably from about 3:1 to about 6.5:1, more preferably from about 3.5:1 to about 5.5:1 and most preferably from about 4:1 to about 5:1, in order to achieve the best particulate soil removal performance. In addition, by using ratios in the range of from about 3.5:1 to about 5.5:1, the 7~
, static control performance of the compositions is not only excellent under typical laundering conditions, but is parti-cularly impressive under stress conditions, such as relative humidity less than about 35%, which generally are very difficult conditions under which to obtain any static control benefits. Preferred compositions may also contain mixed nonionic surfactant systems.
It is preferred that the compositions of the present invention are formulated so as to have a pH of at least about 7 in the laundry solution, at conventional usage concentra-tions, in order to optimize their overall cleaning performance, to aid in their manufacturing and processing, and to minimize the possibility of washing machine corrosion. Lower product pH's (e.g., as low as 6) are acceptable, but preferably the composition is not buffered below 7. It is also preferred that the composition pH be at least about 7.1, especially when a halide, e.g., chloride, cationic is used to avoid corrosion of the equipment used in making the composition. Also, a pH
range of from 7.2 to about 8.0, which is strongly buffered, is desirable, if the cationic material has a substantial level of unquaternized amine, for odor reasons. 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 systems of the present invention may 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 perform-ance may be enhanced by varying the pH of the wash solution during the laundering process. Particularly preferred compo-sitions have a pH of at least about 8 in the laundry solution, in order to optimize the removal of greasy/oily 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 7-~i7 buffer at pH's of from about 8 to 11, such a monoethanolamine, diethanolamine or triethanolamine.
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 diminish-ing the cleaning effectiveness of the compositiGns.
Nonionic Component The nonionic surfactants used in the compositions of the present invention are biodegradable and 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 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 Sur-factants, by M.J. Schick, Marcel Dekker, Inc., 1966, pages607-613.
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 condensa-tion 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 C14 15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C14 15 alcohol with 7 moles of ethylene oxide; the con-densation 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 sur-factants utilize alcohols which contain about 20~ 2-methyl .

, . ...
- -7~7 branched isomers, and are commercially available, under the trademark "Neodol", from Shell Chemical Company. The condensa-tion product of tallow alcohol with 9 moles of ethylene oxide is also a preferred nonionic surfactant for use herein. Par-5 ticularly preferred nonionic surfactants for use in thecompositions of the present invention include the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C12 15 alcohol with 10 7 moles of ethylene oxide, the condensation product of C14 15 alcohol with 7 moles of ethylene oxide, and mixtures of those surfactants.
The compositions of the present invention may contain mixtures of nonionic surfactants falling within the above 15 nonionic surfactant definition, such as: a mixture of the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide ("Neodol 23-6.5".) with the condensation pro-duct of C14 15 alcohol with 7 moles of ethylene oxide ("Neodol 45-7"), in a ratio of from about 4:1 to 1:4, a mixture of the 20 condensation product of C12 15 alcohol with 7 moles of ethylene oxide with "Neodol 45-7", in a ratio of from about 4:1 to about 1:4, preferably about 1:1; or a m-xture of the condensation product of Cg ll alcohol with 8 moles of ethylene oxide, stripped to remove lower ethoxylate and non-25 ethoxylated fractions, with "Neodol 45-7", in a ratio of higher ethoxylate to lower ethoxylate of from about 1:6 to about l:l, preferably about 1:3. The present invention may also contain mixtures of nonionic surfactants, some of which do not fall within the above nonionic surfactant definition 30 (such as alcohol ethoxylates ha~ ing an average of greater than about 9 ethylene oxide groups per molecule, secondary alcohol ethoxylates, or alkyl phenol ethoxylates), as long as at least one of the nonionic surfactants contained in the mixture falls within the above definition of required nonionic surfactants, 35 and that required nonionic surfactant (mixture) is contained in an amount such that it falls within the required nonionic/
cationic ratio. Where the nonionic surfactant mixture contains 975~

a nonionic surfactant (or surfactants) which falls outside of the above nonionic definition, it is preferred that the ratio of the surfactant (or surfactants) within the definition to that which is outside the definition be within the range of from about 1:1 to about 10:1. A specific example of such a surfactant mixture is a mixture of the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide (e.g. "Neodol 23-6.5") and the condensation product of a secondary C15 alcohol with 9 moles of ethylene oxide (e.g., "Tergitol 15-S-9"), in a ratio of lower ethoxylate to higher ethoxylate non-ionic of from about 1:1 to about 6:1; or a mixture of "Neodol 23-6.5" and the condensation product of nonyl phenol with 7 moles of ethylene oxide, having a ratio of "Neodol" to nonyl phenol ethoxylate of about 4:1.
Preferred nonionic surfactant mixtures contain alkyl glyceryl ethers in addition to the required nonionic surfactant.
Particularly preferred are glyceryl ethers having the formulae 2 f 2 and R-O(CH2CH2O)ncH2lcHcH2OH
OH OH
wherein R is an alkyl or alkenyl group of from about 8 to about 18, preferably about 8 to 12, carbon atoms or an alkaryl group having from about 5 to 14 carbon in the alkyl chain, and n is from 1 to about 6, together with the nonionic surfactant component of the present invention, in a ratio of nonionic sur-factant to glyceryl ether of from about 1:1 to about 4:1, particularly about 7:3. Glyceryl ethers of the type useful in the present invention are disclosed in U.S. Patent No.
4,206,070, Jones, issued June 3, 1980 and U.S. Patent 4,098,713, Jones, issued July 4, 1978.
Other nonionic surfactants well known in the detergency arts may be used, in com~ination with one or more of the required nonionic surfactants, to form useful nonionic sur-factant mixtures. Examples of such surfactants are listed in U.S. Patent No. 3,717,630, Booth, issued February 20, 1973, and U.S. Patent No. 3,332,880, Kessler et al, issued July 25, 1967. Nonlimiting examples of suitable nonionic surfactants * Trademark ~, i ' ' '~ ' .

