Low-phosphate detergent composition for fabric washing

Abstract

 Laundry detergent compositions containing no or low levels of phosphate materials and specific mixtures of selected cationic and selected nonionic surfactants, preferably having reduced cationic monomer concentrations of from about 0.005 to about 0.2, are disclosed. These compositions are snusually effective in removing particulate soils from fabrics. A process for laundering fabrics using these compositions is also disclosed.

Description

[0001] This invention relates to laundry detergent compositions containing no or low levels of phosphate materials, which exhibit highly improved particulate soil removal capabilities. These detergent compositions provide surprisingly effective clay soil removal performance even in the absence of detergency builders.

[0002] Nonionic surfactants are generally used in laundry detergent compositions for their ability to remove greasy and oily soils. Cationic surfactant have also been used in detergent compositions,

to provide adjunct fabric care benefits, and not for the purpose of cleaning. Certain cationic surfactants have been included in detergent compositions for the purpose . of yielding a germicidal or sanitization benefit to washed surfaces; see, for example, U.S. Patent 2,742,434, Kopp, issued April 17, 1956; U.S. Patent 3,539,520, Cantor et al, issued November 10, 1970; and U.S. Patent 3,965,026, Lancz, issued June 22, 1976. Other cationic surfactants, such as ditallowalkyldimethylammonium chloride, are included in detergent compositions for the purpose of yielding a fabric- softening benefit, as disclosed in U.S. Patent 3,607,763, Salmen et al, issued September 21, 1971; and U.S. Patent 3,644,203, Lamberti et al, issued February 22, 1972. Such components are also used to control static, as well as soften laundered fabrics as, for example, in U.S. Patent 3,951,879, Wixon, issued April 20, 1976; and U.S. Patent-3,959,157, Inamorato, issued May 25, 1976. All of the above patents being incorporated herein by reference. However, none of these patents indicate that by the careful selection and combination of certain nonionic and cationic surfactants, to achieve specific nonionic:cationic surfactant ratios and reduced cationic monomer concentrations, outstanding removal of particulate soils may be obtained.

[0003] The compositions of the present invention have outstanding cleaning capabilities. In laundry tests, these compositions, not containing any builder components, have been shown to remove clay soils at least as well, and in some cases dramatically better, than fully-built conventional laundry detergent compositions. In addition, the compositions inhibit the transfer of dyes, soften and control static through the washing and drying operations-Further, by selecting the preferred cationic components defined in this application, the compositions additionally provide biodegradability and excellent removal of greasy and oily soils, while also providing, in a single detergent product, particulate soil removal, fabric softening, static control and dye transfer inhibition benefits to the laundered fabrics. The cleaning performance, which is superior to that previously demonstrated, is the result of a heretofore unrecognized cleaning potential of certain selected cationic surfactants when used in the presence of certain selected nonionic surfactants under the conditions specified herein.

[0004] It is an object of this invention to provide laundry detergent compositions which yield outstanding particulate soil removal, and which also provide fabric softening, static control and dye transfer inhibition benefits.

[0005] It is another object of this invention to provide laundry detergent compositions, yielding excellent particulate soil removal, which may be used in a variety of physical forms, such as liquid, solid, paste, granular, powder, or in conjunction with'a carrier such as a substrate.

[0006] It is a further more specific object of this invention to provide specific detergent compositions which yield excellent particulate soil removal and which are biode-- gradable.

[0007] It is a still further specific object of this invention to define specific novel cationic surfactants which are biodegradable and which yield excellent particulate and greasy and oily soil removal performance, as well as fabric softening and static control, in the cationic/nonionic surfactant systems of the present invention.

[0008] It is another specific object of this invention to provide amide-containing cationic/nonionic surfactant- containing compositions which yield both excellent particu--late soil removal and anti-redeposition properties.

[0009] It is yet another object of this invention to provide a process for laundering fabrics which yields especially good particulate soil removal, using cationic and nonionic surfactant-containing detergent compositions.

Disclosure of the Invention

[0010] The present invention relates to laundry detergent compositions, containing from 0 to about 20% phosphate materials, which are especially beneficial for the removal of particulate soils from fabrics, having a pH of at least about 6.5 in the aqueous laundry solution, and which are substantially free of fatty acid polyglycol ether diester compounds, oily hydrocarbon materials and cationic materials containing 13 or more ethylene oxide groups, comprising from about 5 to about 100%, by weight, of a surfactant mixture consisting essentially of

(a) a biodegradable nonionic having the formula

wherein R is a primary or secondary alkyi chain of from 8 to about 22 carbon atoms and n is an aver-" age of from about 2 to about 12, having an HLB of from 5 to about 17; and

(b) a cationic surfactant, free of hydrazinium groups, having the formula

wherein each R¹ is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to four structures selected from the group consisting of



and mixtures thereof, said R¹ containing from about 8 to 22 carbon atoms, and which may additionally contain up to 12 ethylene oxide groups; m is a number from 1 to 3, with no more than one R¹ in a molecule having a total of 16 or more carbon atoms when m is 2, or more than 12 carbon atoms when m is 3; each R² is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group, with no more than one R² in a molecule being benzyl; x is a number from 0 to 11, the remainder of any carbon atom positions being filled by hydrogens; Y is selected from the group consisting of:







wherein p is from 1 to 12,

.wherein each p is from 1 to 12,



(9) mixtures thereof;

L is 1 or 2, the Y groups being separated by a moiety selected from R¹ and R² analogs having from 1 to about 22 carbon atoms and 2 free carbon single bonds when L is 2; Z is an anion in a number to give electrical neutrality to the molecule; said cationic surfactant being at least water-dispersible in admixture with said nonionic surfactant;

the ratio of said nonionic to said cationic surfactant being in the range of from 5:1 to about 1:1 and the said cationic surfactant being present in an amount less than 10 % by weight of the composition. In preferred compositions, the reduced cationic monomer concentration of said surfactant mixture is from about 0.005 to about 0.2.

[0011] The compositions of the present invention are formulated so as to have a pH of at least about 6.5 in the laundry solution at conventional usage concentrations in order to optimize overall cleaning performance; preferably, they are alkaline in nature (pH greater than about 7) when placed in the laundry solution, and preferred compositions have a pH of at least about 7.5. Some of the cationic/ nonionic systems of the present invention will attain optimum removal of greasy/oily soils at higher pHs, while attaining optimum clay removal at relatively lower pHs. In these systems, overall performance may be enhanced by varying the pH of the wash solution during the laundering process. Particularly preferred compositions have a pH of at least about 8 in the laundry solution, in order to improve the removal of bodv soil. In addition to the alkaline laundry solution pH. these preferred compositions should also have the ability to maintain a pH in the laundry solution of from about 8 to 11 throuahout the washing operation (reserve alkalinitv). Such a reserve alkalinity may be obtained bv incorooratina comoounds which buffer at pHs of from about 8 to 11. such as monoethanolamine diethanolamine or triethanolamine.

[0012] The compositions are free of oily hydrocarbon materials, such as dry cleaning solvents mineral oil, paraffin oil and kerosene, because these materials (which are themselves oily in nature) load the washing liquor with excessive oily material, thereby diminishing the cleaning effectiveness of the compositions of the present invention.

[0013] The cationic component is free of hydrazinium groups due to their relatively high toxicity level which makes them unsuitable for use in the compositions of this invention.

[0014] The compositions of the present invention are substantially free of fatty acid polyglycol ether diester compounds, such as polyethylene glycol-600-dioleate or polyethylene glycol-800-distearate. Such additives 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.

