CA1230533A - Fabric cleaning compositions for clay-based stains - Google Patents

Abstract

FABRIC CLEANING COMPOSITIONS FOR CLAY-BASED STAINS

ABSTRACT

Stain removal composition comprise mixtures of grease-cutting solvents and polyamines. The compositions are particularly useful for removing stains comprising a mix-ture of grease and particulate matter from fabrics. Liquid detergents containing said solvents and polyamines in the form of stable oil-in-water microemulsions are disclosed.

Description

~2~

FABRIC CLE~NI~G COMPOSITIONS YOR CLAY-BASED STAINS
Ivan H~TS
Ja~es P. JOHNS~N
John R. W~æR
Technical Field The present invention relates to compositions and processes for removing clay-based soils and stains from fabrics. The compositions are particularly adapted for removing cosmetic stains, which cornprise a mixture of clay-based material and an oily or greasy binder material. Com-positions which comprise a solvent ingredient to disperse the binder and a polyamine material to disperse the clay are provided. These compositions can be used in the form of a simple fabric pre-spotter, or in fully-formulated laundry detergents comprising a mixture of various ingredients de-signed to remove a broad spectrum of stains and soils from fabrics, with particularlv noteworthy benefits on stains caused by cosmetics.

Background Detergent formulators are faced with the task of devising products to remove a broad spectrum pf soils and stains from fabrics. Chemically and physico-chemically, the varieties of soils and stains range the spectrum from primarily oily, through proteinaceous and carbohydrate, to inorganic, and detergent compositions have become more complex as formulators attempt to provide products which handle all types, concurrently. For example, protease en-zymes are commonly used in detergents for blood and gravy stains; amylase enzymes are used for carbohydrate stains;

nonionic surfactants are used ~or hydrocarbon oils; and anio-nic surfactants and b~lilders are~ used Eor particulate soil.
sleach is used to chemically degrade stains that are not amenable to removal by less rigorous treatment.
One of the most difficult stains to remove frorn fabrics is the cosme~ic stain, and from -time immemorial -the persis-tent, telltale smudge of lipstick on a shirtcollar or hand-kerchief has been the downfall of many a miscreant. More-over, the remarkable ability of the modern cosmetic industry to provide products which are more and more long-lasting on the user's skin necessarily means that today's cosmetics are increasingly persistent on fabrics to which they are unin-tentionally applie~.
Chemically, many cosmetics comprise a clay base which serves in part as a filler, thickener, carrier for color bodies, and the like, blended with an oily material which serves partially as a binder, gloss agent and emollient.
Cosmetics are typically manufactured with great care, such that the clay and color bodies are in the form of very fine particles, and are very thoroughly and completely mixed with, and coated by, the oily material, which may be a hy-drocarbon oil, silicone, lipid, or complex mixtures thereof.
While optimal from the standpoint of the cosmetic formulator, the modern cosmetic product causes major problems for the de-tergent formulator, since cosmetics constitute a mix of widely divergent soil types (oily, particulate, clay~ all in .intimate admixture and often brightly coloredO No single detergent ingredient can reasonably be expected to handle such a complex milieu.
The present invention employs oil-removal solvents and clay-removal polyamines. The solvents dissolve the oil base of the cosmetics, thereby exposing their clay component to ~he polyamine materials which disperse and remove it ~rom fabrics.
The use of solvents of the type employed in this in-vention as grease and oil removal ingredients in cleaners -~LZ3(~533 of various types is well-known commercially and from the patent literature. See, for example, U.S. Patent

2.073.464; EPO Applications 0 072 ~88 published ~ebruary ~3, 1983 and 0 040 882 published December 2, 1981; British Patent 1.603.0~7.
~ Iowever, the use of such solvents in combination with polyamine materials in the manner disclosed herein is not believed to have been contemplated, heretoore.

Summary of the Invention The present invention relates to compositions and processes for removing cosmetic stains, and the like, from fabrics, by means of a solvent (especially solvents such as isoparaffinic hydrocarbons, kerosene, petroleum fractions, d-limonene or mixed terpenes, fatty alcohols, benzyl alcohol and mixtures thereo~) and an alkoxylated polyamine (as described more fully hereinafter) at a weight ratio of solvent:polyamine of 10~:1 to 1:20, pre-ferably at least 2:1. The invention also encompasses fully-formulated detergent compositions which comprise conventional detergency ingredients such as detergency builders, enzymes, detersive surfactants, and the like, characterized in that such compositions contain at least about 5% by weight of the aforesaid mixture of solvent and polyamine. Preferably, such fully-formulated deter-gent compositions contain at least 5~ of the solvent and at least 0.2% of the polyamine~

Detailed Descrietion of the Invention The essential solvent and polyamine components, as well as the preferred surfactant components and other optional ingredients used in the practice of the present invention are described in more detail, hereinafter. All percentages and ra-tios mentioned in this specification are by weight, unless otherwise stated.