37~7 g which may be used in conjunction with the required nonionic surfactants, defined above, are: polyethylene oxide conden~
sates of alkyl phenols, such as the "Igepal" surfactants, marketed by the GAF Corporation, and the "Triton" surfactants, marketed by the Rohm and Haas Company; condensation products of aliphatic alcohols with from about 10 to about 25 moles of ethylene oxide, where those alcohols are of a primary, branched or secondary alkyl chain structure; condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, ***
such as the "Pluronic" surfactants, marketed by Wyandotte Chemical Corporation; and condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine, such as the "Tetronic" sur-factants, marketed by Wyandotte Chemical Corporation.
A preferred group of nonionic surfactants useful herein comprises a mixture of "surfactant" and "cosurfactant", con-taining at least one nonionic surfactant falling within the definition of the nonionic surfactants useful herein, as 20 described in Canadian Patent No. 1,059,865, Collins, issued August 7, 1979.
Another preferred mixture of nonionic surfactants com-P 12-13E6.5 and C14_1sEO7 in a ratio of 4 1 to 1 4 This mixture provides a desirable suds pattern during the wash and during rinsing as compared to either surfactant by itself.
Preferred compositions of the present invention are sub-stantially free (less than about 2%, preferably less than about 1%, more preferably none) of fatty acid polyglycol ether di-ester compounds, such as polyethylene glycol-600-dioleate or polyethylene glycol-800-distearate. Such addi-tives offer no advantage, and possibly even result in a disadvantage, in terms of achieving the particulate soil removal and fabric conditioning benefits provided by the present invention.

*Trademark **Trademark ***Trademark ****Trademark 11`~97~7 , 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, preferably from about 16 to about 18, carbon atoms. The remaining groups, if any, attached to the quaternary nitrogen atom, are preferably Cl to C4 alkyl or hydroxyalkyl groups. Although it is preferred that the long chains be alkyl groups, these chains may contain hetero-atoms or other linkages, such as hydroxy groups, double or triple carbon-carbon bonds, and ester, amide, or ether linkages, as long as each chain falls within the carbon atom ranges required given above. Preferred cationic surfactants are those having the formulae R N-CH
R4_N+_R2 X or R -C ¦ X
Il \t R ~-CH2 wherein the Rl and R2 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 Cl to C4 alkyl or hydroxyalkyl groups, and X is any compatible anion, particularly one selected from the group consisting of halide, hydroxide, methylsulfate, or acetate anions.
Mixtures of the above surfactants are also useful in the present invention. These cationic surfactants may also be mixed with other types of cationic surfactants, such as sulfonium, phosphonium, and mono- 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 requirements specified herein.

11~9~

Examples of cationic surfactants which may be used to-gether with those required herein, include those described in Canadian Patent Application Serial No. 306,474, Murphy;
Canadian Patent Application Serial No. 306,456, Cockrell;
Canadian Patent Application Serial No. 306,517, Letton; and Canadian Patent Application Serial No. 306,513, Letton, all of which were filed on June 9, 1978.
Preferred cationic surfactants include ditallowalkyldi-methyl (or diethyl or dihydroxyethyl) ammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecylalkyl (C16; also known as distearyl) dimethyl (or diethyl, or dihydroxyethyl) ammonium chloride, dioctadecylalkyl (C18)-dimethylammonium chloride, dieicosylalkyl-(C20) dimethyl-ammonium chloride, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate (commercially avail-able as "Varisoft 475" from Ashland Chemical Company), or mixtures of those surfactants. Particularly preferred cationic surfactants are ditallowalkyldimethylammonium chloride, ditallowalkyldimethylammonium methyl sulfate, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, and mixtures of those surfactants, with ditallow-alkyldimethylammonium chloride being especially preferred.
Another particularly useful class of cationic surfactant is that in which the two long chains of the cationic surfactant contain a significant amount of unsaturation, such as where at least about 20%, preferably at least about 30~, of the long chains contain at least one double bond. By increasing the percentage of chains containing the double bonds, the per-formance benefits of these cationic materials are increased.
Compounds of this type have the formula R4 - 1+ - R2 X

*Trademark 7~7 wherein Rl and R2 contain an average of from about 15 to about 22 (most preferably from about 16 to about 18) carbon atoms, and at least about 20% of these chains contain at least one double bond; R3 and R4 are Cl to C4 alkyl or hydroxyalkyl groups, and X is any compatible anion, particularly one selected from the group consisting of halide, hydroxide, methylsulfate or acetate anions. Thus, for example, a pre-ferred cationic surfactant is di-partially hydrogenated tallow dimethylammonium halide (especially chloride or methyl sulfate), which is also known as di-softened tallowalkyl dimethylammonium halide. A commercially available compound of this type is "Adogen 470" , sold by Ashland Chemical Company, wherein about 30% of the tallow chains are oleyl in character. Another method of forming similar cationic materials is to synthesize a di-oleyl quaternary ammonium compound and hydrogenate it to the level of unsaturation desired. Compositions made with these cationics show several significant advantages over those made with more conventional cationics (such as ditallowalkyl-dimethylammonium chloride, only about 2% of the long chains of which contain double bonds); particularly these compositions show improved particularly soil removal, especially at low wash temperatures, improved static control and remain in a stable single phase at temperatures down to about 40F.
The cationics of this invention are preferably low in unquaternized amine content. If they contain more than about 1~ unquaternized amine or amine salt the pH of the formula is desirably kept below about 8 to avoid the amine odor.
Also, for odor reasons, it is preferable to use a solvent for the amine quaternization reaction which does not have an objectionable odor, e.g., a liquid nonionic detergent material, ethyl alcohol, etc.
The compositions of the present invention must be formu-lated 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.

