US3925262A - Detergent composition having enhanced particulate soil removal performance - Google Patents

Detergent composition having enhanced particulate soil removal performance Download PDF

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US3925262A
US3925262A US493952A US49395274A US3925262A US 3925262 A US3925262 A US 3925262A US 493952 A US493952 A US 493952A US 49395274 A US49395274 A US 49395274A US 3925262 A US3925262 A US 3925262A
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detergent
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detergent composition
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Robert Gene Laughlin
Robert Lee Stewart
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to CA231,695A priority patent/CA1062579A/en
Priority to DE19752533795 priority patent/DE2533795A1/en
Priority to GB32083/75A priority patent/GB1507543A/en
Priority to BE158837A priority patent/BE831994A/en
Priority to IT25982/75A priority patent/IT1040280B/en
Priority to NL7509120A priority patent/NL7509120A/en
Priority to FR7524025A priority patent/FR2280704A1/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/92—Sulfobetaines ; Sulfitobetaines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds

Definitions

  • Zwitterionic surfactants i.e., those surface active compounds that contain both positive and negative charge centers in the same molecule while being electrically neurtral.
  • U.S. Pat. Nos. 3,668,240 and 3,764,568 to Melvin A. Barbera issued respectively on June 6, 1972, and Oct. 9, 1973, disclose zwitterionic surfactants having a 2, 3-butene moiety between the charge centers.
  • U.S. Pat. No. 3,332,875 to Adriaan Kessler and Phillip Floyd Pflaumer also discloses mixtures of certain olefim sulphoneates with zwitterionic detergents in which the charge centers are separated by a 2-hydroxy propane group.
  • 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 by emulsification or dispersion but also the continued maintenance of the removed soil in suspension in the aqueous solution.
  • the present invention is directed to the discovery that a wider range of zwitterionic compounds, of the type disclosed in the above identified Applications, 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 ethoxylated zwitterionic compounds useful in the present invention possess an ability to remove particulate soil that is independent of water hardness over a wide range of Ca and Mg levels. Furthermore, this performance is rel- 5 parent as it permits a high level of soil removal perfor mance to be obtained with a range of detergent formulations.
  • the nature and level of other components of the formulation can be controlled by the selection of an ethoxylated zwitterionic material having the appropriate level of performance.
  • Another object of the present invention is the provision of detergent compositions having improved particulate and oily soil removal performance in both liquid and granular forms.
  • A. l to 99% by weight of the composition of a watersoluble compound having a formula selected from the R is selected from the group consisting of straight and branched chain C -C alkyl and alkenyl moieties and alkaryl moieties in which the alkyl group has 10-24 carbon atoms;
  • R is selected from the group consisting of straight and branched chain C5-C alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon atoms, and C alkyl and hydroxyalkyl moieties;
  • R is selected from the group consisting of straight and branced chain C -C alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon atoms, C alkyl and hydroxyalkyl moieties and (C H O),H wherein x has a value of about 3 to about 50;
  • R is selected from the group consisting of C C alkylene, C -C alkenylene, 2-hydroxy C alkylene and 2- and 3-hydroxy C alkylene moieties and C -C alkarylene moieties provided that where R, iS '(C2H4O)1-H then R4 iS 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 provided that where R is (C H O),,H then x y 3 10.
  • R is selected from the group consisting of linear and branched C -C alkyl and alkenyl radicals; R, is
  • X is selected from the group consisting of sulfate and sulfonate
  • y and x have values in the range 2-100 provided that 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.
  • 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 pHs other than neutrality, and are extremely difficult to prepare compared to other hydroxy substituted compounds.
  • the ethoxylated zwitterionic compound is one of either w-(N--C alkyl, N-C, alkyLN-polyethenoxy ammonio)-2-polyethenoxyethane-l-sulphonate wherein the total number of ethylene oxide groups lies in the range 15-25 or w-(N C, alkyl, N ,N di- C C;; alkylammonio)-2-polyethenoxy ethane-1 sulphonate wherein the number of ethylene oxide groups in the polyethenoxy chain is in the range 6-12.
  • 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.
  • AMW automatic mini washing machine
  • Tergotometer having a capacity of 1,000 ml. and a cloth/liquor ratio of 1:140.
  • 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 US. gallon hard water (calculated as CaCO 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 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 tumbleddried prior to being graded.
  • a similar washing procedure is used for the Tergotometer with the exception that 5.5 grains/gallon water is employed having a 3:1 ratio of Ca:Mg salts (calculated as CaCO).
  • 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, polycotton (65% DACRON/35% cotton), and polyester (KODEL) swatches which are stained with a standardized illite clay soil.
  • AMW three 5 X 5 inch swatches of each fabric are used in each load, while in the Tergotometer, three ZlX 2% inch swatches of each fabric type are employed.
  • Performance is determined by finding the difference in whiteness (AW) before and after washing as:
  • the results are expressed as a percentage of the soil removal achieved by the standard formulation A under the same conditions.
  • compositions of the present invention contain two essential components, namely the ethoxylated zwitterionic compound and a detergent builder material which may be inorganic or organic in character.
  • Thw zwitterionic and detergent builder may be present in a ratio of from 99;] 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 application 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.
  • the level of ethoxylated zwitterionic compound in the product will lie in the range 5-35% by weight, preferably -25%, and most preferably -20%, the level of the detergent builder being in the range 10-70%, preferably 10-60%, and most preferably -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.
  • this formulation flexibility is due, at least in part, to the ability of the zwitterionic surfactants of the present invention to achieve particulate soil removal performance equivalent to that of commercial heavy duty laundry detergerlits when used in blends with detergent builder materia s.
  • Ethoxylated zwitterionic compounds useful in the present invention may have one or other of the following formulae:
  • R is a hydrocarbon moiety that can be a straight or branched chain C -C alkyl or alkenyl group or an alkaryl group in which the alkyl portion has 10-24 carbon atoms;
  • R, and R are C -C alkyl or hydroxyalkyl groups;
  • R is a C -C alkylene, C -C alkenylene, Z-hydroxy propylene or 2- or 3- hydroxy butylene group or a C -C alkarylene group;
  • X is a sulfonate or sulfate radical; and y has a value in the range 2-100.
  • preferred groups for R are C -C alkyl, particularly C -C alkyl, while preferred groups for R and R, are C alkyl and C hydroxyalkyl, the most preferred groups being methyland hydroxyethylradicals.
  • 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 tetrahyydrofuran 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 wherein y can be, for example, 3, 21, 32, 67, or 99.
  • reaction product (I) 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 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 (11) is then reacted with a tertiary amine of the structure T1 (III) R.
  • Compound (Vl) can optionally be further purified using the mixed bed resin and tested for purity by thin layer chromatography.
  • zwitterionic compounds of the general formula (Vl) can be prepared using any of a variety of tertiary amines (lll).
  • 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.
  • relatively narrowly defined distillation cuts" of polyoxyethylene glycol having any desired average degree of ethoxylation, and containing individual compounds having differing degrees of ethoxylation within the desired range can be used in the reaction.
  • 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 R groups within the scope of this invention.
  • epoxy compounds e.g., butylene epoxide
  • halohydrins e.g., 6-chlorohexanol or 8- bromooctanol
  • Tosyl chloride i.e., p-toluenesulfonyl chloride, 420 grams, 2.2 moles
  • 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 23 with 6N HCl.
  • the aqueous solution was then extracted 3 times with CHCI
  • the CHCI was washed with water, sodium bicarbonate solution, and again with water, then dried over anhydrous sodium sulfate. Evaporation of the CHCl, gave 520 grams of a slightly yellow oil.
  • the ditosylate (B) 86.7 grams (0.12 mole) and 35.8 5 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 byproduct (D) and some unreacted ditosylate (B).
  • Diquaternary ammonium byproduct 9 b Di-long chain derivatives In this derivative, both R, and R are hydrocarbon moieties that can be straight or branched chain C -C alkyl or alkenyl groups; R R and X are as in (i) (a.) above and y has an average value in the range 6-100.
  • R and R 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.
  • 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 C. The reaction mixture was kept at 80C for 24 hours, then adjusted to pH 8-9 with NaOH solution. The resulting tertiary amine was extracted with Cl-lCl and dried over Na SO The tertiary amine (25.6 grams, 0.10 mole) was then refluxed with 72 grams (0.10 mole) of nonaethylene glycol ditosylate (compound B, prepared as in the previous procedure) in acetonitrile for 6 hours.
  • compound B nonaethylene glycol ditosylate
  • R,, R and R: are all hydrocarbon moieties that can be straight or branched chain C C alkyl or alkenyl groups; R, and X are as in (i) (a.) and b.) above and y has a value in the range 6400.
  • R,, R and R 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.
  • Tri-n-octylamine was distilled to insure purity and 42 grams of the purified product (0.12 mole) was reacted with 87 grams (0.l2 mole) of the clitosylate 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 monoand diquaternary material was dissolved in methanol. This mixture was refluxed for 16 hours with 100 grams of Na so predissolved in water.
  • the insoluble salts were filtered and the filtrate was stirred with 500 grams mixed bed resin (Rexyn 300 l-l-OH) for 24 hours. An additional treatment with 500 grams fresh resin was used to further purify the product.
  • R can be a linear or branched Cg-C22 alkyl or alkenyl group, preferably a C "H8 alkyl or alkenyl group; R, can be a C -C alkyl or alkenyl group or can be a C -C 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 be from 1 to but their sum should be greater than l0. 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 l2-25.
  • Ethoquad is a mixture of quaternary ammonium compounds whose predominant component is a di-ethoxylate of the structure wherein y and .x are each nonzero integers whose average sum is, for example, 5, l0, 15, 50, depending on the cut" selected, and R and R, are C -C alkyl and C C alkyl, respectively.
  • 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 0-5C in an ice bath.
  • the mixture is then stirred for about 24 hours at 0-SC.
  • the reaction mixture is poured into water and acidified to a pH of 2-3 with HCl.
  • the foregoing acidified reaction mixture is then extracted 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 wherein y and x are as above.
  • tosylate ester is then dissolved in methanol and refluxed for about 24 hours with about a molar excess of sodium sulfite predissolved in H O.
  • 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 (1) above is recovered by evaporating the solvent.
  • the product can optionally be recrystallized from acetone.
  • R,, R and X are as in (ii) and y and x each have a value in the range l-l00 provided that the sum of y x 2 10.
  • Preferred values for the sum of y x will lie in the range l2-50 and most preferably in the range -25.