[0015] Preferred compositions contain nonionic surfactant to cationic surfactant ratios of from 5:1 to about 5:3, especially from about 10:3 to 10:5, and particularly about 10:4. Compositions may also contain mixed nonionic systems. These mixed nonionic systems may contain nonionic surfactants contain nonionic surfactants which fall outside of the definition of the nonionic surfactant given above (such as alcohol polyethoxylates having

an average of greater than 12 ethylene oxide groups molecule) as long.as at least one of the nonionic surfactants in the mixture falls within the required definition and the ratio of that nonionic surfactant to the cationic surfactant falls within the required nonionic:cationic surfactant ratio. Preferred compositions may also contain fatty amide surfactants, in addition to the cationic and nonionic components. These amide-containing compositions yield excellent particulate soil removal, as well as a particulate soil anti-redeposition benefit. Processes for laundering fabrics with the compositions of the present invention are also taught herein.

[0016] The compositions of the present invention comprise, by weight, from about 5 to about 100 %, particularly from about 10 to about 95%, and most preferably from about 20 to about 90 %, of a mixture of the particularly defined nonionic and cationic surfactants in the ratios stated. It is preferred that the detergent compositions contain at least 1 % of the cationic component; otherwise, sufficient cationic surfactant may not be present in the wash solution to provide the desired cleaning results. Compositions containing 10 %-or more of the cationic component are not encompassed within the present invention. Such large amounts of cationic surfactant are impractical due to commercial availability and cost considerations.

Nonionic Component

[0017] The nonionic surfactants used in the compositions of the present invention are biodegradable and have the formula

wherein R is a primary or secondary alkyl chain of from about 8 to about 22, preferably from about 10 to 18, carbon atoms and n is an average of from about 2 to about 12, preferably from about 2 to about 9, most preferably from about 2 to about 7, and especially from about 4 to about 7. The nonionic surfactants included within the present invention include branched alcohol ethoxylates. The nonionics have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 17, preferably from about 6 to about 14. Especially useful particulate soil removal can be obtained with nonionic surfactants having HLBs of from about 10 to about 13.5. These nonionic surfactants are preferably combined with less soluble cationic materials (such as those having 2 or 3 long alkyl chains). Where more soluble cationic materials are used, nonionic surfactants of lower HLB may be equally as beneficial. HLB is defined in detail in Nonionic Surfactants, by M.J. Schick, Marcel Dekker, Inc., 1966, pp. 607-613, incorporated herein by reference.

[0018] Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of C₁₀ alcohol with 3 moles of ethylene oxide, the condensation product of 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_12-13 alcohol with 3 moles of ethylene oxide, and the same product which is stripped so as to remove the lower ethoxylate and nonethoxylated fractions, the condensation product of C_14-15 alcohol with 7 moles of ethylene oxide, the condensation product of C₁₂ alcohol with 5 moles of ethylene oxide, the condensation product of C_12-13 alcohol with 9 moles of ethylene oxide, the condensation product of C14-15 alcohol with 3 moles of ethylene oxide,. the condensation product of C_14-15 alcohol with 4 moles of ethylene oxide, and the condensation product of C_14-15 alcohol with 9 moles of ethylene oxide. A preferred class of such surfactants are made from substantially linear alcohols, such as those which utilize oxoalcohols containing about 20% 2-methyl branched isomers, commercially available under the tradename Neodol, from Shell Chemical Company.

[0019] The compositions of the present invention may also contain mixtures of nonionic surfactants falling within the above nonionic surfactant definition, or mixtures of nonionic surfactants, some of which do not fall within the above nonionic surfactant definition, as long as at least one of the nonionic surfactants contained in the mixture falls within the above definition of the nonionic surfactants, and the ratio of that nonionic surfactant to the cationic surfactant falls within the required nonionic/cationic ratio. Where the nonionic surfactant mixture contains a nonionic surfactant (or surfactants) which falls outside of the above nonionic definition, the ratio of the surfactant (or surfactants) within the above definition to that which docs not fall within the definition is preferably within the range of from about 1:1 to about 5:1. Specific examples of surfactant mixtures include a mixture of the condensation product of C_14-15 alcohol with 3 moles of ethylene oxide (Neodol 45-3) and the condensation product of C_14-15 alcohol with 14 moles of ethylene oxide (Neodol 45-₁₄), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1; a mixture of the condensation product of C₁₀ alcohol with 3 moles of ethylene oxide together with the condensation product of a secondary C₁₅ alcohol with 9 moles of ethylene oxide (Tergitol 15-S-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 4:1; and a mixture of Neodol 45-3 and Tergitol 15-S-9, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1.

[0020] Preferred nonionic surfactant mixtures contain alkyl glyceryl ether compounds in addition to the required nonionic surfactant. Particularly preferred are glyceryl ethers having the formulae

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 carbons 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 surfactant to glyceryl ether of from about 1:1 to about 4:1, particularly about 7:3.

[0021] Other biodegradable nonionic surfactants well known in the detergency arts may be used, in combination with one or more of the nonionic surfactants falling within the definition of nonionic surfactants required in the present invention, to form useful nonionic surfactant mixtures. Examples of such surfactants are listed in U.S. Patent 3,717,630, Booth, issued February 20, 1973, and U.S. Patent 3,332,880, Kessler et al, issued July 25, 1967, each of which is incorporated herein by reference. Nonlimiting examples of suitable nonionic surfactants which may be used in conjunction with the required nonionic surfactants include the condensation products of aliphatic alcohols with from about 13 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 ₁₃ moles of ethylene oxide per mole of alcohol; and the condensation product of about 14 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms).

cationic Component

[0022] The cationic surfactants used in the compositions of the present invention have the formula

wherein each R¹ is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with' up to three phenyl or hydroxy groups and optionally interrupted by up to four structures selected from the following group:



and mixtures thereof, and which contains from about 8 to 22 carbon atoms. The R¹ groups may additionally contain up to 12 ethoxy groups. m is a number from 1 to 3. No more than one R¹ group in a molecule can have 16 or more carbon atoms when m is 2 or more than 12 carbon atoms when m is 3. Each R² is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one _R² in a molecule being benzyl, and x is a number from 0 to 11, preferably from 0 to 6 The remainder of any carbon atom positions on the Y group are filled by hydrogens. Y is selected from the group consisting of:







wherein p is from 1 to 12,

wherein each p is from 1 to 12,



and (9) mixtures thereof;

L is 1 or 2, with the Y groups being separated by a moiety selected from R¹ and R² analogs (preferably alkylene or alkenylene) having from 1 to about 22 carbon atoms and two free carbon single bonds when L is 2. Z is a water-soluble anion, such as a halide, sulfate, methylsulfate, hydroxide,' or nitrate anion, particularly preferred being chloride, bromide, iodide, sulfate or methyl sulfate anions, in a number to give electrical neutrality of the cationic component. The specific cationic component to be included in a given system depends to a large extent upon the particular nonionic component to be included in the system, and is selected such that it is at least water-dispersible, or preferably water-soluble, when mixed with said nonionic surfactant. The term "water-dispersible" means that the cationic and nonionic surfactants, as well as the anions discussed hereinafter, remain dispersed throughout the. laundry solution during the washing process. Mixtures of the above-defined cationic materials may also be used in the compositions of the present invention. Small amounts of other cationic materials can be tolerated in such mixtures.

[0023] When used in combination with nonionic surfactants, within the specific ratios and the preferred reduced cationic monomer concentrations, defined hereinafter, these cationic components provide excellent soil removal characteristics, confer static control and fabric softening benefits to the laundered fabrics, and inhibit the transfer of certain dyes among the laundered fabrics in the wash solution. Preferred cationic surfactants are those which have critical micelle concentrations less than about 500 ppm.

[0024] In preferred cationic materials, L is equal to 1 and Y is

or mixtures thereof. However, L may be 2 and, in that case, the cationic component contains 2 cationic charge centers. of the present invention include phosphonium and.sulfonium materials.

[0025] Where m is equal to 1, it is preferred that x is equal to 3 and R² is a methyl group. Preferred compositions of this mono-long chain type include those in which R¹ is a C₁₀ to C ₁₈ alkyl group. Particularly preferred compositions of this class include C₁₂ alkyl trimethylammonium halide, C₁₄ alkyl trimethylammonium halide, coconutalkyl trimethylammonium halide, tallowalkyl trimethylammonium halide, and C₁₆ alkyl trimethylammonium halide.

