EP0000235A1

EP0000235A1 - Low-phosphate detergent composition for fabric washing

Info

Publication number: EP0000235A1
Application number: EP78200065A
Authority: EP
Inventors: Alan Pearce Murphy
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1977-06-29
Filing date: 1978-06-28
Publication date: 1979-01-10
Also published as: GB2040984A; AU3759678A; NL7815011A; FR2416944B1; ATA469278A; BE10T1; DE2857157A1; FR2416944A1; IT1097133B; SE449372B; SE7906524L; CH648344A5; DE2857157C2; IT7825098A0; AT396690B; GB2040984B; AU524807B2

Abstract

Laundry detergent compositions containing no phosphate or low levels of phosphate materials and specific mixtures of selected nonionic surfactants and selected cationic surfactants are disclosed. The nonionic/cationic surfactant mixtures are formulated to have "cloud point" characteristics and, preferably, reduced cationic monomer concentrations as defined herein. These compositions are unusually effective in removing greasy and oily soils and body soils from fabrics; they are also effective in the removal of particulate soils. A process is disclosed for laundering fabrics using compositions containing nonionic surfactants and cationic surfactants.

Description

Technical Field

This invention relates to laundry detergent compositions which exhibit highly improved greasy and oily soil and body soil removal capabilities. The compositions may be free of phosphate; alternatively, they may contain low levels of phosphate materials but not amounts in excess of about 20% by weight. These detergent compositions provide an unexpectedly high level of greasy and oily soil (such as motor oil, triolein, animal fat and lipstick) removal; they also provide excellent removal of particulate soils, especially clay soils, as well as fabric care benefits, such as fabric softening, static control, and dye transfer inhibition.

Backaround Art

Nonionic surfactants are generally included in laundry detergent compositions for their ability to attack greasy and oily soils. Cationic surfactants are also used in detergent compositions primarily to'provide adjunct fabric
selected nonionic surfactants in accordance with the cloud point and reduced cationic monomer concentration requirements specified herein.
It is an object of this invention to provide laundry detergent compositions which yield outstanding greasy and oily soil and body soil removal.
It is another object of this invention to provide laundry detergent compositions which have excellent particulate soil removal performance and fabric conditioning benefits, in addition to outstanding greasy and oily soil and body soil removal performance, in the presence or absence of builder components.
It is a further object of this invention to provide - detergent compositions which may be used in a variety of physical forms, such as liquid, paste, granular, solid, powder, or in conjunction with a carrier such as a substrate.
It is a still further object of this invention to provide a process for laundering fabrics to remove greasy and oily soil and body soil, as well as particulate soil, using cationic and nonionic surfactant-containing detergent compositions.

Disclosure of the Invention

The present invention relates to phosphate-free laundry detergent compositions or, alternatively, compositions which contain levels of phosphate which are no greater than about 20%, by weight, that comprise from about 5 to 100%, by weight, of a surfactant mixture consisting essentially of:

(a) a biodegradable ncnionic surfactant having the formula R(CC₂H₄)_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, and having an HLB of from about 5 to about 17; and
(b) a cationic surfactant, free of hydrazinium groups, having the formula R¹ _mR² _xY_L ^Z wherein each R¹ is an organic group containing a straight or branched alkyl or alkenyl group opticnally substituted

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 R and R² analogs having from one to about twenty-two carbon atoms and 2 free carbon single bonds when L is 2, Z is an anion in a number sufficient to dive electrical neutrality, said cationic surfactant being at least water-dispersible in with said nonionic surfactant;
said composition having a pH of at least 6.5 in the aqueous laundry solution, and being substantially free of oily hydrocarbon materials and caticnic materials containing about 13 or more ethylene oxide groups, the ratio of said nonionic to said cationic surfactant being in the range of from 5.1·1 to about 100:1, and the "cloud point", as described hereinafter, of said surfactant mixture being from about 0 to about 95°C. Preferred compositions are those in which the reduced cationic monomer concentration of said surfactant mixture is from about 0.002 to about 0.2.

_m

The compositions of the present invention are formulated so as to have a pH of at least 6.5
Preferred compositions may contain mixed cationic and/or mixed nonionic surfactant systems. The cationic surfactants should all be within the definition of the cationic surfactants set forth above although small amounts of other cationic materials can be tolerated. The mixed nonionic surfactant systems may contain nonionic surfactants- which fall outside of the definition given above (such as alcohol ethoxylates having an average of greater than 12 ethylene oxide groups per molecule) as long as at least one of the nonionic surfactants in the mixture falls within the definition of the nonionic surfactants, and that nonionic surfactant is included in an amount so as to fall within the required ratio of nonicnic to cationic surfactants. When the nonionic surfactant mixture contains a nonionic surfac- 'tant (or surfactants) which falls outside of the definition of nonionic surfactants, the ratio of the surfactant (or surfactants) within the above definition to that which does not fall within the definition preferably is in the range of from about 1:1 to about 5:1.
The compositions of the present invention comprise, by weight, from about 5 to 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 about 1% of the .cationic component; otherwise, sufficient cationic surfactant may not be present in the wash solution to provide the desired cleaning and conditioning results. Further, preferred compositions do not contain more than about 10% of the cationic component, due to cost and commercial availability considarations.
Compositions of the present invention may contain up to about 60% of an electrolyte (althoagh low levels of from about 1 to 20% are preferred), such as a detergency builder, as well as other adjunct components conventionally found in laundry detergent components, as more fully
The primary use of the compositions of the present invention is in conventional home laundry operations. The compositions may also be used for other detegenay purposes, including the pretreatment of greasy and oily soots and in industrial laundry operations.