*Trademark ~,~

11`~97~7 These compounds tend to be relatively non-biodegradable, do not enhance the cleaning or fabric conditioning benefits pro-vided by the compositions and may, in some circumstances, decrease the overall laundering performance provided by them.
5 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 and may be advantageously included in the compositions of the present invention.
In particularlv preferred embodiments of the present invention, the detergent compositions additionally contain from about 2 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., coconutalkyl ammonia amide, diethanol amides, and ethoxylated amides).
These amides are water-soluble or at least water dispersible.
In relation to the nonionic/cationic surfactant system, the 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 addition of the amide component results in a composition which exhibits improved antiredeposition of both clay and greasy/oily soils. This development is described in greater detail in 25 Canadian Patent Application Serial No. 306,559, Cambre, filed June 29, 1978. Preferred amides are C8-C20 monoethanol amides, C8-C20 diethanol amides, and amides having the formula O H

R-C-N-CH2CH20CH2CH20H, wherein R is a C8-C20 alkyl group, and mixtures thereof.
Particularly preferred amides are those where the alkyl group contains from about 10 to about 16 carbon atoms, such as coconut alkyl monoethanol or diethanol amide. Such compounds are commercially available under the trademarks "Superamide GR"

.
. ~ , .
"

, , l~L~97~t7 from Onyx Chemical Co., Jersey City, N.J., "Superamide F-3"
from Ryco, Inc., Conshohocken, Pa., and "Gafamide CDD-518"
available from GAF Corp., New York, N.Y.
These amide components may also be added in small amounts, i.e., from about 2% to about 5%, to act as suds modifiers.
Specifically, 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 may also contain additional inyredients 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 may 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, those described below.
Preferred silicone-type suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, Bartolotta et al. The silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types. The silicone material can be described as a siloxane having the formula:
17 \
tsiot \ R' wherein x is from about 20 to about 2,000, and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. Polydimethylsiloxanes (R and R' are methyl) having a molecular weight within the range of from about 200 to about 200,000, and higher, are all useful as suds controlling agents.

3~ 7~iP7 Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exhibit useful suds controlling properties.
Examples of such ingredients include diethyl-, dipropyl-, dibutyl-, methyl-ethylphenylmethyl-polysiloxanes and the like.
Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica. A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably tri-methylsilanated) silica having a particle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m2/gm intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 19:1 to about 1:2.
The silicone suds suppressing agent is advantageously releas-ably incorporated in a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier.
Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S. Patent

4,136,045, Gault et al, issued January 23, 1979. 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 35C-115C and a saponification value of less than 100 represent additional examples of a preferred suds regu-lating component for use in the subject compositions, and are described in detail in U.S. Patent 4,056,481, Tate, issued November 1, 1977. The microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants. Preferred microcrystalline waxes have a melting point from about 65C to 100C, a molecular weight *Trademark ~! ,.

,.

in the range from 400-1,000; and a penetration value of at least 6, measured at 77F by ASTM-D1321. Suitable examples of the above waxes include: microcrystalline and oxidized microcrystalline petrolatum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; candelilla; and carnauba wax.
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 monoleyl phosphates, which can contain di- and trioleyl phosphates.
The alkyl phosphate esters frequently contain some tri-alkyl phosphate. Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.g. mono-stearyl phosphate, up to about 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl phosphate.
Other adjunct components which may be included in the compositions of the present invention, in their conventional art-established levels for use (i.e., from about 0 to about 40%), include semi-polar nonionic (such as amine oxides), anionic, zwitterionic and ampholytic cosurfactants; detergency builders; bleaching agents; bleach activators; soil release agents (particularly copolymers of ethylene terephthalate and polyethylene oxide terephthalate, such as "Milease T"
sold by ICI, United States, as disclosed in U.S. Patent No.
4,132,680, Nicol, issued January 2, 1979; fillers; optical brighteners; germicides; pH adjusting agents; alkalinity sources; hydrotropes; enzymes; enzyme-stabilizing agents;
perfumes; solvents; carriers; suds modifiers; opactifiers;
and the like. However, because of the numerous and diverse performance advantages of the present invention, certain con-ventional components, such as cosurfactants and detergency builders, as well as fabric softening and static cGntrol agents, will not generally be necessary in a particular formulation, giving the compositions of the present invention *Trademark 7~7 a potential cost advantage over conventional detergent/
softener compositions. In fact, because the compositions of the present invention give such outstanding clay removal performance, even in a builder-free environment, and across the range of water hardness conditions, for environmental reasons the compositions of the present invention contain less than about 15% phosphate materials. Preferred compositions contain less than 7~ phosphate, and may even be substantially, or totally free of such phosphate materials, without decreas-ing the performance of the compositions. Further, in orderto achieve optimal particulate soil removal performance, the compositions of the present invention contain less than 10%, and are preferably substantially free of, silicate materials.
Preferred compositions of the present invention are also sub-stantially free of carboxymethylcellulose in order to optimizethe clay removal performance of the system. Finally, while the compositions of the present invention may contain anionic materials, such as anionic surfactants and hydrotropes (e.g., alkali metal toluene sulfonates), it is preferred that par-ticular anionic materials be contained in amounts sufficientlysmall such that not more than about 10%, preferably not more than about 5%, 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 sur-factant, decreases the overall cleaning and fabric condition-ing performance of the composition. Suitable anionic materials may 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 3 (such as sodium toluene sulfonate), it may be contained in an amount up to about 40%, by weight, of the cationic surfactant;
where the anionic material has a dissociation constant of at least about 1 x 10 5, but less than about 1 x 10 3, it may be contained in an amount up to about 15%, by weight, of the cationic surfactant; and where the anionic material has a :

