MXPA00000134A - Granular detergent composition containing an optimum surfactant system for cold temperature laundering - Google Patents

Abstract

A granular detergent composition which includes a surfactant system containing linear alkylbenzene sulfonate, acyclic quaternary ammonium salt, alkyl sulfate and alkyl ethoxy sulfate surfactants in selected molar ratios is provided. The composition has improved performance in cold temperature (i.e., 5°C to 30°C) laundering operations.

Description

COMPOSITION GRANULATED DETERGENT CONTAINING A SYSTEM OF OPTIMAL SURGICAL AGENT FOR LAUNDRY A COLD TEMPERATURE FIELD OF THE INVENTION The invention generally relates to granular detergent compositions used in laundry operations at cold temperature (eg, 5 ° C to 30 ° C). More particularly, the invention is directed to a granular detergent composition containing an optimally selected surfactant system in which the linear alkylbenzene sulphonate surfactants are contained in selected molar ratios with other surfactants such as alkyl sulfates, alkyl ethoxy sulfates, and cationic surfactants. The compositions Resulting detergents unexpectedly show superior cleaning development, especially in low temperature water.

BACKGROUND OF THE INVENTION Typically, conventional detergent compositions contain mixtures of various surfactants in order to remove a wide variety of soils and stains from the surfaces of articles to be washed. Currently, the formulators of detergent compositions -_M «,.-_ *» _____ - .-. .__ ^. The materials used for cold water laundry operations generally incorporate high levels of linear alkylbenzene sulphonate surfactant in their detergent products since they are very effective in cold and hot water washing conditions. 5 Linear alkylbenzenesulfonate surfactants have also been frequently used for their ability to provide excellent cleansing of grease and oil stains. Combinations of linear alkybenzene sulfonate surfactants and adjunctive surfactants such as alkyl sulfate surfactants are desirable because combine the excellent cleaning of fat and oil of alkylbenzenesulfonate (together with good cleaning on a wide range of types of dirt) with the excellent development of removal of particulate dirt from alkyl sulfate surfactants and the like. As long as the alkyl sulfate surfactants are easily derived from renewable sources, It would be desirable to provide a detergent composition which can provide a comparable or improved cleaning development wherein the alkylbenzene sulfonate surfactants are partially or completely replaced with adjunct surfactants which can be easily made from natural, renewable, petrolatum-free starting materials and which they clean one wide variety of stains and dirt. However, a major problem associated with the alkyl sulfate surfactants is that they do not work extremely well under cold temperature washing conditions. Such surfactants from ^^^^^^^^^^^^^^^^^^^^ g ^^^^^^^^^^^^ g ^^^^^^^^^^^^^^^^^^^^^ they undergo a poor dissolution in the wash liquor when they are included at significant levels, which naturally leads to a poor cleaning development. In this way, the total replacement or significant replacement of the linear alkylbenzene sulfonate surfactants has been difficult. Such problems have also been experienced with other surfactants such as cationic surfactants and alkyl ethoxy sulfate surfactants. An important part of consumers in the world have had no choice but to wash their laundry with cold water, which can have large amounts of hard water (for example, North America), which severely restrict the flexibility of the formulation with regarding the use of the adjunct surfactant with the linear alkylbenzenesulfonate surfactant based on detergent products. Accordingly, it would be desirable to have a detergent composition containing an optimum surfactant system development containing a linear alkylbenzenesulfonate surfactant together with other surfactants resulting in improved cleaning in cold-temperature laundry operations. Accordingly, it would be desirable to have a granular detergent composition that exhibits a superior development under cold temperature laundry (eg, 5 ° C to 30 ° C). It would also be desirable to have a detergent composition that substantially includes renewable or more biodegradable components in the surfactant system and that - - ^^ - -. U i ?? m - t. . . mA? ** .. »» ****** > . they can clean a wider variety of stains and soils while also showing an improved cleaning development.

TECHNICAL BACKGROUND U.S. Patent No. 5,512,699 to Connor et al discloses a variety of detergent compositions containing multiple detersive surfactants.