~L2~33 Solvent ~ The solvents employed herein can be any of the well-known "degreasing" solvents com~only known Eor use in, for example, the commercial laundry and drycleanin~ indus-try, in the hard-surface cleaner industry and the metalwor-king industry. Typically, such solvents comprise hydro-carbon or halogenated hydrocarbon moie-tles of -the alkyl or cycloalkyl type, and have a boiling point well above room temperature.
The formulator of compositions of the present type will be guided in the selection of solvent partly by the need to provide good grease-cutting properties, and partly by aesthe-tic considerations. For example, kerosene hydrocarbons function quite well in the present compositions, bu-t can be malodorous. Kerosene can be used in commercial laundries.
For home use, where malodors would not be tolerated, the formulator would be more likely to select solvents which have a relatively pleasant odor, or odors which can be reaso-nably modified by perfuming. Such solvents include, for example, the terpenes and terpenoid solvents obtainable from citrus fruits, especially orange terpenes and d-limonene.
senzyl alcohol is another relatively pleasant smelling sol-vent for use herein.
Excellent solvents for use herein are paraffins and the mono- and bicyclic mono-terpenes, i.e., those of the hydrocarbon class, which include, for example, the terpinenes, limonenes and pinenes, and mixtures thereof. Highly preferred materials of this type are d-limonene and the mixture of terpene hydrocarbons obtained from the essence of oranges (e.g.
cold-pressed orange terpenes and orange terpene oil phase ex fruit juice). Also useful are, for example, terpenes such a dipentene, alpha-pinene, beta=-pinene and the mixture of terpene hydrocarbons expressed from lemons and grape-fruit.
The examples disclosed hereinafter describe various other solvents which can be used herein.

~l2~ ;3~

Polyami~es - It is to be understood that the term "polyamines"
as used herein represents generically the alkoxylated polyami-nes, both in their amine form and in their quaternized form.
Such materials can conveniently be represen-ted as molecules of the empirical structures with repeating unLts:

t N - R tx Amine form I

alkoxy and R

1? ~ X Ouaternarized alkoxy wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R may be a Cl-C20 hydrocarbon; the alkoxy groups are polyethoxy, polypropoxy, and ~he like, with polyethoxy having a degree of polymerization of 2-30, most preferably, 10 to 20; x is an integer of at least 2, preferably from ; 2-20, most preferably 3-5; and X~ is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
The most hi~hly preerred polyamines for use herein are the so-called ethoxylated polyethylene imines, i.e., the polymerized reaction product of ethylene oxide with ethylene-imine, having the general formula:
--~N - CH2-CH2 ~x (E+O)y wherein x is an integer of 3 to 5 and y is an integer of 10 to 20.
Surfactants - In addition to the solvent and polyamine, it is optional, but highly prcferred, that the compositions herein contain organic sur~ace-active a~ents ("surfactants") to provide the usual cleaning benefits associated wi-th the use of such materials.
Water soluble detersive surfactants useful herein in-clude well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, ~-sulfonates o~ fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art. In general, such detersive surfactants contain an alkyl group in the Cg-Cl8 range; the anionic detersive surfactants are most commonly used in the form of their sodium, potassium or triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups. U.S. Patents 4,111,855 and 3,995,669 contain detailed listings of such typical detersive surfactants. Cll-Cl~ alkyl benzene sulfo-nates, C12-C18 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
The surfactant component can comprise as little as 1% of the compositions herein, but preferably the composi-tions will contain 1~ to 40~, preferably 5% to 30%, of sur-factant. Mixtures of the ethoxylated nonionics with anionics such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred for through-the-wash cleansing of a broad spectrum of soils and stains from fabrics.
Fatty Acid/Soap Ingredient - Fatty acids (generally C10-Cl8 chain length) and their water-soluble salts (i.e., common "soaps", especially alkali metal soaps) can be used in the present compositions not only for their detersive-surfactant properties, but also to provide an additional . ~,~

