CA1062579A - Detergent composition having enhanced particulate soil removal performance - Google Patents

Abstract

Abstract of the Disclosure Detergent compositions are disclosed incorporating combinations of specified ethoxylated zwitterionic compounds with detergent builders and other types of surfactants to give enhanced particulate soil removal.

Description

-` 1062S79 sackground of the Invention This invention relates to detergent compositions having improved particulate soil removal capability. More particularly, this invention relates to detergent compositions incorporating certain ethoxylated compounds which provide unexpectedly good clay soil removal.
Zwitterionic surfactants, i.e., those surface active compounds that contain both positive and negative charge centers in the same molecule while being electrically neutral, are 10 known. For example, U.S. Patent Nos. 3,668,240 and 3,764,568 to Melvin A. Barbera,.issued respectively on June 6, 1972, and October 9, 1973, disclose zwitterionic surfactants having a 2,3-butene moiety between the charge centers. U.S. Patent No. 3,332,875 to Adriaan Kessler and Phillip Floyd Pflaumer also discloses mixtures of certain olefin sulphonates with zwitterlonic detergents in which the charge centers are separated by a 2-hydroxy propane group. U.S. Patent Nos.
3,452,066 and 2,781,390 to Hans S. Mannheimer, issued res-pectively on June 24, 1969 and February 12, 1957, outline a range of z~itterionic surfactants which optionally may be sub-stituted with a wide variety of oxygen-ccntaining groups between the positive and negative charge centers. U.S. Patent No.
3,i69,311 to Leonard J. Armstrong and Eldon de Vere Dawald issued October 3b, 1973, discloses carboxylic compounds having ethylene oxide groups.between the charge centers but fails to recognize the effect of the various structural param~ters on the performance of the molecule in removing soil, especially particulate soil.
In contrast, the present invention concerns detergent compositions incorporating certain zwitterionic surfactants in a polyethenoxy group of a size that permits not only adsorption of the molecule from an aqueous system onto particulate and other soils, and the subsequent removal of the soil b~ emul-sification or dispersion but also the continued maintenance of the removal soil in suspension in the aqueous solution.
However, the present invention is directed to the discovery that a wider range of zwitterionic compounds, in combination with certain detergent builder materials can provide unexpectedly good particulate soil removal and also good oily soil removal from hard surfaces and textile materials.
The ~thoxylated zwitterionic compounds useful in the present invention possess an ability to remove particulate soil that is independent of water hardness over a very wide range or Ca and Mg levels. Furthermore, this performance is re-latively insensitive to temperature changes in the range of 70F. - 140F., the normal range for domestic cleaning functions.
The importance of such a development is readily ap-parent as it permits a high level of soil removal performance to be obtained with a range of detergent formulations. Further-more, the nature ~and level of other components of the for-mulation can be controlled by the selection of an ethoxylated zwitterionic material having the appropriate level of per-formance.
Accordingly, it is an object of the present invention to provide detergent compositions incorporating ethoxylated zwitterionic compounds that have good particulate and oily soil removal performance.
Another object of the preseht invention is the pro-vision of detergent compositions having improved particulate and oily soil removal performance in both liquid and granular forms.

Summary of the Invention In its broadest aspect the present invention embraces a detergent composition comprising:
a) 1% to 99% by weight of the composition of a water-soluble compound having a formula selected from the group consisting of: 12 i) 1 1 (C2H4O)yR4X

wherein R1 is selected from the grou~ consisting of straight and branched chain C8-C30 alkyl and alkenyl moieties and alkaryl moieties in which the alkyl group has 10-24 carbon atoms; R2 is selected from the group consisting of straight and branched chain C8-C21 alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon ato~s, and .
Cl 4 alkyl and hydroxyalkyl moieties; R3 is selected from the group consisting of straight and branched chain C8-C21 alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon atoms, C1 4 alkyl and hydroxyalkyl moieties 20 and -(C2H4O)XH wherein x has a value of about 3 to about 50;
R4 is selected from the group consisting of Cl-C8 alkylene, C3-C8 alkenylene, 2-hydroxy C3 alkylene and 2- and 3-hydroxy C4 alkylene moieties and Cl-C4 alkarylene moieties provided that where R3 is -(C2H4O~XH then R4 is -CH2-CH2-; X is an anion selected from the group consisting of sulfate and sul-fonate radicals; and y has a value in the range of 2-100 provided that where R3 is -(C2H4O)xH then x + y > 10.
_ ~ +
ii) Rl - N - (C2H4)y-l CH2CH2 M

(C2H40) X--1 -- CH2CH2 - wherein Rl is selected from the group consisting of linear and branched C8-C30 alkyl and alkenyl radicals;
R2 is selected from the group consisting of linear and branched C8-C30 alkyl and alkenyl radicals and Cl-C4 alkyl and hydroxyalkyl radicals; X is selected from the group consisting of sulfate and sulfonate;
y and x have values in the range 2-100 provided that y + x > 12;
M is a cation selected from the group consisting of alkali metal, ammonium and alkanolammonium ions.
B.) 99% to 1% by weight of the composition of a detergent builder, which may be organic or inorganic.
In the context of the present invention, ethoxylated zwitterionic compounds having hydroxy substituents on the carbon atoms immediately adjacent the nitrogen atom and/or X moiety are not preferred as they are unstable in water, especially at pH's other than neutrality, and are extremely difficult to pre-pare compared to other hydroxy substituted compounds.
Preferably the ethoxylated zwitterionic compound is one of either ~-(N-C16_18 alkyl, N-Cl 3 alkyl,N- polyethenoxy ammonio) - 2-polyethenoxyethane-1-sulphonate wherein the total number of ethylene oxide groups lies in the range 15-25 or ~-(N-C12_18 alkyl,N,N-diCl-C3 alkylammonio) -2-polyethenoxy ethane-l-sulphonate wherein the number of ethylene oxide groups in the polyethenoxy chain is in the range 6-12.