BRIEF DESCRIPTION OF THE INVENTION The invention meets the needs identified above by providing a granular detergent composition that includes a surfactant system containing linear alkylbenzenesulfonate, acyclic quaternary ammonium salt, alkyl sulfate surfactants and alkyl ethoxysulfate at selected molar ratios resulting in unexpected superior cleaning performance in laundry operations at cold temperature (for example, 5 ° C to 30 ° C). The granular detergent composition of the invention incorporates the linear alkylbenzenesulfonate surfactant with adjunctive surfactants such as alkyl sulfate which cleans a wider variety of stains and soils and which are more biodegradable to provide a detergent composition that retains or improves the development under the conditions of washing at cold temperature It has been particularly difficult for such surfactant systems according to one aspect of the invention to provide a granular detergent product having improved performance. Granular detergent comprises: (a) from about 1% to about 90% by weight of a surfactant system including (i) acyclic quaternary ammonium salt surfactant and linear alkylbenzene sulfonate surfactant in a molar ratio ranging from about 1: 8 to about 1: 72, wherein said quaternary ammonium salt surfactant has the formula: R4- N- R5 wherein R 4 is an acyclic aliphatic C 10 -C 22 hydrocarbon group, R 5 is R 4 or saturated C 1 -C 4 alkyl or hydroxyalkyl groups, and R 6 is R 4 or R 5 and A- is an anion; (ii) alkyl sulfate surfactant on a scale of molar ratio with the linear alkylbenzenesulfonate surfactant of from about 1: 3 to about 1: 20; (iii) alkyl ethoxy sulfate surfactant on a scale of molar ratio with the linear alkylbenzenesulfonate surfactant of from about 1: 15 to about 1: 42, wherein the alkyl ethoxy sulfate surfactant has an ethoxylation degree of about 1 to 5; (b) al ^ j¡j¿ & Ufe ^^^^ | jgg 8j less about 1% by weight of a builder; and (c) the balance of detergent ingredients attached. In accordance with another aspect of the invention, a highly preferred granular detergent composition is provided. The granular detergent composition comprises: (a) from about 5% to about 40% by weight of a surfactant system including (i) acyclic quaternary ammonium salt surfactant and linear alkylbenzenesulfonate surfactant in a molar ratio of about 1: 10 to about 1: 63, wherein said ammonium salt surfactant Quaternary has the formula: R5 R4- N- R5 R6 wherein R4 is an acyclic aliphatic C-? 0-C22 hydrocarbon group, R5 is R4 or saturated C1-C4 alkyl or hydroxyalkyl groups, and R6 is R4 or R5 and A- is an anion; (I) alkylsulfate surfactant on a scale of molar ratio with the linear alkylbenzenesulfonate surfactant of from about 1: 5 to about 1: 15; (iii) alkyl ethoxy sulfate surfactant on a scale of molar ratio with the linear alkylbenzenesulfonate surfactant of from about 1: 20 to about 1: 35, wherein the alkyl ethoxy sulfate surfactant has an ethoxylation degree of about 1 to 5; (b) al to || ^ sg ^^ fe less about 1% by weight of a builder; and (c) the equilibrium of detergent ingredients attached. Laundry laundry methods are also provided which comprise the step of contacting the laundry with an effective amount of a granular detergent composition as described herein in an aqueous solution. All percentages and ratios used herein are expressed as per hundred by weight (anhydrous base) unless otherwise indicated. All documents are incorporated herein by reference. In consecuenseIt is an object of the present invention to provide a granular detergent composition that exhibits superior performance in cold temperature laundry operations. It is also an object of the present invention to provide said detergent composition which includes substantially renewable or more biodegradable components in the surfactant system and which can clean a wider variety of stains and soils while also exhibiting an improved cleaning performance. These and other objects, features and advantages of the present invention will become apparent upon reading the