fL~3~ 3 detergency builder function by virtue oE their ability to interact with water hardness cations. As will be described more fully hereinafter, fat~y acids and soaps are particu-larly useful when preparing fully-formulated, homogeneous oil-in-water liquid detergents comprising the solvent and polyamine in an aqueous carrier. Usage levels of 0.5 - 50 are typical.
Other Optional Ingredients - The compositions herein can contain other ingredients which aid in their cleaning per-~ormance. For example, it is highly preferred that through-the-wash detergent compositions con~ain a detergent builder and/or metal ion sequestrant. Compounds classifiable and well-known in the art as detergent builders include the nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicates, and mixtures thereo~.
Metal ion sequestrants include all of the above, plus mate-rials like ethylenediaminetetraacetate, the amino-polyphos-phonates and phosphates (D~QUEST) and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here. See U.S. Patent 3,579,454 for typical examples of the use of such materials in various cleaning compositions. In general, the builder/sequestrant will comprise about 0.5% to 15% of the composition. Citrate is one of the most preferred builders since it is readily soluble in the aqueous phase of heavy-duty liquid detergent compositio~s.
The compositions herein also preferably contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains. Amylase and protease enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents.
Commercial detersive enzymes (preferably a rnixture of amylase and protease) are typically used at levels of 0.001% to 2~, and higher, in the present compositions.
Ingredients such as propane diol and/or formate .~' ~L~Z3~5i33 and calcium can be added to help st~biliz~ the en~ymes in well-known fashion, according to the desires of the formu-lator.
Moreover, the compositions herein can contain, in addi-tion to ingredients already mentioned, various other op-tio-nal ingredients typically used ln commercial products to provide aes-thetic or additional product performance benfits.
Typical ingredients include pH regulants, perfumes, dyes, optical brighteners, soil suspending agents, hydrotropes and gel control agents, freeze-thaw stabi.lizers, bactericide~, preservati~es, suds control agents and the like.
Water-alcohol (e.g., ethanol, isopropanol, etc.) mixtures can be used as the carrier vehicle in liquid compositions, and alkylated polysaccharides can be used to increase the stability and performance characteristics of the compositions.
The compositions herein are preferably formulated in ; the neutral to alkaline pH range r generally in the range of pH 6.5 - 9.0, preferably about 6.8 - 7.5~ Materials such as sodium hydroxide, potassium hydroxide, the alkanol amines such as triethanol-amines, or magnesium hydroxide, can be used to adjust the pH, as desired. Preferred pH adjusting agents are described hereinafter.
The preferred compositions herein are in liquid ~orm, which can be prepared by simply blending the essential and optional ingredients in a fluid (preferably aqueous) carrier.
As mentioned hereinabove, fatty acid or soap can be used in such liquid compositions to provide clear, homogeneous microemulsions of the solvent in an aqueous carrier. Solid or granular compositions can be prepared by adsorbing the solvent and polyamine in a suitable granular carrier, for example, in a sodium sulfate, sodium perborate (bleach) or spray-dried detergent granule carrier.
In one process aspect, the compositions herein in the form of liquids or pastes can be used to pre-treat soiled fabrics by rubbing a few milliliters o~ the compositon directly onto and into the soiled area, followed by laundering in standard fashion. In a through-the-wash mode, the compo-~ r ,~ .

~LZ3~!~3~

si~ions are typically used at a concentrat:ion of at least500 ppm, preferably 0.1~ to l..5~ in an aqueous laundry bath at pH 6.5 - 10 to launder fabrics. The laundering can be carried out over the range erom 5C to the boil, with excellent resul~s.

_ndustrial Application The following examples describe a varie-ty of formula-tions which can be prepared in the manner of the present invention using the mixed solvent/polyamine ingredients.
The examples are given by way of illustration and are not intended to be limiting of the scope of the invention. In the formulations listed, the terms l'x1land llyl~ are stated in parentheses to designate the degree of polymerization and degree of alkoxylation of the polyamine. For some "polyami-nesl', the designation R is also included~ thereby denotinga quaternarized polyamine. For such quaternarized materials, the resultin~ anion ~ is of no consequence to cleaning performance, and is not designated. In all examples, R is -CH2-CH2- and alkoxyl is ethoxyl, unless otherwise specified.
Example I
Following the teachings of U.S. Patent 3,664,962, a spot remover in stick form is prepared by blending the fol-lowing ingredients, extruding the resulting mass through a 1.25 cm die, and packaging the resulting stick in an alumi-num foil wrapper.
Ingredient Percent Sodium stearate 22.0 d-Limonene 15.0 Benzyl alcohol 8.0 30 2-Propanol Z2.0 Polyamine (x=2; y=6avg.) 10.0 Sodium dodecyl benzene sulfonate3.5 Water to 100 ~lZ~3~35~3 -- 10 ~
In use, the foil wrapper is peele~ away from a portion of the stick, which is then rubbed briskly onto -the area of a garment soiled with cosmetic, or the like, stains. The garment is thereafter brushed, or optionally laundered, to remove the stain, together with residues from the stick.
Example II
~ liquid fabric pre--treatmen~ and through-the-wash detergency booster is prepared by blending the followincJ
ingredients.
IngredientParts by Weight Paraffin oil (deodorized) 20 Polyamine (x=3; y=15 avg.) 7 Water 50 Ethoxylated sorbitan oleate 3 In a preferred method of use, a few (1-10) milliliters of the composition of Example II are applied directly to an area oE fabric stained with clay/grease soil and rubbed briskly into the stained area. The fabric is thereafter laundered with a commercial laundry detergent (e.g., VIZIR) according to lable instructions.
In an alternate mode, the composition of Example II is added directly to an aqueous laundry bath, generally at a level of 500 - 5000 ppm, depending on the desires of the user and the soil load, together with a commercial laundry deter-gent, to enhance cleaning performance.
The composition of Example II can be diluted (1:1) with water or water-ethanol and packaged in an aerosol or manual pump dispenser for use as a spot remover.
Example III
A granular detergent composition comprising the solvent/
polyamine composi'cions of the present invention can be pre-pared by blending the solvent/polyamine with a spray-dried . ~