of ethylene oxide, a
alcohol polyethoxylate containing an average of 5 moles of ethylene oxide, a C₁₀ alcohol polyethoxylate containing an average of 4 moles of ethylene oxide, a C₁₄ alcohol polyethoxylate containing an average
of 4 moles of ethylene oxide. This last surfactant is particularly useful for cold water laundering of fabrics. Preferred nonionic surfactants useful in the compositions of the present invertion include a C₁₀ alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, a C_12-13 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, and the same product which is stripped to remove substantially all lower ethoxylate and nonethoxylated fractions, a C_14-15 alcohol polyethoxylate containing an average of 7 moles of ethylene oxide, a C_12-13 alcohol polyehoxylate containing an average of 6.5 moles of ethylene oxide, a C₁₂ alcohol polyethoxylate containing an average of 5 moles of ethylene oxide, a coconut alcohol polyethoxylate containing an average of 5 moles of ethylene oxide, a C_12-13 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, a C_14-15 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, a C_14-15 alcohol polyethoxylate containing an average of 4 moles of ethylene oxide, and a C_14-15 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide.
Specific examples of nonionic surfactant mixtures in which both components are within the definition of the nonionic comnonent include: a mixture of a alcohol nonionic component include: a mixture of a C_14-15 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide (Neodol 45-3) and a C_14-15 alcohol polyethoxylate containing an average of 7 moles of ethylene oxide (Neodol 45-7), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1, a mixture of a C₁₀ alcohol polyethoxylate containing an average of 3 moles of ethylene oxide together with a secondary C₁₅ alcohol polyethoxylate containing an average of 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-3, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1.
Preferred nonicnic surfactant mixtures contain alkyl glyceryl ether compounds in addition to the required nonionic surfactant. Especially preferred glyceryl ethers have the formulae
wherein R is an alkyl or alkenyl group of from about 3 to about 18, preferably 3 to 12, carbon atoms or an alkaryl group having from about 5 to 14 carbon atoms in the alkyl chain, and R is from 1 to about 5. These materials are used in compositions with the nonionic surfactant component of the present invention in the ratio of nonionic surfactont to glyceryl ether of from about 1:1 to about
portioularly about 7:3.
Preferred compositions of the preset invention are substantially free of fatry acid polyglycol ether di-aster compounds, such as polyethylene glycol-600-dioleate or polyethylene.
such additives offer no advantage, and
oven result in a disadvantage in terms of achieving
removal and fabric conditioning potential of the present invention.
Other 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 useful 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 3,332,180, 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 defined above include the condensation products of aliphatic alcohols with ethylene oxide, which differ in terms of alkyl or ethylene oxide chain length (e.g., more than twelve ethylene oxide groups.per molecule) so as to fall outside the definition, given above.
These supplemental nonionic surfactants may also be of the semi-polar type, including water-soluble amine oxides containing one alkyl moiety of from about 10 to 28 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups. A preferred amine oxide is C_12-14 alkyl dimethyl amine oxide. In addition to their surface-active properties, these compounds may also be included, in amounts of from about 3 to about 20% of the composition, so as to modify the sudsing properties of the detergent compositions, to make them compatible with parti- cular types of laundering conditions. Other semi-polar surfactants include water-soluble phosphine oxides containing one alkyl moiety of about 10 to 28 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms, and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 28 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.

Cationic Component

The cationic surfactants used in the compositions of the present invention have the formula R¹ _mR² _XY_L ^Z -as hereinbefore defined.
The particular cationic component to be included in a given system depends to a.large extent upon the particular nonionic component to be used; it is selected such that it is at least water-dispersible when mixed with the nonionic surfactant. The cationic surfactant is chosen, in light of the particular nonionic surfactant used, in order to satisfy the cloud point requirements of the detergent composition, discussed below. Mixtures of these cationic materials may also be used in the compositions of the present invention. Preferred cationic surfactants are those having critical micelle concentrations of less than about 500 ppm, especially less than about 100 ppm.
In preferred cationic materials, L is equal to 1, p is from 1 to 12, preferably from 1 to 10, and Y is
or mixtures thereof. However, L may be equal to two, there by yielding cationic components containing two cationic charge centers. An example of a di-cationic component is given below: alkanolamine, prefernbly monoethanolamine, as an alkalinity source and to increase body soil removal. For example, coconutalkyl trimethylammohium chloride may be combined with the condensation product of C₁₂ alcohol with 5 moles of ethylene oxide, the condensation product of C_12-13 alcohol with 5.3 moles of ethylene oxide, or mixtures thereof, in nonionic cationic ratios of from 5. 1:1 to about 20:1, especially 5.1:1 to about 9:1. In another composition, coconutalkyl trimethylammonium chloride is combined with the condensation product of C_14-15 alcohol with 7 moles of ethylene oxide, in nonionic:cationic ratios of from 5.1:1 to about 15:1.
Another preferred composition utilizes cationic surfactants of the formula
, wherein R¹, R² and Z are as defined above, in combinationwith the condensation product C₁₂-C₁₃ alconols with 5 to 10 moles of ethylene oxide or the condensation product of C₁₄-C₁₅ alcohol with 5 to 10 moles of ethylene oxide, such as the condensation praduct of C₁₂ alcohol with 5 moles of ethylene oxide, the condensation prodnot of C_12-13 alcchol with 5.5 moles of ethylene oxide, the condensation product of C_14-15 alcchol with 7 moles of ethylene oxide, and mixtures thereof, in nonionic:cationic ratios of from 5. 1:1 to about 15:1, partioularly about 7:1.
There m is equal to 2 it is preferred that x is equal to 2, and that R² is a methyl group. In this Instance R¹ must not have more than 14 carbon atoms. A preferred cationic meterial of this class is dicoconutalkyl
dimethylammonium holide.
Other cationic materials which are useful in the compo- sitions of the present invention include phosphonium and sulfonium materials.
In preferred cationic materials, described above, 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 R is a C₁₀ to C₁₈ alkyl group. Particularly preferred components of this class include C₁₆ (^palmitylalkyl) trimethylammonium halide, tallowalkyl trimethylammonium halide and coconutalkyl trimethylammonium halide. In preferred systems, tallowalkyl trimethylammonium or coconutalkyl trimethyammonium materials are combined with a nonionic surfactant selected from the condensation prouducts 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, 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 nonionic: cationic ratios of from 5.1:1 to about 30:1, particularly from about 7:1 to about 20:1, most preferably about 10:1. In addition to outstanding grease/oil removal, excellent particulate removal is obtained using the condensation product of C₁₂-C₁₃ alcohol with 2 to 4 moles of ethylene oxide or the condensation product of C_14-C₁₅ alcohol with 3-6 moles of ethylene oxide, in nonionic/cationic ratios of from 5.1:1 to about 10:1. These compositions may also contain up to about 15% of Preferred compounds of this type
utilize dicoconutalkyl dimethylammonium halide together with the condensation product of C₁₂-C₁₃ alcohol with 6 to 10 moles of ethylene oxide or the condensation product of C₁₄-C₁₅ alcohol with 5 to 9 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_14-15 alcohol with 7 moles of ethylene oxide, and mixtures thereof, in nonionic:cationic ratios of from 5.1:1 to about 15:1, especially from about 6:1 to about 12:1. Outstanding removal of particulate soils, in addition to excellent greasy/oily soil removal, may be obtained using the condensation product of C₁₂-C₁₃ alcohol with 4 to 8 moles of ethylene oxide or the condensation product of C₁₄-C₁₅ alcohol with 4 to 8 moles of ethylene oxide, in nonionic/cationic ratios of 5.1:1 to about 15:1.
Where tri-long chain materials are used (m=3), it is preferred that x is equal to 1 and that R² is a methyl group. In these compositions

R¹ is a C₈ to C₁₁ alkyl group. Particularly preferred tri-long chain cationic materials include trioctylalkyl (C₈) methyl ammonium halide and tridecylalkyl (C₁₀) methyl ammonium halide.