following detailed description of the preferred embodiment and the appended claims. _____ §Hiá _____? __ £ a__m__. -_- »« --__ 3M * á- 'DETAILED DESCRIPTION OF THE PREFERRED MODALITY The granular detergent composition essentially contains a surfactant system having linear alkylbenzenesulfonate ("LAS") surfactants, acyclic quaternary ammonium salt ("AQAS"), alkyl sulfate ("AS") and alkyl ethoxysulfate ("AES") and a detergency builder The detergent ingredients attached can also be included in the detergent composition. The invention relates mainly to a specially selected surfactant which unexpectedly maintains a balance between the LAS surfactant and the adjunct surfactants including AES, AS and AQAS. Although not intended to be limited by theory, it is believed that the present invention selects amounts of AES, AS and AQAS expressed in molar ratios of LAS to result in a granular composition that unexpectedly has improved water solution, and therefore cleaning performance. driven. Previously, the inclusion of adjunctive surfactants such as AES, AS and AQAS with LAS alone or in combination, resulted in a low dissolution or low cleaning of all typical stains and soils. However, the present invention involves the unexpected discovery that by the use of selected adjunctive surfactants (eg, AES, AS and AQAS) with a LAS surfactant at selected molar ratios, a composition can be produced having above all a yield of Improved cleaning and dissolution in a variety of stains and dirt. For this purpose, the molar ratio of AQAS to LAS is preferably from 1: 8 to about 1: 72, more preferably from about 1: 10 to about 1: 63, and more preferably from about 1: 15 to around 1:42. The molar ratio of AS to LAS is preferably from about 1: 3 to about 1: 20, more preferably from about 1: 5 to about 1: 15, and more preferably from about 1: 8 to about 1: 12 The molar ratio of AES to LAS is preferably from about 1: 15 to about 1: 42, more preferably from about 1: 20 to about 1: 35, and more preferably from about 1: 24 to about 1:30. The preferred LAS is linear C10-18 alkylbenzene sulfonate. and the preferred AQAS is the quaternary ammonium chloride of dimethylhydroxyethyl (or wherein R 4 is an acyclic C 2-Cu aliphatic hydrocarbon group, R 5 is a methyl group, R 6 is a hydroxyethyl group and A- is a chloride anion in the chemical formula mentioned above), although other quaternary ammonium salts may be used as detailed below. Even more preferably, the molar ratio of the LAS surfactant to the sum of the surfactant of AS, the AES surfactant and the AQAS surfactant is greater than about 1: 1. The total surfactant system is present in the composition in an amount of from about 1% to about 90%, preferably from about 5% to about 40%, more preferably from ^^^ - - - "n" - ** - "- ** ^ ^ about 10% to about 30% by weight. Additionally, a detergency builder is included in the composition at levels of at least about 1%, preferably from about 10% to about 70%, and more preferably from about 20% to about 50% by weight of the composition. Preferably, the composition is substantially free of phosphate builders. The granular composition also preferably includes adjunct detergent ingredients selected from the group consisting of bleaching agents, bleach activators, enzymes, polymeric anti-redeposition agents, polymeric dispersants, polymeric soil release agents, chelators, perfumes, dye transfer inhibitors and mixtures thereof. Highly preferred compositions include from about 10% to about 30% sodium carbonate, from about 20% to about 40% sodium sulfate, from about 1% to about 10% sodium polyacrylate, from about 0.1% to about 5% of enzymes selected from the group consisting of proteases , cellulases, lipases, amylases and mixtures thereof. Optionally, the composition includes alkyl ethoxylate ("EA") on a scale of molar ratio with the LAS surfactant or less than about 1: 10, preferably from about 1: 1 to about 1: 24. Preferably, the AE surfactant is C12-13 alkyl ethoxylate with an ethoxylation degree of from about 2 to about 9.