~06Z~q9 Performance Testing _ In this specification the assessment of particulate and oily soil removal performance both of detergent formulations of the invention and of comparative formulations is carried out using the following procedures.
a.) Particulate soil removal testing This is carried out in either an automatic mini washing machine (AMW) having a capacity of 4,700 ml.
and a cloth/liquor ratio of 1:30 or a Tergotometer having a capacity of 1,000 ml. and a cloth/liquor ratio of 1:140. In both instances the machines are fitted with horizonally rotating paddle agitators, the AMW having a speed of 100 RPM, while the Tergotometer uses a speed of 80 RPM.
The AMW washing procedure involves a 12-minute wash cycle at 105F in 7 grains per U. S. gallon hard water (calculated as CaCO3) using a 2:1 ratio of Ca:Mg salts. The first two minutes of the cycle are used for product dissolution following which the fabric load is added and washed for the remaining 10 minutes. A 5-minute rinse cycle then follows, 2 minutes of which is with agitation, the remaining 3 minutes being a spin to remove excess moisture. The fabrics are then tumble-dried prior to heing graded.

~ A similar washing procedure is used for the Tergoto-meter with the exception that 5.5 grains/gallon water is employed having a 3:1 ratio of Ca:Mg salts (calculated as CaCO3). The wash is followed by one rinse cycle of three minutes in 80F water of the same hardness, level, and type as for the wash, after which the swatches are machine-dried before being graded.
The fabric load for particulate soil removal testing comprises a mixture of white cotton, poly-cotton (65~
DACRO ~/35~/ cotton), and polyester (KODEL~ swatches which are stained with a standardized illite clay soil.
For the A~, three 5" x 5" swatches of each fabric are used in each load, while in the Tergotometer, three

2 1/2" x 2 1/2" swatches of each fabric type are employed.
The results (expressed as relative clay removal index) for each formulation represent a percentage of the whiteness value achieved by a commercial synthetic de-tergent standard tested at the same time under identical conditions. This standard formulation hereinafter designated as "A" has the following composition by weight:

Sodium C12 alkylbenzene sulphona~te 7.55 ~ Sodium Tallow alkyl sulphate 9.25 Coconut alcohol + 6 mole EO 0.60 Diethanolamide 1.60 Sodium Tripolyphosphate 50.00 Sodium Silicate solids 5.90 Sodium sulphate 14.20 Moisture 10.00 Miscellaneous 0.30 100. 00 Grading of Performance Swatches are graded before and after washing on a Gardner Whiteness meter reading the L, a, and b coordinates.
Whiteness (W) is calculated as:
W = 7L - 4OLb ; Performance is determined by finding the difference in whiteness (~W) before and after washing as:
Q W = Wafter ~ Wbefore This is compared to the commercial Control Product A by calcu-lating ~W as a percentage of ~W given by the Control Product in each batch.
The Relative Clay Removal Index= ~W for Test Samplex 100 ~W for Control Product A
b.) Grease and oil removing testing Identical equipment and washing conditions are used to evaluate grease and oil removal perform-ance. The fabric load comprises a mixture of green polycotton (65% DACRO ~/35% cotton) and polyester (KODE ~) swatches, four 2 1/2" x 2 1/2" swatches of each type being used in the tergotometer.

Two triglyceride stains, namely bacon grease and vegetable oil, and two hydrocarbon-based stains, namely dirty motor oil and simulated lipid soil are employed.
Following washing and drying, the swatches are graded visually on a scale whose absolute values are described below:
5. Complete removal 4. Discernible stain remaining

3. Moderate amount of soil remaining 2. Large amount of soil remaining 1. Very large amount of soil remaining 0. No change, original amount of stain remaining As in the particulate soil removal performance test, the results are expressed as a percentage of the soil removal achieved by the standard formulation A under the same conditions.

DETAILED DESCRIPTION OF THE INVENTION
The compositions of the present invention contain two essential components, namely the ethoxylated zwitterionic com-pound and a detergent builder material which may be inorganic or organic in character. The zwitterionic and detergent builder may be present in a ratio of from 99:1 to 1:99 by weight, preferably from 20:1 to 1:10 by weight, and most preferably from 5:1 to 1:5 by weight of the composition. The precise levels of the zwitterionic and builder components will depend on the nature of the zwitterionic compound and the type of product to be formulated. For example, a product intended for prewash treatment of laundry to remove specific stains by direct iapplication to the fabric will be formulated to contain a lower level of zwitterionic compound and different optional ingredients than a product designed as a main wash detergent.
For use as a main wash detergent, the level of ethoxy-lated zwitterionic compound in the product will lie in the range 5%-35% by weight, preferably 10%-25%, and most preferably 15%-20%, the level of the detergent builder being in the range 10%-70%, preferably 10%-60%, and most preferably 20%-45% by weight.
Such a main wash detergent can be formulated as a conventional granule or as a liquid, paste, flake, ribbon, noodle, pellet, or tablet. As will be shown hereinafter, this formulation flexi-bility is due, at least in part, to the ability of the zwitter-ionic surfactants of the present invention to achieve particulate soil removal performance equivalent to that of commercial heavy duty laundry detergents when used in blends with detergent builder materials.

ETHOXYLATED ZWITTERIONIC COMPOUNDS
. _ _ Ethoxylated zwitterionic compounds useful in the present invention may have one or other of the following formulae:

i) 1 ,N (C2H4O)y - R4 - X

a.) Mono-long chain derivatives In this derivative, Rl is a hydrocarbon moiety that can be a straight or branched chain C8-C30 alkyl or alkenyl group or an alkaryl group in which the alkyl portion has 10-24 carbon atoms; R2 and R3 are Cl-C4 alkyl or hydroxyalkyl groups; R4 is g _ ~062579 a Cl-C8 alkylene, C3-C8 alkenylene, 2-hydroxy propylene or 2- or 3- hydroxy butylene group or a Cl -C4 alkarylene group; X is a sulfonate or sulfate radical; and y has a value in the range 2-100.
In this embodiment, preferred groups for Rl are C12-C18 alkyl, particularly C14-C16 alkyl, while preferred groups for R2 and R3 are Cl_3 alkyl and C2 3 hydroxyalkyl, the most preferred groups being methyl- and hydroxethyl- radicals. The preferred range of values for y is 6-50, more preferably 6-25, and most preferably 9-12.
The synthesis of the above compounds can be achieved using readily available commercial starting materials. One such synthetic route is as follows. Sodium hydride is slowly and stoichiometrically reacted (2:1 molar ratio) with polyethylene glycol in a solution of tetrahydrofuran under an atmosphere of an inert gas, e.g., argon. The reaction is carried out over a period of 4-10 hours in an ice bath to cool the reaction, which is exothermic. The polyethylene glycol used is the commercially available material comprising a mixture of compounds having chain lengths from about 4 to about 100. The resultant product is the sodium salt represented by (I) Na (CH2cH2) yCH2CH2 Na wherein y can be, for example, 3, 21, 32, 67, or 99.
A stoichometric amount of tosyl chloride dissolved in tetrahydrofuran is then added slowly to reaction product (I), cooled in an ice bath, and the resultant mixture is stirred for 12 to 20 hours to form (II) CH3- ~ -So2-o(cH2cH2o)y+l 2 ~ 3 i.e., the polyethylene glycol ditosylate. Pyridine or other suitable base is added to the mixture, and the solution is then poured into ice water and acidified with HCl to a pH of about 2-3. The aqueous solution is then extracted with chloroform, rinsed with water and the chloroform extract is dried over sodium sulfate to give purified polyethylene glycol ditosylate (II).
The ditosylate (II) is then reacted with a tertiary amine of the structure (III) Rl - ~

wherein Rl, R2 and R3 are as defined above. The reaction of (III) with (II) is conveniently carried out neat, or with a suitable solvent as N,N-dimethyl formamide or CH3CN at temperatures of 80C to about 100C to produce a mixture of ,R2 (IV) Rl ~+ ~ (C2H4O)y+l 2 ~ - CH3, 3 ~ -SO3-and (V) Dicationic ammonium byproducts The mixture of (IV) and (V) is then dissolved in methanol and refluxed from 20-40 hours with an aqueous solution of sodium sulfite. The unreacted (V) and other ionic materials are removed by contacting the above solution with a mixed bed ion exchange resin, followed by filtration of the solution and evaporation of the solvent to give, as the predominant zwitter-ionic product.

I +
(VI) 1 ~ (C2H4O)y C2H4S3 Compound (VI) can optionally be further purified using the mixed bed resin and tested for purity by thin layer chromatography.
It will be appreciated that zwitterionic compounds of the general formula (VI) can be prepared using any of a variety of tertiary amines (III). Moreover, zwitterionic compounds having any desired, specific degree of ethoxylation (y) can be prepared by fractionating the polyethylene glycol used in the reaction and using the desired fraction in the synthesis scheme.
Alternatively, relatively narrowly defined distillation "cuts"
of polyoxyethylene glycol having any desired average degree of ethoxylation, and containing individual compounds having differ-ing degrees of ethoxylation within the desired range, can be used in the reaction. It will be further understood that sodium salt (I) can be reacted with a variety of epoxy compounds (e.g., butylene epoxide) or halohydrins (e.g., 6-chlorohexanol or 8-bromooctanol) to provide zwitterionics having various R4 groups within the scope of this invention.

A specific preparation of a mono-long chain ethoxy-lated zwitterionic compound useful in the present invention was as follows:

Preparation of 26-dimethyloctadecylammonio-3,6,9,12,15,18,21, 24 octaoxahexacosane-l-sulfonate Preparation of Nonaethyleneglycol (A). Under nitrogen, 46 grams (2 moles) of sodium pellets were added cautiously to2,664 ml (20 moles) of previously dried and distilled tri-ethyleneglycol. The temperature was kept below 100C. After all the sodium had reacted, the temperature was adjusted to 100C and 187 grams (1 mole) of 1,2-bis-(2-chloroethoxy) ethane was added in a slow stream. The mixture was heated overnight at 100C (still under nitrogen) and then filtered hot to remove most of the sodium chloride. Excess triethyleneglycol was stripped under vacuum and the mixture was again filtered while hot. The material was purified by molecular distillation and has a b.p. of 170-175C at 0.001 mm.
Preparation of Nonaethyleneglycol ditosylate (B) The nonaethyleneglycol (A), 300 grams, (0.72 moles) was dissolved in 800 ml (10.3 moles) of dry pyridine and cooled to 0C. Tosyl chloride (i.e., _-toluene-sulfonyl chloride, 420 grams, 2.2 moles) was added, with stirring, in small portions.
After the addition was complete, the temperature increased to 10C and the clear reaction mixture became cloudy. The mixture was stirred at 0-10C for an additional 3 hrs., then poured into an equal volume of ice water and acidified to pH 2-3 with 6N
HCl. The aqueous solution was then extracted 3 times with CHC13. The CHC13 was washed with water, sodium bicarbonate solution, and again with water, then dried over anhydrous sodium sulfate. Evaporation of the CHC13 gave 520 grams of a slightly yellow oil. Thin layer chromatography indicated an impurity which remained at the origin. The oil was dissolved in warm benzene (40C) and extracted with warm water to remove the polar impurity. The benzene was dried, filtered and concentrated to yield 423 grams of a yellowish oil (B).