  • the cation M can be alkali metal, ammonium, and alkanolammonium, e.g. ethanolammonium or methanolammonium but is most preferably sodium.
  • the disulfonate (ll) is prepared in the same manner as the mono-sulfonate (1), but using excess tosyl chloride (about 3:1 mole ratio, or greater) in the first step and a larger excess of sodium sulfite (:1 mole ratio) in the second step.
  • lfa cation, M other than sodium is desired in the final product, the corresponding sulfite can be used in the second step.
  • the sodium form of compound (11) 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 (1) and (11) are easily prepared 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.
  • diethoxylated amino starting materials can be employed in the foregoing reaction scheme.
  • Ethoquad derivatives having variations in groups R, and R are commercially available, e.g., compounds wherein R, is an average C cut.
  • precursor compounds having varying sums ofy and x can be selected according to the desires of the user. Compounds wherein y and x are of approximately equal length, the sum ofy and x being from about 12 to about 25, most preferably from 15 to about 25, are especially useful herein.
  • Ethomeens a tradename of a class of compounds marketed by the Armak Company, a division of the Armour Company
  • Ethomeens can be quaternized to produce variations of the commercial Ethoquads.
  • Ethomeens of the general formula R-N(C H O) H(C,H O),,H, when R is alkyl can be reacted with excess alkyl iodide or hydroxy-substituted alkyl iodide (CH l, C l-1 1, 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.
  • 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 steps involved.
  • the ethoxylated zwitterionic compounds useful in the present invention desirably display appreciable solubility in aqueous media.
  • 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 199% 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 (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, borates, and aluminosilicates.
  • polyphosphates of value in the present invention are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from about 6 to about 21. Particularly preferred are the alkali metal tripolyand pyrophosphates.
  • Suitable phosphonate builder salts are the water-soluble salts of ethane l-hydroxy-l, 1- diphosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethylidene, isopyropylidene benzylmethylidene and halo methylidene phosphonates.
  • Phosphonate builder salts of the aforementioned types are disclosed in U.S. Pat. Nos. 3,159,58l and 3,213,030 issued Dec. 1,1964 and Oct.
  • Preferred silicate builders are the alkali metal silicates, particularly those having a SiO :Na O ratio in the range 1.6:] to 3.211.
  • other silicates may also be useful such as for example magnesium silicate,
  • 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 Nov. 15, 1973, the disclosure of which is incorporated herein by reference.
  • 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:
  • 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 equivalent/- gram and a calcium ion exchange rate of at least about 2 grains/U.S. gallon/minute/gram.
  • Detergent compositions incorporating aluminosilicate builder salts of this type are disclosed in the commonly assigned copending application Ser. No. 450,266 of Corkill, Madison, and Burns filed Mar. 11, 1974, which disclosure is incorporated herein by reference.
  • 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 l, 3, 5- tricarboxylic acid and 1, 3, S-trihydroxy benzene-2, 4, -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.
  • 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.
  • 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.
  • a zwitterionic compound usage level of 125 ppm the addition of builder restores the level of perfor- 14 mance 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 performance in the absence of builder is not particularly good. The results 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).
  • 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 ethox'ylated zwitterionic to'be lowered considerably (Runs 8 8t 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.
  • combination with detergent builders at a zwitterionic level of ppm in solution provides an improvement that in most cases matches and even exceeds the performance of the control product used at recommended concentrations.
  • 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.
  • COMPOUND SOLUTION TYPE SOLUTION COTTON COTTON ESTER I (N-C H,,N,N-bi
  • CH, ammonia) 250 94 98 98 TABLE III-continued CLAY SOIL REMOVAL PERFORMANCE OF A RANGE OF ETHOXYLATED ZWITTERIONIC COMPOUNDS IN COMBINATION WITH A CARBONATE/SILICATE BUILDER SYSTEM (SILICATE RATIO SiO,:Na,O 3.2:1) Conditions: l Minute Wash in Tergotometer, Mineral Hardness '1 grains/gallon (Ca:Mg 2:l (i/SgF R I CLAY REMOVAL INDEX ETHOXYLATED LEVEL LEVEL ZWITTERIONIC PPM IN BUILDER PPM IN POLY- POLY- NO.
  • COMPOUND SOLUTION TYPE SOLUTION COTTON COTTON ESTER (CH,CI-I,O),CH,CH,SO,
  • the detergent compositions may be nonionic, zwitterionic, ampholytic, anionic, 0r
  • Nonionic, zwitterionic, and ampholytic cosurfactants may be present in amounts ranging from -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
  • Anionic cosurfactants are preferably incorporated in amounts not exceeding 100% by weight of the ethoxylated zwitterionic compound for similar reasons.
  • Another optional ingredient that may be incorporated is an enzyme for removal of protein-based or carbohydrate-based stains.
  • Enzymes for removing proteinbased stains are proteolylic in nature, such as those sold under the trade names Alcalase” and Esterase” by Novo Industries A/S Denmark or under the trade names *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. Pat. No. 3,553,139 issued on Jan. 5, 1971, to McCarty, Roald, DeOude, Blomeyer, and Cracco which disclosure is hereby incorporated by reference.
  • a further ingredient that may be incorporated to improve product performance is a bleaching agent of the halogen or oxygen-containing type.
  • a bleaching agent of the halogen or oxygen-containing type examples include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-% by weight of the finished product, preferably 15% by weight.
  • oxygen containing bleaches include sodium perborate, sodium percarbonate, and potassium nonopersulphate that are incorporated at levels of 5-30%, preferably 10-25% by weight of the final product.
  • 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.
  • compositions of the present invention may also be included.
  • suds boosters include coconut and tallow monoand di-alkanolamides, particularly ethanolamides and C alkyl di-lower alkyl amine oxides.
  • Typical suds depressors include long chain fatty acids such as those discarded in U.S. Pat. No. 2,954,347 issued Sept. 27, 1960, to Wayne St. John and combinations of certain nonionics therewith as disclosed in U.S. Pat. No. 2,954,348 issued Sept. 27,
  • hydrotropes and anticaking additives such as salts of lower alkyaryl sulphonic acids, salts of a-sulphosuccinic acid, and a-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.
  • hydrotropes and anticaking additives such as salts of lower alkyaryl sulphonic acids, salts of a-sulphosuccinic acid, and a-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.
  • C -C alkyl acid phosphates and their condensation 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 or 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 provides a slight particulate soil removal benefit on synthetic fabrics.
  • specific optional components such as enzymes may require the selection of a product pH that will permit op timum 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 spraydrying 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 l-l0% 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 F).
  • Built liquid detergent compositions may also be single phase liquids provided that the builder can be solubilized in the mixture at its level of use.
  • Such liquids conventionally contain 10-25% total surfactant, l020% builder which may be organic or inorganic, 5-10% of a hydrotrope system and 50-60% of water. Liquids of this type also have low viscosity (l00-l50 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 characteristics to maintain stable dispersions and to prevent phase separation or solid settlement.
  • 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 wherein R is selected from the group consisting of straight and branched chain C -C alkyl and alkenyl moieties and alkaryl moieties in which the alkyl group has 10-24 carbon atoms;
  • R is selected from the group consisting of straight and branched chain C -C alkyl and alkenyl moieties, alkaryl moieties in which the alkyl 2 group has 6-16 carbon atoms, and C alkyl and hydroxyalkyl moieties;
  • R is selected from the group consisting of straight and branched chain C -C alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon atoms, C alkyl and hydroxyalkyl moieties and (C,H O),H wherein x has a value of about 3 to about 50;
  • R is selected from the group consisting of C -C alkylene, C -C alkenylene, Z-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and C -C alkarylene moieties provided that where R, is -(C,H 0),H then R is Cl-l,-Cl-l,;
  • X is an anion selected from the group consisting of sulfate and sulfonate radicals
  • y has a value in the range of 2-100 provided that where R, is (C,H O),H then x y a 10;
  • R is selected from the group consisting of linear and branched C -C alkyl and alkenyl radicals
  • R is selected from the group consisting of linear and branched C -C alkyl and alkenyl radicals and C -C 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 2 12;
  • M is a cation selected from the group consisting of alkali metal, ammonium and alkanolammonium ions;
  • a detergent composition according to claim I 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.
  • 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 alkanolammonium salts of ethylene diamine tetra acetic acid, nitrilotriacetic acid, citric acid, oxydisuccinic acid, carboxymethoxysuccinic acid, benzene pentaand hexa-carboxylic acid, 1, 3, 5- trihydroxy benzene-2, 4, 6-trisulfonic acid, and copolymers of maleic anhydride with vinyl methyl ether and ethylene.
  • the detergent builder is an organic detergent builder selected from the group consisting of alkali metal ammonium and alkanolammonium salts of ethylene diamine tetra acetic acid, nitrilotriacetic acid, citric acid, oxydisuccinic acid, carboxymethoxysuccinic acid, benzene pentaand hexa-carboxylic
  • a detergent composition according to claim I wherein the zwitterionic compound has the formula 23 S.
  • a detergent composition comprising A. l99% by weight of the composition of a compound having the formula wherein R,, R, and R are each selected from the group consisting of branched and straight chain C -C alkyl and alkenyl radicals;
  • R is selected from the group consisting of C C,
  • alkylene C -C alkenylene, Z-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkyl group contains from l-4 carbon atoms;
  • X is an anion selected from the group consisting of sulfate and sulfonate radicals
  • y has an average value in the range of 6-l00;
  • a detergent composition comprising A. l99% by weight of the composition of a compound having the formula:
  • R and R are each selected from the group consisting of branched and straight chain C -C alkyl and alkenyl radicals;
  • R is selected from the group consisting of C -C alkyl and hydroxyalkyl moieties
  • R is selected from the group consisting of C C;
  • alkylene C C alkenylene, Z-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkyl group contains l-4 carbon atoms;
  • X is an anion selected from the group consisting of sulfate and sulfonate radicals
  • y has an average value in the range of 6-100
  • R is selected from the group consisting of branched and straight chain Cg-Cgm alkyl and alkenyl radicals; R, and R are each selected from the group consisting of C C, alkyl and hydroxyalkyl moieties; and R is selected from the group consisting of C --C, alkylene, C -C alkenylene, 2-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkylene group has l-4 carbon atoms; and y has a value of from about 6 to about 20.
  • R is a C -C alkyl moiety
  • R, and R are independently selected from C,-C alkylene and hydroxyalkylene moieties
  • R is a CH,CH,-moiety
  • y has a value from about 6 to about 12.
  • composition according to claim 1 incorporating an organic detergent selected from the group consisting of anionic, nonionic, ampholytic, and zwitterionic surfactants.