Surfactant System As described above, the surfactant system of the composition preferably includes LAS, AS, AES and AQAS surfactants, and optionally of AE. It should be understood that additional surfactants, as described herein, may be added to the composition and / or similar types of surfactants may be substituted by one or more of the surfactants listed herein. Additional detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughiin et al; issued on December 30, 1975, which are incorporated herein by reference. Examples of useful AQAS surfactants are the monoalkyltrimethylammonium salts such as monosebotrimethylammonium chloride, mono (hydrogenated tallow) trimethylammonium chloride, palmityltrimethylammonium chloride and soyatrimethylammonium chloride, sold by Witco Chemical Company under the tradename Adogen® 471, Adogen ® 441, Adogen® 444, and Adogen® 415, respectively. In said salts, R 4 is an acyclic aliphatic Ci 6 -C 8 hydrocarbon group, and R 5 and R 6 are methyl groups. Monochloride (hydrogenated tallow.trimethylammonium and monosebotrimethylammonium chloride are preferred.) Other examples include dialkyldimethylammonium salts such as ditallowdimethylammonium chloride Examples of commercially available dialkyldimethylammonium salts that can be used ~ * * - > .-. ^ .Jd ________ i_______t_____J in the present invention are di (hydrogenated tallow) dimethylammonium chloride (trade name Adogen® 442), ditallowdimethylammonium chloride (trade name Adogen® 470), distearyldimethylammonium chloride (trade name Arosurf® TA-100), all available from Witco Chemical Company, dimethyl stearylbenzylammonium chloride sold under the trade names Varisoft® SDC by Witco Chemical Company and Ammonyx® 490 by Onyx Chemical Company. Also preferred are those selected from the group consisting of di (hydrogenated tallow) dimethylammonium chloride, ditallowdimethylammonium chloride. Additional examples include N, N-dimethyl-N-lauryl- (2-hydroxyethyl) ammonium chloride, N, N-dimethyl-N-myristyl- (2-hydroxyethyl) ammonium chloride, NN-dimethyl-N chloride -cocyl- (2-hydroxyethyl) ammonium, N, N-dimethyl-N-tallow- (2-hydroxyethyl) ammonium chloride. Mixtures of the above examples are also included within the scope of the present invention. In the cationic nitrogenous salts described above, the anion A- provides charge neutrality. More frequently, the anion used to provide charge neutrality in said charges is halide, such as chloride or bromide. However, other anions can be used, such as methylsulfate, ethylsulfate, hydroxide, acetate, formate, citrate, sulfate, carbonate, and the like. Chloride and methylsulfate are preferred herein as anion A-. Other useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980 and in U.S. Patent 4, 239,759, Murphy, ^) flBiaa a? liMM • Ü ^ ililililfl issued on December 16, 1980, which are incorporated herein by reference. Of the surfactants, anionics and nonionics are preferred and anionics are most preferred. Non-limiting examples of preferred anionic surfactants useful herein include conventional Cn-C ?8 alkylbenzene sulphonates, primary, branched and random C C 0 -C20 alkyl sulfates, C10 secondary alkyl sulphates (2,3) -C? 8 of the formula CH3 (CH2) x (CHOS03-M +) CH3 and CH3 (CH2) and (CHOS03-M +) CH2CH3l where x and (y +1) are integers of at least about 7, preferably at less about 9, and M is a cation soluble in water, especially sodium, unsaturated sulfates such as oleyl sulfate, and C-io-Ciß alkylalkoxy sulfates ("AEXS"; especially ethoxysulfates of EO 1-7). Optionally, other useful exemplary surfactants include C 1 io-C-iß alkylalkoxycarboxylates (especially the EO 1-5 ethoxycarboxycarboxylates), the glycerol ethers of C 10-18, the alkyl polyglycosides of C-io-C-is and their polyglycosides sulfates, and alpha-sulfonated fatty acid esters. If desired, conventional non-ionic and amphoteric surface-active agents such as C-? 2-C? 8 alkyl ethoxylates including so-called narrow peak alkyl ethoxylates and C6-C-? 2 alkylphenol alcoxylates (especially ethoxylates and ethoxy / propoxy mixed) ), C? 2-C? 8 betaines and sulfobetaines ("sultaines"), C10-C? 8 amine oxides and the like can also be included in the total compositions. Fatty acid amides can also be used N-alkyl polyhydroxy of C-IO-C-IS- Typical examples include the C 2 -C 18 N-methylglucamides; see WO 9,206,154. Other surfactants derived from sugar include the N-alkyl polyhydroxy fatty acid amides, such as N- (3-methoxypropyl-9-Cg-C-8 glucan.) N-propyl can be used through the C12-C18 glucamides. of N-hexyl for low foaming Conventional C-? o-C2O soaps can also be used.If high foaming is desired, branched chain C? oC-16 soaps can be used. Anionic and non-ionic are especially useful Other conventional useful surfactants are listed in standard texts.