Another type of preferred cationic surfactant for use
the compositions of the present invention are the alkoxy-
alkyl quaternaries. Examples of such compounds are
below:
wherein each p is from 1 to 12, preferably from 1 to 10 with the total ethylene oxide groups in a molecule not exceeding about 13), and each R is a C₁₀ to C₂₀ alkyl group. It is preferred that these compounds contain no more than a total of about 10, preferably no more than about 7, ethylene oxide groups in order to obtain the best removal of greasy and oily soils.
compositions of the present invention.
A particular 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, alkenyl, alkyl phenyl, or
wherein s is from 0 to 5; R is C₁ to C₂₀ alkylene or alkenylene; a is 0 or 1, n is 0 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 saia 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, sulfate, and nitrate, more preferably chloride, bromide, iodide, methyl sulfate and sulfate.
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 chain and its nitrogen-
These preferred cationic components are useful in nonionic/cationic surfactant mixtures which have a ratio of nonionic to cationic of from about 1:1 to ubout 100:1. However, when used in the compositions of the present invention they are used in surfactant mixtures which have nonionic to cationic surfactant ratios of from 5.1:1 to about 100:1, partioularly from 5.1:1 to about 50:1, most preferably from about 6:1 to 40:1, especially from about 6:1 to about 20:1.
Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula:
of well as those compounds in which the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide lindage.
Particularly preferred examples of this type of cat-
surfactant include stearoyl choline ester quaternary
halides R² = C₂₇ alkyl), palmitoyl choline ester
ammonium halides (R² =C₂₅ alkyl), myristoyl
quaternary ammonium halides (R² = C₁₁ alkyl),
choline ester quaternary ammonium halides (R² =
alkyl).
Additional preferred cationic components of the choline
variety are given by the struetural formulas below,
may be from 0 to 20
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 quaternized 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.
Another type of novel, particularly preferred cationic material has the formula :
In the above formula, each R¹ is a C₁ to C₄ alkyl or hydroxyalkyl 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, or alkylbenzyl group, preferably a 4₈ 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 I, and t may be 0 or 1, but t is 1 when a is 1; and m is from 1 to 5, preferably 2. Z² is selected from the group consisting
Z¹ is selected from the group consisting of:
and at least one of Z¹ and Z^- groups is selected from the group consisting of ester, reverse ester, amide or reverse amide. X is an anion which makes the compound at least water dispersible, and is selected from the group consisting of halides,' methyl sulfate, sulfate, and nitrate, particularly chloride, bromide iodide, methyl sulfate and sulfate. Mixtures of the above structures can also be used.
These surfactants, when used in the compositions of the present invention, yield excellent particulate soil, body soil, and greasy and oily soil removal. In addition, the detergent compositions control static and soften fabrics laundered therewith, and inhibit the transfer of dyes in the wash solution. Further, these novel cationic surfactants are environmentally desirable, since both their long chain alkyl segments and their nitrogen segments are biodegradable.
Preferred embodiments of this type of cationic component are esters in which R¹ is a methyl group and Z² is an ester or reverse ester group. Particular examples of these compounds are given below, in which t is 0 or 1 and y is from 1 to 20.
The preferred derivatives, described above, may be prepared by the reaction of a long chain alkyl
(preferably polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride,
form the corresponding acid chloride. The acid chloride
then reacted with dimethylaminoethanol to form the
amine ester, which is then quaternized with a methyl halide to form the desired ester compound. Another way of preparing these compounds is by the direct
of the appropriate long chain ethoxylated rboxylic acid together with 2-haloethanol or dimethyl
in the presence of heat and an acid catalyst. ceaction product formed is then guaternized with
or used to quaternize trimethylamine to form
desired ester compound.

Formulation Criteria

Utilising the nonionic and cationic components,
above, preferred compositions of the present Anvention are formulated using the guidance provided by the reduced Monomer Concentration (C_R) of the cationic
the laundry solution. Specificaly, the
of a C_R value for a given nonionic and cationic
will determine the ratio in which to combine thoss surfactants. The Reduced Monomer Concentration
is obtained bu dividing the concentration
monomer present in the aundry solution
micelle concentration (CUC) of the umfactuat. As used in this application, VMC's are
at 105°F in water containing 7 grains/gallon
hardness, unless otherxise stated. The
monomer concentration of the ronionic/

surfactant mixture is defined by equetions (1) through (3), given below. The nonionic/cationic surfactant mixtures preferred in the present invention are those haying reduced monomer concentrations in the range of from about 0.002 to about 0.2, preferably from about 0.002 to about 0.15, and most preferably from about 0.002 to about 0.08.. As nonionic and cationic components of greater purity are utilized, the narrower C_R ranges become more preferred.
Proceedings of the Second Internetional Congress of Surface Activity, III, 449, Academic Press, Inc. (1957). The equatios below extend this concept of reduced monomer concentration to multi-component systems, utilizing surfactant monomer concentrations. The concept of surfactant monomer concentration is derived from the discussion in Clint, J. Chem. Soc. Far. Trans., I, 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/l.) = 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.)
c^* ₂ = critical micelle concentration of cationic surfactant (moles/l.)
α = total mole fraction of nonionic surfactant in the solution = C₁/(C₁ + C₂)
3 = a constant base upon the heat of mixing = -2.3
c^m ₁ = nonionio monomer concentration
c^m ₂ = 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 ₌ e^B(1-x)2
f₂ = cationic activity coefficient in the mixed micelle = e^Bx2
◁ = f₂c*₂ - f₁c*₁
C_R = reduced cationic monomer concentration
M₁ = molecular weight of nonionic surfactant
M₂ molecular weight of cationic surfactant
W = total analytical surfactant concentration in the solution (ppm) = sum of the cationic and nonionic concentrations (ppm) ⁼ W₁+W₂ (wnerein "1'' denotes nonionic surfactant and "2" denotes cationic surfactant)
Y = weight fraction of nonionic surfactant in the composition

The above equation is solved for the nonionic monomer concentration by taking its positive root (equation (12) in Clint).
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:
For a given cleaning test for a nonionic/cationic system, x was found by inserting the values known from the teah (i.e., c*₁, c*₂, α, C and β) into equation (1) and colving 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 vaiues obtained were then used to solve for the cationic
concentrations using the following equation:
The C_R value was then calculated using equation (3).
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.
This range of C_R (i.e., 0.002 to 0.2) can then be used to determine the range of optimum nonionic/cationic ratios 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*₁ 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 C_R range, solve for x using the equation
by standard numerical iterative techniques to an error in x of less than 0.001;
(b) find the range of Y from the equation
using 100 ppm and 10,000 ppm as the boundary values for W, for each end of the C_R range;
(c) the nonionic/cationic ratio (NCR) range for optimum performance is then within the range obtained by substituting the boundary values for Y into the formula

Put another way, steps (b) and (c) may be combined into a single equation which may be solved directly for the NCR.
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 C_R 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 concen- cration of about 1,000 ppm in the above calculation will be a satisfactory approximation for the entire rance. As used herein, if a concentration range is not specified, the 1,000 ppm C_R is meant.
By way of example, the optimum ratio for grease/oil removal for Composition A of Example I, herein, given
calculated below. For this system, the following
cither known or selected as indicated:
1,000 ppm (selected as representative of usage conditions)

c₁ = 1.957 x10^-5 ppm
c₂ = 2.1875 x 10^-5 ppm
B = -2.3
M₁ = 406.7
M₂ = 320
C_R = 0.0073 (selected for optimum greasy/oily soil removal performance, but could be any value between 0.002 and 0.2)

Substituting the values for and C_R into equation (a):
(1-x)e^-2.8x2 = 0.0073.
Solving iteratively for x, it is found that x'= 0.922.
Using this value for x, it is found that

f₁ = 0.983
f₂ = 0.0925
Δ = (0.0925) (2.1875 x 10^-5) - (0.983) (1.967 x 10^-5) = -1.73 x 10^-5