9~57 dissociation constant of less than about 1 x 10 5 (such as sodium Cll 8 linear alkylbenzene sulfonate), it may be con-tained only in amounts up to about 10%, by weight, of the cationic surfactant. Preferred compositions are substantially free of such anionic materials.
Examples of cosurfactants and detergency builders which may be used in the compositions of the present invention are found in U.S. Patent No. 3,717,630, Booth, issued February 20, 1973; and Canadian Patent Application Serial No. 306,474, 10 Murphy, filed June 29, 1978. 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.
Compositions of the present invention may contain from about 0.005% to about 3%, preferably from about 0.01% to about 1%, of an optical brightener. Nonionic brighteners are preferred because of their compatibility with the nonionic and cationic surfactants utilized herein. Nonionic brighten-ers include those of the coumarin and benzoxazole classes; a particularly preferred brightener being 4-methyl-7-diethyl amino coumarin, commercially available under the trademarks "Tinopal SWN" from Ciba-Geigy Corp., Ardsley, N.Y., "Hiltamine Arctic White SOL", available from Hilton-Davis Chemical Co., Cincinnati, Ohio, and "Calcofluor White SD", available from American Cyanamid, Wayne, N.J. Other brighteners useful herein include bis(benzoxazol-2-yl)trio-phenes, 1,2-bis(benzoxazol-2-yl)ethylenes, 1,4-bis(benzoxazol-2-yl)naphthalenes, 4,4'-bis(benzoxazol-2-yl)-stilbenes, 2-(styryl)benzoxazoles, 2(styryl)naphthoxazole, or 2-(4-phenylstilben-4'-yl)-5-tertbutyl benzoxazole.
Preferred compositions of the present invention contain from about 0.05~ to about 1.5%, preferably from about 0.05% to about 1%, and most preferably from about 0.1% to about 0.8%, of polyacids capable of forming water-soluble calcium complexes, such as organo-phosphonic acids, particularly alkylene-~`

1~9757 polyamino-polyalkylene phosphonic acids. These materials include ethylenediamine tetramethylene phosphonic acid, hexa-methylene diaminetetramethylene phosphonic acid, diethylene triaminepentamethylene phosphonic acid, and aminotrimethylene phosphonic acid.
Other preferred embodiments of the present invention include an alkaline proteolytic enzyme having an iso-electric point of greater than about 8. The enzyme is present in an `
amount from 0 001% to about 2%, preferably from about 0.005%
to about 0.8%, especially from about 0.02~ to about 0.2%, and are particularly useful when used in conjunction with the polyacids, described above. The most preferred proteolytic enzyme preparations for use in this invention are derived from bacillus subtilis, such as ALCALASE , manufactured by Novo Industri A/S, and MAXATASE , manufactured by Gist-Brocades N.V. These most preferred enzyme species have an isoelectric point in the range from about 8.5 to about 9.2.
These polyacid and enzyme components, as well as the benefits they provide, are discussed in detail in U.S. Patent 4,100,262, Arnau et al., issued August 29, 1978, and U.S.
Patent 4,111,855, Barrat et al., issued September 5, 1978.
Compositions which include these components are particularly useful for the hand-laundering of fine fabrics, such as wool.
The compositions of the present invention may be produced in a variety of forms, including liquid, solid, qranular, paste, powder or substrate compositions. Preferred substrate articles may be formulated according to U.S. Patent No.
4,170,165 of Flesher et al, issued October 9, 1979. 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 (Cl 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 *Trademarks '~`' 1~97~7 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 con-ventionally-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 composi-tions and the method of the present invention.
EXAMPLE I
The particulate soil removal performance of the present invention was tested against a built, commercially-available heavy duty laundry detergent composition, in the manner described below. Composition A, a liquid composition of the present invention, was formulated by mixing together the components given below; Control 1 is a more conventional granular detergent formulation.
25 Composition A
Component Weight %
"Neodol" 23-6.51 28 Ditallowalkyldimethylammonium chloride 7 Ethanol 15 30 Water 50 Condensation product of C12 13 alcohol, having about 20%
2-methyl branching, with ~.5 moles of ethylene oxide, commercially available from Shell Chemical Company.

