Classifications

• • 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.

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Cited By (46)

Citations (1)

• 1974
  • 1974-08-01 US US493952A patent/US3925262A/en not_active Expired - Lifetime
• 1975
  • 1975-07-17 CA CA231,695A patent/CA1062579A/en not_active Expired
  • 1975-07-29 DE DE19752533795 patent/DE2533795A1/de not_active Withdrawn
  • 1975-07-31 NL NL7509120A patent/NL7509120A/nl not_active Application Discontinuation
  • 1975-07-31 IT IT25982/75A patent/IT1040280B/it active
  • 1975-07-31 GB GB32083/75A patent/GB1507543A/en not_active Expired
  • 1975-07-31 BE BE158837A patent/BE831994A/xx not_active IP Right Cessation
  • 1975-07-31 FR FR7524025A patent/FR2280704A1/fr active Granted

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