[0026] In order to be sufficiently water-soluble or water-dispersible, the cationic surfactant must satisfy the following chain-length criteria. Where m is equal to 2, only one of the R¹ chains can be longer than 16 carbon atoms. Thus, ditallowdimethylammonium chloride and di- stearyldimethylammonium chloride, which are used conventionally as fabric softeners and static control agents in detergent compositions, are not included within the definition of the cationic components used in the present invention. Preferred di-long chain cationics of this type include those in which x is equal to 2 and R² is a methyl group. In this instance it is also preferred that R¹ is a C₁₀ to C₁₄ alkyl group. Particularly preferred cationic materials of this class include di-C₁₀ alkyldimethylammonium halide, di-C₁₂ alkyldimethylammonium halide materials, and dicoconutalkyl dimethylammonium halide.

[0027] Where m is equal to 3, only one of the R¹ chains can be greater than 12 carbon atoms in length. In this instance, it is preferred that x is equal to 1 and that R² is a methyl group. In these compositions it is preferred that R¹ is a C₈ to C₁₂ alkyl group. Particularly preferred tri-long chain cationics include trioctylalkylmethylammonium halide, and tridecylalkyl- methylammonium halide.

[0028] Another type of preferred cationic surfactant for use in the compositions of the present invention arc the alkoxylated alkyl quaternaries. Examples of ethoxylated compounds are given below:

wherein each p is from 1 to 12, preferably from 1 to 10, most preferably from 1 to 7, with the total ethylene oxide groups in a molecule not exceeding about 12. Each R is a C₁₀ to C₂₀ alkyl group.

[0029] The compositions of the present invention are formulated so as to be substantially free of ethoxylated cationic surfactants which contain an average of about 13 or more, and especially more than-about 10, moles of ethylene oxide per mole of surfactant. These compounds tend to be relatively nonbiodegradable, do not enhance the cleaning or fabric conditioning benefits provided by the compositions and may, in some circumstances, decrease the overall laundering performance provided by them.

[0030] The following formulations have been found to be especially suitable for removing particulate soils, and providing fabric softening, static control and dye transfer inhibition benefits, in a conventional home laundering operation.

(a) Tallowalkyltrimethylammonium halide or methylsulfate,such as chloride, together with a nonionic surfactant selected from the condensation product of C₁₂-C₁₃ alcohol with 2 to 4 moles of ethylene oxide and the condensation product of C₁₄-C₁₅ alcohol with 3 to 6 moles of ethylene oxide, such as the condensation product of C_12-13 alcohol with 3 moles of ethylene oxide, the condensation product of C_14-15 alcohol with 4 moles of ethylene oxide, or mixtures thereof, in a nonionic:cationic ratio of from 5:1 to about 5:3.

(b) Tallowalkyltrimethylanmonium halide or methylsulfate, such as chloride, together with a nonionic surfactant selected from the condensation product of C₁₂-C₁₃ alcohol with 5 to 7 moles of ethylene oxide and the condensation product of C₁₄-C₁₅ alcohol with 5 to 8 moles of ethylene oxide, such as the condensation product of C₁₂ 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_14-15 alcohol with 7 moles of ethylene oxide, or mixtures thereof, in a nonionic:cationic ratio of from 5:1 to about 1:1, especially from 5:1 to about 4:1. Compositions which exhibit both excellent particulate and greasy/oily soil removal may be formulated by combining this cationic material with the condensation product of C₁₂-C₁₃ alcohol with 4 to 10 moles of ethylene oxide or the condensation product of C₁₄-C₁₅ alcohol with 6 to 10 moles of ethylene oxide, in nonionic:cationic ratios of from 5:1 to about 1:1.

(c) Coconutalkyltrimethylammonium halide or methylsulfate, such as chloride, together with a nonionic surfactant selected from the condensation product of C₁₂-C₁₃ alcohol with 2 to 4 moles of ethylene oxide and the condensation product of C₁₄-C₁₅ alcohol with 3 to 6 moles of ethylene oxide, such as the condensation product of C_12-13 alcohol with 3 moles of ethylene oxide, the condensation product of C_14-15 alcohol with 4 moles of ethylene oxide, or mixtures thereof in a nonionic:cationic ratio of from 5:1 to about 1:1.

(d) Coconutalkyltrimethylammonium halide or methylsulfate, such as chloride, together with a nonionic surfactant selected from the condensation product of C₁₂-C₁₃ alcohol with 5 to 7 moles of ethylene oxide and the condensation product of C₁₄-C₁₅ alcohol with 5 to 8 moles of ethylene oxide, such as the condensation product of the condensation product of C₁₂ 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_14-15 alcohol with 7 moles of ethylene oxide, or mixtures thereof, in a nonionic: cationic ratio of from 5:1 to about 1:1, a cationic ratio especially about 3:1. Compositions which exhibit both excellent particulate and greasy/oily soil removal may be formulated by combining this cationic material with the condensation product of C₁₂-C₁₃ alcohol with 4 to 10 moles of ethylene oxide or the condensation product of C₁₄-C₁₅ alcohol with 6 to 10 moles of ethylene oxide, in nonionic: cationic ratios of from 5:1 to about 1:1.

(e) A cationic surfactant of the formula

, wherein R¹, R² and _Z are as defined above, together with a nonionic surfactant selected from the condensation products of C₁₂-C₁₅ alcohols with 2 to 4 moles of ethylene oxide, such as the condensation product of C_12-13 alcohol with 3 moles of ethylene oxide, the condensation product of C_14-15 alcohol with 4 moles of ethylene oxide, or mixtures thereof, in a nonionic:cationic ratio of from about 3:1 to about 1:1.

(f) A cationic surfactant of the formula

, wherein R¹, R² and Z are as defined above, together with a nonionic surfactant selected from the condensation products of C₁₂-C₁₅ alcohols with 5 to 10 moles of ethylene oxide, such as the condensation product of C₁₂ 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_14-15 alcohol with 7 moles of ethylene oxide, or mixtures thereof, in a nonionic: cationic ratio of from 5:1 to about 1:1.

(g) Dicoconutalkyldimethylammonium halide, or methylsulfate such as chloride, together with a nonicnic surfactant selected from the condensation proctuct of C₁₂-C₁₃. alcohol with 4 to 8 moles of ethylene oxide or the conden- ^sati^on product of C₁₄-C₁₅ alcohol with 4 to 8 moles of ethylene oxide, such as the condensation product of C₁₂ 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_14-15 alcohol with 7 moles of ethylene oxide, or mixtures thereof, in a nonionic:cationic ratio of from 5:1 to about 1:1, especially from about 4:1 to about 2:1. Compositions which give both excellent particulate and greasy/oily soil removal can be obtained by combining this cationic surfactant with the condensation product of C₁₂-C₁₃ alcohol with ₆ to ₁₀ moles of ethylene oxide in nonionic:cationic ratios of from 5:1 to about 4:1.

(h) Tri-C₁₂alkylmethylammonium halide or methylsulfate, such as chloride, together with a nonionic surfactant selected from the condensation product of C₁₂-C₁₃ alcohol with 6 to 10 moles of ethylene oxide and the condensation product of C₁₄-C₁₅ alcohol with 6 to 10 moles of ethylene oxide, such as the condensation product of C_12-13 alcohol with 6.5 moles of ethylene oxide, the condensation,product of C_12-13 alcohol with 9 moles of ethylene oxide, the condensation product of C_14-15 alcohol with 7 moles of ethylene oxide, the condensation product of C_14-15 alcohol with 9 moles of ethylene oxide, or mixtures thereof, in a nonionic: cationic ratio of from 5:1 to about 1:1, especially from 5:1 to about 5:3..