9~

Control 1 Component Weight %
Sodium salt of the sulfated reaction product of tallow alcohol condensed with 3 moles 5.5 of ethylene oxide Sodium tallowalkyl sulfate 5.5 Sodium Cll 8 linear alkylbenzene sulfonate 7.0 Sodium silicate solids (2.0r) 12.0 Sodium tripolyphosphate, anhydrous 24.4 Sodium sulfate 36.8 Polyethyleneglycol 6000 0.9 Moisture and minors balance to 100 (includes perfume and brightener) For each test, 3 cotton and 3 polyester fabric swatches were used. The swatches were stained with a slurry of clay in water; the 6 swatches containing a total of about 1.5 grams of the clay material. For each treatment, the 6 swatches were run through one cycle (which includes predissolve, wash, rinse, and spin steps) of a 1.5 gallon capacity automatic mini-washer.
Composition A was used in the washer at a concentration of about 1800 parts per million (an active concentration of 620 ppm), while Control 1 was used at a concentration of about 1,500 parts per million. The swatches were machine dried, and the particulate soil removal for each treatment was determined using a Hunter Whiteness Meter. The results, given below, are in filtered Hunter Whiteness Units, with higher numbers indicating better particulate removal. The above pro-cedures were carried out using 100F wash water containing7 and12 grains per gallon of mixed calcium and magnesium hardness, and using a wash temperature of 125 F, at a hardness of 7 grains per gallon.

~, ~

, i~97~7 , .

Wash water temperature100 F 100 F 125 F
Water Hardness (grains/gallon) 7 12 7 Polyester Composition A 57 56 69 Control 1 32 25 26 least significant difference 3 2 2 Cotton Composition A 45 47 53 Control 1 40 42 40 10 least slgnificant difference 4 1 2 These data demonstrate the superior particulate soil removal performance, over a range of wash temperature, water hardness and fabric conditions, of the compositions of the present invention when compared with a more conventional laundry detergent formulation. It must be emphasized that Composition A, a totally unbuilt composition, demonstrated these benefits, in spite of the fact that Control 1 contains significant amounts of phosphate builder materials.
Similar cleaning results are obtained when the cationic surfactant in Composition A is replaced, in whole or in part, by ditallowalkyldimethylammonium methyl sulfate, ditallow-alkyldimethylammonium iodide, dihexadecylalkyldimethylammonium chloride, dihexadecylalkyldihydroxylethylammonium methyl sulfate, dioctadecylalkyldimethylammonium chloride, dieicosyl-alkyl methyl ethyl ammonium chloride, dieicosylalkyl dimethyl-ammonium bromide, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, or mixtures of these surfactants.
Substantially similar results are also obtained where the nonionic surfactant in Composition A is replaced, in whole or in part, by the condensation 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 9 moles of ethylene oxide; the 35 condensation product of C12 13 alcohol with 6.5 moles of , .

11~)97~7 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 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 10C14 15 alcohol with 7 moles of ethylene oxide; and other mixtures of those surfactants.
Excellent cleaning 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.

The dye transfer inhibition properties of Composition A
of Example I were compared to those of a more conventional, built laundry detergent composition in the following manner.
Control 2 20 Component Weight %
Sodium salt of the sulfated reaction product of tallow alcohol condensed with 3 moles of ethylene oxide5.5 Sodium tallowalkyl sulfate 5.5 25 Sodium Cll 8 linear alkylbenzene sulfonate 7.0 Sodium silicate solids (2.Or)12.0 Sodium tripolyphosphate, anhydrous 24.4 Sodium Zeolite A, Hydrated 18.0 (~3~ average diameter) 30 Sodium sulfate 18.8 Polyethyleneglycol 6000 0.9 Moisture and minorsbalance to 100 (includes perfume and brightener) While a full size automatic washing machine was filling with 100F water, having a mixed calcium/magnesium hardness of 7 grains per gallon, the detergent compositions were added to the wash solution. In one set of runs, Composition A was used ~.

7~7 at a level of 1400 parts per million (an active concentration of 500 ppm), while in the second set of runs Control 2 was used at a concentration of about 1500 parts per million.
After the washing machine was filled with water, four white cotton terry fabrics and one piece (9" x 20") of navy blue sweatshirt were added to the wash solution. After one complete washing cycle, the fabrics were removed and dried.
Upon visual inspection it was seen that while the fabrics washed with Composition A were still white, those washed in Control 2 had a noticeable blue tinge. To confirm these visual results, a Hunter Whiteness Meter was used to determine the "b" value of the laundered fabrics. This "b" value indicates the amount of blue color in the fabric; with 0 indicating no blue color present, and increasingly negative numbers denoting increasing amounts of blue color in the fabric. On two runs with Composition A, the Hunter "b" readings were 0 on each run.
However, on two runs using Control 2, Hunter "b" readings of -4 and -5, indicating a definite presence of blue color in the fabrics, were obtained. These data demonstrate that Composition A, a composition of the present invention, was able to inhibit the transfer of dye from the blue sweatshirt fabric onto the white cotton terry fabrics, while Control 2, a more conventional laundry detergent composition, was not able to effectively do so.
EXAMPLE III
Using the method described in Example II, the dye trans-fer inhibition properties of a composition of the present invention were tested against a similar composition which included a mono-long chain quaternary ammonium surfactant, rather than the required di-long chain quaternary ammonium surfactant.
Before the test procedure was begun, the white cotton terry fabrics used were found to have a Hunter Whiteness "b"
value of -0.78. One set of terries was washed using Composi-tion A, of Example I, at a usage concentration of about 1400parts per million, while a second set of cotton terries was washed in a similar composition containing a mixture of Neodol \ `~ `