Deputy detergency builders One or more detergency builders may be used to improve the performance of the compositions described herein. For example, the detergency builder may be selected from the group consisting of aluminosilicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates, and mixtures thereof. Another particularly suitable option is to include amorphous material coupled with the crystalline microstructures in the builder material. In this way, the builder material includes a "blend" of crystalline microstructures and amorphous material or microstructures to give improved builder performance. Other suitable detergency builders are described below.

Preferred builders include aluminosilicate ion and sodium carbonate exchange materials. The aluminosilicate ion exchange materials used herein as a builder preferably have a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rates and capacity are a function of several interrelated factors that derive from the method by which the aluminosilicate ion exchange material is produced. In this regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. No. 4,605,509 (Procter &Gamble), the disclosure of which is incorporated herein by reference. Preferably, the aluminosilicate ion exchange material is in the "sodium" form, since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit as high a rate and exchange capacity as those provided by the sodium form. In addition, the aluminosilicate ion exchange material is preferably in overdried form to facilitate the production of the brittle detergent agglomerates as described herein. The aluminosilicate ion exchange materials used herein preferably have a particle size diameter that optimizes their effectiveness as builders. The term "particle size diameter", as used herein, represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and microscope. electronic scanning (SEM). The preferred particle size diameter of the aluminosilicate is from about 0.1 microns to about 10 microns, more preferably from about 0.5 microns to about 9 microns. More preferably, the particle size diameter is from about 1 micron to about 8 micron. 10 Preferably, the aluminosilicate ion exchange material has the formula Na2 [(AI02) z (Si02) and] xH20 Where z and "y" are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and "y" is from about 10 to about 264. More preferably, the aluminosilicate has the formula Na2 [(AI02) 12 (SiO2) 12] xH20 where x is from about 20 to about 30, preferably about 27. Said preferred aluminosilicates are commercially available, for example, under designations Zeolite A, Zeolite B and Zeolite X.

Jaí ________ d ______ á_l_Ml _________________ f__tt_ÉM _______ Í_IU Alternatively, naturally occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein may be made as described in Krummel et al, U.S. Pat. No. 3,985,669, the disclosure of which is incorporated herein by reference. The aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaC03 hardness / gram, calculated on an anhydrous basis, and which is preferably on the scale of about 300 to 352 mg equivalent of CaC03 hardness / gram. Additionally, the instant aluminosilicate ion exchange materials are further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ / gallon / minute / -gram / gallon, and more preferably on a scale of about 2 grains Ca ++ / gallon / minute / -gram / gallon around 6 grains Ca ++ / gallon / minute / -gram / gallon.