~23~33 commercial laundry detergent. ~lowever, in a preferred mode, the solvent/polyamine is admixed with non-neutralized anionic surfactant, which is then admixed with alkaline detergency builder and other optional detergency ingredients, whereby the surfactant is neutralized _n situ in the product. This method of formulating solvent-containing granular detergents is des-cribed by A.Davidsohn in the report of the original lectures, 3rd International Congress of Surface Activity Cologne, payes 165 to 172 at 171 (1960).
Following the operating procedures suggested by David-sohn, there is prepared a granular detergent of the formu-lation:
Ingredient Percent C121avg.)alkyl benzene sulfonate9.6 (acid form) 15 C12-15 alkyl ethoxylate(EO avg. 9) 1.4 - Sodium perborate.4H2O 22.0 Sodium tripolyphosphate 19.0 Orange terpene 10.0 Polyamine (x=3; y=16) 1.0 20 Sodium sulfate 20.0 C16-C18 hardened soap (suds control) 1.5 Enzymes (protease/amylase mix) 1.5 Carboxymethyl cellulose 2.0 water, optical brightener, minors to 100 The composition of Example III is used in standard fa-shion to launder fabrics. In a preferred mode, ca. 2g.
of the compusition is admixed with ca. 5ml wate~ to form a paste which is then rubbed into heavily soiled areas of fabrics, prior to laundering with the composition.
Examples IV - IX
The following examples relate to compositions within the scope of this invention with solvents which are particularly suitable in industrial, heavy-duty laundry and cleaning , ~

i3;:3 l.2 -plants, and the like. It will bc appreci~ted by the formulator that some of the solvents employed in such composit:ions may be unsuitable for general home use, due to malodors, poten-tial for skin irritation, low flash poin-ts, and the like.
However, such compositions are entirely suitable for use un-der properly controlled conditions by professional operators who take such matters i.nto consideration. In Examples IV-IX, all ingredients are listed as parts by weigh-t.
INGREDIENT IV V VI VII VIII IX
10 Stoddard solvent 100 - - - - 250 Trichloroethylene - 10 Naphtha - - 30 - - -Petrole~m Ether(b.p.80-85C)- - - 60 100 Mineral spirits . - ~ - 20 15 Benzyl alcohol - - - - 100 Butyl carb.itol (T.M.) - - - - - 50 Polyamine (A-F*) 5(A)10(B) 15(C)100(D) 20(E) 150(F) Water 100 100200 - 250 350 Coconut soap - ~ 25 20 C alkyl benzene 12 sulfonate 50 5 - - 10 20 C alcohol ethoxylate 12-15 (EOAvg 9) 50 - - - - 20 C alkyl phenol 9 (ethoxylated (EOAvg 6) - 2 10 100 10 Mg~OH)2 to pH shown 7.0 7.17.5 - 7.7 8.1 *Polyamines A-F used in Examples IV-IX have the general formulae disclosed hereinbefore and are as follows:
A x = 2; y = 2; R = ethylene; alkoxy = ethoxy B x = 20; y = 30; R = propylene; alkoxy = propoxy C x = 3; y = 15; R = ethylene; alkoxy = ethoxy; R = butyl D x = 5; y = 9; R = butylene; aloxy = butoxy E x = ~0; y = 10; R = hexylene; aloxy = ethoxy; R : dodecyl F x = 3; y = 20; R = ethylene; alkoxy = ethoxy; R = eicosyl - ~LZ:~S33 ~leavy-~uty l,iquid Detergents Having thus described a variety of compositions in accordance with the invention, special attention is now directed to highly preferred formulations which are particularly useful as heavy duty liquid de-tergents -that are suitable for laundering all manner of fabrics in a typi.cal home laundering operation. The heavy duty liquid detergents disclosed herein-after are formulated with a variety of detersive ingredients to provide excellent cleaning of a wide variety soils and stains, and wherein the solvent/polyam.ine contributes significantly to the removal of clay/grease and dirty mo~or oil stains from fabrics.
It is to be understood that, while such formulations can be prepared as water-in-oil emulsions, they are preferably prepared in the form of oil-in-water emulsions (wherein the solvent is considered the "oil" phase) and are most preferably .in the form of substantially clear, homogeneous oil-in~water microemulsions. The formulator of heavy duty liquid detergents will appreciate that using water as the carrier phase in such compositions is a significant cost saving, and will further appreciate that an aqueous carrier phase contributes importan~ly to ease-of-formulation, since water-soluble detersive ingredients can be more readily incorporated into oil-in-water emulsions than in water-in-oil emulsions. Surprisingly, when used in a pre-treatment mode, the oil-in-water emulsions herein are comparable .n grease-cutting performance to water-in-oil emulsions, which have much higher concentrations of solvent.
The compositions herein with high concentrations of surfactant and fatty acid/soap may be packaged in high density polyethylene bottles without solvent loss.
Example X
A heavy-duty liquid detergent in the form o~ a clear, homogeneous oil-in water emulsion which shows excellent performance with a wide variety of clay soil types of stain is prepared as follows:

'~`

~2~S~3 INGREDIENT PARTS BY WEIGHT
Polyamine (x=5; y=15) 1.5 Ethanol 3.0 Potassium hydroxide (50% in water)8.0 5 Alkyl (Cll 8) benzene sulphonic acid 11.0 Alkyl (Cl~/15) ethoxylate (E07) 15.0 Potassium citrate monhydrate (63,5% in water) 2.4 Dequest* 2060 S (TM) . 1.2 Sodium formate (40% in water) 2.5 10 Ca as CaC12 6H2O 60 ppm Orange Terpenes 10.0 Lauric / myristic acid (60/40) 12.5 Oleic acid 2.5 Maxatase** (TM) enzyme 0.71 15 Termamyl*** (TM) enzyme 0.10 Optical brightener (anionic) 0.23 Perfume 0.5 Dye 20 ppm Water to 100 20 Product pH 7 3 * Diethylene triamine pentamethylene phosphonic acid (Monsanto) ** KNGS, supplier .*** NOVO, supplier The above composition is prepared by blending the indicated ingredients to provide a clear, stable microemulsion. In laundry tests, particularly with a pre-treatment step, the composition gives excellent performance on a wide variety of stains, including cosmetics and dirty motor oil.
Preferred compositions of the foregoing microemulsion type will generally contain 10-20% of the fatty acid mix and be formulated at pH 6.6-7.3.

! ~ \

~2~0533 EXAMPLE X I
The composition of Example X is modified slightly by using 0.6 parts by weight of magnesium hydroxide in place of 1.2 parts of potassium hydroxide (50~) to adjust pH to 7Ø The resulting product is a homogeneous microemulsion.
EXAMPLE X I I
The composition of Examples X and XI are modified by replacing the orange terpene by a mixture of deodorized paraffin oil (iso-C10-C12) (7.5~ of the total composition) and orange terpenes (2.5% of the total composition). This change in the solvent component in no way detracts from the performance attributes of the compositions, but allows the perfumer more latitude for introducing non-citrus perfume notes. Anionic optical brightener (0.01 - 0.5~) may be added, as desired.
SOLVENT SELECTION
As disclosed hereinabove, final selection of the solvent system for use in the present compositions will be dependant upon soil type and load, aesthetics (odour) etc. However, a number of criteria can be used to guide this selection.
For example, the solvent should be substantially water immiscible; and, it should of course be capable of solubi-lizing a broad range of problem greasy soils. In this latter respect thermodynamic solubility parameters (Hansen Parameters) are useful in making the solvent selection.
Any solvent can be described by the Hansen Parameters ~d ~p ~h ~d being the dispersion component; ~p the polarity component; and ~h the hydrogen bonding component.
Likewise, key greasy problem soils can be described by "pseudo"
Hansen Parameters. In order to do this the solubility of each greasy stain in a broad range of solvents of different Hansen Parameters is first assessed. This can be done by immersing the greasy stain on a range of different fabric types (cotton, polyester cotton, acrylic) in each solvent ~LZ30~;33 in turn for a fixed time (say, 5 minutes) under fixed agita-tion. On removal, excess solvent is drained-off and the st~ined fabric is washed for 5 minutes in cool water containing 1%
concentration of a typical liquid laundry detergent. Following final rinsing in cold water and drying, the stain removal can be assessed visually or by any other suitable technique.
By proceeding in this way, those solvents giving best removal of each problem greasy stain can be identified, and thereby the range of each Hansen Parameter required for optimum removal of that particular stain can be assessed. Thus, for each stain a map of Hansen Parameters can be developed, and solvent/solvent combinations can be selected on this basis to give the target performance profile.
~lthough not intended to be limiting of the present invention, the above technique indicates that mixed solvent/solvent compositions with Hansen Parameters in the range ~d ~7 to 9?, ~p (o to 4)~ ~h ( to 7) allow the formulation of microemulsions with superior greasy stain removal performance. The solvent combination can be targeted against particular greasy stains, such as motor oil, where the optimum Hansen Parameter range is ~d (7 to 9)~ ~h ( to 4) ~p (0 to 3) or marker ink, where the optimum range is ~d (769), ~h (2 to 11), ~p (2 to 7), or targeted more broadly against mixed stains by selecting an intermediate point in the range of Hansen Parameters.
Some preferred solvents and solvent mixtures herein, especially: orange terpenes (d-limonene), paraffins (especially iso-C10-C12); cyclohexane; kerosene; orange terpene/benzyl alcohol; (60/40), n-paraffins (C12 15) / hexanol (50/50), fall within the Hansen Parametexs, as stated.
These solvents and solvent mixtures are typically used at concentrations of 5 - 20%, preferably 5 - 10%, in the present compositions. Slightly polar solvents such as benzyl alcohol or n-hexanol can be used with water-immiscible solvents such as terpenes and paraffin oil atlevels of 0 - 10%. Various other solvent mixtures are disclosed in Example XIX, hereinafter.