Abstract

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

United States Patent Laughlin et al.
DETERGENT COMPOSITION HAVING ENHANCED PARTICULATE SOIL REMOVAL PERFORMANCE Inventors: Robert Gene Laughlin; Robert Lee Stewart, both of Cincinnati, Ohio Assignee: The Procter & Gamble Company,
Cincinnati, Ohio Filed: Aug. 1, 1974 Appl. No: 493,952
US. Cl. 252/526; 252/545; 252/546; 260/50l.l2 Int. Cl. ..CllD 3/066;CIID l/l8 Field of Search 252/526, 545, 546, DIG. ll, 252/155; 260/50l.l2; 8/26 Dec. 9, 1975 Primary Examiner.lohn D. Welsh Attorney, Agent, or Firm.lulius P. Filcik; Thomas H. OFlaherty; Richard C. Witte 57 ABSTRACT 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.
11 Claims, No Drawings DETERGENT COMPOSITION HAVING ENHANCED PARTICULATE SOIL REMOVAL PERFORMANCE BACKGROUND OF THE INVENTION This invention relates to detergent compositions haveing improved particulate soil removal capability. More particularly, this invention relates to detergent compositions incorporating certain ethoxylated compound 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 neurtral, are known. For example, U.S. Pat. Nos. 3,668,240 and 3,764,568 to Melvin A. Barbera, issued respectively on June 6, 1972, and Oct. 9, 1973, disclose zwitterionic surfactants having a 2, 3-butene moiety between the charge centers. U.S. Pat. No. 3,332,875 to Adriaan Kessler and Phillip Floyd Pflaumer also discloses mixtures of certain olefim sulphoneates with zwitterionic detergents in which the charge centers are separated by a 2-hydroxy propane group. U.S. Pat. Nos. 3,452,066 and 2,781,390 to Hans S. Mannheimer, issued respectively on June 24, l969and Feb. 12, 1957, outline a range of zwitterionic surfactants which optionally may be substituted with a wide variety of oxygen-containing groups between the positive and negative charge centers. U.S. Pat. No. 3,769,31 l to Leonard J. Armstrong and Eldon de Vere Dawald issued Oct. 30, 1973, discloses carboxylic compounds having ethylene oxide groups between the charge centers but fails to recognize the effect of the various structural parameters 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 by emulsification or dispersion but also the continued maintenance of the removed soil in suspension in the aqueous solution.
Some of these compounds are effective in the absence of conventional detergent additives such as builders, surfactants etc. and form the subject of the commonly assigned co-tiled Ser. No. 493,951, filed Aug. 1, 1974 Applications by Robert G. Laughlin, Eugene P. Gosselink, William A. Cilley, and Vincent P. Heuring and Robert G. Laughlin, Eugene P. Gosselink, and William a. Cilley Ser. No. 493,956, filed of even date (Attorneys Docket No. 2102), both Applications being entitled Detergent Compounds." The disclosures of both said Applications are hereby incorporated herein by reference.
However, the present invention is directed to the discovery that a wider range of zwitterionic compounds, of the type disclosed in the above identified Applications, 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 ethoxylated zwitterionic compounds useful in the present invention possess an ability to remove particulate soil that is independent of water hardness over a wide range of Ca and Mg levels. Furthermore, this performance is rel- 5 parent as it permits a high level of soil removal perfor mance to be obtained with a range of detergent formulations. Furthermore, the nature and level of other components of the formulation can be controlled by the selection of an ethoxylated zwitterionic material having the appropriate level of performance.
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 present invention is the provision 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. l to 99% by weight of the composition ofa watersoluble compound having a formula selected from the R, is selected from the group consisting of straight and branched chain C -C alkyl and alkenyl moieties and alkaryl moieties in which the alkyl group has 10-24 carbon atoms;
R, is selected from the group consisting of straight and branched chain C5-C alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon atoms, and C alkyl and hydroxyalkyl moieties;
R is selected from the group consisting of straight and branced chain C -C alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon atoms, C alkyl and hydroxyalkyl moieties and (C H O),H wherein x has a value of about 3 to about 50;
R is selected from the group consisting of C C alkylene, C -C alkenylene, 2-hydroxy C alkylene and 2- and 3-hydroxy C alkylene moieties and C -C alkarylene moieties provided that where R, iS '(C2H4O)1-H then R4 iS 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 provided that where R is (C H O),,H then x y 3 10.
wherein R is selected from the group consisting of linear and branched C -C alkyl and alkenyl radicals; R, is
selected from the group consisting of linear and branched C -C alkyl and alkenyl radicals and C C 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 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 pHs other than neutrality, and are extremely difficult to prepare compared to other hydroxy substituted compounds.
Preferably the ethoxylated zwitterionic compound is one of either w-(N--C alkyl, N-C, alkyLN-polyethenoxy ammonio)-2-polyethenoxyethane-l-sulphonate wherein the total number of ethylene oxide groups lies in the range 15-25 or w-(N C, alkyl, N ,N di- C C;; alkylammonio)-2-polyethenoxy ethane-1 sulphonate wherein the number of ethylene oxide groups in the polyethenoxy chain is in the range 6-12.
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 US. gallon hard water (calculated as CaCO 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 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 tumbleddried prior to being graded.
A similar washing procedure is used for the Tergotometer with the exception that 5.5 grains/gallon water is employed having a 3:1 ratio of Ca:Mg salts (calculated as CaCO 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, polycotton (65% DACRON/35% cotton), and polyester (KODEL) swatches which are stained with a standardized illite clay soil. For the AMW, three 5 X 5 inch swatches of each fabric are used in each load, while in the Tergotometer, three ZlX 2% inch 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 detergent standard tested at the same time under identical conditions. This standard formulation hereinafter designated as A has the following composition by weight:
Sodium C alkylbenzene sulphonate 7.55 Sodium Tallow alkyl sulphate 9.25 Coconut alcohol 6 mole E0 0.60 Diethanolamide [.60 Sodium Tripolyphos hale 50.00 Sodium Silicate soli s 5.90 Sodium sulphate 14.20 Moisture 10.00 Miscellaneous 0.30
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:
Performance is determined by finding the difference in whiteness (AW) before and after washing as:
A W: alter hen":
This is compared to the commercial Control Product A by calculating AW as a percentage of AW given by the Control Product in each batch.
AW for Test Sample A W for Control Product A The Relative Clay Removal lndex= Complete removal Discernible stain remaining Moderate amount of soil remaining Large amount of soil remaining Very large amount of soil remaining 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 compound and a detergent builder material which may be inorganic or organic in character. Thw zwitterionic and detergent builder may be present in a ratio of from 99;] 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 application 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 ethoxylated zwitterionic compound in the product will lie in the range 5-35% by weight, preferably -25%, and most preferably -20%, the level of the detergent builder being in the range 10-70%, preferably 10-60%, and most preferably -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 flexibility is due, at least in part, to the ability of the zwitterionic surfactants of the present invention to achieve particulate soil removal performance equivalent to that of commercial heavy duty laundry detergerlits when used in blends with detergent builder materia s.
ETHOXYLATED ZWITTERIONIC COMPOUNDS Ethoxylated zwitterionic compounds useful in the present invention may have one or other of the following formulae:
a. Mono-long chain derivatives In this derivative, R is a hydrocarbon moiety that can be a straight or branched chain C -C alkyl or alkenyl group or an alkaryl group in which the alkyl portion has 10-24 carbon atoms; R, and R, are C -C alkyl or hydroxyalkyl groups; R is a C -C alkylene, C -C alkenylene, Z-hydroxy propylene or 2- or 3- hydroxy butylene group or a C -C 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 R are C -C alkyl, particularly C -C alkyl, while preferred groups for R and R, are C alkyl and C hydroxyalkyl, the most preferred groups being methyland hydroxyethylradicals. 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 tetrahyydrofuran 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 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 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 (11) is then reacted with a tertiary amine of the structure T1 (III) R.
wherein R R, and R 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 CH CN at temperatures of to about C to produce a mixture of The mixture of (1V) 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 65 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 zwitterionic product,
Compound (Vl) 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 (Vl) can be prepared using any of a variety of tertiary amines (lll). 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 differing 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 R groups within the scope of this invention.
A specific preparation of a mono-long chain ethoxylated zwitterionic compound useful in the present invention was as follows:
Preparation of 26-dimethyloctadecylammonio-3,6,9,12,15 l 8,2] ,24 octaoxahexacosanel -sulfonate Preparation of Nonaethyleneglycol (A) Under nitrogen, 46 grams (2 moles) of sodium pellets were added cautiously to 2,664 ml (20 moles) of previously dried and distilled triethyleneglycol. The temperature was kept below 100C. After all the sodium had reacted, the temperature was adjusted to 100C and 40 187 grams (1 mole) of l,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 l70-l75C at 0.00! 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 C. Tosyl chloride (i.e., p-toluenesulfonyl chloride, 420 grams, 2.2 moles) was added, with stirring, in small portions. After the addition was complete, the temperature increased to C 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 23 with 6N HCl. The aqueous solution was then extracted 3 times with CHCI The CHCI, was washed with water, sodium bicarbonate solution, and again with water, then dried over anhydrous sodium sulfate. Evaporation of the CHCl, 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 (C) 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,l2,15,l8,2l,24 octaoxahexacosylammonium(C) tosylate (C).
The ditosylate (B) 86.7 grams (0.12 mole) and 35.8 5 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 byproduct (D) and some unreacted ditosylate (B).
Preparation of 26-dimethyloctadecylammonio- 3 ,6,9,l2,15 l 8,2] ,24 octaoxahexacosanel -sulfonate The mixture of monoquat (C) and diquat (D) prepared above was dissolved in 1 liter of methanol. so-
dium sulfite (100 grams, 0.79 moles) was added and the reaction mixture was refluxed with stirring for 5 hours. Additional methanol was added and te insoluble salts were filtered. The solvents were removed to yield a solid product. 0 Purification The above solid reaction product was dissolved in 1 liter of methanol and stirred with 386 grams of a mixed bed (Rexyn 300 l-lOH, commercially available from the Fisher Scientific Co.) resin for 5 hours. The solu- 25 tion was then passed through a column of fresh resin 35 dimethyloctadecylamine can be replaced by dimethyl ca,- so,ci (A) H0(C.H,
Diquaternary ammonium byproduct 9 b. Di-long chain derivatives In this derivative, both R, and R are hydrocarbon moieties that can be straight or branched chain C -C alkyl or alkenyl groups; R R and X are as in (i) (a.) above and y has an average value in the range 6-100. Preferably R and R 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 C. The reaction mixture was kept at 80C for 24 hours, then adjusted to pH 8-9 with NaOH solution. The resulting tertiary amine was extracted with Cl-lCl and dried over Na SO The tertiary amine (25.6 grams, 0.10 mole) was then refluxed with 72 grams (0.10 mole) of nonaethylene glycol ditosylate (compound B, prepared as in the previous procedure) in acetonitrile for 6 hours. The solvent was evaporated and the resulting mixture of monoand diquaternary compounds was dissolved in methanol and refluxed 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 H" N (CH,CH.0),CH,cH,so,-
I IT or 26-dioctylmethylammonio-3,6,9,12,15 l 8,2 l ,24- octaoxahexacosanel -sulfonate.
c. Tri-long chain derivatives In this derivative, R,, R and R:, are all hydrocarbon moieties that can be straight or branched chain C C alkyl or alkenyl groups; R, and X are as in (i) (a.) and b.) above and y has a value in the range 6400. Preferably R,, R and R 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.l2 mole) of the clitosylate 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 monoand diquaternary material was dissolved in methanol. This mixture was refluxed for 16 hours with 100 grams of Na so predissolved in water. The insoluble salts were filtered and the filtrate was stirred with 500 grams mixed bed resin (Rexyn 300 l-l-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 dissolving the product in [1,0, acidifying to pH 4, and extracting with CHCl The CHCL, extract was rinsed with sodium bicarbonate, dried and evaporated to give a light yellow viscous oil, identified as or trioctylammonio-3,6,9,l 2, l 5 ,1 8,21 ,24-octaoxahexacosane-l-sulfonate.
In this structure, R can be a linear or branched Cg-C22 alkyl or alkenyl group, preferably a C "H8 alkyl or alkenyl group; R, can be a C -C alkyl or alkenyl group or can be a C -C 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 be from 1 to but their sum should be greater than l0. 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 l2-25.
The preparation of zwitterionic compounds of this type is accomplished using commercially available starting materials. A typical starting material is marketed under the tradename 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 wherein y and .x are each nonzero integers whose average sum is, for example, 5, l0, 15, 50, depending on the cut" selected, and R and R, are C -C alkyl and C C 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 0-5C in an ice bath. The mixture is then stirred for about 24 hours at 0-SC. At the end of that time the reaction mixture is poured into water and acidified to a pH of 2-3 with HCl.
The foregoing acidified reaction mixture is then extracted 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 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 molar excess of sodium sulfite predissolved in H O. 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 (1) above is recovered by evaporating the solvent. The product can optionally be recrystallized from acetone.
where R,, R and X are as in (ii) and y and x each have a value in the range l-l00 provided that the sum of y x 2 10. Preferred values for the sum of y x will lie in the range l2-50 and most preferably in the range -25. The cation M can be alkali metal, ammonium, and alkanolammonium, e.g. ethanolammonium or methanolammonium but is most preferably sodium.
The disulfonate (ll) is prepared in the same manner as the mono-sulfonate (1), but using excess tosyl chloride (about 3:1 mole ratio, or greater) in the first step and a larger excess of sodium sulfite (:1 mole ratio) in the second step. lfa 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 (11) 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 (1) and (11) are easily prepared 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 reaction scheme. For example, Ethoquad derivatives having variations in groups R, and R are commercially available, e.g., compounds wherein R, is an average C cut. Moreover, precursor compounds having varying sums ofy 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 ofy 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 tradename of a class of compounds marketed by the Armak Company, a division of the Armour Company) can be quaternized to produce variations of the commercial Ethoquads. Thus, Ethomeens of the general formula R-N(C H O) H(C,H O),,H, when R is alkyl, can be reacted with excess alkyl iodide or hydroxy-substituted alkyl iodide (CH l, C l-1 1, 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 steps involved.