~.
' - ~

7~7 23-6.5 and tallowalkyltrimethylammonium chloride, in a nonionic:
cationic ratio of 4:1, at a usaye concentration of about 1400 parts per million. After washing in the presence of the blue sweatshirt material and drying, the terries washed with Compo-sition A were found to have a Hunter Whiteness "b" value of -0.79; a value essentially equivalent to the value of the terries prior to the wash. The terries washed with the tallow-alkyltrimethylammonium chloride composition were found to have a Hunter Whiteness "b" value of -2.13. These data demonstrate that the compositions of the present invention, which utilize di-long chain quaternary ammonium materials, offer a dye transfer inhibition benefit which is far superior to that offered by similar mixtures of nonionic and cationic surfac-tants, which utilize a conventional mono-long chain quaternary 14 ammonium surfactant of similar chain length.
EXAMPLE IV
The static control benefits of a liquid detergent compo-sition of the present invention,having the specific formulation given below, were demonstrated in the following manner. The composition was formulated by combining the ingredients in the proportions stated.
Component Weight "Neodol" 23-6.5 28 Ditallowalkyldimethylammonium chloride 7 25 Sodium toluene sulfonate 2 Ethanol 15 Water 48 A load of clothing was washed in a full size washing machine, using the composition given above at a usage concen-30 tration of about 1400 parts per million in 22 gallons of 100F
water, 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 clothing and contained cotton, polyester/cotton, nylon and polyester materials. The washed load was subsequently placed in an automatic dryer, ~J `

7~;7 the drum of which had been cleaned with an alcohol-soaked cloth, and drled for a period of 60 minutes. The fabric load was then removed from the dryer and placed in a grounded Faraday Cage. The overall charge reading of the materials in the Faraday Cage was read and recorded as individual items were removed from the Cage. When all the fabrics had been removed, the total voltage charge for the fabric load could be determined. This value was then divided by the total area of the fabric load (18.5 sq. yds.) to determine the voltage per square yard of the load.
The composition, described above, gave a voltage per square yard reading of 0.95, with no individual clings of fabrics observed as they were removed from the Faraday Cage.
Conventional laundry detergent compositions, tested in the same manner, generally give voltage per square yard readings of between about 4 and 10 volts per square yard, with numerous individual clings being observed, depending upon the relative humidity at the time the test is carried out. Thus, it is seen that the compositions of the present invention give excellent static control performance when compared to conven-tional laundry detergent compositions.

EXAMPLE V
A heavy duty liquid laundry detergent composition, having the formula given below, is made by combining the ingredients in the proportions specified.
Component Weight %
Neodol 23-6.5 28.0 Ditallowalkyldimethylammonium chloride 7.0 Ethanol 15.0 30 Dye 0-05 Perfume 0 35 Water balance to 100 This composition demonstrates outstanding removal of particulate soils, and fabric softening, static control, and dye transfer inhibition benefits when used to launder fabrics.

- 11~97~

The composition may also contain relatively small amounts of conventional opacifiers, such as about 0.05% of TiO2, to enhance its appearance.
EXAMPLE VI
A liquid laundry detergent product of the present inven-tion is formulated by combining the components given below in the proportions specified.
Component Weight %
Condensation product of C14 15 alcohol, having about 20% 2-methyl branching,2with 7 moles of ethylene oxide 20.0 Methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium3 lO.0 15 Ethanol 15.0 Dye 0.1 Perfume 0.35 Water balance to 100 Neodol 45-7, commercially available from Shell Chemical Company.
3Varisoft 475, commercially available from Ashland Chemical Company.
This composition gives excellent removal of particulate soils , as well as static control, fabric softening and dye transfer inhibition benefits, in the automatic laundering process. This composition may also be adsorbed onto a finely divided water-insoluble carrier, such that the carrier con-stitutes about 20~ by weight of the total composition, in order to form a particulate detergent product. Further, the compo-sition may be coated onto a woven or nonwoven substrate sheet,dried, and used in the laundering process.
EXAMPLE VII
A liquid laundry detergent composition, having the formu-lation given below, is made by combining the components in the proportions specified.

~,.

Component Weight Condensation product of Cg_ll alcohol, with 8 moles of ethylene oxide, stripped to remove nonethoxylated and lower ethoxylated fractions4 30 Ditallowalkyldimethylammonium methyl sulfate 5 Isopropyl alcohol 12 Sodium tripolyphosphate 3 10 Mid-cut coconutalkyl ammonia amide 3 DB-5445 (trademark) Water and minorsbalance to 100 Dobanol 91-8T, commercially available from Shell Chemical Company. ("Dobanol 91-8T" is a trademark).
5a suds suppressor, containing a siloxane/glycol copolymer together with solid silica and a siloxane resin, commer-cially available from Dow Corning Corporation.
This composition p~ovides excellent cleaning of particu-late soils, as well as static control, fabric softening and dye transfer inhibition benefits, when used in the conventional automatic laundering process.
Substantially similar results are also obtained where the above composition contains lauramide in place of the coconut ammonia amide.
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 suds sup-pressor component in the above composition is replaced, in whole or in part, by a silicone suds suppressor selected from the group consisting of trimethyl-, diethyl-, dipropyl-, di-butyl-, 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.
Substantially similar performance is also obtained where the above composition additionally contains sodium silicate, at an amount of about 3% of the total composition.
$~

9~7 EXAMPLE VIII
A heavy duty liquid laundry detergent composition, having the formula given below, is made by combining the ingredients in the proportions specified.