(i) Tri-C_8-10alkylmethylammonium halide or methylsulfate, such as chloride, together with a nonionic surfac- tant selected from the condensation product of C₁₂-C₁₃ alcohol with 5 to 10 moles of ethylene oxide, and the condensation product of C₁₄-C₁₅ alcohol with 6 to 10 moles of ethylene oxide, such as the condensation product of C₁₂ 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_12-13 alcohol with 9 moles of ethylene oxide, the condansation product of C_14-15 alcohol with 7 moles of ethylene oxide, the condensation product of C_14-15 alcohol with 9 moles of ethylene oxide, or mixtures thereof, in a nonionic/cationic ratio of from about 3:1 to about 1:1.

[0031] A particularly preferred type of cationic component. has the formula

wherein R¹ is C₁ to C₄ alkyl or hydroxyalkyl; R² is C₅ to C₃₀ straight or branched chain alkyl or alkenyl, alkyl phenyl, or

wherein s is from 0 to 5; R³ is C₁ to C₂₀ alkylene or alkenylene; a is 0 or l, n is C or 1, and n is 1 when a is 1; m is from 1 to 5; Z¹ and Z² are each selected from the group consisting of

and wherein at least one of said groups is an ester, reverse ester, amide or reverse amide; and X is an anion which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, and nitrate, preferably chloride, bromide, iodide, sulfate, or methyl sulfate.

[0032] In addition to the advantages of the other cationic surfactants disclosed herein, this particular cationic component is environmentally desirable, since it is biodegradable, yielding environmentally acceptable compounds, both in terms of its long alkyl fragment and

nitrogen-containing fragment.

[0033] Where this type of biodegradable cationic surfactant is used, it is preferred that the detergent compositions have a pH of not greater than about 11, preferably less than about 10, in the laundry solution, in order to minimize hydrolysis of the cationic surfactant.

[0034] Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula:

as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.

[0035] Particularly preferred examples of this type of cationic surfactant include stearoyl choline ester quaternary ammonium halides (R² = C₁₇ alkyl), palmitoyl choline ester quaternary ammonium halides (R² = C₁₅ alkyl), myristoyl choline ester quaternary ammonium halides (R² = C₁₃ alkyl), lauroyl choline ester ammonium halides (R² = C₁₁ alkyl), and tallowyl choline ester quaternary ammonium halides (R² = C₁₅-C₁₇ alkyl).

[0036] Additional preferred cationic components of the choline ester variety are given by the structural formulas below, wherein p may be from 0 to 20.

[0037] The preferred choline-derivative cationic substances, discussed above, may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternizcd with a methyl halide, forming the desired cationic material. The choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize trimethylamine, forming the desired cationic component.

[0038] Another type of novel, particularly preferred cationic material has the formula

In the formula, each R¹ is a C₁ to C₄ alkyl or hydroxy- alkyl group, preferably a methyl group. Each R² is either hydrogen or C₁ to C₃ alkyl, preferably hydrogen. R³ is a C₄ to C₃₀ straight or branched chain alkyl, alkenyl, alkyl phenyl, or alkyl benzyl group, preferably a C₈ to C₁₈ alkyl group, most preferably a C₁₂ alkyl group. R is a C₁ to C₁₀ alkylene or alkenylene group. n is from 2 to 4, preferably 2; y is from 1 to 20, preferably from about 1 to 10, most preferably about 7; a may be 0 or 1, and t may be 0 or 1, but t must be 1 when a is 1; and m is from 1 to 5, preferably 2. Z² is selected from the group consisting of:

Z¹ is selected from the group consisting of:

and wherein at least one of said Z¹ and Z² groups is selected from the group consisting of ester, reverse ester, amide and reverse amide. X is an anion which will make the compound at least water-dispersible, and is selected from the group consisting of halides, methyl sulfate, and nitrate, particularly chloride, brimide, iodide, sulfate, sulfate. Mixtures of the above structures can also be used

[0039] These surfactants, when used in the compositions of the present invention, yield excellent particulate soil, body soil, and grease and oil soil removal. In addition, the detergent compositions control static and soften the fabrics laundered therewith, and inhibit the transfer of certain dyes in the washing solution. Further, these novel cationic surfactants are environmentally desirable, since both their long chain alkyl fragments and their nitrogen fragments are biodegradable, in that they degrade to yield environmentally acceptable compounds. Where this type of biodegradable cationic surfactant is used, it is preferred that the detergent compositions have a. pH-of not greater than about 11, preferably less than about 10, in the laundry solution, in order to minimize hydrolysis of the cationic surfactant.

[0040] Preferred embodiments of this type of cationic component are the esters in which R¹ is a methyl group and Z² is an ester or reverse ester group, particular formulas of which are given below, in wchich t is 0 or 1 and y is from 1 to 20.

[0041] The preferred derivatives, described above, may be prepared by the reaction of a long chain alkyl polyalkoxy (preferably polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride, to form the corresponding acid chloride. The acid chloride is then reacted with dimethylaminoethanol to form the appropriate amine ester, which is then quaternized with a methyl halide to form the desired choline ester compound. Another way of preparing these compounds is by the direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or dimethyl aminoethanol, in the presence of heat and an acid catalyst. The reaction product formed is then quaternized with methylhalide or used to quaternize trimethylamine to form the desired choline ester compound.

[0042] As a guide in formulating compositions which deliver excellent particulate soil removal, the reduced cationic monomer concentration may be used. Thus, the nonionic and cationic components, defined above, may be combined into a surfactant mixture which has a ratio corresponding to a reduced cationic monomer concentration (C_R) of from about 0.005 to about 0.2, preferably from about 0.008 to about 0.15, particularly from about 0.01 to about 0.1. A C_R value within this range will yield a composition which exhibits optimum particulate soil removal performance. Where the nonionic and cationic components used are pure, the more narrow C_R ranges are preferred. In a preferred method of . preparing the compositions of the present invention, the nonionic and cationic surfactants are intimately and completely mixed together prior to the addition of anv additional components to the mixture. This intimate premixing of the nonionic and cationic components enhances performance of the compositions.

[0043] An approximation of the C_R of a surfactant mixture is obtained by dividing the concentration of the cationic surfactant monomer in the laundry solution by the critical micelle concentration (CMC) of the surfactant. As used in this application, CMC's are determined at 105°F in water containing 7 grains/gallon of mixed hardness, unless otherwise stated. For purposes of this application, C_R is calculated according to the equations given below.

[0044] The concept of reduced monomer concentration is derived from the discussion in Tamamushi and Tamaki, Proceedings of the Second International Congress of Surface Activity, III, 449, Academic Press, Inc (1957) and in Clint, J. Chem. Soc. Far. Trans., 1,71, 1327 (1975), incorporated herein by reference, in the context of an ideal solution, and is based on the following quadratic equation (equation (11) in Clint):

wherein in the above and the following equations:

C = total analytical surfactant concentration in the solution (moles/I.) = sum of the cationic and nonionic concentrations = C₁ + C₂ (wherein "1" denotes nonionic surfactant and "2" denotes cationic surfactant)

c*₁ = critical micelle concentration (CMC) of nonionic surfactant (moles/l.)

c₂ = critical micelle concentration of cationic surfactant (moles/l.)

a = total mole fraction of nonionic surfactant in the solution ⁼ C₁/(C₁ + C₂)

β = a constant based upon the heat of mixing = -2.8

c^m₁ = nonionic monomer concentration

c^m₂ = cationic monomer concentration

e = base of Napierian logarithm system = 2.71828

x = mole fraction of the nonionic surfactant in the micelle at concentration C

f₁ = nonionic activity coefficient in the mixed micelle = c^8(1-x)2

f₂ = cationic activity coefficient in the mixed micelle = e^8x2

◁ = f₂c^*₂ - f₁, c^*₁

W = total analytical surfactant concentration in the solution (ppm) = sum of the cationic and nonionic concentrations (^ppm) ⁼ W₁+W₂ (wherein "1" denotes nonionic surfactant and "2" denotes cationic surfactant)

Y = weight fraction of nonionic surfactant in the composition

[0045] The above equation is solved for the nonionic monomer concentration by taking its positive root (equation (12) in Clint).