Preparation of dimethyloctadecyl-26-tosyloxy-3,6,9,12, 15,18,21,24 octaoxahexacosylammonium tosylate (C). The ditosylate (B) 86.7 grams (0.12 mole) and 35.8 grams of distilled dimethyloctadecylamine were heated at reflux for 5 hrs. in 400 ml of acetonitrile. The solvent was then removed to give 120 grams of a mixture consisting of the monoquaternary tosylate (C), diquaternary ammonium by-product (D) and some unreacted ditosylate (B), Preparation of 26-dimethyloctadecylammonio-3,6,9,12, 15,18,21,24 octaoxahexacosane-l-sulfonate. The mixture of monoquat (C) and diquat (D) prepared above was dissolved in 1 liter of methanol. Sodium sulfite (100 grams, 0.79 moles) was added and the reaction mixture was refluxed with stirring for 5 hours. Additional methanol was added and the insoluble salts were filtered. The solvents were removed to yield a solid product.
Purification. The above solid reaction product was dissolved in 1 liter of methanol and stirred with 386 grams of a mixed bed (Rexyn ~ 300 H-OH, commercially available from the Fisher Scientific Co.) resin for 5 hours. The solution was then passed through a column of fresh resin (350 grams of Rexyn ~ 300) at a rate of 2 liters per 7 hours. The methanol solution was then concentrated to yield 31.8 grams of a light yellow oil which was recrystallized from acetone to give a white crystal-line, hygroscopic product. This product was identified as the title compound (E in the following schematic).
The following sequence sets forth the above procedure in abbreviated form to clarify the structures of compounds prepared thereby. In the sequence, the dimethyloctadecylamine can be replaced by dimethylhexadecylamine, dimethylnonadecyl-amine, dimethyleicosylamine, and dimethyldocosylamine, ~06257'~
respectively, and the corresponding compounds wherein R1 is C16, Clg, C20, and C22 are secured, respectively.

HO~C2H40)3H ~ Na O (C2H40)3H (ClCH2CH20)2C2H4 , (A) ~(F2H4)9H ~

S020 (C2H40) 9 - 2S ~CH3 18~37N(CH312 - C

~C) . C18H37 1 - (C2H4o) 9 - 02S~CH Na2S3 , CH3~S

,; . . . .
(D) Diquaternary ammo~ium byproduct (E) C18H37 ~ ~ (C2H4o)8 C2H4503 - -~F) 2 CH3 ~ S03 , Na ~, .
~A !
;_,,, .1 b.) Di-long chain derivatives ; In this derivative, both Rl and R2 are hydrocarbon moieties that can be straight or branched chain C6-C21 alkyl or alkenyl groups; R3, R4, and X are as in (i) (a.) above and y has an average value in the range 6-100. Preferably Rl and R2 are identical and comprise alkyl groups each having 10 to 16 carbon atoms, most preferably alkyl groups each having 10 to 24 carbon atoms. Preferred values for y lie in the range 9 to 50, most preferably in the range 12 to 25.
A specific preparation of a di-long chain alkyl ethoxylated zwitterionic compound useful in the present invention was as follows:
Methylation of di-n-octylamine was accomplished by slowly mixing 50 grams of the secondary amine with, first, formic acid (30.03 grams), and then formaldehyde, at 0C. The reaction mixture was kept at 80C for 24 hours, then adjusted to pH 8-9 with 10~ NaOH solution. The resulting tertiary amine was extracted with CHC13 and dried over Na2SO4. The tertiary amine (25.6 grams, 0.10 mole) was then refluxed with 72 grams (0.10 mole) of nonaethylene glycol ditosylate (compound B, pre-pared as in the previous procedure) in acetonitrile for 6 hours.
The solvent was evaporated and the resulting mixture of mono-and diquaternary compounds was dissolved in methancl and re-fluxed with 100 grams of sodium sulfite (predissolved in water) for 16 hours. Excess sulfite and other salts were filtered and the filtrate was stirred for 16 hours with 500 grams of a mixed bed resin (Rexyn ~ 300). A second treatment with fresh resin was necessary to remove all impurities. The solvents were evaporated to complete dryness and the product, 22 grams of a light yellow viscous oil, was identified as fH3 8 17 1 (CH2cH2)8cH2cH2s3 or 26-dioctylmethylammonio-3,6,9,12,15,18,21,24-octaoxahexa-cosane-l-sulfonate.

c.) Tri-long chain derivatives In this derivative, Rl, R2, and R3 are all hydrocarbon moieties that can be straight or branched chain C6-C16 alkyl or alkenyl groups; R4 and X are as in (i) (a.) and (b.) above and 10 y has a value in the range 6-100. Preferably Rl, R2, and R3 are each identical and each comprise an alkyl group having 8-16 carbon atoms in the chain. Most preferably each chain contains 8-12 carbon atoms. y has a preferred value in the range 9-50, most preferably in the range 12-50.
A specific preparation of a tri-long chain alkyl ethoxylated zwitterionic compound was as follows:

Tri-n-octylamine was distilled to insure purity and 42 grams of the purified product (0.12 mole) was reacted with 87 grams (0.12 mole) of the ditosylate of nonaethylene glycol (compound B in the mono-long chain preparation) in dry N,N-dimethylformamide at 100C for 2 hours. The dimethylformamide was removed and the mixture of mono- and diquaternary material was dissolved in methanol. This mixture was refluxed for 16 hours with 100 grams of Na2SO3 predissolved in water. The in-soluble salts were filtered and the filtrate was stirred with 500 grams mixed bed resin (Rexyn ~ 300 H-OH) for 24 hours. An additional treatment with 500 grams fresh resin was used to further purify the product. Thin layer chromatography still indicated an impurity, which was subsequently removed by dis-solving the product in H2O, acidifying to pH 4, and extracting with CHC13. The CHC13 extract was rinsed with sodium bicarbonate, dried and evaporated to give a light yellow viscous oil, identified as 8H17 ~ ~ (CH2cH2)8 CH2CH2S3 or trioctylammonio-3,6,9,12,15,18,21,24-octaoxahexacosane-1-sulfonate ' " R2 ii) Rl - ~ - (C2H4O)y_l ~ CH2CH2 X (I) ( 2 4 ) x In this structure, R1 can be a linear or branched C8-C22 alkyl or alkenyl group, preferably a C16 18 alkyl or alkenyl group; R2 can be a C8-C30 alkyl or alkenyl group or can be a Cl-C4 alkyl or hydroxyalkyl group, preferably a methyl group;
and X can be a sulfonate or sulfate radical.

The number of ethylene oxide groups in each chain can 20 be from 1 to 100 but their sum should be greater than 10.
Normally there will be approximately the same number in each chain, the sum of the groups in both chains preferably having a value in the range 12-50 and most preferably in the range 12-25.
The preparation of zwitterionic compounds of this type is accomplished using commercially available starting materials.