5 Component Weight Neodol 45-7 11.8 Condensation product of C12 15 alcohol having about 20% 2-methyl branching, with 7 moles of ethylene oxide6 11.8 Ditallowalkyldimethylammonium chloride 5.25 Ethanol 13.2 Potassium hydroxide 0.1 Potassium bicarbonate 0.8 Water and minors (including perfume and opacifier) balance to 100 6Neodol 25-7, commercially available from Sheel Chemical Company.
This composition demonstrates outstanding removal of particulate soils, and fabric softening, static control, and dye transfer inhibition benefits when used to launder fabrics.
EXAMPLE IX
A heavy duty liquid laundry detergent composition, having the formula given below, is made by combining the ingredients in the proportions specified.
Component Weight %
Neodol 45-7 23.62 Ditallowalkyldimethylammonium chloride 5.25 Ethanol 15.00 30 Coconutalkyl monoethanol amide2.88 "Tinopal SWN" optical brightener 0.7 Perfume 0 35 Water balance to 100 This composition demonstrates outstanding removal of particulate soils, and fabric softening, static control and dye transfer inhibition benefits when used to launder fabrics.

- . , ~ .
, .

i~g75~

Substantially similar results are obtained where the coconutalkyl monoethanol amide is replaced, in whole or in part, by coconutalkyl diethanolamide or an amide having the formula O H
R-C-N-CH2CH2OcH2cH2OH~
wherein R is a coconutalkyl group or a C16 alkyl group.
Excellent results are also obtained where the amide and brightener components in the above composition are removed, and are replaced by water.
EXAMPLE X
A heavy duty liquid laundry detergent composition, having the formula given below, is made by combining the ingredients in the proportions specified.
Component Weight %
Neodol 45-7 24.0 Di-softened tallowalkyldimethylammonium chloride6 4.8 Ethanol 15.0 Potassium bicarbonate 0.5 20 Perfume 0.35 Water and minorsbalance to 100 6Adogen 470, commercially available from Ashland Chemical Company.
This composition demonstrates outstanding removal of particulate soils, and fabric softening, static control and dye transfer inhibition benefits when used to launder fabrics.
In addition, the composition provideq benefits over similar compositions utilizing more conventional cationic components, such as ditallowalkyldimethylammonium chloride, in terms of improved static control and particulate soil removal (especially at lower wash temperatures) and better processing characteristics, in that it forms a single phase product which remains stable at lower storage temperatures.

97~7 , .

EXAMPLE XI
A heavy duty liquid detergent composition.
Component Weight %
C12_13 alcohol polyethoxylate (6.5) 12 C14_15 alcohol polyethoxylate (7.0) 12 Dimethyl ditallow ammonium chloride 4.8 Ethanol 15 Sodium citrate 0.5 Perfume, dye, etc. 0.35 1,2-bis(6-methylbenzoxazol-2-yl) 0.017 ethylene H2O Balance EXAMPLE XII
Component Weight %
Condensation Product of C12 15 alcohol with 7 moles of ethylene oxide 20-25%
Ditallowalkyldimethyl ammonium chloride 4-5%
Proteolytic enzyme (MAXATASE-containiny 1.5 Anson unit/gram) 1.0%
Ethylenediaminetetramethylene phosphonic acid 0.3%
Ethanol 5-10%
Water Balance to 100

Claims (41)

1. A low phosphate laundry detergent composition, having a pH in the laundry solution of greater than about 7, containing from 0% to about 15% phosphate and from 0% to about 10%
silicate materials, and being substantially free of ethoxylated cationic surfactants containing more than an average of about 10 moles of ethylene oxide per mole of surfactant, comprising from about 5% to about 100% of a surfactant mixture consisting essentially of:
(a) a nonionic surfactant 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, and having an HLB of from 5 to about 14, or a mixture of such surfactants; and (b) 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 surfactants;
the ratio of said nonionic surfactant to said cationic sur-factant being in the range of from about 2:1 to about 9:1.

2. A composition according to Claim 1 wherein the ratio of nonionic surfactant to cationic surfactant is from about 3:1 to about 6.5:1.

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. A composition according to Claim 3 wherein R1 and R2 are alkyl groups.

5. A composition according to Claim 4 wherein, in the non-ionic surfactant, R is a primary alkyl chain containing an average of from about 10 to about 16 carbon atoms and n is an average of from about 2 to about 9.

6. A composition according to Claim 5 wherein the ratio of nonionic surfactant to cationic surfactant is from about 3.5:1 to about 5.5:1.

7. A composition according to Claim 6 wherein the nonionic surfactant is selected from the group consisting of the con-densation 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 nonethoxylated fractions; the condensation product of C9-11 alcohol with 8 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 tallow alcohol with 9 moles of ethylene oxide; and mixtures thereof.

8. A composition according to Claim 7 wherein the cationic surfactant is selected from the group consisting of ditallow-alkyldimethylammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecylalkyldimethylammonium chloride, dioctadecylalkyldimethylammonium chloride, dieicosylalkyl dimethylammonium chloride, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, and mixtures thereof.

9. A liquid detergent composition according to Claim 8 which additionally contains up to about 20% ethanol.

10. A composition according to Claim 9 wherein the nonionic surfactant is selected from the group consisting of the con-densation 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 C12-13 alcohol with 6.5 moles of ethylene oxide; and mixtures thereof.