~230533 As can be seen from the foregoing, the present invention encompasses a varietv of formulations in the form of stable, solvent-containing emulsions. A superior heavy duty liquid detergent composition can also be prepared using a solvent system comprising diethyl phthalate (preferred) or dibutyl phthalate in combination with the terpenes (preferably, orange terpene) or dipentene, or paraffin oils, or (most preferably) mixtures thereof. The following is a representative example of such a composition.
EXAMPLE XIII

Ingredient Parts by weight Polyamine (x=5;y=l5) l.5 Potassium Hydroxide (50 % Aq.) 8.0 Ethanol 3.0 Cll 8 Alkyl Benzene Sulphonic Acid ll.0 Cl4/l5 Alkyl Ethoxylate (E0 7) 15.0 Potassium Citrate (63.5 Aq.) 2.4 Deodorized Paraffin Oil *7.5 Orange Terpene 2.5 Dibutyl phthalate 3.0 Lauric/Myristic Acids (60/40) 12.5 Enzymes (per Ex. X) l.0 Water and minors with pH
adjusted with cyclohexvl amine to 6.9 to l00 * Cl0-Cl2 Iso-paraffins In Example XIII, the dibutyl phthalate can be replaced by an equivalent amount of diethyl phthalate.

~12~533 It will be appreciated that many of the foregoing compositions comprising the terpene hydrocarbons will ne-cessarily have a rather strong citrus odor that may not be entirely acceptable to all formulators of such compositions.
It has now been discovered that the C6-Cg alkyl aromatic solvents, especially the C6-C~ alkyl benzenes, preferably octyl benzene, exhibit excellent grease-removal properties and have a low, pleasant odor~ Likewise, the olefin sol-vents having a boiling point of at least about 1~0C, espe-cially alpha-olefins, preferably l-decene cr l-dooecene, are excellent grease-removal solvents.
The combinat~on of the aforesaid alkYl-aromatic or olefin solvents with polar liquids such as benzyl alcohol, n-hexanol, Butyl Carbitol (Trade Mark; 2-(2-butoxyethoxy) ethanol) or the phthalic acid esters cons.itute additional examples of preferred non-polar/polar solvents that are preferred for use in the practice of this invention.
The following additional examples further illustrate oil-in-water microemulsions. In Example ~VII, the use of the quaternary ammonium compound to adjust the pH of the formulation to a pH just barely below neutrality contributes importantly to product performance while maintaining long-term m1croemulslon stability.

,S:33 _XAMPLE YIV
Ingredient % By Weight Cll 8 Alkyl benzene sulphonic acid lO.O
C1~/15 Alkyl ethoxylate (EO 7) 10.9 Coconut fatty acid (broad cut) 18,2 Oleic acid 2,3 Monomethyl ethanolamine 5,8 l-Decene 9.1 Ethanol (95~) 2,7 Dequest (50~)l l.09 Formic acid 0.18 K3 citrate. H2O (63.5% in H2O) 4,4 CaCl2 2H2 0-05 Maxatase enzyme (protease) 0.73 Termamyl enzyme (amylase) 0.10 Ethoxylated polyamine 2 1.73 Perfume/optional brightener/dye 0.5 Water Balance Product pH 6.6 2~ l. Diethylene triamine pentamethylenephosphonic acid 2. Tetraethylene pentamine 105 EO units/molecule The composition of Example XIV is a stable, oil-in-water microemulsion suitable for use as a laundry detergent.

_XAMPLE XV
The composition of Example XIV is modified by replacing the l-Decene by the same amount (9.1% total formulation) of n-octyl benzene, Product pH "as is" : 6,6.

~230~33 EXAMPLE XVI
The composition of Example XIV is modified by replacing the l-Decene by any of the following solvent mixtures (per-centages of total formulation being specified in parentheses):
l-Decene (6.1~)/D.iethylphthalate (3.0%); 1- Doc.ecene (5.9%)/
Benzyl alcohol (3.2%); n-octyl benzene (6.2~)/Diethyl phthalate (2.9%); n-octyl benzene (5.0~)/ Butyl carbitol (4-1~); Diethyl phthalate (6~)/liquidClo iso-paraffin(2 orange terpene(2%). Product pH's as is : 6.6.