[0046] By modifying this equation based on the assumptions of a regular, rather than an ideal, solution, the C_R range for optimum performance was derived from the following equation:

[0047] For a given cleaning test for a nonionic/cationic system, x was found by inserting the values known from the test (i.e., c^*₁, c^*₂, α, C and β) into equation (1) and solving iteratively for x, such that the error in x is less than 0.001. This procedure was repeated for a large number of such tests, over varying usage conditions. The x values obtained were then used to solve for the cationic monomer concentrations using the following equation:

The C value was then calculated using equation (3).

[0048] The C_R values obtained cover a large number of combinations and ratios of various nonionic and cationic surfactants, at various concentrations and temperatures, which have been evaluated for their ability to clean greasy/oily soils. The examination of the resulting data revealed that for a given system the optimum cleaning of greasy/oily soils was found at a C_R value of from about 0.002 to about 0.2.

[0049] This range of C_R (i.e., 0.002 to 0.2) can then be used to determine the range of optimum nonionic/cationic vrios for any given combination of nonionic surfactant and cationic surfactant, for the desired wash concentration within the overall wash concentration range of from 100 parts per million (ppm) to 10,000 ppm of surfactant. This calculation is carried out in the following manner, where β, C_R, c*₁, c*₂, M₁ and M₂ are known for a given nonionic/ cationic surfactant pair:

(a) for a given nonionic surfactant, cationic surfactant, and for each end of the CR range, solve for x using the equation

by standard numerical iterative techniques to an error in x of less than 0.001;

(h) find the range of Y from the equation

using 100 ppm and 10,000 ppm as the boundary values for for each end of the C_R range;

(c) the nonionic/cationic ratio (NCR) range for optimum porfomance is then within the range obtained by substituting the boundary values for Y into the formula

[0050] Put another way, steps (b) and (c) may be combined . into a single equation which may be solved directly for the NCR.

[0051] The above procedure is relevant only to wash solution concentrations above the critical micelle concentration of the nonionic/ cationic mixture. For concentrations which are as high as about five times the critical micelle concentration, C_R is essentially independent of concentration. This means that for conventional laundry usage concentrations (e.g., 100 ppm to 10,000 ppm, and especially from about 250 ppm to about 3,000 ppm), the CR of most commercial cationic/ nonionic surfactant mixtures (wherein the cationic component has a CMC of less than about 100 ppm, measured at 105°F water containing 7 grain/gallon of mixed calcium and magnesium hardness) will be independent of the actual usage concentration, so that using a concentration of about 1,000 ppm in the above calculation will be a satisfactory approximation for the entire range. As used herein, if a concentration range is not specified, the 1,000 ppm C_R is meant.

[0052] In addition to these reduced cationic monomer criteria, the nonionic/cationic surfactant mixture may also satisfy the specific cloud point requirements, given below. In addition to outstanding particulate soil detergency, these preferred compositions will be optimized for the removal of greasy/oily soils. Thus, in preferred compositions, the cloud point of the nonionic/cationic mixture (and in preferred embodiments the nonionic/cationic mixture plus any electrolytes present in the composition) falls between about 0 and about 95°C, preferably between about 10 and about 70°C, more preferably between about 20 and about 70 °C, especially between about 30 and about 50°C. For cold water detergency, the surfactant mixture should have a cloud point between about 0 and about 25°C. The fact that a composition has a cloud point within these temperature ranges assures that the composition can be utilized under laundry temperature conditions to achieve outstanding removal of greasy/oily soils. If a composition does not have a cloud point within the temperature range specified, it will not yield outstanding greasy/oily soil cleaning within that temperature range. The compositions will exhibit their best grease/oil removal-performance when'the temperature of the wash solution in which they are .used falls within about 20°C, preferably within about 15°C, and most preferably.within about 10°C, of the cloud point of the nonionic/cationic surfactant mixture. Put another way, the laundry solution temperature range in which the preferred compositions deliver optimum grease/oil removal lies between the cloud point-temperature of the system in the absence of .the cationic component, and about 30°C, preferably about 25°C, most preferably about 20°C, above that cloud point temperature.

[0053] As used herein, the term "cloud point" means the temperature at which a graph which plots the light scattering intensity of the composition versus wash solution temperature begins to sharply increase to its maximum value, under the following experimental conditions:

[0054] The light scattering intensity is'measured using a Model VM-12397 Photogoniodiffusometer, manufactured by Societe Francaise d'instruments de controle et d'analyses, France (the instrument being hereinafter referred to as (SOFICA). The SOFICA sample cell and its lid are washed with hot acetone and allowed to dry. The surfactant mixture is made and put into solution with distilled water at a concentration of 1000 ppm. Approximately a 15 ml. smaple of the solution is placed into the sample cell, using a syringe with a 0.2µ nucleopore filter. The syringe needle passes through the sample cell lid, so that the cell interior is not exposed to atomospheric dust. The sample is kept in a variable temperature bath, and both the bath and the sample are subject to constant stirring. The bath temperature is heated using the SOFICA's heater and cooled by the addition of ice (heating rate 1°C/minute); the temperature of the sample is determined by the temperature of the bath. The light scattering intensity of the sample is then determined at various temperatures, using a green filter and no polarizer in the SOFICA.

Fatty Amide Component

[0055] In particular pref-erred embodiments of the present invention the nonionic surfactant/cationic surfactant mixture additionally contains from about 2 to about 25%, preferably from about.2 to about 16%, and most preferably from about 3 to about 10%, of a fatty amide surfactant.

[0056] The ratio of the total cationic and nonionic components to the amide component in the composition is in the range of from 5:1 to about 50:1, preferably from about 8:1 to 25:1. when these compositions are formulated in accordance with the ratio and the preferred reduced cationic monomer concentration limits given herein, they result in excellent particulate soil removal performance, as well as improved soil anti-redeposition characteristics.

[0057] Amides useful in these preferred compositions include, but are not limited to, carboxylic acid amides, sulfonic acid amides, phosphonic acid amides, and boronic acid amides. Preferred amides include those having the formulae:

. wherein R¹ is a C₈-C₂₀ alkyl, alkenyl, alkyl phenyl or alkyl

group, preferably C_10-C₁8 alkyl, and most preferably C₁₁alkyl; and each R² is hydrogen, or C₁^-C₈ alkyl or hydroxyalkyl,preferably hydrogen. Specific examples of thesecompositions include a mixture of stearoyl choline bromido(present) in the washing solution at 120 parts per

the condensation product of coconut alcohol with 5

ethylene oxide (present in the wash solution at about 357 parts per million), and a mid-cut coconut alkyl amoniaamide (R¹ =coconut alkyl and R²is hydrogen; present inthe wash solution at about 50 parts per million): and a miktureof stearoyl choline bromide (100ppm) ; the condensation produit of coconut alcohol with 5 moles of ethyl- ene oxide(357 ppm), and lauramide (R¹ = C₁₁ and R² is hydrogeneat 45 ppm).

Additional Components

[0058] While the compositions of the present invention may contain additive materials conventionally used in detergent compositions, the amount of anion-producing materials, and hence. anions, which will make the particular cationic surfactant used in the compositions non-water dispersible should be minimized. Whether a particular anion constitutes-an "interfering anion" depends upon the physical and chemical properties (such as structure and dissociation constant) of the particular anions and cationic surfactants used in a given composition. It is preferred that anionic materials be contained in amounts sufficiently small such that not more than about 10 molar percent, preferably not more than about 5 molar percent, 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.

[0059] 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 1x10^-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 -5 -3 least about 1x10 ^-5, but less than about 1x10^-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 dissociation constant of less than about 1x10 ^-3, (such as sodium C_11-8 linear alkylbenzene sulfonate), it should be contained only in amounts up to about 10%, by weight, of the cationic surfactant.