A typical starting material is marketed under the trademark Ethoquad, by the Armak Company of the Armour Company. Ethoquad is a mixture of quaternary ammonium compounds whose predominant component is a di-ethoxylate of the structure Rl 2 4 )Y

2 ( 2H4)xH

wherein y and x are each non-zero integers whose average sum is, for example, 5, 10, 15, 50, depending on the "cut" selected, and 1 2 e C12 C18 alkyl and Cl-C3 alkyl, respectively In general terms, the compounds herein are prepared by dissolving Ethoquad in pyridine or other suitable base and cooling the mixture to a temperature of about 0C. Tosyl chloride is slowly added to the Ethoquad mixture at a 1:1 stoichiometric ratio while the reaction mixture is kept at about OC-5C in an ice bath. The mixture is then stirred for about 24 hours at OC-5C. At the end of that time the reaction mix-ture is poured into water and acidified to a pH of 2-3 with HCl.
The foregoing acidified reaction mixture is then ex-tracted with chloroform and the extract is rinsed first with sodium bicarbonate solution, then with water; the extract is then dried over anhydrous sodium sulfate. After evaporation of the chloroform extract, an oily residue is obtained. This is the mono-tosylate ester of the structure 18 37 (C2H4O)y - O2S ~ CH3 N / , Cl CH3 / (C2H4)xH

wherein y and x are as above.
The foregoing tosylate ester is then dissolved in methanol and refluxed for about 24 hours with about a lO molar excess of sodium sulfite predissolved in H2O. The reaction mixture is cooled and excess sodium sulfite and sodium tosylate are removed by filtration. The filtrate is stirred with a mixed bed (anion-cation) resin to purify the product. A second resin treatment can optionally be used to remove substantially all traces of all cationic and anionic impurities. The purified mono-sulfonate corresponding to (I) above is recovered by evaporating the solvent. The product can optionally be re-crystallized from acetone.

N ~ C2H4O)y 1 ~ CH2CH2 ~ X ~ M (II) (C2H40) X-l - CH2CH2 where Rl, R2, and X are as in (ii) and y and x each have a value in the range l-lO0 provided that the sum of y + x > 10. Preferred values for the sum of y + x will lie in the range 12-50 and most preferably in the range 15-25. The cation M can be alkali metal, ammonium, and alkanolammonium, e.g. ethanolammonium or methanolammonium but is most preferably sodium.

The disulfonate (II) is prepared in the same manner as the mono-sulfonate (I), but using excess tosyl chloride (about 3:1 mole ratio, or greater) in the first step and a larger excess of sodium sulfite (20:1 mole ratio) in the second step. If a cation, M, other than sodium is desired in the final product, the corresponding sulfite can be used in the second step.
Alternatively, the sodium form of compound (II) can be ion-exchanged in standard fashion to any desired cation, M. The resin purification treatment is unnecessary when preparing the disulfonate.
The sulfates of the type (I) and (II) are easily pre-pared by reacting one or two moles of chlorosulfonic acid with the Ethoquads, respectively. The same consideration with regard to selection of cation M holds true for the sulfates as for the sulfonates.
It will be appreciated that a variety of diethoxylated amino starting materials can be employed in the foregoing re-action scheme. For example, Ethoquad derivatives having variations in groups Rl and R2 are commercially available, e.g., compounds wherein Rl is an average C12 cut. Moreover, precursor compounds having varying sums of y and x (within the recited range) can be selected according to the desires of the user.
Compounds wherein y and x are of approximately equal length, the sum of y and x being from about 12 to about 25, most preferably from 15 to about 25, are especially useful herein.
It will be further appreciated that a variety of other starting materials can be employed to prepare various di-ethoxylated precursors of the present zwitterionic compounds.
For example, the Ethomeens (a trademark of a class of compounds marketed by the Armak Company, a division of the Armour Company) 1062S~9 can be quaternized to produce variations of the commercial Ethoquads. Thus, Ethomeens of the general formula R-N(C2H40)X
H(C2H40)yH, when R is alkyl, can be reacted with excess alkyl iodide or hydroxy-substituted alkyl iodide (CH3I, C2H5I, etc.) to produce a quaternary ammonium compound which can be sulfated or sulfonated on one or both ethylene oxide groups in the manner disclosed above.
It should be appreciated that mixtures of any of these zwitterionic compounds in any proportions may be used in the compositions of the present invention. Such mixtures may be produced intentionally by blending individual species or may arise as a result of the choice of feedstocks or as a result of the processing s~eps involved.
Th~ ethoxylated zwitterionic compounds useful in the present invention desirably display appreciable solubility in aqueous media. A solubility in water at 25C of at least 50 ppm, preferably more than 75 ppm appears to be necessary for satisfactory particulate ~oil removal performance, but the preferred materials have solubilities in water of 10/~-30C/~ by weight.
The second essential component of a composition in accordance with the present invention is a detergent builder material. This can be present at a level of from 1%-~9/~ by weight of the composition, the actual level being dependent on the end use of the composition and its desired physical form.
Inorganic detergent builders that are useful in compositions in accordance with the present invention are the alkali metal, ammonium and alkanolammonium, polyphosphates (exempllfied by the tripolyphospnates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, borates, and aluminosilicates.
Specific examples of polyphosphates of value in the present invention are the alkali metal tr-ipolyphosphates, sodium, gotassium ànd ammonium pyrophDsphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranses from about 6 to about 21. Particularly preferred are the alkali metal tripoly- and pyro- phosphates.
Examples of suitabie phosphonate builder salts are the water-soluble salts of ethane l-hydroxy-l, l-diphosphonate particularly the sodium and potassium salts, the water-soluble ~i ~062579 salts of methylcne diphosphonic acid e.g. the trisodium and tri-potassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tri-potassium ethylidene, isopropylidene benzylmethylidene and halo methylidene phosphonates. Phosphonate builder salts of the aforementioned types are disclosed in U. S. Patent Nos.-3,159,581 and 3,213,030 issued December l, 1964 and October 19, 1965,to Diehl; U. S. Patent No. 3,422,021 issued January 14, 1969, to Roy; and U. S. Paten~ Nos. 3,400,148 and 3,422,137 lG issued September 3, 1968, and Janury 14, 1969 to Quimby.
Preferred silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1-6:1 to 3-2:1. However, other silicates may also be useful-such as for example magnesium silicate, which can serve as a crispening agent in granular formulations as a stabilizing agent for oxygen bleaches such as sodium perborate, and as a component of suds control systems.
Examples of preferred carbonate builders include sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application DOS No. 2,321,001 published on November 15, 1973.
Alkali metal borates which are of value in the present invention include sodium tetraborate, decahydrate, and potassium pentaborate tetrahydrate.
Aluminosilicate builder salts found to be useful in the present invention have the general formula:

Nazt~A102)z (SiO2)~,] X H20 ~'' wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264. Such aluminosilicates also should have a particle size diameter in the range 0.1 to 100 microns, a calcium ion exchange capacity of at least about 200 milligram equiva-lent/gram and a calcium ion exchange rate of at least about 2 grains/U.S. gallon/minute/gram. Detergent com-positions incorporating aluminosilicate builder salts of this type are disclosed in Canadian patent 1,035,234, issued July 25, 1978.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, alkali metal, ammonium and alkanolammonium, salts of ethylene diamine tetraacetic acid, nitrilo triacetic acid, phytic acid, mellitic acid, and mixtures thereof with benzene penta carboxylic acid, benzene 1, 3, 5-tricarboxylic acid and 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, citric acid, itaconic acid, oxydisuccinic acid, carboxy-methyloxysuccinic acid, poly maleic acid, and copolymers of maleic anhydride with ethylene or vinyl methyl ether. Specific disclosures of these and other suitable organic detergent builders occur in U. S. Patent No. 3,308,067 issued March 7, 1967, to Diehl; Japanese Patent Application No.
73,703 filed May 24, 1971, and published January 8, 1973;
U. S. Patent Nos. 3,699,159, 3,758,420, and 3,812,044 issued October 17, 1972, September 11, 1973, and May 21, 1974 in the names of Connor and Krummel; and U. S. Patent No. 3,635,830 issued January 18, 1972 in the names of Lamberti and Konort.
Mixtures of any of the above detergent builders can also be used, several particularly advantageous combinations being disclosed in U. S. Patent Nos. 3,356,613 and 3,392,121 issued respectively on December 5, 1967 and July 9, 1968 to Gedge.
The accompanying Tables illustrate the particulate soil removal performance given by combinations of ethoxylated zwitterionic compounds useful in the present invention and various detergent builders.
Table I shows the effect of a variety of builders both inorganic and organic, on the clay soil removal performance of two ethoxylated zwitterionic compounds that show good performance on their own. At a zwitterionic compound usage level of 250 ppm, an overall performance improvement is seen for addition of any builder, with marked benefits on cotton and polyester fabrics.
At a zwitterionic compound usage level of 125 ppm, the addition of builder restores the level of performance in most instances to that provided by 250 ppm ethoxylated zwitterionic compound alone and in some instances exceeds it.
Table II shows a similar result for two ethoxylated zwitterionic compounds whose particulate soil removal perform-ance in the absence of builder is not particularly good. Theresults show that certain detergent builders can raise the clay removal performance of these "poorer" materials to the level achieved by the ethoxylated zwitterionic compounds that have good performance on their own and can in some instances even match the performance of the control product A at its higher usage concentration (1400 ppm).
The efficacy of builder-ethoxylated zwitterionic com-pound combinations for a range of zwitterionic compound structures is demonstrated in Table III. It can be seen that a combination incorporating the C8 alkyl dimethyl derivative 106Z5~9 (Run No. 4) does not provide good particulate soil removal per-formance (c.f. C12 alkyl and C14 alkyl materials in Table II) but that performance improves slightly for the di-C8 derivative (Run No. 5) and then shows a marked increase for the derivative in which total substitution of the methyl side chains by C8 alkyl groups has taken place (Run No. 6). Runs 9 and 10 illustrate the desirability of exceeding a given solubility in water, where it can be seen that the prior solubilization in methanol of a compound having a low water solubility (cir. 50 ppm by weight) provided some increase in performance but was not essential in obtaining an appreciable level of particulate soil removal. The influence of builder and ethoxylated zwitterionic level is shown in Table IV where it can be seen that the use of a builder combination having efficient mineral hardness removal characteristics can permit the level of ethoxylated zwitterionic to be lowered considerably (Runs 8 & 9). The use of less efficient builder systems do not provide the same degree of formulation flexibility in that the particulate soil removal performance correlates more directly with the level of the ethoxylated zwitterionic compound (Runs 3, 4, & 5).
The particulate soil removal results demonstrate that for those ethoxylated zwitterionic compounds having inherently good performance, combination with a detergent builder permits a substantial reduction in the zwitterionic level, the reduction being associated with the efficacy of the builder in controlling mineral hardness. For those ethoxylated zwitterionic compounds that do not have such good particulate soil removal performance, combination with detergent builders at a zwitterionic level of 125 ppm in solution provides an improvement that in most cases matches and even exceeds the performance of the control product used at recommended concentrations.
Grease and oil removal performance results for combin-ations of ethoxylated zwitterionic compounds and detergent builders are set out in Table V. Combinations using the C16 dimethyl octaethenoxy compounds, the C14 homologue, and 1:1 blends of these two materials all show an overall improvement in grease and oil removal for the incorporation of a detergent builder but the effect varies both with the fabric and stain type. In general, a noticeable improvement is seen on polyester fabrics for both types of stain but the effect is more variable on poly-cotton blends, particularly with triglyceride-type stains.
In summary, the addition of a detergent builder to the ethoxylated zwitterionic compounds of the present invention improves grease and oil removal on synthetic fabrics, while having an effect on cotton blends which is dependent on the stain type and the nature of the builder combination.