Substituting these values into equation (b), it is found that:
Y = 0.938
Substituting this value for Y into equation (c), the nonionic/cationic ratio is determined.
It will be noted that this ratio corresponds to the ratio actually found in Example I, Composition A.
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
more preferably between about 20 and about 65°C, especially between about 30 and about 50°C. For cold Warer detergency, the surfactant mixture should have a
point between about 0 and about 25°C. The fact Than a composition has a cloud point within these temperature ranges assures that the composition can be utilized under laundry temperature conditions to achieve nupstanding removal of greasy/oily soils. If a compo-
does not have a cloud point within the temperature
specified, it will not yield the outstanding
the present invention inside that temperature range. The compositions
exhibit their best grease/oil removal performance
the temperature of the wash solution in which they are
within about 20°C, preferably within about
most preferably within about 10°C, of the
the nonionic/cationic surfactant mixture.
another way, the laundry solution temperature range
preferred compositions deliver optimum
removal lies between the cloud point temper-
the system in the absence of the cationic
and about 30°C, preferably about 25°C, most preferably about 20°C, above that cloud point temperature. As used herein, the term "cloud point" means the
which a graph which plots the light
intensity of the composition versus wash solution temperature begins to sharply increase to its maximum value, under the following experimental conditions:
The light scattering intensity is measured using a Model VM-12397 Photogoniodiffusometer, manufactured by Societo Francaise d'instruments de controle ct- 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. sample of the solution is placed into the sample cell, using a syringe with a 0.2p 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 rateX 1°C/minute); the temperature of the sample is determined by the temperature of the bath. The light scattering (90° angle) intensity of the sample is then determined at various temperatures, using a green filter and no polarizer in the SOFICA.
The preferred nonionic and cationic components used in the present compositions are chosen, combined, and used based on three basic criteria : (1) the final composition must satisfy the cloud point criteria, given above, and should be such that the surfactant mixture cloud point temperature is within about 20°C of normal wash solution temperatures, (2) the reduced cationic monomer concentration of the surfactant mixture preferably falls within the range defined above ; and (3) the concentration of the detergent composition in the wash solution should be sufficient to give the desired cleaning performance under normal laundering temperatures.
in the present inven
surfactants which have relative. low CMCs and low cloud points (i.e., the temperature at which an aqueous solution of the surfactant exhibits turbidity). These surfactants can be used to prepare detergent compositions, laundry solutions of which, at lower temperatures, will form the desired nonionic/cationic mixture cloud point without requiring the addition of other ingredients, such as electrolytes or anionic surfactants. Such detergent compositions make it easier to fulfill the cloud point requirements set forth herein, and yield outstanding removal of greasy and oily soils from fabrics.
In formulating and utilizing the compositions of the present invention, it is preferred, for typical American automatic washing conditions, that the nonionic surfactant, the cationic surfactant, and any additional components be chosen and used in amounts such that the temperature at which the detergent composition in the aqueous laundry solution has a cloud point, as'defined above, will be between about 30°C and 50°C, preferably at about 45°C. Where the compositions are used under different washing conditions, the compositions are formulated such that, at the desired use concentration, they exhibit their cloud point at a temperature which is within about 20°C of the desired washing temperature. Thus, for example, in Japan (where washing temperatures are generally lower than those used in the United States), the compositions are desirably formulated so as to have their cloud point close to about 15°C.
The cloud point temperature for a given composition in the wash solution depends upon the physical and
properties (such as CMC and solubility) of the
nonionic and additional components included
composition, and may no lowernd by inerensing the alkyl chain langths of the nonionic or cationic
by doereasing the
of ethoxylation of the nonionic component,
as phosphates, polyposphonates,
or sulfates, particularly ir rolatively low amounts (such as from about 1 to about 15% of a given
More specifically, it is preferred that the detergent compositions of the present invention, when used in the aqueous laundry solution, have cloud points which fall within about 15°C, preferably within about 10°C, and most preferably within about 5°C, of the temperature of the laundry solution. It has been found that when these laundry solution temperature/cloud point relationships are met, the greasy and oily soil removal capacity of the laundry solution increases dramatically.
Although not intending to be bound by theory, it is believed that when a detergent composition of the present invention is in a laundry solution with oily- soiled fabrics, the cationic component is adsorbed onto the fabric, thereby neutralizing the negative charge on the fabric. This charge neutralization enhances the adsorption of the nonionic surfactant onto the fabric, thereby causing the roll up of the oily soil. The soil is then easily removed by agitation. It is by formulating cationic/nonionic surfactant mixtures which satisfy the cloud point and the preferred reduced cationic monomer concentration requirements that this mechanism, and hence, greasy/oily soil removal, is optimized.

Fatty Amide Component

In a particular embodiment of the present invention the nonionic surfactant/cotionic surfactant mixture 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. Any nonionic surfactant conventionally used in detergent compositions may be used in these compositions; however
defined above, in order to maximise the cleaning benetits obtained.
In ronionic/cationic systems,
the ratio of the total cationic and nonionic components to the amide component included, is in the range of from about 5:1 to about 50:1, preferably from about 8:1 to about 25:1. These compositions result in excellent particulate soil removal performance, as well as improved soil antiredeposition characteristics
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 C₈ to C₂₀ alkyl, alkenyl, alkyl phenyl or alkyl benzyl, preferably C₁₀ to C₁₈ alkyl, and most preferably C₁₁ alkyl; and each R² is hydrogen, or C₁ to C₈ alkyl or hydroxyalkyl, preferably hydrogen. Specific examples of these compositions include a mixture of stearoyl choline bromide (present in the washing solution at 120 ppm), coconu alcohol polyethoxylate containing an average of 5 moles of ethylene oxide (present in the wash solution at about 357 ppm), and a midcut coconutalkyl ammonium amide (present in the wash solution at about 50 ppm); and a mixture of stearoy choline bromide (100 ppm), coconut alcohol polyethoxylate containing an average of 5 moles of ethylene oxide (357 ppm), and lauramide (R¹ equals C₁₁ and R² is hydrogen; at 45 Ppm).

Additional Components

The compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, at their conventional art-established levels. These additional components are preferably selected such that the composition as a whole satisfies the cloud point criteria described above..
The compositions of the present invention may contain up to about 15%, preferably up to about 5%, and most preferably from about 0.1% 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, to St. John, and combinations of certain nonionics therewith, as disclosed in U.S. Patent 2,954,348, issued September 27, 1960, to 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.
Preferred silicone suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, Bartolotta et al, incorporated herein by reference. 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'
suds regulating component for use in the
tions, and are described in detail in U.S. Patent 4,056,481, Tate, issued November 1, 1977, incerperatea herein by reference. 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 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 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 monooleyl phosphates, which can contain di- and trioleyl phosphates.
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, u^p to 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl phosphate.
The detergent compositions of the present invention may, subject to the limitations.on phosphate, discussed above, also include from about 1 to about 60%, preferably low levels of from about 1 to about 15%, of electrolyte components, such as conventional detergency builders, especially alkaline, polyvalent anionid builder salts. ' The alkaline salts primarily serve to maintain pH of the cleaning solution in the range of from about 7 to about 12, preferably from about 6 to about 11, to modify the cloud point of the detergent composition, and to provide a source of ionic strength. However, it is important to emphasize that the compositions of the present invention are capable of previding excellent cleaning even in the complete absence of such builder materials.
Suitable detergent builder salts useful herein can be of the polyvalent inorganic or polyvalent organic type, or mixtures of these varieties. Nonlimiting examples of suitable water-soluble, inorganic alkaline detergent builder salts include: alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates, and sulfates. Specific examples of such salts include sodium and potassium tetraborates, perborates, bicarbonates,, carbonates, tripolyphosphates, orthophosphates, pyrophosphates and hexametaphosphates.
Examples of suitable organic alkaline detergency builder salts include: (1) water-soluble aminopolyacetates, for example, sodium and potassium ethylenediamine tetraacetate, nitrilotriacetate, and N-(2-hydroxyethyl)nitrilotriacetates;

(2) water-soluble salts of phytic acid, for example, sodium and potassium phytates; and
(3) water-soluble polyphosphonates, including sodium, potassium, and lithium salts of ethane-1-hydroxy-1,1- diphosphonic acid; sodium, potassium, and lithium salts of ethylene diphosphonic acid; and the like.