[0060] It is preferred, in order to minimize the effects of interfering anions, that the compositions of the present invention be substantially free of phosphate, polyphosphate, silicate, and polycarboxylate builder anions, carboxymethyl cellulose, and anionic surfactants; particularly preferred are those which are substantially free of phosphate, polyphosphate, and carboxymethyl cellulose materials. The compositions of the present invention contain from 0 to about 20% of phosphate materials; and, even though they contain no or low levels of phosphate materials, exhibit an outstanding level of particulate soil removal. It is preferred that the compositions be substantially free of phosphate materials both for performance and environmental reasons.

[0061] The compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, consistent with the restrictions on interfering anions, stated above, at their conventional art-established levels. Very low levels (i.e., from about 1 to about 15%)of electrolytes, such as perborates, phosphates, polyphosphonates, carbonates or sulfates, may.have a beneficial effect on cleaning performance.

[0062] The compositions of the present invention may contain up to about 15%, preferably up to about 5%, and most preferably from about .1 to 2%, of a suds suppressor component. Typical suds suppressors include long chain fatty acids, such as those described in U.S. Patent 2,954,347, issued September 27, 1960, St. John, and combinations of certain nonionics therewith, as disclosed in U.S. Patent 2,954,346,. issued September 2.7, 1960, .Schwoeppe, both disclosures being' incorporated herein by reference. Other suds suppressor components useful in the compositions of the present invention include, but are not limited to, those described below.

[0063] Preferred suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, ' Bartolotta et al., incorporated herein by reference, relative to a silicone suds controlling agent. 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:

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. The polydimethylsiloxanes (R and R' are methyl) having a molecular weighl within the range of from about 200 to about 200,000, and higher, are all useful as suds controlling agents. Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exchibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-ethyl-, phenylmethyl-polysiloxanes and the like. Additonal 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 trimethylsilanted) silica having a particle size in the range from about 10.millimicrons to 20 millimicrons and a specific surface are 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 releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.

[0064] Particularly useful suds suppressors are the self- emulsifying silicone suds suppressors,
such as DB-544, commercially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.

[0065] 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, such waxes are described in U.S. Patent 4,056,481, Tate, issued November 1, 1977, incorporated herein by reference. The microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic sufactants. Preferred microcrystalline waxes have a melting point from about 65°C to 100°C, a molecular weight in the range from.400-1,000; and a penetration value of at least 6, measured at 77°F by ASTM-D1321. Suitable examples of the above waxes include: microcrystalline and oxidized microcrystalline petrolatum waxes; Fischer-Tropsch and oxidized . Fisher-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; candelilla; and carnauba wax.

[0066] Alkyl phosphate esters represent an additional pref- erred 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.

[0067] The alkyl phosphate esters frequently contain some trialkyl phosphate. Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.g., monostearyl phosphate, up to about 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl phosphate

[0068] Other compatible adjunct components which may be included in the compositions of the present invention, . in their conventional art-established levels of use, include bleaching agents, bleach activators, soil suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents,enzymes, enzyme stabilizing agents, perfumes, fabric softening components, static control agents, and the like. However, because of the numerous and diverse performance advantages of the compositions of the present invention, many components, such as static control agents, fabric softening agents and germicides, will not usually be necessary.

[0069] The compositions of the present invention may be manufactured and used in a variety of physical forms, such as solid, powder, granular, paste, or liquid. The compositions are particularly well-suited for incorporation into substrate articles for use in the home laundering process. These articles consist of a water-insoluble substrate which releasably incorporates an effective amount, preferably from about 3 to 120 grams, particularly from about 20 to 80 grams, of the detergent compositions of the present invention. A particularly preferred substrate article incorporates a bleaching component and a bleach activator on the substrate, together with the nonionic/cationic surfactant mixture.

[0070] In a particularly preferred method of making the detergent compositions of the present invention, the specifically defined nonionic and cationic surfactants are intimately and completely mixed at a temperature of from about 25°C to about 95°C, preferably from about 40°C to about 90°C, prior to the addition of any additional components. By using this process, the components are taken from their original liquid or powder form and are made into a thick paste, which is ideally suited for use in the substrate articles, described above.

[0071] When this process is used to make the compositions of the present invention, the components are present in nonionic:cationic ratios.of from 5:1 to about 1:1, preferably from 5:1 to about 5:3, and more preferably from about 10:3 to about 10:5, and are formed into mixtures which satisfy the reduced cationic monomer concentration requirements, herein. In one particularly preferred embodiment of this process, the components are intimately mixed together at a temperature of about 25°C. In this embodiment, it is preferred that the anion contained in the cationic surfactant be bromide. Thus, when stearoyl.choline bromide, a powder having the following formula,

Br is intimately mixed at a temperature of about 25°C with the condensation product of C₁₂ alcohol with 5 moles of ethylene oxide, a liquid, at a nonionic: cationic ratio of about 10:4, a thick paste product is formed. Substantially similar results are obtained when the nonionic surfactant is the condensation product of coconut alcohol with 5 moles of ethylene oxide.

[0072] In another particularly preferred embodiment of this process, the components are intimately mixed together at a temperature of at least about 65°C. In this embodiment, it is preferred that the anion contained in the cationic surfactant be chloride. Thus, when stearoyl choline chloride, a powder, is intimately mixed at a temperature of about 80°C with the condensation product of C₁₂ alcohol with 5 moles of ethylene oxide, a liquid, at a nonionic:cationic ratio of about 10:4, a thick paste product is formed. If the same components are mixed together at about 25°C the mixture remains a liquid, which is much lass desirable for use in making substrate articles. Substantially similar results are obtained when the nonionic surfactant is the condensation product of coconut alcohol with 5 moles of ethylene oxide.

[0073] The compositions of the present invention are used in the laundering process by forming an aqueous solution (preferably one having a temperature of from about 10 to about 50°C). containing from about 0.01 (100 parts per million) to 0.3% (3,000 ppm), preferably from about 0.02 to 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 performance. Further, the compositions also provide fabric softening, static control, and dye transfer inhibition benefits to the fabrics laundered therewith.

[0074] Although not intending to be bound by theory, it is believed that the clay removal mechanism is as follows. At the optimum nonionic:cationic ratio, as defined by the reduced cationic monomer concentration, the cationic surfactant adsorbs onto the clay soil (negatively-charged) in a mono-layer, neutralizing the charge. This neutralized charge results in a hydrophobic surface which increases the adsorption of the nonionic surfactant onto the clay surface. The clay soil is then easily removed by the agitation.

[0075] .It has been found that when the nonionic/cationic compositions of the present invention are used in a laundry solution, a threshhold concentration of at least about 50, preferably about 100, most preferably about 150, parts per million on the cationic component must be present in the laundry solution in order to give the particulate soil removal benefit. Under conventional United States laundry conditions, which generally utilize from about 150 to 1500 parts per million of a detergent composition in the laundry solution, nonionic surfactant to cationic surfactant ratios of from 5:1 to about 1:1 are necessary in order to provide this threshhold concentration in the laundry solution.

[0076] All percentages, parts, and ratios used herein are by weight unless otherwise specified.

[0077] The following nonlimiting examples illustrate the compositions and the method of the present invention.

EXAMPLE I

[0078] A detergent composition of the present invention, has the following formulation:

[0079] This detergent composition, having a nonionic: cationic ratio of about 10:4, was used in the aqueous laundering solution at a concentration of about 500 ppm, and had a pH in the laundry solution of about 6.5. The composition had outstanding clay soil removal performance.

[0080] Substantially similar cleaning results are obtained where the detergent composition of the present invention does not contain the sodium chloride component, indicating that for the particular detergent composition defined above, sodium chloride does not contribute "interfering anions" to the laundry solution of the disclosed detergent compositions.