The 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 ppm ap pears to be necessary for satisfactory particulate soil removal performance, but the preferred materials have solubilities in water of 10-30% 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 199% 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 (exemplified by the tripolyphosphates, 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 tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from about 6 to about 21. Particularly preferred are the alkali metal tripolyand pyrophosphates.
Examples of suitable phosphonate builder salts are the water-soluble salts of ethane l-hydroxy-l, 1- diphosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethylidene, isopyropylidene benzylmethylidene and halo methylidene phosphonates. Phosphonate builder salts of the aforementioned types are disclosed in U.S. Pat. Nos. 3,159,58l and 3,213,030 issued Dec. 1,1964 and Oct. 19, 1965, to Diehl; U.S. Pat. No. 3,422,021 issued Jan. 14, 1969, to Roy; and U.S. Pat. Nos. 3,400,148 and 3,422,137 issued Sept. 3, 1968, and .Ian. 14, 1969 to Quimby, said disclosures being incorporated herein by reference.
Preferred silicate builders are the alkali metal silicates, particularly those having a SiO :Na O ratio in the range 1.6:] to 3.211. However, other silicates may also be useful such as for example magnesium silicate,
13 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 Nov. 15, 1973, the disclosure of which is incorporated herein by reference.
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:
zl( s)z X 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 equivalent/- gram and a calcium ion exchange rate of at least about 2 grains/U.S. gallon/minute/gram. Detergent compositions incorporating aluminosilicate builder salts of this type are disclosed in the commonly assigned copending application Ser. No. 450,266 of Corkill, Madison, and Burns filed Mar. 11, 1974, which disclosure is incorporated herein by reference.
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 l, 3, 5- tricarboxylic acid and 1, 3, S-trihydroxy benzene-2, 4, -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. Pat. No. 3,308,067 issued Mar. 7, 1967, to Diehl; Japanese Pat. No. 73,703 filed May 24, 1971, and published Jan. 8, 1973; U.S. Pat. Nos. 3,699,159, 3,758,420, and 3,812,044 issued Oct. 17, 1972, Sept. 11, 1973, and May 21, 1974 in the names of Connor and Krummel; and U.S. Pat. No. 3,635,830 issued Jan. 18, 1972 in the names of Lamberti and Konort, which disclosures are hereby incorporated by reference.
Mixtures of any of the above detergent builders can also be used, several particularly advantageous combinations being disclosed in U.S. Pat. Nos. 3,356,613 and 3,392,121 issued respectively on Dec. 5, 1967 and July 9, 1968 to Gedge, which disclosures are also incorporated herein by reference.
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 perfor- 14 mance 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 performance in the absence of builder is not particularly good. The results 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 compound combinations for a range of zwitterionic compound structures is demonstrated in Table 11]. it can be seen that a combination incorporating the C alkyl dimethyl derivative (Run No. 4) does not provide good particulate soil removal performance (c.f. C alkyl and C alkyl materials in Table II) but that performance improves slightly for the di-C derivative (Run No. 5) andthen shows a marked increase for the derivative in which total substitution of the methyl side chains by C 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 ethox'ylated zwitterionic to'be lowered considerably (Runs 8 8t 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 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 combinations of ethoxylated zwitterionic compounds and detergent builders are set out in Table V. Combinations using the C dimethyl octaethenoxy compounds, the C 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.
TABLE I CLAY SOIL REMOVAL PERFORMANCE OF ETHOXYLATED ZWI'ITERIONIC COMPOUNDS IN COMBINATION WITH DETERGENT BUILDERS Conditions: I Minute Wash in Tergotometer, Mineral Hardness 7 grains/gallon (CazMg 2:I Temp. I"?
RELATIVE ETHOXYLATED LEVEL LEVEL CLAY REMOVAL INDEX ZWI'I'IERIONIC PPM IN BUILDER PPM IN POLY POLY- NO. COMPOUND SOLUTION TYPE SOLUTION COTTON COTTON ESTER I (N-C .II,,N,N-bisCH, ammonio) 250 75 96 95 (CI-I,CH,O),CH,CH,SO,
2 I 62 88 77 3 250 Na,P,O,., 250 I04 I00 I01 4 I25 Na,P,O,., 250 I00 97 I05 5 250 Na,P,O, 250 II I I02 H2 6 I25 Na.P,O, 250 92 90 I06 7 250 Na.,(AIO,.SiO ,.),,27H,O 500 I04 94 I07 8 I25 500 93 93 t 9 250 CziCO*,/Na,CO I00/200 93 95 104 I0 I25 I00/200 63 93 99 I I 2S0 Sodium NTA I H7 98 122 I2 I25 Sodium NTA I80 98 97 I16 I3 2S0 Sodium citrate 300 88 94 IOI I 250 CH(COONa),OCH,COONa 300 III I03 I06 I5 I25 CH(COONa),OCH,COONa 300 I04 IOI I04 I I6 250 Na,CO*,/Na,SiO,* 200/200 92 I06 I09 l7 (N-C l-l Nfl-bisCH, ammonio) 250 I01 (CI-I,CH,O C I I,'CII,SO, I 8 250 Na,C0,/Na,SiO," 200/200 94 I07 I I5 SiO, N I 3.2:I "ClCO, surface are: I00 m'lgrarn (-0,02.u)
TABLE II CLAY SOIL REMOVAL PERFORMANCE OF ETI-IOXYLATED ZWITIERIONIC COMPOUNDS IN COMBINATION WITH DETERGENT BUILDERS Conditions: 10 Minute Wash in Tergotometer, Mineral Hardness 7 grains/gallon (Ca:Mg 2:! Temp. I05"!= RELATIVE ETHOXYLATED LEVEL LEVEL CLAY REMOVAL INDEX ZWITTERIONIC PPM IN BUILDER PPM IN POLY- POLY- NO. COMPOUND SOLUTION TYPE SOLUTION COTTON COTTON ESTER I (N-C I-I,,N,N-bilCI-I, ammonia) 250 S3 69 46 (CI-I,CI-I,O) CH,CI'I,SO, 2 4| 52 24 3 250 Na,P,0 250 94 90 98 4 125 Name 250 62 73 39 5 250 Na hO, 250 94 88 99 6 I25 Na P,O, 250 77 80 80 7 250 Na,,(AIO,.SiO,.) 27H ,O 250 85 92 88 8 I25 250 61 75 44 9 250 CaCO'JNafiO, I00/200 92 96 84 I0 I25 I00/200 70 7B 44 I I 2S0 Sodium NTA I80 I00 94 I09 I2 I25 Sodium NTA I80 55 65 33 I3 250 CH(COONa),OCI-I,COONa 300 98 I03 99 I4 I25 CH(COONa),OCI-I,COONa 300 86 84 55 I 5 250 Na,CO*,/Na,SiO,' 200/200 80 92 75 I6 (N-C H Nfl-bilcl-l, ammonia) 250 50 46 33 (CH CI-I,O).CI-I,CH,S0, I 7 250 Na,CO,/Na SiO, 200/200 68 67 4 I sto p 3.2:I "CICO lurflce are. 100 mlgrnm (-0.02p)
TABLE III CLAY SOIL REMOVAL PERFORMANCE OF A RANGE OF ETI-IOXYLATED ZWITTERIONIC COMPOUNDS IN COMBINATION WITH A CARBONATE/SILICATE BUILDER SYSTEM (SILICATE RATIO SiO,:Nn,0 3.2:I) Conditions: I0 Minute Wuh in Tergotometer, Mineral Hardness 7 grains/gallon (Ca:Mg=2:1), CLAY REMOVAL INDEX ETI'IOXYLATED LEVEL LEVEL ZWI'I'I'ERIONIC PPM IN BUILDER PPM IN POLY- POLY- NO. COMPOUND SOLUTION TYPE SOLUTION COTTON COTTON ESTER I (N-C H,,N,N-bi|CH, ammonia) 250 94 98 98 TABLE III-continued CLAY SOIL REMOVAL PERFORMANCE OF A RANGE OF ETHOXYLATED ZWITTERIONIC COMPOUNDS IN COMBINATION WITH A CARBONATE/SILICATE BUILDER SYSTEM (SILICATE RATIO SiO,:Na,O 3.2:1) Conditions: l Minute Wash in Tergotometer, Mineral Hardness '1 grains/gallon (Ca:Mg=2:l (i/SgF R I CLAY REMOVAL INDEX ETHOXYLATED LEVEL LEVEL ZWITTERIONIC PPM IN BUILDER PPM IN POLY- POLY- NO. COMPOUND SOLUTION TYPE SOLUTION COTTON COTTON ESTER (CH,CI-I,O),CH,CH,SO,
2 250 Na,CO /Na,SiO, 200/200 104 I03 I 13 3 (N-C .H N,N-bisCH; ammonio) 250 200/200 H 99 I09 (CH,CH,O),CH,CH,SO,
4 (N4I,H -,N,NbisCH;. ammonia) 250 200/200 46 53 39 (CH CH,O),CH,CH,SO,
5 (N,N-bisC,H NCH, ammonio) 250 200/200 52 62 33 (cmcinoncmcmso,
6 (N,N,N-trisC I-I ammonio) 250 200/200 82 92 I01 (CH,CH,O),CH,CH,SO;
7 (N,N-bisC H,,N-CH, ammonio) 250 200/200 I01 95 109 (CH,CH,O),CH,CH,SO,
9 (N-C ,H;, N,N-bisCH, ammonio) 250 200/200 58 93 I12 (CH,CH,O),CH;CH, SO,
I0 (predissolved in methanol) 250 200/200 I04 I09 1 I4 TABLE IV EFFECT OF VARIATIONS IN LEVEL OF ETHOXYLATED ZWITTERIONIC COMPOUND AND BUILDER ON CLAY SOIL REMOVAL PERFORMANCE Conditions: I0 Minute Wash in Tergotometer, Mineral Hardness T grains/gallon (CazMg 2: I Temp. IO5F RELATIVE ETHOXYLATED LEVEL LEVEL CLAY REMOVAL INDEX ZWITTERIONIC PPM IN BUILDER PPM IN POLY- POLY- NO. COMPOUND SOLUTION TYPE SOLUTION CO'I'ION COTTON ESTER N-c H MN-bisCH, 250 94 98 98 (E0 ),CI-I,C H,SO, 2 2S0 NmCOJNafiiO, 200/200 I04 I03 I I 3 3 I 3 Name... 250/200/200 5 I 42 Na,CO; Na,SiO," 4 50 250/200/200 63 8| 5 I 250/200/200 85 103 I06 6 I25 I25/200/200 73 I08 7 I25 /200/200 75 I04 8 63 Na,,(AIO,SiO,),,27I-I,0 600 75 IOI I06 Na,COJNa,SiO,' 2001200 9 125 600 I09 I07 ZOO/200 'SiO,:Na,O 32:l
TABLE V GREASE a OIL REMOVAL PERFORMANCE FOR COMBINATIONS OF I ETHOXYLATED ZWI'I'IERIONIC COMPOUNDS AND DETERGENT BUILDERS Conditions: 10 Minute Tergotometer Wash at I00"F in 5.5 grains/US. gallon Mineral Hardness (CazM ilzl) ETHOXYLATED LEVEL LEVEL ZWITTERIONIC PPM IN BUILDER PPM IN POLYCOTTON POLYESTER N0. COMPOUND SOLUTION TYPE SOLUTION TO K: I-IC I: TO 1: HC I: l (N-C' H MN-biscH, ammonia) 250 91 132 75 I02 (CI-I,CH,O ),CI-I,CI-I,SO, 2 250 Na,P,O 250 97 I43 98 109 3 s00 Nan(Al0,.SiO,.),,27H,O 500 a I 2| 99 1 I5 4 (N-C H,.N,N-bisCH, ammonlo) 250 I00 75 80 99 (CH,CI-I,O),CH,Cl-I,SO, 5 I: 250 Na,P,O 250 76 I22 I00 I26 6 250 Na..(AI0,.si0,.)1,27H,o s00 63 93 as I 1 I 7 Cut/C compound mixture I25/l25 91 121 77 9| 8 125/125 Na,P,O 250 I27 86 I I2 I23 9 125/!25 Na,,(AIO,.SiO,.),,27H,O 500 78 I2I I04 1 I7 Optional Components of the present invention may also contain other ingredients conventionally employed in such products. The