Attached detergent ingredients The adjunct ingredients include other builders, bleach activators, bleach activators, foam impellers or foam suppressors, anti-rust and anti-corrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, alkalinity sources without detergency builders, chelating agents, smectite clays, enzymes, agents .-A-j-sAtta-h - * ,,. .-___, _ - __-___._-_- enzyme stabilizers and perfumes. See Patent of E.U.A. 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., Incorporated herein by reference. Other builders can generally be selected from various alkali metals, ammonium or substituted ammonium phosphates, polyphosphates, phosphates, polyphosphonates, carbonates, borates, polyhydroxysulfonates, polyacetates, carboxylates, and water soluble polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the foregoing. Preferred for use herein are phosphates, carbonates, C10-18 fatty acids. polycarboxylates, and mixtures thereof. Most preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and disuccinates, and mixtures thereof (see below). Compared with amorphous sodium silicates, the crystalline layered sodium silicates show a clearly increased calcium and magnesium ion exchange capacity. In addition, stratified sodium silicates prefer magnesium ions to calcium ions, a feature necessary to ensure that substantially all of the "hardness" is removed from the wash water. Said crystalline layered sodium silicates, however, are generally more expensive than amorphous silicates, as well as other detergency builders. Accordingly, in order to provide a reliable laundry detergent, the proportion of the crystalline layered sodium silicates used must be judiciously determined. The crystalline layered sodium silicates suitable for use herein preferably have the formula NaMSix02x +? and H20 wherein M is sodium or hydrogen, x is from about 1.9 to about 4 and "y" is from about 0 to about 20. More preferably, the crystalline layered sodium silicate has the formula NaMSi205 and H20 wherein M is sodium or hydrogen, and "y" is from about 0 to about 20. These and other crystalline stratified sodium silicates are described in Corkill et al, US Patent No 4,605, 509, previously incorporated herein by reference. Specific examples of inorganic phosphate builders are sodium potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of about 6 to 21, and orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1, 1-diphosphonic acid and the sodium and potassium salts of ethane, acid 1, 1 , 2-triphosphonic. Other phosphorus builder compounds are described in US Patents. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, which are incorporated herein by reference. Examples of non-phosphorus, inorganic detergency builders are tetraborate decaylate and silicates having a weight ratio of 5 SiO2 to alkali metal oxide of about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Water soluble, non-organic phosphorus builders useful herein include the various alkali metals, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Polymeric polycarboxylate detergent builders are described in the patent of E.U.A. 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference. Such materials include the water soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and acid methylenemalonic. Some of these materials are useful as water-soluble anionic polymers as described below, but only if they are intimately mixed with the anionic surfactant without soap. l ^ j ^ jgjgÜl s & ^ g ^ gg g¡jfc¡s¡? Other polycarboxylates suitable for use herein are the polyacetalcarboxylates described in the U.S. Patent. 4,144,226, issued March 13, 1979 to Crutchfield et al, and Patent of E.U.A. 4,246,495, issued March 27, 1979 to Crutchfield et al, which are hereby incorporated by reference. Said polyacetalcarboxylates can be prepared by contacting under conditions of polymerization of a glyoxylic acid ester and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to the chemically stable end groups to stabilize the polyacetal carboxylate against the fast depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition. Particularly preferred polycarboxylate builders are ethercarboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate ducuccinate described in U.S. Pat. 4,663,071, Bush et al, issued May 5, 1987, the description of which is incorporated herein by reference. Bleaching agents and activators are described in the U.S. Patent. 4,412,934, Chung et al, issued November 1, 1983, and in the U.S. Patent. 4,483,781, Hartman, issued on 20 November 20, 1984, which are incorporated herein by reference. Chelating agents are also described in the U.S. Patent. 4,6663,071, Bush et al, from column 17, line 54 to column 18, line 68, incorporated herein by reference. The foam modifiers ^^^^^ ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ optional and are described in the US Patents 3,933,672, issued January 20, 1976 to Bartoletta et al, and 4,136,145, issued January 23, 1979 to Gault et al, which are incorporated herein by reference. Smectite clays suitable for use herein are described in the U.S. Patent. 4,, 762,645, Tucker et al, issued August 9, 1988, column 6, line 3 to column 7, line 24, incorporated herein by reference. Additional builders suitable for use herein are listed in the Baskerville Patent, column 13, line 54 to column 16, line 16 and in the U.S. Patent. 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference. In order to make the present invention easier to understand, reference is made to the following examples, which are intended to be illustrative only and are not intended to be limiting in scope.

EXAMPLES l-IV The following examples illustrate various compositions within the scope of the invention. *** • • - *** ~~ *? * Á (% < in weight) Base granule I II III IV C-15 alkyl sulfate 1.8 0.7 1.3 1.8 Linear alkylenebenzene sulfonate of C? 2 15.8 16.8 16.2 15.5 Alkylethoxysulfate of C14-? 5 (EO = 223) 0.7 0.7 0.6 0.7 Quaternary ammonium chloride 0.3 0.3 0.4 0.6 dimetlhydroxyethyl of C-? 2-i4 C? 2-? 3 alkyl ethoxylate (EO = 9) 0.5 0.5 0.5 0.5 Sodium sulphate 28.2 28.2 28.2 28.2 Brightener 0.1 0.1 0.1 0.1 Sodium silicate 1.0 1.0 1.0 1.0 Polyethylene glycol (MW = 4000) 1.2 1.2 1.2 1.2 Sodium polyacrylate (MW = 4500) 2.4 2.4 2.4 2.4 Sodium perborate 0.7 0.7 0.7 0.7 Nonaloxybenzenesulfonate sodium 0.7 0.7 0.7 0.7 Aluminosilicate 25.8 25.8 25.8 25.8 Mix / Spray Enzyme1 protease 0.2 0.2 0.2 0.2 Enzyme2 protease 0.1 0.1 0.1 0.1 (water and minor agents) The remainder The remainder The rest FN3 commercially sold by Genencor, Inc 2CAREZYME commercially sold by Novo Nordisk The compositions exemplified above are made by combining granule ingredients as a mixture, and spray drying at a low level of residual moisture. The remaining dry ingredients are mixed in granulated form with the granules and spray-dried in a rotating mixing cylinder and the liquid ingredients are sprinkled into the resulting granules to form the finished granular detergent composition. Alternatively, the ingredients may be agglomerated in one or more mixers to form detergent-based agglomerates which are then mixed with other ingredients which may include granules. spray dried such as those exemplified herein. All exemplified detergent compositions have unexpectedly improved cleaning performance and solubility in wash water. Having thus described the invention in detail, it will be clear to those skilled in the art that various changes can be made without departing from the scope of the invention and the invention is not considered to be limited to what is described in the specification. riiíiilteiMHÉHÉÉÍ ^ ÉÉ