[0081] Substantially similar results are also obtained where the cationic surfactant used in the above composition is replaced by C₁₂ alkyl trimethylammonium chloride, C₁₄ alkyl trimethylammonium bromide, di-C₁₀ alkyl dimethylammonium chloride, di-C₁₂ alkyl dimethylammonium chloride, tri-C₈ alkyl methylammonium bromide, tri-C₁₀ alkyl methylammonium chloride, or the cationic surfactants listed below:

[0082] Substantially similar cleaning results are also obtained where the cationic surfactant used above is replaced by a mixture of dicoconutalkyl dimethylammonium bromide (A) together with C₁₂ alkyl trimethylammonium chloride (B) in a ratio of A:B of about 4:1, 3:1, 2:1, 1:1, 1:2, or 1:4; a mixture of

together with di-C₁₀ alkyl dimethylammonium chloride_' (D) in a ratio of C:D of about 5:1, 3:1, 1:1, 1:3 or 1;5; or a mixture of C, above, together with

in a ratio of C:E of about 7:1, 3:1,_.2:1, 1:1, 1:2, 1:3, 1:4, or 1:7.

[0083] Essentially similar results are also obtained where the nonionic component of the above composition is replaced with the condensation product of C₁₀ alcohol with 3 moles of ethylene oxide (IILB=9), the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of coconut alcohol with 7 moles of ethylene oxide (HLB=12.8), the condensation product of C_12-13 alcohol with 6.5 moles of ethylene oxide (HLB=12), the condensation product of C_12-13 alcohol with 3 moles of ethylene oxide (HLB=7.9) , and the same product which is stripped so as to remove unethoxylated and lower ethoxylate fractions, the condensation product of C₁₂ alcohol with 5 moles of ethylene oxide, the condensation product of C_12-13 alcohol with 9 moles of ethylene oxide, and the condensation product of C_14-15 alcohol with 3, 4 or 9 moles of ethylene oxide. A mixture of the condensation product of C_14-15 alcohol with 3 moles of ethylene oxide together with the condensation product of C_14-15 alcohol with 7 moles of ethylene oxide in a ratio of lower ethoxylate

to higher ethoxylate nonionic of about 2:1, an alkyl glyceryl ether having the structural formula:

in a ratio of alcohol ethoxylate to glyceryl ether of about 7:3.

[0084] Results substantially equivalent to those obtained above are also obtained where the detergent composition has a ratio of nonionic surfactant to cationic surfactant of 1:1, 10:3, 5:3, 10:5, or 5:1.

[0085] Substantially similar results are also obtained where the detergent composition is formulated, such as by the addition of monoethanolamine, to have a pH in the laundry solution of about 7, 8, 8.5, 9 or 10.

EXAMPLE II

[0086] A laundry detergent composition of the present invention has the following formulation:

[0087] The detergent composition of the present inven- _tion had a ratio of nonionic surfactant to cationic surfactant of about 10:4 and was used in the aqueous laundering solution at a concentration of about 500 ppm, having a pH in the laundry solution of about 6.5.

[0088] The detergent composition of the present invention, as formulated above, yields excellent particulate soil removal performar.ce,,good grease and oil removal, and gives fabric softening, static control and dye transfer inhibition benefits to fabrics laundered therewith.

[0089] Substantially similar results arc obtained where .the nonionic component of the above composition is replaced by the condensation product of C₁₀ alcohol with 3 moles of ethylene oxide, the condensation product of C₁₂ alcohol with 5 moles of ethylene oxide (HLB=11), the condensation product of coconut alcohol with 5 moles of.ethylene oxide, the condensation product of coconut alcohol with 7 moles of ethylene oxide, the condensation product of ^C _12-13 alcohol with 6.5 moles of ethylene oxide, or the condensation product of C14-1 alcohol with 7 moles of ethylene oxide.

[0090] Substantially similar results are also obtained when the ratio of nonionic surfactant to cationic surfactant used in the above composition is 10:3, 20:7, 10:5, 20:11, 5:3, 5:4, or 1:1.

[0091] Similar results are also obtained where the cationic surfactant, used above, is replaced by one of the following surfactants:

EXAMPLE III

[0092] A detergent composition of the present invention was formulated by combining the condensation product of coconut alcohol with 5 moles of ethylene oxide (IILB=10. 5) together with one of the prefered actions surfactants of the present invention



in a ratio of nonionic surfactant to cationic surfactant of about 10:4 (C_R: 0.071). This detergent composition had a pII in the wash'solution of about 8.5, and was used in the washing solution at a concentration of about 500 ppm. A second detergent composition of the present invention was formulated by combining the same nonionic and cationic surfactants in the same ratio as above. The composition also contained monoethanolamine as an alkalinity source, in an amount such that the monoethanolamine was present at about 30 ppm in the washing solution when the entire composition was used at a concentration of about 530 ppm. The pH of the second detergent composition in the laundry solution was about 9.3.

[0093] Identical polyester/cotton blend swatches were stained with a mixture of soil collected from air conditioning filters and a mineral oil/olive oil/oleic acid blend. The stained swatches were then washed using each of the above two detergent compositions in a one gallon washing machine which simulates the action of a commercial washing machine. The washing operation was carried out for 10 minutes using water having a temperature of about 100°F (38°C) and containing 7 grains per gallon of mixed calcium and magnesium hardness.

[0094] The soil removal performance was calculated by using the weight removal percentage, averaged across the three stained swatches washed in each composition. Both compositions gave excellent soil removal performance. However, the cationic/nonionic mixture containing monoethanolamine and having the higher. alkalinity had a soil removal of about 73%, while the lower pII cationic/nonionic mixture had a soil removal of about 50%. These data demonstrate that improved soil removal performance is obtained by the use of cationic/nonionic detergent compositions having a higher alkalinity such as that obtained by the inclusion of monoethanolamine.

[0095] Substantially similar results are obtained when other sources of alkalinity, such as sodium hydroxide, sodium carbonate, triethanolamine, and sodium silicate, are used, in comparable amounts, in place of or in combination with the monoethanolamine.

[0096] Similar results are also obtained where the nonionic component used above is replaced by the condensation product of C₁₀ alcohol with 3 moles of ethylene oxide, the condensation product of coconut alcohol with 6 moles of ethylene oxide, the condensation product of coconut alcohol with 7 moles of ethylene oxide, the condensation product of C12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of ^C_14-15 alcohol with 7 moles of ethylene oxide, or the condensation product of C_12-13 alcohol with 3 moles of ethylene oxide stripped so. as to remove the.lower ethoxylate and unethoxylated fractions.

[0097] . Excellent cleaning results are also obtained where the detergent compositions used contain nonionic to cationic surfactant ratios of about 5:1, 4:1, 10:3, 20:7, 20:9, 2:1, 5:3, or 1:1.

[0098] Excellent cleaning results are also obtained where the nonionic component is replaced by a mixture of the condensation product of_.C _14-15 alcohol with 3 moles of ethylene oxide together with the condensation product of C_14-15 alcohol with 7 moles of ethylene oxide, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of about 2:1; or a mixture of the condensation product of coconut alcohol with 5 moles of ethylene oxide together with an alkylglyceryl ether having the formula:

in a ratio of alcohol ethoxylate to glyceryl ether of about 7:3.