Additional organic builder salts useful herein include the polycarboxylate materials described in U.S. Patent 3,364,103, incorporated herein by reference, including the water-soluble alkali salts of mellitic acid. The water-soluble salts of polycarboxylate polymers and copolymers, such as those described in U.S. Patent 3,368,067, incorporated herein by reference, are also suitable as builders herein.
A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosill- cates, particularly those described in Belgium Patent 814,874, issued November 12, 1974, incorporated herein by reference. This patent discloses and claims detergent compositions containing sodium aluminosilicates having the formula Na_z(AlO₂)_z(SiO₂)_y ^-XH₂O, wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to about 0.5:1, and X is an integer from about 15 to about 264, said aluminosilicates having a calcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least about 2 grains/gallon/minute/ gram. A preferred material is Na₁₂(SiO₂ ^-AlO₂)₁₂ ^-27H₂O.
Mixtures of organic and/or inorganic builders may be used herein. One such mixture of builders is disclosed in Canadian Patent 755,038 and consists of a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
Other preferred builder materials which may be used in the compositions of the present invention include alkali metal carboxymethyl tartronates, commercially available at about 76% active together with about 7% ditartronate, about 3% diglycolate, about 6% sodium carbonate, and about 8% water; and anhydrous sodium carboxymethyl succinate, commercially available at about 76% active together with about 22.6% water, and a mixture of other organic materials, such as carbonates.
In addition to the cationic and nonionic surfactants discussed above, the detergent compositions of the present invention may additionally contain up to about 50%, preferably from about 5 to about 30%, of anionic surfactants, zwitterionic surfactants, or mixtures of such- surfactants. Surfactants of these types useful in the compositions of the present invention 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 27, 1967, both of which are incorporated herein by reference. Specific nonlimiting examples of surfactants suitable for use in the instant compositions arc as follows: These surfactants arc selected such that the composition as
monomer toncentration criterla deseribed above.
Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful as an anionic surfactant herein.
metal

armonium and alkanol-
fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 tc about 20 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soaps.
Another class of anionic surfactant includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkvl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants which can be used in the present detergent compositions are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C₈-C₁₈ carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkyl- brenzene sulfonates, in which the alkyl group contains
9 to about 15 carbon atoms in straight chain or branched chain configurations, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383, incor-
herein by reference.
anionic surfactant compounds useful herein
the sodium alkyl glyceryl ether sulfonates,
those ethers or higher alcohols derived from
and coconut oil; sodium coconut oil fatty acid
sulfonates and sulfates; and sodium or
salts of alkyl phenol polyethylene oxide ether
1 to about 10 units of ethylene
molecule and wherein the alkyl groups contain
8 to about 12 carbon atoms.
The alkaline earth metal salts of synthetic anionic surfactants are useful in the present invention. In particular, the magnesium salts of linear alkylbenzene sulfonates, in which the alkyl group contains from 9 to about 15, especially 11 to 13, carbon atoms, are useful.
Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon - atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Preferred water-soluble anionic organic surfactants for use herein include linear chain alkylbenzene sulfonates containing from about 10 to 16 carbon atoms in the alkyl group; alkyl sulfates containing from about 10 to 20 carbon atcms; the coconut range alkyl glyceryl sulfonates; and alkyl ether sulfates wherein the alkyl moiety contains from about 10 to 20 carbon atoms and wherein the average degree of ethoxylation varies between about 1 and 6.
Specific preferred anionic surfactants which may be used herein include: sodium-linear C₁₀-C₁₂ alkylbenzene sulfonate; triethanolamine C₁₀-C₁₂ alkylbenzene sulfonate; sodium tallow alkyl sulfate; sodium coconut alkyl glyceryl ether sulfonate; and the sodium salt of a sulfated condensation product of C₁₄-C₁₈ alcohol with from about 1 to about 10 moles of ethylene oxide.
It is to be recognized that any of the foregoing anionic surfactants can either be used separately or in mixtures.
Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic moieties can be straight or branch chain, wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains anionic water-solubilizing group. Particularly-preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patent 3,925,262 and U.S. Patent 3,929,678. The inclusion of these surfactants in the compositions supplement the excellent greasy and oily soil removal performance with outstanding clay soil removal performance.
Particularly preferred ethoxylated zwitterionic surfactants have the formulae:
and
The above compounds which contain 8 moles of ethylene oxide are also preferred. Additional preferred zwitterionic surfactants include those having the formula
wherein the sum of x + ^y is equal to about 15.
While the compositions may advantagecusly contain electrolytes, anionic surfactants and zwitterionic surfactants, as described above, selected so as to satisfy the cloud point requirement, a preferred class of compositions is substantially free of interfering anions, which may interact with the cationic component and thereby hinder cleaning and fabric conditioning performance. What constitutes an "interfering anion" depends upon the nonionic and cationic components contained in a detergent composition, as well as properties of the particular anion, such as structure, bulk and dissociation constant. In these compositions - the anionic materials should 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. For example, in preferred compositions, 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 , but less than about 1 x 10 , 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 1 x 10^-5 (such as sodium C_11.8 linear alkylbenzene sulfonate), it may be contained only in amounts up to about 10% by weight, of the cationic surfactant. Particularly preferred compositions of this type are those substantially free of phosphate, poly- phosphate, silicate, and polycarboxylate builder anions, carboxymethylcellulose, and anionic surfactants.
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.. Buffers may also be added to control the pH of the compositions, with low molecular weight amino acids, particularly glycine, being preferred where the composition is in the form of a clear-liquid. However, because of the numerous and diverse performance advantages of the compositions of the present invention, many components, such as builders, static control agents, fabric softening agents and germicides, generally will not be necessary. The compositions of the present invention may additionally contain monoethanolamine, diethanolamine, or triethanolamine components in amounts up to about 30%, preferably from about 5 to about 20%. These components are useful as alkalinity sources and in formulating clear homogeneous liquid products which satisfy the cloud point requirements when placed in an aqueous laundry solution.
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 releaseably incorporates an effective amount, preferably from about 20 to 80 grams of the detergent composition of the present invention. A particular preferred substrate article incorporates a bleaching component and a fieacn
the substrate, together with the nonionic/cationic surfactant mixture.
A particularly preferred composition of the present invention is an aqueous heavy-duty liquid laundry composition containing from about 10 to about 50%, preferably about 15 to 40%, of the nonionic surfactant, from about 1 to about 10%, preferably about 1 to 6%, of the cationic surfactant; and which additionally contains from about 5 to about 30%, preferably about 10% of monoethanolamine, diethanolamine, triethanolamine, or mixtures thereof. These compositions may also contain from about 3 to about 20% of an anionic surfactant, particularly one of the ethoxylated or nonethoxylated alkyl sulfate variety. One embodiment of buch a composition contains monoethanolamine, coconut trimethylammonium chloride as at least a portion of the cationic component, and a mixture of the condensation product of secondary C₁₂ alcohol with an average of 7 moles of ethylene oxide together with the condensation product of secondary C₁₂ alcohol with an average of 5 moles of ethylene oxide, in a ratio of higher ethoxylated nonionic to lower ethoxylated nonionic of about 3:1, as the nonionic surfactant. In these compositions, the amounts and ratios of the component may be varied so as to produce a clear, homogeneous product which exhibits the required cloud point characteristics in the aqueous laundry solution.