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Optional Components In addition to the ethoxylated zwitterionic compound and the detergent builder, the detergent compositions of the present invention may also contain other ingredients convention-ally employed in such products. The principal optional component is a cosurfactant which may be nonionic, zwitterionic, ampholytic, anionic, or cationic. Nonionic, zwitterionic, and ampholytic cosurfactants may be present in amounts ranging from 5-95% by weight of a composition containing the ethoxylated zwitterionic detergent builder combination. Cationic surfactants containing a hydrophilic moiety in the molecule (e.g. hydroxy, hydroxyalkyl, and ethenoxy groups) can also be utilized at these levels, but cationic surfactants not possessing such groupings serve to de-press the particulate soil removal performance of the ethoxylated zwitterionic compounds. Anionic cosurfactants are preferably incorporated in amounts not exceeding 100% by weight of the ethoxylated zwitterionic compound for similar reasons.
Specific cosurfactant-ethoxylated zwitterionic com-pound mixtures are disclosed in U.S. Patent 3,929,678, issued December 30, 1975.
Another optional ingredient that may be incorporated is an enzyme for removal of protein-based or carbohydrate-based stains. Enzymes for removing protein-based stains are prote-olylic in nature, such as those sold under the trade mark "Alcalase" and "Esterase" by Novo Industries A/S Denmark or under the trade mark "Maxatase" and "AZ Protease" by Gist-Brocades N.V.
the Netherlands. These materials are normally incorporated at levels of up to 1% by weight, preferably 0.25% to 0.75% by weight, and are preferably coated or prilled with inert additives to minimize dust formation and improve storage stability. A wide range of enzyme materials and means for their incorporation into synthetic detergent granules is disclosed in U.S.P. 3,553,139 issued on January 5, 1971, to McCarty, Roald, DeOude, Blomeyer, and Cracco.
A further ingredient that may be incorporated to im-prove product performance is a bleaching agent of the halogen or oxygen-containing type. Examples of the hypohalite bleach type include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphon-amides. Such materials are normally added at 0.5%-10% by weight of the finished product, preferably 1%-5% by weight.
Examples of oxygen containing bleaches include sodium perborate, sodium percarbonate, and potassium non-opersùlphate that are incorporated at levels of 5-30%, preferably 10-25% by weight of the final product. The inclusion of organic bleach activators such as phthalic anhydride, tetra acetyl ethylene diamine, tetra acetyl methylene diamine or tetra acetyl glycouril lead to the in situ production during the washing process of the corresponding organic peroxy acids which have enhanced low temperature bleaching performance. Activators of this type are normally used with sodium perborate, at usage levels of 5-15% by weight of the final product.
Materials to boost or modify the sudsing pattern of the compositions of the present invention may also be included.
Examples of suds boosters include coconut and tallow mono- and di-alkanolamides, particularly ethanolamides and C12 15 alkyl di-lower alkyl amine oxides. Typical suds depressors include long chain fatty acids such as those disclosed in U. S. Patent 2,954,347 issued September 27, 1960, to Wayne St. John and com-binations of certain nonionics therewith as disclosed in U. S.
Patent 2,954,348 issued September 27, 1960, to Eugene Schwoeppe.

~06Z57~

Other optional ingredients in granular products include hydrotropes and anticaking additives such as salts of lower alky-aryl sulphonic acids, salts of a -sulphosuccinic acid, and ~ -sulphobenzoic acid, and urea, normally utilized at levels of 0.5% to 5% by weight of the final product, preferably at levels of 1%-3% by weight. C12-C18 alkyl acid phosphates and their con-densation products with ethylene oxide may also be incorporated at similar levels for control of crutcher mix viscosity. Antire-deposition agents such as carboxymethyl cellulose, hydroxyethyl cellulose, and their derivatives may also be incorporated.
Anti-tarnish and anti-corrosion agents, perfume and color may also be included, the last ingredient being conveniently added either as a general color or in the form of a speckle applied to a separate granule fraction of the entire formulation or to a granulate of one or more of the ingredients.
The pH of detergent formulations in accordance with the present invention can lie anywhere within the range 5-12 but is preferably chosen to fall within the range 8.0 -10.5 as this pro-vides a slight particulate soil removal benefit on synthetic fabrics. However, the use of specific optional components such as enzymes may require the selection of a product pH that will permit optimum functioning of the component concerned.
Granular formulations embodying the compositions of the present invention may be formed by any of the conventional techniques i.e., by slurrying the individual components in water and then atomizing and spray-drying the resultant mixture, or by pan or drum granulation of the components.
Liquid formulations embodying the compositions of the present invention may contain builders or may be unbuilt. If the compositions are unbuilt, they will conventionally contain approximately 30-50% total surfactant, from 1-10% of an organic base such as mono, di, or tri-alkanolamine, a solubilization system such as alkali metal halide and a lower primary alcohol such as ethanol or isopropanol and approximately 30%-40% water.
Such compositions will normally be homogeneous single phase liquids of low viscosity (approximately 100-150 centipoises at 75F).

Built liquid detergent compositions may also be single phase liquids provided that the builder can be solu-bilized in the mixture at its level o~ use. Such liquids conventionally contain 10%-25% total surfactant, 1~o~20%
builder which may be organic or inorganic, 5%-1~/o oE a ~ydrotrope system and 5~o~6~o of water. Liquids of this type also have low viscosity (100-150 c.p.s. at 75F) ~
Built liquid detergents incorporating components that form heterogeneous mixtures or levels of builder that cannot be completely dissolved can also embody the compositions of the present invention. Such liquids conventionally employ viscosity modifiers to produce systems having plastic shear character-istics to maintain stable dispersions and to prevent phase separation or solid settlement.
~he following examples serve to illustrate the present invention:

A concentrated detergent formulation having the consistency of a thick paste was prepared having the following composition by weight:

w-(hexadecyl dimethyl ammonio)- 38.4 2-octaethenoxy ethane-l-sulphonate Sodium Carbonate 30.8 Sodium Silicate (SiO2:Na2O = 3 2:1) 30.8 100,. 0% .