[0099] Substantially similar cleaning results are also obtained where the cationic component is replaced by _C12 alkyl trimethylammonium chloride, C₁₄ alkyl trimethylammonium bromide, di-C_lO alkyl dimethylammonium bromide, di-C₁₂ alkyl dimethylammonium chloride, tri-C alkyl methylammonium bromide, tri-C₁₀ alkyl methylammonium chloride, or cationic components having the formulae given below:





Br

EXAMPLE IV

[0100] A detergent composition of the present invention was formulated by combining the condensation product of coconut alcohol with 5 moles of ethylene oxide together with the cationic surfactant having the formula:

such that the ratio of nonionic surfactant to cationic surfactant was about 10:4. The detergent composition was used in the laundry solution at a concentration of about 500 ppm. A second.detergent composition of the present invention was formulated so as to contain the same nonionic and cationic components in the same ratio, but which additionally contained a ^C_12-16 alkyl fatty acid ammonia amide, present in an amount such that the amide component would be present in the washing solution at a concentration of 50 ppm when the composition was used at a concentration of 500 ppm. This composition had a pH in the laundry solution of about 8.4. Nine swatches (3 cotton, 3 polyester, and in-water suspension and were washed in a one gallon washing machine which simulates the action of a commercial washing machine, using each of the above two detergent compositions. Two 11" x 11" 100% cotton terry cloths, with loop construction, were added to each washing machine as rcdeposition sites for the soil removed from the stained swatches. The washing process was carried out for 10 minutes in water of about 100°F (38°C) , containing 6.5 grains per gallon of mixed calcium and magnesium hardness. After washing the cloths in the respective test treatments and subsequently drying them, the reflectance of the terry cloths were read using a Hunter Reflectometer. The cleaning performance of both detergent compo- sitions on the stained swatches was excellent. In addition, the first composition, containing only the nonionic and cationic components, yielded terry cloths having a reflectance of 53 Hunter Whiteness units, while the second composition, which additionally contained the amide component, yielded terry cloths having a reflectance of 71 Hunter Whiteness Units. These data demonstrate the improved soil antiredepo- sation properties which are obtained by the inclusion of an amide component in the cationic/nonionic detergent compositions of the present invention.

[0101] Substantially similar results are obtained where the amide component is present in such an amount such that the concentration of amide in the washing solution is about 80 ppm, 75 ppm, 65 ppm, 55 ppm, 40 ppm or 30 ppm. Similar results are also obtained where is the amide component used above is replaced by amidas having the formula:

wherein R¹ is C₈ alkyl, C ₁₀ alkyl, C₁₂ alkyl, C₁₃ alkyl, -C15 alkyl or C₁₇ alkyl, and R is hydrogen, methyl, ethyl, propyl, or hydroxymethyl.

[0102] Excellent results are also obtained where the nonionic surfactant'used above is replaced by the condensation product of C₁₀ alcohol with 3 moles of ethylene oxide, the condensation product of coconut alcohol with 6 moles of ethylene oxide, the condensation product of coconut alcohol with 7 moles of ethylene oxide, the condensation product of C_12-l3 alcohol with 6.5 moles of ethylene oxide, the condensation product of C _14-15 alcohol with 7 moles of ethylene oxide, or the condensation product of C_12-13 alcohol with_.3 moles of ethylene oxide stripped so as to remove nonethoxylated and lower ethoxylate fractions. Excellent results are also obtained wherein the nonionic component is replaced by a mixture of the condensation product of C₁₀ alcohol with 3 moles of ethylene oxide together with the condensation product of a secondary C₁₅ .alcohol with 9 moles of ethylene oxide, in a ratio of lower ehoxylate nonionic to-higher ethoxylate nonionic of about 3:1; or the mixture of the condensation product of coconut alcohol with 5 moles of ethylene oxide together with an alkyl glyceryl ether having the formula:

wherein the ratio of nonionic surfactant to glyceryl

[0103] Substantially similar results are also obtained wherein the ratio of nonionic surfactant to cationic surfactant in the above compositions is 5:1, 10:3, 20:7 20:9, 2:1, 5:3, or 1:1.

[0104] Excellent results are also obtained where the cationic component of the above compositions is replaced by C₁₂ alkyl trimethylammonium chloride, C₁₄ alkyl trimethylammonium chloride, di-C₁₀ alkyl dimethylamonium bromide, di-C₁₂ alkyl dimethylammonium bromide, tri-C₈ alkyl methylammonium chloride, or tri-C₁₀ alkyl methylammonium bromide.

EXAMPLE VI

[0105] A solid particulate detergent composition of the present invention, having the formulation given below, is made by mixing together the following componements.

Claims

1. A detergent composition, having a pH of at least about 6.5 in the aqueous landry solution, being substantially free of oily hydrocarbon materials, fatty acid polyglycol ether diester materials, and cationic materials containing about 13 or more ethylene oxide groups, and containing from 0 to about 20 % phosphate materials, characterised in that comprises from about 5 % to about 100 % of a surfactant mixture consisting essentially of:

(a) a biodegradable nonionic surfactant having the formula R(OC₂H₄)_nOH, wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12, having an HLB of from about 5 to about 17;

(b) a cationic surfactant, free of hydrazinium grups, having the formula R¹_mR²_xY_LZ wherein each R¹ is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to four structures selected from the group consisting of



and mixtures thereof, said R containing from about 8 to about 22 carbon atoms, and may additionally contain up to 12 ethylene oxide groups; m is a number from 1 to 3, with no more than one/R¹ group in a molecule having a total of 16 or more carbon atoms when m is 2, or more than 12-carbon atoms when m is 3; each R² is an alkyl or hydroxy-alkyl group group containing from 1 to 4 carbon atoms or a benzyl group, with no more than one R²in a molecule being benzyl; x is from 0 to 11, the remainder of any carbon, atom position being filled.by hydrogens; Y is selected from the group







wherein p is from 1 to 12,

wherein each p is from 1 to 12



and (9) mixtures thereof;

L is 1 or 2, the Y groups being separated by a moiety selected from the group consisting of R¹ and R analogs having from 1 to about 22 carbon atoms and two free carbon single bonds when L is 2; Z is an anion in a number sufficient to give electrical neutrality to the molecule; said cationic surfactant being at least water-dispersible in admixture with said nonionic surfactant;

the ratio of said nonionic surfactant to said cationic surfactant being in the range of from about 1:1 to 5:1, and the cationic surfactant being present in a amount less then 10 % of the composition.

2. A composition according to Claim 1,characterised in that said surfactant mixture has a reduced cationic monomer concentration of from about 0.005 to about 0.2.

3. A composition according to Claim 2,characterised in that said surfactant mixture has a reduced cationic monomer concentration of from about 0.008 to about 0.15.

4. A composition according to any one of Claims 1-3, characterised in that L is equal to 1.

5. A composition according to Claim 4, wherein p is from 1 to 10, and Y is selected from the group consisting of:

and mixtures thereof.

6. A composition according a any one of Claims 1-5, characterised in that, in the nonionic surfactant, R is a C₁₀ to C₁₈ alkyl group.

7. A composition according to any one of Claims 1-6, characterised in that,in the nonionic surfactant, n is from 2 to 7.

8. A composition according to any one of Claims 1-7, characterised in that it is substantially free of phosphate, polyphosphate, silicate, and polycarboxylate builder anions, carboxymethylcellulose, and anionic surfactants.

9, A composition acccrding to any one of Claims 1-8, characterised in that, the ratio of nonionic surfactant to cationic surfactant is from 5:1 to about 5:5.

10. A composition according to Claim 9, characterised in that the ratio of nonionic surfactant to cationic surfactant is from about 10:3 to about 10:5.

11. A composition according to any one of Claims 1-10, characterised in that, in the cationic surfactant, m is equal to 1, x is equal to 3, and-R is a C₁₀ to C₁₈ alkyl group.

13. A composition according to Claim 11, characterised in that the nonionic surfactant is selected from the group consisting of the condensation product of C₁₀ alcohol with 3 moles of ethylene oxide; the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of C₁₂ alcohol with 9 roles of ethylene oxide, the condensation product of C_12-13 alcohol with 3 moles of ethylene oxide, and the same condensation product which is stripped so as to remove lower and nonethoxylated fractions, the condensation product of C_12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C_12-13

with 9 moles of ethylene oxide, the condensation product

alcohol with 3 moles of ethylene oxide, the condensatior product of C_14-15 alcohol with 4 moles of ethylene oxide, the condensation product of C_14-15 alcohol with 7 moles of ethylene

condensation product of C_14-15 alcohol with 9 moles of

oxide, and mixtures thereof.