In addition to the ethoxylated zwitterionic compound principal optional component is a cosurfactant which and the detergent builder, the detergent compositions may be nonionic, zwitterionic, ampholytic, anionic, 0r
cationic. Nonionic, zwitterionic, and ampholytic cosurfactants may be present in amounts ranging from -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 .Qrve to depress 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 compound mixtures are disclosed in the commonly assigned cofiled Application of Robert G. Laughlin and Vincent P. Heuring, Ser. No. 493,953, filed Aug. l, 1974, the disclosures of which are hereby incorporated by reference.
Another optional ingredient that may be incorporated is an enzyme for removal of protein-based or carbohydrate-based stains. Enzymes for removing proteinbased stains are proteolylic in nature, such as those sold under the trade names Alcalase" and Esterase" by Novo Industries A/S Denmark or under the trade names *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. Pat. No. 3,553,139 issued on Jan. 5, 1971, to McCarty, Roald, DeOude, Blomeyer, and Cracco which disclosure is hereby incorporated by reference.
A further ingredient that may be incorporated to improve 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 sulphonamides. Such materials are normally added at 0.5-% by weight of the finished product, preferably 15% by weight.
Examples of oxygen containing bleaches include sodium perborate, sodium percarbonate, and potassium nonopersulphate 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 monoand di-alkanolamides, particularly ethanolamides and C alkyl di-lower alkyl amine oxides. Typical suds depressors include long chain fatty acids such as those discarded in U.S. Pat. No. 2,954,347 issued Sept. 27, 1960, to Wayne St. John and combinations of certain nonionics therewith as disclosed in U.S. Pat. No. 2,954,348 issued Sept. 27,
1960, to Eugene Schwoeppe, both disclosures being incorporated herein by reference.
Other optional ingredients in granular products include hydrotropes and anticaking additives such as salts of lower alkyaryl sulphonic acids, salts of a-sulphosuccinic acid, and a-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. C -C alkyl acid phosphates and their condensation 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 or 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 provides 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 op timum 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 spraydrying 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 l-l0% 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 F).
Built liquid detergent compositions may also be single phase liquids provided that the builder can be solubilized in the mixture at its level of use. Such liquids conventionally contain 10-25% total surfactant, l020% builder which may be organic or inorganic, 5-10% of a hydrotrope system and 50-60% of water. Liquids of this type also have low viscosity (l00-l50 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 characteristics to maintain stable dispersions and to prevent phase separation or solid settlement.
The following examples serve to illustrate the present invention:
EXAMPLE l A concentrated detergent formulation having the consistency of a thick paste was prepared having the following composition by weight:
m-(hexadecyl dimethyl ammonio)- 38.4% Z-octaethenoxy ethane- 1 -sulphonate Sodium Carbonate 30.8 Sodium Silicate (SiO,:Na,0 3.2:1) 30.8
Cotton, polycotton, and polyester cloth swatches that had been soiled with a standardized illite clay soil were given a minute wash with this product in the tergotometer at 105F using water of mineral hardness 7 grains/gallon (CazMg 2:1). Product concentration was adjusted to give 250 ppm of zwitterionic compound in solution. Following rinsing and drying, the swatches were then graded instrumentally for clay soil removal using 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 conditions, were as fol- Using the product concentrations 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:
Cotton Polycotton Polyester What is claimed is:
l. 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 wherein R is selected from the group consisting of straight and branched chain C -C alkyl and alkenyl moieties and alkaryl moieties in which the alkyl group has 10-24 carbon atoms;
R: is selected from the group consisting of straight and branched chain C -C alkyl and alkenyl moieties, alkaryl moieties in which the alkyl 2 group has 6-16 carbon atoms, and C alkyl and hydroxyalkyl moieties;
R is selected from the group consisting of straight and branched chain C -C alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 6-16 carbon atoms, C alkyl and hydroxyalkyl moieties and (C,H O),H wherein x has a value of about 3 to about 50;
R is selected from the group consisting of C -C alkylene, C -C alkenylene, Z-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and C -C alkarylene moieties provided that where R, is -(C,H 0),H then R is Cl-l,-Cl-l,;
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 provided that where R, is (C,H O),H then x y a 10;
wherein R is selected from the group consisting of linear and branched C -C alkyl and alkenyl radicals;
R, is selected from the group consisting of linear and branched C -C alkyl and alkenyl radicals and C -C 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 2 12;
M is a cation selected from the group consisting of alkali metal, ammonium and alkanolammonium ions; and
B. 99to 1% by weight of the composition of a detergent builder.
2. A detergent composition according to claim I 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 alkanolammonium salts of ethylene diamine tetra acetic acid, nitrilotriacetic acid, citric acid, oxydisuccinic acid, carboxymethoxysuccinic acid, benzene pentaand 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 I wherein the zwitterionic compound has the formula 23 S. A detergent composition according to claim 4 wherein R is selected from the group consisting of straight and branched chain Clrcw alkyl and alkenyl moieties and x y has a value in the range of l25.
6. A detergent composition comprising A. l99% by weight of the composition of a compound having the formula wherein R,, R,, and R are each selected from the group consisting of branched and straight chain C -C alkyl and alkenyl radicals;
R is selected from the group consisting of C C,
alkylene, C -C alkenylene, Z-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkyl group contains from l-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-l00; and
B. 994% by weight of the composition of a detergent builder. 7. A detergent composition according to claim 6 wherein y has a value of at least 9.
8. A detergent composition comprising A. l99% by weight of the composition of a compound having the formula:
wherein R and R are each selected from the group consisting of branched and straight chain C -C alkyl and alkenyl radicals;
R is selected from the group consisting of C -C alkyl and hydroxyalkyl moieties;
R, is selected from the group consisting of C C;
alkylene, C C alkenylene, Z-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkyl group contains l-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-! by weight of the composition of a detergent builder. 9. A detergent composition according to claim 1 wherein the compound has the formula:
wherein R is selected from the group consisting of branched and straight chain Cg-Cgm alkyl and alkenyl radicals; R, and R are each selected from the group consisting of C C, alkyl and hydroxyalkyl moieties; and R is selected from the group consisting of C --C, alkylene, C -C alkenylene, 2-hydroxy propylene, and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkylene group has l-4 carbon atoms; and y has a value of from about 6 to about 20.
10. A detergent composition according to claim 9 wherein R is a C -C alkyl moiety; R, and R, are independently selected from C,-C alkylene and hydroxyalkylene moieties; R is a CH,CH,-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.
1. k i i III