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A granular detergent composition characterized in that: (a) from 1% to 90% by weight a surfactant system includes (i) acyclic quaternary ammonium salt surfactant and linear alkylbenzene sulfonate surfactant on a ratio scale molar from 1: 8 to 1: 72, wherein said quaternary ammonium salt surfactant has the formula: R5 R4- N- R5 A "R6 wherein R 4 is acyclic aliphatic C 1 or C 2 hydrocarbon group, R 5 and R 4 or saturated C 1 -C 4 alkyl or hydroxyalkyl groups, and R 6 is R 4 or R 5 and A- is an anion; (ii) alkyl sulfate surfactant on a molar ratio scale with said linear alkylbenzenesulfonate surfactant from 1: 3 to 1:20; (iii) alkyl ethoxy sulfate surfactant on a molar ratio scale with said linear alkylbenzenesulfonate surfactant from 1: 15 to 1: 42, wherein said alkyl ethoxy sulfate surfactant has an ethoxylation degree of 1 to 5; (b) at least 1% by weight of a builder, (c) the balance of the detergent ingredients attached.

2. A detergent composition according to claim 1, further characterized in that said linear alkyl benzene sulphonate surfactant is linear alkylbenzenesulfonate of C? O-? B-

3. A detergent composition of according to claims 1-2, further characterized in that R4 is an acyclic aliphatic C-? 2-C? 4 hydrocarbon group, R5 is a methyl group, R6 is a hydroxyethyl group and A- is a chloride anion.

4. A detergent composition according to claims 1-3, further characterized in that said surfactant system further includes alkyl ethoxylate on a molar ratio scale with said linear alkylbenzenesulfonate surfactant of from 1: 1 to: 24.

5. A detergent composition according to claim 4, further characterized in that said alkyl ethoxylate is C-? 2-? 3 alkyl ethoxylate with an ethoxylation degree of 2 to 9. A detergent composition according to claim 1 -5, further characterized in that said adjunct ingredients are selected from the group consisting of bleaching agents, bleach activators, enzymes, polymeric antiredeposition agents, polymeric dispersants, polymeric soil release agents, chelators, perfumes, dye transfer inhibitors and mixtures thereof. 7. A detergent composition according to claims 1-6, further characterized in that said ratio scale molar and said quaternary ammonium salt surfactant to said linear alkylbenzene sulfonate surfactant is from 1: 10 to 1: 63. 8. A detergent composition according to claims 1-7, further characterized in that said molar ratio scale of said alkyl sulfate surfactant to said linear alkyl benzene sulfonate surfactant is from 1: 5 to 1: 15. 9. A detergent composition according to claims 1-8, further characterized in that said molar ratio of said linear alkylbenzenesulfonate surfactant to the sum of said alkyl sulfate surfactant, and said alkyl ethoxy sulfate surfactant and said salt surfactant of quaternary ammonium is 1: 1. 10. A laundry laundry method characterized by the step of contacting said laundry with an effective amount of a granular detergent composition according to claims 1-9 in an aqueous solution. RES YU lrcífthjjEEENNN OF THE INVENTION A granular detergent composition is provided which includes a surfactant system containing linear alkylbenzenesulfonate, acyclic quaternary ammonium salt, alkyl sulfate surfactants and alkyl ethoxysulfate at selected molar ratios; the composition has improved performance in laundry operations at cold temperature, for example, 5 ° C to 30 ° C. X VM / * mmr * sll P99 / 1709F