_ AMPLE XVII
The compositions of Examples XIV, XV, and X~iI are modified by adding sufficient cyclohexyl amine or dioctyl-di~.ethyl am~onium chloride to ad~ust the "as is" ~ of the compositions from 6.6 to 6.94. The resulting compositions exhibit exceptional-ly good fabric cleaning and whiteness maintenance.

EXAMPLE XVIII
An extra-heavy duty laundry additive composition is as follows.

Ingredient Percent by ~eight l-Decene 20 n-Octyl benzene 10 Diethyl phthalate 10 Polyamine (x=5 y=15) 10 Sodium tripolyphosphate to 100.

Another preferred olefin solvent herein b~ virtue of its relatively low odor is the so-called "P-4" polymer, available from a number of petrochemical suppliers to the detergent industry as a raw material for branched a1kvl ben-zene. P-4 is an isomer mix of the condensation product of 4-moles of propylene, i.e., C12 ~ranched olefins- P-4 is non polar, and is preferably used in combination with a polar solvent such as benzyl. alcohol,diethylphthate, Butyl Carbitol, or the like .

~L2~0533 Otller useful polar solvents herein include the "cello-solves" e.g. alkoxyl alkanols such as 2-bu-toxyethanol; C6-C12 alkanols (including benzyl alcohol) such as dodecanol, phe-nethyl alcohol, diglycolether acetates,hexyl cellosolve and hexyl carbitol, and the like.

22 ~Z30S33 EXAMPLE XIX
The following are additional examples of grease-removal solvent mixtures which can be used with the alkoxylated polyamines in the manner of this invention.
ComPosition Inqredient Percent A Octyl benzene 70%
Diethyl phthalate 30%
B l-Decene 70%
Diethyl phthalate 30%
C Octyl benzene 80%
Benzyl alcohol 20%
D n-Octyl benzene 90%
Butyl carbitol 10%
E l-Decene 65%
Dibutyl phthalate 35%
F n-Octyl benzene 30%
l-Decene 40%
Benzyl alcohol 10%
Butyl carbitol 20%
G l-Decene 80%
n-Hexanol 20%
H l-Decene 60%
Diethyl phthalate 40%
I l-Dodecene 80%
Hexyl cellosolve 20%
J Mixed 1:1 nonyl/hexyl benzene 35%
2-Dodecene 35%
Dimethyl phthalate 30%

In a preferred method of use aspect, the compositions herein are used in an aqueous laundering liquor at a liquor pH of 6.5-8.0 (measured as 1% of composition in water) to launder fabrics. Excellent cleaning is attained by agitating fabrics in such liquors at this in-use pH
range~

23 _ 1230533 Nitroqen-functional Stabilizers/pH Requlants - As disclosed in Examples XIII and XVII, above, various alkyl and cyclo-alkyl amines, quaternary ammonium compounds, as well as amine oxides, constitute a highly preferred class of pH regulants and stabilizers in the oil-in-water microemulsion detergent compositions of the present type.
Apparently, such materials may somehow associate with the fatty acid or anionic surfactants to form a complex which stabilizes the microemulsified oil (solvent). While the nitrogen functional compounds do not boost the pH very much towards the alkaline range (only several tenths of a pH unit, measured on the product formulated "as is~') the resulting boost in detergency performance, especially enzymatic cleaning performance, is substantial.
Parenthetically, it is to be understood that with regard to pH adjustments in the compositions up to about pH 6.5-6.6, any of the well-known base materials can be used, for example, triethanolamine, alkali metal hydroxide and the like. Potassium hydroxide is preferred over sodium hydroxide, inasmuch as the ease of formulation of stable systems is increased substantially by the potassium cation.
Dioctyl dimethyl ammonium chloride is a highly preferred quaternary used herein as a pH-regulant, but there can also be mentioned the following quaternaries in increasing order of preference of use: coconut trimethyl ammonium chloride (6.66); di-coconut dimethyl ammonium chloride (6.84); coconut benzyl dimethyl ammonium chloride (6.84); and dihexyl dimethyl ammonium chloride (6.89).

3~ The numbers in parentheses denote the pH achievable by adding the respective quaternaries to a liquid oil-in-water microemulsion containing fatty acid and formulated at an "as is" pH of 6.5. For the preferred dioctyl dimethyl ammonium chloride, the pH figure is 6.9q.