Laundry Processes

In its broadest aspect, this invention envisions a process for cleaning solid surfaces soiled with greasy and/or oily materials utilizing an aqueous laundry soiution comprising from about 0.01% to about 0.3% by weight or a
within about 20°C, preferably within about 15°C. more preferably within about 10°C cf the cloud point of the nonionic/ cationic surfactant mixture. It is, generally, at the point where the laundry solution temperature is equal to the cloud point that a given system will give its best greasy/oily soil removal performance. Particularly preferred laundry solutions are those in which the ratio of the nonionic surfactant to cationic surfactant is from 5.1:1 to about 100:1, particularly from 5.1:1 to about 50:1, more particularly from about 6:1 to about 40:1, especially from about 6:1 to about 20:1.
Prior to this invention, it was totally unexpected that combinations of nonionic and cationic surfactants, even with a builder present, could provide cleaning of either greasy and oily soils or particulate soils which was competitive with commercial fully-built anionic detergents. Further, there was no indication that reduced cationic monomer concentration and cloud point were critical elements to obtaining removal of greasy and oily soils. It was therefore totally unexpected that such combinations could be used to provide superior performance even in low or non-phosphate systems, as well as in systems containing no builder or relatively non-effective builders.
Such performance is obtained where the newly-discovered cloud point and reduced cationic monomer concentration criteria, set forth herein, are met in the washing process. The process requires that the laundry solution be near the cloud point temperature of the detergent composition, which in general is well above the nonionic's CMC. The cationic surfactant concentration should not be too low or too high above the cationic's CMC for optimal greasy/oily soil removal performance. These criteria and the numerous other constraints set by considerations, such as ecological desirability and safety, help define the preferred compositions set forth herein.
With the process of this invention, it is also possible to achieve superior particulate soil removal if sufficient cationic surfactant is present in the laundry solution.
It may be necessary to balance the need for a relatively high concentration of cationic surfactant (e.g., at least about 50 ppm) with other factors and it will be recognized that for very high nonionic:cationic ratios it may not be possible, at present usage concentrarions, to achieve the best particulate soil removal. However, the particulate soil removal and greasy/oily soil removal achieved by these processes are superior to that provided by any known commercial-detergent while permitting the detergent formulator to meet the ecological and safety concerns of the present day.
In addition to the benefits found in cleaning, the present invention provides an impressive array of secondary, but extremely desirable, benefits which are almost anknown in the conventional anionic detergent compositions and processes of the prior art. For example, depending upon the identity and concentrati.on of the cationic component, it is possible to provide the benefits known in the prior art for such cationics, e.g., antibacterial action, antistatic effects, softening effects for textiles, and an effect not heretofore noted, the prevention or minimization of the transfer of certain.dyes from one fabric-to another in the cleaning process.
In general, the compositions of the present invention are used in the laundering process by forming an aqueous solution containing from about 0.01 (100 ppm) to 0.3% (3000 ppm), preferably from about 0.02 to 0.2%, most preferably from about 0.03 to about 0.15%, of the nonionic/cationic detergent mixture, within the cloud point and reduced monomer concentration limitations defined above, and agitating the soiled fabrics in that solution. The faprics are chen rinsed and dried. When used in this manner, the compositions. of the present invention yield exceptionally good greasy and oily soil removal, as well as particulte sell removal and fabric conditioning berformance

laundry, industrial laundry or hard surface cleaning operations, concentrations as high as about 2% may be used.
All percentaqes, parts, and ratios used herein are by weight unless otherwise specified.
The follcwing nonlimithing examples illustrate the compositions and method of the present invention.

EXAMPLE I

Two compositions of the present invention were formulated by mixing together the components given below in the amounts specified. The cationic surfactants were chosen so as to be at least water-dispersible when the compositions were used in the laundry solution.

Composition B is about 35 °C.

The cleaning performance of these compositions was tested against that of a standard granular detergent composition having the following formulation:
For each of the above detergent compositions a set of three 11" x 11" swatches (one made of double knit polyester, one a 65/35 polyester/cotton blend, and one cotton) were each stained with four separate stains (dirty motor oil, lipstick, triolein, and a clay-in- water suspension). The three swatches were then added to an average six pound load of clean mixed fabrics, containing cotton, polyester, and cotton/polyester fabrics, and the load was washed in a full scale henmore washer using one of the compositions described above. Each of the compositions was added to the washing solution at a usage concentration of about 0.1%. Composition A had a pH of 8 in the washing solution, and Composition B had a pH of about 9.7. The wash water was at a temperature of 105°F (40°C) and contained 9 grains per gallon of natural hardness. After the laundering was complete, each of the swatches was graded for the removal of each stain on 1 to 10 scale, with 0 signifying complete removal and 10 signifying no removal at all. For each treatment, the total of the clay removal grades were added up and the total of the grease/oil removal grades were added up. Thus, for each treatment the clay removal score could range from 0, for complete removal, up to 30, for no removal; and for the grease and oil stains, the scores could range from 0, for complete removal, up to 90, for no removal. The results obtained are summarized in the table below.
These data demonstrate the excellent grease and oil soil removal performance, as well as the excellent particulate soil removal performance, obtained by the use of the compositions of the present invention, even in the absence of any builder components.
Substantially similar results are obtained where the nonionic components in Compositions A and B, above, are replaced by a C_14-15 alcohol polyethoxylate containing an average of 4 moles of ethylene oxide (HLB = 8.9), a C_12-13 alcohol polyethoxylate containing an average of 6.5 moles of ethylene oxide, a C_14-15 alcohol polyethoxylate containing an average of·7 moles of ethylene oxide (HLB = 11.5) a C_12-13 alcohol polyethcxylate containing an average of 3 moles of ethylene oxide (HL3 = 7.9), and the same product which is stripped so as to remove substantially all lower ethoxylate and unethoxylated fractions, a secondary C₁₅ alcohol polyethoxylate containing an average of 9 moles of ethylene oxide (HL3 = 12.7), a coconut alcohol pclyethoxy- late containing an average of 5 moles of ethylene oxide, a C₁₀ alcohol polyethoxylate containing an average of moles of ethylene oxide, a C₁₄ alcohol polycthoxylate containing an average of 6 moles of ethylene oxide, a C₁₂ alcohol polyethoxylate containing an average of 4 moles of ethylene oxide, a C_12-13 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide (HLB = 13.3), a C_14-15 alcohol polyethoxylate containing an average of 3 moles of ethylene-oxide (HLB = 8.9), a C_14-15 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide (HLB = 12.8), and mixtures of those surfactants.
Excellent cleaning results are also obtained where the ratio of nonionic surfactant to cationic surfactant in Compositions A and B, above, are 6:1, 7:1, 9:1, 10:1, 12:1, 17:1, 20:1, or 25:1.
Similar results are also obtained where the sodium carbonate and sodium silicate components of Composition B, above, are replaced in whole or in part by other alkali metal tetraborates, perborates, bicarbonates, or carbonates in comparable amounts.
Substantially similar results are also obtained where the cationic surfactants of Compositions A and B are replaced in whole or in part with decylalkyl trimethylammonium chloride, decylalkyl trimethylammonium hydroxide, C₁₄ alkyl trimethylammonium chloride,
tridecylalkyl methylammonium chloride, a mixture of methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate (VARISOFT 475) together with coconutalkyl trimethylammonium chloride (ADOGEN 461) in a ratio of VARISOFT to ADOGEN of about 1:1, 3:3, 3:1, 2:3, or 1:3; or a mixture of palmitylalkyl trimethylammonium chloride with coconutalkyl trimethylammonium chloride in a ratio of palmityl to coconut compound of about 3:1, 2:1, 3:2, 1:1, 1:2, or 1:3, cr surfactants having the following formulae:

EXAMPLE II

The following two detergent compositions of the present invention were formulated by combining the components described below in the specified amounts. The cationic surfactants were chosen so as to be at least water-dispersible when the compositions were used in the laundry solution.
Composition C had a reduced cationic monomer ccncen- tration of about 0.005, and a cloud point of about
while Composition D had a reduced cationic monomer concentration about 0.0135, and a cloud point of about
The grease/oil and particulate soil removal performance of each composition was then tested using the method described in Example I, above. Both compositions were used at a product concentration of about · 0.1% in the washing solution, in water having a temperature of 105°F (40°C). Composition C had a pH of 8 and Composition D had a pH of 7.9 in the washing solution. Composition C was used in water containing 7 grains per gallon of natural hardness, while Composition D was used in water containing 7, 14,
grains per gallon of natural hardness.
performance of these compositions is
below.
The above compositions yielded excellent grease and oil soil removal, was well as particulate soil removal and fabric conditioning benefits, even in the presence of increased concentrations of hardness in the washing solution, without requiring the presence of builder components.
Excellent cleaning results are also obtained where the ratio of nonionic surfactant to cationic surfactant in Compesitions C and D, above, are about 10:1, 15:1, 20:1, 25:1, 30:1, 40:1, or 50:1.

EXAXPLE III

Two compositions of the present invention were formulated by combining the components described below in the given amounts and proportions. Each of these detergent compositions, when added to a 105°F laundry solution appeare turbid, indicating the presence of separated phases in the laundry solution.
The grease/oil and particulate soil removal perfermance of Compositions E and F were then tested against the control composition of Example I using the test method described in Example I, above. All washes were done using water at 105°F (40°C), containing 7 grains per gailon, of natural hardness. Compositions E and G were used at the usage concentration of about 0.1% in the laundry solution, while the control composition was used at a usage concentration of 0.14%. Composition E had a pH of 10.2 in the laundry solution. The soil removal results obtained are summarized in the table below:
These data demonstrate the outstanding
soil removal performance and particulate

EXAMPLE IV

A composition of the present invention was formulated by combining the components given below in the stated proportions.
The soil removal performance of this composition was tested against that of a stndard, low-phosphate granular laundry detergent composition having the formulation given below, using the test method desaribed in Example I.

are summarized
These data indicate the outstanding greasy/oily soil removal and particulate soil removal performance which are obtained by using the compositions of the present invention.

EXAMPLE V

The relationship between greasy/oily soil removal performance and cloud point/laundry solution temperature was demonstrated in the following manner. The detergent composition tested was a mixture of the condensation product of C₁₂ alcohol with 5 moles of ethylene oxide and C₁₆ alkyl.trimethylammonium chloride, in a nonionic:cationic ratio of 19:1. The composition was used at a concentration of 1000 ppm'in distilled water.
The greasy/oily soil removal performance of this composition was tested, as a function of wash water temperature, using a Tergotometer having one 10 minute wash cycle and two 2 minute rinse cycles. For each test, two 7.5 cm square desized polyester knit swatches were weighed. The swatches were then stained with 200 mg. technical grade triolein (containg 0.0083% Oil Red-0, for visualization), and weighed again. The swatches were allowed to age for about 2 hours, and were washed in the Tergotometer (1000 ml water; 1000 ppm of the detergent composition)', air dried, and reweighed. The percent triolein removal was calculated using the formula: 100 x [wt (soiled) - wt (washed)]/[wt (soiled) - wt (clean)]. This procedure was repeated at a series of wash water temperatures.
The light scattering intensity of the detergent composition, as a function of solution temperature, was determined as follows
The light scattering intensity was measured using a Model MV-12397 Phctogoniodiffusometer, manufactured by Societe Francaise d'instruments de controls et d'analyses, France (the instrument being hereinafter referred to as SOFICA). The SOFICA sample cell and its lid were washed with hot acetone and allowed to dry. The surfactant mixture was made and put into solution with distilled water, at a concentration of 1000 ppm. Approximately a 15 ml. sample of the solution was placed into the sample cell, using a syringe with a 0.2µ nucleopore filter. The syringe needle passed through the sample cell lid, so that the cell interior was not exposed to atomospheric dust. The sample was kept in a variable temperature bath, and both the bath and the sample were subject to constant stirring. The bath temperature was heated using the SOFICA's heater and cooled by the addition of ice (heating rate χ1°C/minute); the temperature of the sample was determined by the temperature of the bath. The light scattering intensity of the sample was then determined at various temperatures, using a green filter and no polarizer in the SOFICA.
The results of these tests are summarized in the following table.
These data show that the optimum triolein removal for this detergent composition occurs in a wash solution having a temperature of about 50°C; this is approximately the same temperature at which the light scattering of the solution begins to sharply increase in moving toward its maximum value (i.e., the cloud point of the nonionic/cationic surfactant mixture). It is therefore seen that by using this detergent composition in a wash solution having a temperature close (i.e., within about 20°C) to the composition's cloud point, the maximum triolein removal for that composition is achieved.

EXAMPLE VI

A heavy duty liquid laundry detergent composition, having the formula given below, is formulated by mixing together the following components in the stated proportions.
This product has a cloud point which falls between 30°C and 50°C and when used in an automatic laundering operation at a concentration of about has a pH of about 7.5, and provides excellent removal of both particulate and greasy/oily soils.