Claims (11)

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
2. A DETERGENT COMPOSITION ACCORRDING TO CLAIM 1 WHEREIN THEE 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 alkanolammonium salts of ethylene diamine tetra acetic acid, nitrilotriacetic acid, citric acid, oxydisuccinic acid, carboxymethoxysuccinic 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
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
7. A detergent composition according to claim 6 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:
9. A detergent composition according to claim 1 wherein the compound has the formula:
10. A detergent composition according to claim 9 wherein R1 is a C12-C18 alkyl moiety; 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.
US493952A 1974-08-01 1974-08-01 Detergent composition having enhanced particulate soil removal performance Expired - Lifetime US3925262A (en)

Priority Applications (8)

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US493952A US3925262A (en) 1974-08-01 1974-08-01 Detergent composition having enhanced particulate soil removal performance
CA231,695A CA1062579A (en) 1974-08-01 1975-07-17 Detergent composition having enhanced particulate soil removal performance
DE19752533795 DE2533795A1 (en) 1974-08-01 1975-07-29 DETERGENT COMPOSITIONS
BE158837A BE831994A (en) 1974-08-01 1975-07-31 DETERGENT COMPOSITION WITH IMPROVED PERFORMANCE IN THE REMOVAL OF SPECIAL SOILS
GB32083/75A GB1507543A (en) 1974-08-01 1975-07-31 Detergent composition having enhanced particulate soil removal performance
IT25982/75A IT1040280B (en) 1974-08-01 1975-07-31 DETERGENT COMPOSITION EQUIPPED WITH GREATER CAPACITY OF REMOVING DIRT OF A PARTICLE CHARACTER
NL7509120A NL7509120A (en) 1974-08-01 1975-07-31 PROCEDURE FOR PREPARING A DETERGENT WITH A STRONG DISTRIBUTED SOIL REMOVING ACTION.
FR7524025A FR2280704A1 (en) 1974-08-01 1975-07-31 DETERGENT COMPOSITION WITH IMPROVED PERFORMANCE IN THE REMOVAL OF SPECIAL SOILS

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BE (1) BE831994A (en)
CA (1) CA1062579A (en)
DE (1) DE2533795A1 (en)
FR (1) FR2280704A1 (en)
GB (1) GB1507543A (en)
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US4000091A (en) * 1975-04-02 1976-12-28 The Procter & Gamble Company Built detergent compositions
US4000092A (en) * 1975-04-02 1976-12-28 The Procter & Gamble Company Cleaning compositions
US4072622A (en) * 1974-10-10 1978-02-07 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Stable aqueous suspension of water-insoluble, calcium-binding aluminosilicates and organic suspending agents
US4072621A (en) * 1974-11-13 1978-02-07 The Procter & Gamble Company Detergent composition
US4083813A (en) * 1976-10-01 1978-04-11 The Procter & Gamble Company Process for making granular detergent composition
US4113644A (en) * 1975-02-20 1978-09-12 Ashcraft William R Protected glassy phosphate detergent additive
US4116852A (en) * 1975-02-14 1978-09-26 The Procter & Gamble Company Builders and built detergent compositions
US4125475A (en) * 1974-12-23 1978-11-14 Texaco Inc. Detergents containing a fatty alcohol builder and a water-insoluble inorganic absorbent
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US4255148A (en) * 1974-10-03 1981-03-10 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Process and apparatus for machine washing and cleaning with low-phosphate or phosphate-free washing solutions
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US4397777A (en) * 1977-02-08 1983-08-09 Colgate Palmolive Company Heavy duty laundry detergent
EP0112593A2 (en) * 1982-12-23 1984-07-04 THE PROCTER & GAMBLE COMPANY Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
EP0112592A2 (en) * 1982-12-23 1984-07-04 THE PROCTER & GAMBLE COMPANY Zwitterionic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
FR2619823A1 (en) * 1987-08-31 1989-03-03 Colgate Palmolive Co NON-AQUEOUS LIQUID DETERGENT COMPOSITIONS FOR HIGH TEMPERATURE LAUNDRYING, AND APPLICATIONS THEREOF
US5342549A (en) * 1990-01-29 1994-08-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine
US5445756A (en) * 1990-10-22 1995-08-29 The Procter & Gamble Company Stable liquid detergent compositions containing peroxygen bleach suspended by a hydropholic silica
US5531933A (en) * 1993-12-30 1996-07-02 The Procter & Gamble Company Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
US5540864A (en) * 1990-12-21 1996-07-30 The Procter & Gamble Company Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol
US5540865A (en) * 1990-01-29 1996-07-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine
US5607618A (en) * 1992-08-22 1997-03-04 Hoechst Aktiengesellschaft Use of a water-soluble copolymers based on acrylamidoalkylenesulfonic acid as a detergent additive
EP0780467A2 (en) 1995-12-18 1997-06-25 Shell Internationale Researchmaatschappij B.V. Degreasing compositions
EP0839900A1 (en) 1996-10-31 1998-05-06 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
US6121225A (en) * 1998-12-21 2000-09-19 Condea Vista Company Stable aqueous enzyme compositions
US6323170B1 (en) 1994-10-28 2001-11-27 The Procter & Gamble Co. Floor cleaners which provide improved burnish response
US6680286B1 (en) 2000-11-14 2004-01-20 Sanyo Chemical Industries, Ltd. Detergent composition comprising a quaternary ammonium salt of a carboxyl containing polymer
WO2005055286A2 (en) * 2003-12-01 2005-06-16 Konarka Technologies, Inc. Zwitterionic compounds and photovoltaic cells containing same
US20060138380A1 (en) * 2003-06-26 2006-06-29 Torsten Kulke Aqueous liquid compositions of cyclodextrine or cyclodextrine derivatives and a process using the said composition
US20060293212A1 (en) * 2005-05-05 2006-12-28 Ecolab Inc. Stable solid compositions of spores, bacteria, fungi and/or enzyme
JP4856624B2 (en) * 2004-03-19 2012-01-18 ビーエーエスエフ ソシエタス・ヨーロピア Modified polyaminoamide
US20220033705A1 (en) * 2014-10-22 2022-02-03 China Petroleum & Chemical Corporation Anionic-cationic-nonionic surfactant, production and use thereof
US11959050B2 (en) * 2015-11-12 2024-04-16 Ecolab Usa Inc. Low-foaming warewash detergent containing mixed cationic / nonionic surfactant system for enhanced oily soil removal