-- 24 -- ~2~0~3 Suitable alkyl and cyclo-alkyl amines useful herein (with attendant pH's) include: coconutalkyl diethanol amine (6.65): coconutalkyl dimethyl amine (6.75); trioctyl amine (7.0): and cyclohexyl amine (7.5).
Suitable amine oxides herein include coconutalkyl dimethylamine oxide (6.7) and dioctyl methylamine oxide (est. 7).
It is to be understood that the foregoing ni~rogen compounds can be added to the compositions until the desired pH is obtained. To achieve the pH listed, from 0.5% to 5% of the compounds are typically used in the compositions. Cyclohexyl amine (l-5%) is most preferred for use herein.
In general terms, the most highly preferred oil-in-water microemulsion form of the compositions herein comprise:
a) 10% to 70% water (carrier):
b) 5% to 20% grease removal solvent or solvent mixture:
c) 5% to 35% fatty acid or fatty acid~soap mixture:
d) 1% to 40% detersive surfactant e) 0.001% to 2% detersive enzyme:
f) at least 0.2% alkoxylated polyamine; and g) said composition being adjusted to a pH (undiluted) of 6.6-7.5 using a nitrogenous material (as described) especially cyclohexylamine.
Microemulsion stability of such composition can be estimated visually by watching for phase separation; or can be monitored quantitatively by standard turbidometric techniques. Product "as is" pH is measured at ambient (23C) temperature using a commercial pH meter. The electrode is immersed in the product and the meter is allowed to stabi-lize before reading.

- 25 123~33 EXAMPLE XX
A highly preferred liquid laundry detergent by virtue of the low odor properties o~ its grease removal solvent system, its stability in microemulsion ~orm, and its enzymatic cleaning activity (by virtue of its pH) is as ~ollows.

Inqredient Parts bY Weiqht Alkyl(Cll 8)benzene sulfonic acid 11.0 Alkyl(C14/15)ethoxylate (~07) 12.0 Topped whole cut coconut fatty acid (l) 20~5 C10~ soparaffins 4 Diethyl phthalate 6.0 Cyclohexylamine 2.0 Monomethyl ethanolamine (2) 4.3 Potassium citrate monohydrate (63.5% in water) 2.4 Dequest 2060 S 1.7 Ethoxylated polyamine (x=5, y=15) 1.5 Ethanol 3.0 Potassium hydroxide (50% in water) (2) 3.0 Formic acid O.Z
CaC12 2H20 0,05 Optical brightener (anionic) 0.18 Maxatase enzyme (3) 0.71 Termamyl 300L enzyme (9) 0.10 Dye 20 ppm Perfume 0-5 Water up to 110 parts Product pH 6.9 3~ (1) Chain length mixture: Clo(5%) C12(55%) C14(22%) C18(2%) oleic(10%) (2) To adjust pH to 6.6 (3) From KNGS

(4) From NOVO

- 26 ~230533 The composition of Example XX is used in an aqueous laundry bath at a concentration of lOOml/10 liters and provides an in-use pH of about 7,2 tvaries with water hardness).

Claims (11)

Claims:

1. A stain removal composition, comprising:
a) a grease-removal solvent; and b) an alkoxylated polyamine of the formula:

wherein R is hydrocarbyl having from 2 to 6 carbon atoms, R' is C1 to C20 hydrocarbon, alkoxy is selected from poly-ethoxy, polypropoxy, polybutoxy or mixtures thereof, hav-ing a degree of polymerization of 2-30, x is an integer of at least 2 and X? is an anion wherein the weight ratio of the solvent:alkoxylated polyamine is in the range of 100:1 to 1:20.

2. A composition according to claim 1 wherein the alkoxylated polyamine is the polymerized reaction product of ethylene oxide with ethylene imine.

3. A composition according to claim 2 wherein the alkoxylated polyamine is of the formula:

wherein x is an integer from 3 to 5 and y is an integer from 10 to 20.

4. A composition according to claim 1, 2 or 3 which contains at least 5% of the mixture of solvent and alkoxylated polyamine.

5. A detergent composition comprising conventional detersive ingredients, comprising at least 5% of grease-removal solvent and at least 0.2% alkoxylated polyamine of the formula:

wherein R is hydrocarbyl having from 2 to 6 carbon atoms, R' is C1 to C20 hydrocarbon, x is an integer of at least 2 and X is an anion.

6. A detergent composition according to claim 5 wherein the alkoxylated polyamine is the polymerized reaction product of ethylene oxide with ethylene imine.

7. A composition according to claim 1 which is in the form of an oil-in-water microemulsion.

8. A composition according to claim 7 which addi-tionally contains from 0.5% to 50% of fatty acid or soap.

9. A composition according to claim 8 wherein the solvent is selected from terpenes, paraffin oil, C6-C9 alkyl benzenes, liquid olefins and mixtures thereof.

10. A composition according to claim 9 wherein the solvent is selected from a mixture of:
(a) terpenes, iso-paraffins, C6-C9 alkyl benzenes or liquid olefins; and (b) benzyl alcohol, diethylphthalate, dibutylphtha-late or 2-(2-butoxyethoxy)ethanol at a weight ratio (a):(b) of 1:10 to 10:1.

11. A method of laundering fabrics by agitating said fabrics in an aqueous liquor containing a compo-sition according to claim 1.