FXAXPLE VII

A substrate article, for use in the automatic laundering operation, is made by inprecnating an 8" x 11" sheet of a Scott
having an air permeability of about
a basis weight of about 77.5 grams per eq. yd., and a thickness of 44 mils, with about 50 grams of the composition described in Example VI, above. The sheet is then dried to remove excess moisture. This article provides a convenient method for introducing the compositions of the present invention into the laundering solution, as well as providing excellent cleaning, statis control, fabric softening and dye transfer inhibition performance.
A substrate article may also be made by coating one side of an
sheet of melt-blown polypropylene, having a thickness of about 29 mils, a basis weight of about 58.5
and an air permeability of about 66
with about 60 grams of the detergent composition described in Example VI, placing an identical
over the coated sheet, and heat-sealing together the
two substrates, enclosing the
the article.

EXAMPLE VIII

A solid particulate detergent composition of the present invention, having the formulation given below, is made in the following manner.
The nunionic and cationic components are mixed together, and are then mixed with the solid urea, while concurrently being warmed. The resultant product is then mixed with the carbonate, silicate and minor components. This product, when used in an automatic laundering operation at conventional usage concentrations, has a pH of about 9, and provides excellent particulate and greasy/oily soil removal.

EXAMPLE IX

A solid particulate detergent composition of the present invention, having the formulation given below, is made in the manner described in Example VIII, above.
This product, when used in an automatic washing machine at conventional usage concentrations, has a pH of about 9, and provides excellent particulate and greasy/oily soil removal performance.

EXAMPLE X

A heavy duty liguid laundry detergent composition, having the formula given below. is formulated by mixing together the following components in the stated proportions. The composition, when formulated, has a turbid appearance.
This product, when used in an automatic laundering operation at a concentration of
has a pH of about 9.5, and provides excellent removal of both particulate and greasy/oily
The product may also be used as. a pretreatment
onto greasy/oily soils prior to the laundering operation.
A heavy duty liquid laundry detergent composition of the present invention, having the formula given below, is formulated by mixing tegether the following components in the stated proportions.
This product, when used in an automatic laundering operation at a concentration of about 0.05%, has a pH of about and provides excellent removal of greasy/ oily, body, and particulate soils, as well as providing static control and dye transfer inhibition benefits to the fabrics laundered therewith.
Substantially similar results are obtained where the cationic component is replaced, in whole or part, with palmitylalkyl trimethylammonium chloride, or hydrogenated tallowalkyl trimethylammonium chloride; and the nonionic component is replaced, in whole or part, with the condensa- tion product of C₁₂ alcohol with 5 moles of ethylene oxide, the condensation product of C_14-15 alcohol with 7 moles of ethylene oxide, or mixtures thereof.

EXAMPLE XII

A heavy duty liquid laundry detergent composition, having the formula given below, is formulated by mixing- together the following components in the stated proportions. The composition, when formulated, has a clear, homogeneous appearance.

temperatures than do American washing conditions.

EXAMPLE XIII

This product provides excellent removal of particulate, greasy/oily
when used under conventional Japanese leundry concitions, which gonerally utilize lower water temperatures than do American washing conditions.

EXAMPLE XIV

A heavy duty liquid laundry detergent composition, having the formula given below, is formulated by mixing together the following components in the stated proportions. The composition, when formulated, has a clear, homogeneous appearance.
This product has desirable sudsing characteristics and provides excellent removal of particulate, greasy/ oily and body soils when used under conventional Japanese laundry conditions, which generally utilize lower water temperatures than do American laundering conditions.

EXAMPLE XV

A heavy duty liquid laundry detergent composition, having the formula given below, is formulated by mixing together the following compenents in the stated proportions. The composition, when formulated, has a clear, homogeneous appearance.
This product has desirable sudsing characteristics and provides excellent removal of particulate, greasy/ oily, and body soils when used under conventional Japanese laundry conditions, which generally utilize lower water temperatures than do American laundering conditions.

EXAMPLE XVI

A heavy duty liquid detergent composition, having the formula given hereinaftor, was prepared by mixing together the listed components in the stated proportions.
- The above composition was homogeneous and storage- stable over prolonged periods of time. In addition, it provided, by reference to prior art compositions, unexpectedly superior greasy stain removal performance.
Substantially similar results are obtained where the cationic component is replaced, in whole or in part, by a comparable level of a quaternized nitrogen-containing ingredient selected from the group consisting of: coconut- alkyl trimethylammonium chloride, coconutalkyl trimethyl- ammonium bromide, benzyl dihydroxyethylmethylammonium chloride, ethoxylated coconutalkyl quaternary ammonium compounds wherein from 2 to 8 moles of ethylone oxide are condensed onto the nitrogen, and mixtures thereof.

Claims

wherein
primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and
average of from about 2 to about
having an HLB of from about 5 to about

(b) a cationic surfactant, free of hydrazinium groups, having the formula
wherein
is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to 3 phenyl or hydroxy groups and optionally interruptod by up to
selected from the group consisting of

and mixtures thereof,
about 8 to about 22 carbon atoms, and which may additionally contain up to about 12 ethylene oxide groups; m is a numbe from 1 to 3, with each R¹ having not more than 14 carbon atoms when m is 2 and not more than 11 carbon atoms when m is 3 ; each R² is an alkyl or hydroxy alkyl 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 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,

and
2. The compostion according to Claim 1 characterized in that the surdactant mixutre has a cloud point of from about 18 to about 70°C.
3. A composition according to Claim 1 or Claim 2, characterized in that L is equal to 1.
4. A composition according to any one of claims 1-3, characterized in that, in the nenionie surfactant, n is from 2 to 9.
5. A composition according to any one of claims 1-4, characterizes, in that it in substantially free of phosphate materials.
6. A composition according to any one of claims 1-5, characterized in that Y is selected from the group consisting of
where p is from 1 to 12.
7. A composition according to Claim 6 wherein Y is

m is 1, x is 3, R⁺ is a C₁₀ to C₁₈ alkyl group and each

R² is a methyl group.
8. A composition according to any one of claims 1-7 wherein'the ratio of nonionic surfactant to cationic surfactant is from 6:1 tc about 20:1.
9. A composition according to any one of claims 1-8, characterized in that it additionally contains up to about 50 % of a component selected from the group consisting of anionic surfactants, zwitterionic surfactants, and mixtures thereof.
10. A composition according to any one of claims 1-9, characterized in that the total number of carbon atoms contained in the R¹ and R² groups of the cationic surfactant is no greater than 28.
11. A composition according to any one of Claims 1-3, characterized in that the nonionic surfactant is selected from the group consisting of C₁₂-C₁₃ alcohols condensed with 4 to 10 moles of ethylene oxide, C₁₄-C₁₅ alcohols condensed with 6 to 10 moles of ethylene oxide; and mixtures thereof; and which contains said nonionie surfactant and cationic surfactant in a ratio of from 5.1:1 to about 30:1.
12. A composition according to, any one of Claims 1-3, characterized in that the nonionic surfactant is selected from the group consisting of the condensation product of C₁₂-C₁₃ alcohol with 6 to 10 moles of ethylene oxide, the condensation product of C₁₄-C₁₅ alcohol with 5 to 9 moles of ethylene oxide, and mixtures thereof; wherein, in the cationic surfactant, x is 2, m is 2, and each R¹ is a coconutalkyl group; and the ratio of nonionic surfactant to cationic surfactant is from 5.1:1 to about 15:1.