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US4126574A (en) * 1973-09-07 1978-11-21 Henkel Kommanditgesellschaft Auf Aktien Surfactant-containing aluminosilicates and process
US4215007A (en) * 1974-07-04 1980-07-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Process for the manufacture of low-phosphorus or phosphorus-free detergents containing aluminosilicates
US4255148A (en) * 1974-10-03 1981-03-10 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Process and apparatus for machine washing and cleaning with low-phosphate or phosphate-free washing solutions
US4148603A (en) * 1974-10-04 1979-04-10 Henkel Kommanditgesellschaft Auf Aktien Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates
US4169075A (en) * 1974-10-10 1979-09-25 Henkel Kommanditgesellschaft Auf Aktien Process for the production of powdery washing agents by spray-drying
US4438012A (en) 1974-10-10 1984-03-20 Henkel Kommanditgesellschaft Auf Aktien Stable aqueous suspension of water-insoluble, calcium-binding aluminosilicates and nonionic suspending agents
US4072622A (en) * 1974-10-10 1978-02-07 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Stable aqueous suspension of water-insoluble, calcium-binding aluminosilicates and organic suspending agents
US4072621A (en) * 1974-11-13 1978-02-07 The Procter & Gamble Company Detergent composition
US4125475A (en) * 1974-12-23 1978-11-14 Texaco Inc. Detergents containing a fatty alcohol builder and a water-insoluble inorganic absorbent
US4116852A (en) * 1975-02-14 1978-09-26 The Procter & Gamble Company Builders and built detergent compositions
US4113644A (en) * 1975-02-20 1978-09-12 Ashcraft William R Protected glassy phosphate detergent additive
US4000092A (en) * 1975-04-02 1976-12-28 The Procter & Gamble Company Cleaning compositions
US4159277A (en) * 1975-04-02 1979-06-26 The Procter & Gamble Company Zwitterionic compounds with a tetramethylene oxide moiety between the cationic and anionic charge centers
US4000091A (en) * 1975-04-02 1976-12-28 The Procter & Gamble Company Built detergent compositions
US4165334A (en) * 1975-09-05 1979-08-21 The Procter & Gamble Company Detergent compounds and compositions
US4138371A (en) * 1976-04-07 1979-02-06 Gaf Corporation Washing method using amphoteric surface active agents
US4083813A (en) * 1976-10-01 1978-04-11 The Procter & Gamble Company Process for making granular detergent composition
US4179268A (en) * 1976-11-25 1979-12-18 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Method of machine washing of solid soiled materials by reversibly contacting the circulating wash liquid with aluminosilicates
US4397777A (en) * 1977-02-08 1983-08-09 Colgate Palmolive Company Heavy duty laundry detergent
EP0032837B1 (en) * 1980-01-22 1984-09-26 THE PROCTER & GAMBLE COMPANY Zwitterionic surfactant compounds and detergent compositions containing them
EP0032837A1 (en) * 1980-01-22 1981-07-29 THE PROCTER & GAMBLE COMPANY Zwitterionic surfactant compounds and detergent compositions containing them
US4301044A (en) * 1980-01-22 1981-11-17 The Procter & Gamble Company Biodegradable zwitterionic surfactant compounds
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
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US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
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EP0112593A3 (en) * 1982-12-23 1987-09-02 The Procter & Gamble Company Detergent compositions containing ethoxylated amines havdetergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties ing clay soil removal/anti-redeposition properties
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
FR2619823A1 (en) * 1987-08-31 1989-03-03 Colgate Palmolive Co NON-AQUEOUS LIQUID DETERGENT COMPOSITIONS FOR HIGH TEMPERATURE LAUNDRYING, AND APPLICATIONS THEREOF
US4830782A (en) * 1987-08-31 1989-05-16 Colgate-Palmolive Company Hot water wash cycle built nonaqueous liquid nonionic laundry detergent composition containing amphoteric surfactant and method of use
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US5342549A (en) * 1990-01-29 1994-08-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine
US5540865A (en) * 1990-01-29 1996-07-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine
US5445756A (en) * 1990-10-22 1995-08-29 The Procter & Gamble Company Stable liquid detergent compositions containing peroxygen bleach suspended by a hydropholic silica
US5540864A (en) * 1990-12-21 1996-07-30 The Procter & Gamble Company Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol
US5607618A (en) * 1992-08-22 1997-03-04 Hoechst Aktiengesellschaft Use of a water-soluble copolymers based on acrylamidoalkylenesulfonic acid as a detergent additive
US5531933A (en) * 1993-12-30 1996-07-02 The Procter & Gamble Company Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
US6323170B1 (en) 1994-10-28 2001-11-27 The Procter & Gamble Co. Floor cleaners which provide improved burnish response
EP0780467A2 (en) 1995-12-18 1997-06-25 Shell Internationale Researchmaatschappij B.V. Degreasing compositions
EP0839900A1 (en) 1996-10-31 1998-05-06 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
US6121225A (en) * 1998-12-21 2000-09-19 Condea Vista Company Stable aqueous enzyme compositions
US6680286B1 (en) 2000-11-14 2004-01-20 Sanyo Chemical Industries, Ltd. Detergent composition comprising a quaternary ammonium salt of a carboxyl containing polymer
US20060138380A1 (en) * 2003-06-26 2006-06-29 Torsten Kulke Aqueous liquid compositions of cyclodextrine or cyclodextrine derivatives and a process using the said composition
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WO2005055286A3 (en) * 2003-12-01 2005-09-29 Konarka Technologies Inc Zwitterionic compounds and photovoltaic cells containing same
US20050211292A1 (en) * 2003-12-01 2005-09-29 Konarka Technologies, Inc. Zwitterionic compounds and photovoltaic cells containing same
US7220914B2 (en) * 2003-12-01 2007-05-22 Konarka Technologies, Inc. Zwitterionic compounds and photovoltaic cells containing same
JP4856624B2 (en) * 2004-03-19 2012-01-18 ビーエーエスエフ ソシエタス・ヨーロピア Modified polyaminoamide
US20060293212A1 (en) * 2005-05-05 2006-12-28 Ecolab Inc. Stable solid compositions of spores, bacteria, fungi and/or enzyme
AU2006246411B2 (en) * 2005-05-05 2010-09-16 Ecolab Inc. Stable solid compositions of spores, bacteria, fungi or enzyme
US20220033705A1 (en) * 2014-10-22 2022-02-03 China Petroleum & Chemical Corporation Anionic-cationic-nonionic surfactant, production and use thereof
US11959050B2 (en) * 2015-11-12 2024-04-16 Ecolab Usa Inc. Low-foaming warewash detergent containing mixed cationic / nonionic surfactant system for enhanced oily soil removal

Also Published As

Publication number Publication date
NL7509120A (en) 1976-02-03
IT1040280B (en) 1979-12-20
BE831994A (en) 1976-02-02
GB1507543A (en) 1978-04-19
DE2533795A1 (en) 1976-02-12
FR2280704A1 (en) 1976-02-27
CA1062579A (en) 1979-09-18
FR2280704B1 (en) 1980-09-26

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