11. A composition according to Claim 10 wherein the nonionic surfactant is a mixture of the condensation product of C12 15 alcohol with 7 moles of ethylene oxide and the condensation product of C14-15 alcohol with 7 moles of ethylene oxide, in a ratio of from about 4:1 to about 1:4.

12. A composition according to Claim 10 wherein the ratio of nonionic surfactant to cationic surfactant is from about 4:1 to about 5:1.

13. A composition according to Claim 12 wherein the cationic surfactant is selected from the group consisting of ditallow-alkyldimethylammonium chloride, ditallowalkyldimethylammonium methyl sulfate, methyl (1) tallowalkyl amido ethyl (2) tallow-alkyl imidazolinium methyl sulfate, and mixtures thereof.

14. A composition according to Claim 13 wherein the cationic surfactant is ditallowalkyldimethylammonium chloride.

15. A composition according to Claim 3 wherein the ratio of nonionic surfactant to cationic surfactant is from about 3.5:1 to about 5.5:1.

16. A composition according to Claim 3 which contains no more than about 7% phosphate materials.

17. A composition according to Claim 16 which is substan-tially free of phosphate materials.

18. A composition according to Claim 3 which is substantially free of silicate materials.

19. A composition according to Claim 3 which contains no more than about 10% of the cationic surfactant.

20. A composition according to Claim 3 which contains at least about 15% of the mixture of nonionic and cationic surfactants.

21. A composition according to Claim 3 which additionally contains from about 2% to about 25% of a water-soluble or water dispersible fatty amide surfactant.

22. A composition according to Claim 21 wherein the fatty amide surfactant is selected from the group consisting of C8-C20 monoethanol amides, C8-C20 diethanol amides, amides having the formula , wherein R is a C8-C20 alkyl group, and mixtures thereof.

23. A composition according to Claim 22 wherein the fatty amide surfactant is selected from the group consisting of coconutalkyl monoethanol amide, coconutalkyl diethanol amide, and mixtures thereof.

24. A composition according to Claim 3 wherein the cationic surfactant has the formula where R1 and R2 contain an average of from about 16 to about 22 carbon atoms and at least about 20% of these claims contain at least one double bond, R3 and R4 are C1 to C4 alkyl or hydroxyalkyl groups, and X is selected from the group consisting of halide, hydroxide, methylsulfate and acetate anions.

25. A composition according to Claim 24 wherein the nonionic surfactant is selected from the group consisting of the con-densation 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 C12-13 alcohol with 6.5 moles of ethylene oxide;
and mixtures thereof.

26. A composition according to Claim 24 wherein the cationic surfactant is di-partially hydrogenated tallowalkyl dimethyl-ammonium chloride.

27. A composition according to Claim 3 wherein the cationic surfactant is selected from the group consisting of ditallow-alkyldimethylammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecylalkyldimethylammonium chloride, dioctadecylalkyldimethylammonium chloride, dieicosylalkyl dimethylammonium chloride, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, and mixtures thereof.

28. A composition according to Claim 3 wherein the nonionic surfactant is selected from the group consisting of the con-densation 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 nonethoxylated fractions; the condensation product of C9-11 alcohol with 8 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 tallow alcohol with 9 moles of ethylene oxide; and mixtures thereof.

29. A composition according to Claim 3 which is substantially free of carboxymethylcellulose.

30. A composition according to Claim 3 which additionally contains up to about 5% of suds suppressor component.

31. A composition according to Claim 3 which contains anionic materials selected from the group consisting of:
anionic materials having a dissociation constant of at least about 1 x 10-3 in amounts up to about 40%, by weight, of the cationic surfactant; anionic materials having a dissociation constant of at least about 1 x 10-5 and less than about 1 x 10-3 in amounts up to about 15%, by weight, of the cationic surfactant; and anionic materials having a dissociation constant of less than about 1 x 10-5 in amounts up to about 10%, by weight, of the cationic surfactant.

32. A composition according to Claim 31 which is substan-tially free of anionic materials.

33. A composition according to Claim 3 which is substan-tially free of ethoxylated cationic surfactants which contain more than an average of about 7 moles of ethylene oxide per mole of surfactant.

34. A composition according to Claim 3 which additionally contains from about 0.005% to about 3% of a nonionic optical brightener.

35. The composition of Claims 1, 2 or 3 wherein said compo-sitions are essentially free of fatty acid polyglycol ether di-ester compounds.

36. A method of cleaning fabrics, while simultaneously pro-viding fabric softening, static control, color fidelity and dye transfer inhibition benefits, said method comprising the agitation of the fabrics in an aqueous solution containing from about 0.01 to about 0.3% of the detergent composition of Claim 1.

37. The composition of Claim 1 which additionally contains from about 0.05% to about 1.5% of polyacid capable of forming water-soluble calcium complexes.

38. The composition of Claim 37 wherein said polyacid is selected from the group consisting of ethylenediamine tetramethylene phosphonic acid, hexamethylene diaminetetra-methylene phosphonic acid, diethylene triaminepentamethylene phosphonic acid, aminotrimethylene phosphonic acid, and mixtures thereof.

39. The composition of Claim 1, 37, or 38 which additionally contains from about 0.001% to about 2% of an alkaline pro-teolytic enzyme having an iso-electric point of greater than about 8.

40. A composition according to Claim 4, 5 or 6 wherein said compositions are essentially free of fatty acid polyglycol ether di-ester compounds.

41. A composition according to Claim 7 or Claim 8 wherein said compositions are essentially free of fatty acid poly-glycol ether di-ester compounds.