~-~

Cotton, polycotton, and polyester cloth swatches that had been soiled with a standardized illite clay soil were given a ten minute wash with this product in the tergotometer at 105F
using water of mineral hardness 7 grains~gallon (Ca:Mg = 2:1).
Product concentration was adjusted to give 250 ppm of zwitter-ionic compound in solution. Following rinsing and drying, ths swatches were then graded instrumentally for clay soil removal ùsing a Hunter Color Difference meter. The results, expressed as a percentage of the performance achieved by the Standard Formulation A used at 0.10~ concn. by wt. under the same condi-tions, were as follows:

- Cotton Polycotton Polyester 92% 106~ 109%

Example II

A solid powdered formulation was prepared having the following composition:

~ -(N-octadecyi, N-methyl, N-polyethenoxy 27.8%
ammonio)-2-polyethenoxy ethane-l-sulphonate wherein the total number of ethylene oxide groups in the molecule was 14 . Sodium Tripolyphosphate 27.8 Sodium Carbonate 22.2 Sodium Silicate (SiO2:Na2O = 3-2:1) 22.2 . _ '100.0 ,~

Using the product concen~rations and adopting-the Testing Procedure set out in Example I, the following results were obtained,expressed as a percentage of the performance of the Control Product A under the same conditions:

CottonPolycotton Polyester 104% 99% 106%

~' , J

Claims (11)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A detergent composition comprising A) 1% to 99% by weight of the composition of a compound having the formula selected from the group consisting of i) wherein R1 is selected from the group consisting of straight and branched chain C8-C30 alkyl and alkenyl moieties and alkaryl moieties in which the alkyl group has 10-24 carbon atoms;
R2 is selected from the group consisting of straight and branched chain C8-C21 alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon atoms, and C1-4 alkyl and hydroxyalkyl moieties;
R3 is selected from the group consisting of straight and branched chain C8-C21 alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon atoms, C1-4 alkyl and hydroxyalkyl moieties and -(C2H4O)XH
wherein x has a value of about 3 to about 50;
R4 is selected from the group consisting of C1-C8 alkylene, C3-C8 alkenylene, 2-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and C1-C4 alkarylene moieties pro-vided that where R3 is -(C2H4O)xH then R4 is -CH2-CH2-;
X- is an anion selected from the group consisting of sulfate and sulfonate radicals;
and y has a value in the range of 2-100 pro-vided that where R3 is -(C2H4O)xH then x + y ? 10; and ii) wherein R1 is selected from the group consisting of linear and branched C8-C30 alkyl and alkenyl radicals; R2 is selected from the group consisting of linear and branched C8-C30 alkyl and alkenyl radicals and C1-C4 alkyl and hydroxyalkyl radicals;
X- is selected from the group consisting of sulfate and sulfonate;
y and x have values in the range of 2-100 provided that y + x ? 12;
M is a cation selected from the group consisting of alkali metal, ammonium and alkanolammonium ions; and .B) 99% to 1% by weight of the composition of a detergent builder.

2. A detergent composition according to Claim 1 wherein the detergent builder is an inorganic detergent builder selected from the group consisting of alkali metal, ammonium, and alkanolammonium polyphosphates, carbonates, bicarbonates, silicates, aluminosilicates, borates, and sulfates.

3. A detergent composition according to Claim 1 wherein the detergent builder is an organic detergent builder selected from the group consisting of alkali metal ammonium and alkanol-ammonium salts of ethylene diamine tetra acetic acid, nitrilo-triacetic acid, citric acid, oxydisuccinic acid, carboxy-methoxysuccinic acid, benzene penta- and hexa-carboxylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulfonic acid, and copolymers of maleic anhydride with vinyl methyl ether and ethylene.

4. A detergent composition according to Claim 1 wherein the zwitterionic compound has the formula wherein R1 is selected from the group consisting of straight and branched chain C16-C22 alkyl and alkenyl moieties, R2 is a C1-C3 alkyl group and x + y has a value in the range of 12-50.

5. A detergent composition according to Claim 4 wherein R1 is selected from the group consisting of straight and branched chain C16-C18 alkyl and alkenyl moieties and x + y has a value in the range of 15-25.

6. A detergent composition comprising A) 1% - 99% by weight of the composition of a compound having the formula wherein R1, R2, and R3 are each selected from the group consisting of branched and straight chain C6-C16 alkyl and alkenyl radicals;
R4 is selected from the group consisting of C1-C8 alkylene, C3-C8 alkenylene, 2-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkyl group contains from 1-4 carbon atoms;
X- is an anion selected from the group consisting of sulfate and sulfonate radicals; and y has an average value in the range of 6-100; and B) 99%-1% by weight of the composition of a detergent builder.

7. A detergent composition according to Claim 3 wherein y has a value of at least 9.

8. A detergent composition comprising A) 1%-99% by weight of the composition of a compound having the formula:

wherein R1 and R2 are each selected from the group consisting of branched and straight chain C6-C21 alkyl and alkenyl radicals;
R3 is selected from the group consisting of C1-C4 alkyl and hydroxyalkyl moieties;
R4 is selected from the group consisting of C1-C8 alkylene, C3-C8 alkenylene, 2-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkyl group contains 1-4 carbon atoms;
X- is an anion selected from the group consisting of sulfate and sulfonate radicals; and y has an average value in the range of 6-100;
B) 99%-1% by weight of the composition of a detergent builder.

9. A detergent composition according to Claim 1 wherein the compound has the formula:

wherein R1 is selected from the group consisting of branched and straight chain C8-C30 alkyl and alkenyl radicals; R2 and R3 are each selected from the group consisting of C1-C4 alkyl and hydroxyalkyl moieties;
and R4 is selected from the group consisting of C1-C8 alkylene, C3-C8 alkenylene, 2-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkylene group has 1-4 carbon atoms; and y has a value of from about 6 to about 20.

10. A detergent composition according to Claim 9 wherein R1 is a C12-C18 alkyl moiety; and R2 and R3 are independently selected from C1-C3 alkylene and hydroxyalkylene moieties; R4 is a -CH2CH2- moiety; and y has a value from about 6 to about 12.

11. A composition according to Claim 1 incorporating an organic detergent selected from the group consisting of anionic, nonionic, ampholytic, and zwitterionic surfactants.