LAUNDRY COMPOSITIONS

Abstract: Fabric softening is provided by water-soluble di-C₆₋₁₀ qua­ ternary ammonium salts and clay. Through-the-wash fabric softening is achieved concurrently with fabric cleaning by means of clays and water-soluble quaternaries. Compositions and sheet-form articles embodying soluble quaternary softeners are described.

Description: Technical Field The present invention relates to means of softening fabrics, wherein water-soluble quaternary ammonium salts are used to provide fabric softness and anti-static benefits. Detergent compositions in spray-dried form containing said salts and a smectite clay softener are disclosed. BACKGROUND The use of softeners to treat fabrics subsequent to a washing operation is a well-known laundering practice. Fabric softeners are, in the main, water-insoluble cationic materials that are incompatible with anionic detersive surfactants used in most fabric washing compositions. For that reason, the softening operation is generally carried out in the laundry rinse bath after the surfactant has been removed from the washing machine. This entails additional work for the user. Formulators of fabric laundering compositions have long sought means whereby the fabric washing and softening could be done concurrently. Methods employing clay softeners, mixtures of clays and various amine materials and the like, are described in the following patent applications: German 29 64114.3, 28 57163.3, 24 39541.3, 23 34899.4 and EP-A-0 023 367, 0 026 528 and 0 028 432. The use of mixtures of amines and soaps (salts of fatty acids) as through-the-wash softeners is disclosed in U.K. Patent 1 514 276. The prior art also describes the use of various cationic materials in sheet form. See U.S. Patent 4 220 562. The present invention employs a water soluble quaternary ammonium salt in an otherwise conventional spray-dried detergent composition matrix, and clay, to provide cleaning and softening concurrently through-the-wash. The quaternary ammonium salts used herein provide improved softening and anti-static benefits, especially when applied to polyester fabrics and/or when the compositions herein are used at relatively high laundering temperatures (60° C, and above). SUMMARY OF THE INVENTION The detergent compositions (preferably, spray-dried) herein may be described succinctly as containing conventional detergent ingredients such as detersive surfactants (including anionics), detergency builders, optical brighteners, detersive enzymes, fabric bleaches, and the like, all at rather conventional levels, as well as clay fabric softeners (preferably, smectite clays), said compositions being characterized in that they contain at least 0.1 % (preferably 1.0 % to 15 %) of a water-soluble di-C₆₋₁₀ alkyl quaternary ammonium salt. The compositions are formulated to contain not more than 3 % (preferably not more than 1 % - 2 %) of a nonionic detersive surfactant. The ingredients and means for preparing the compositions are disclosed more fully hereinafter. All weights and proportions are by weight, unless otherwise specified. DETAILED DESCRIPTION OF THE INVENTION As noted hereinafter, the detergent compositions of this invention comprise, in major part, conventional ingredients that are quite familiar to formulators of granular detergent compositions. One of the major advantages of the water-soluble quaternary ammonium salts used herein is that they are entirely compatible with such conventional detergent ingredients, used at conventional concentrations (with the exception of the nonionic detersive surfactants). WATER-SOLUBLE QUATERNARY AMMONIUM SALTS The water-soluble quaternaries employed herein are the di-C₆₋₁₀ materials, such as the dimethyl di-C₆-C₁₀ ammonium bromides, chlorides and methylsulfates. An article appearing in "SEIFEN-ÖLE FETTE-WACHSE" Nr 10-2. Juniheft 19 June, 1975, beginning at page 273, describes such materials and discloses that they are commercially available under the Trademark "BARDAC". The article describes the antimicrobial properties of these quaternaries and mentions (page 275) their use with anionic and nonionic detergents. However, this article does not disclose the use of these quaternaries in compositions of the present type, with restricted amounts of nonionic surfactants, nor with softener clays, to soften fabrics in the manner of the present invention. The compounds preferred for use herein (at preferred 1%-5% levels) are the di-octyl dimethyl-, didecyl dimethyl-, octyl decyl dimethyl- and dihexyldimethyl ammonium salts, e.g., chlorides and bromides, or mixtures thereof. Ethyl, propyl or butyl may be substituted for methyl, so long as the compounds are water-soluble. Methyl is preferred. The quaternaries are used in combination with a smectite clay softener, most preferably, at a weight ratio of quaternary: clay in the range of 1:100 to 100:1, preferably 0.5:1 to 1:1. Softener Clay : The above-disclosed quaternaries are most preferably used in granular detergent compositions, where they are used in combination with a detergent-compatible clay fabric softener. Such clay softeners are well-known in the detergency patent literature and are in broad commercial use, both in Europe and in the United States. Included among such clay softeners are various heat-treated kaolins and various multi-layer smectites. Preferred clay softeners are smectite softener clays that are described in German patent document 2 334 899 and in U.K. Patent 1 400 898 which can be referred to for details. Softener clays are used in the preferred compositions at levels of at least 1 %, generally 1-20%, preferably 2-7 %. Detersive Surfactants - The detergent compositions of this invention will contain organic surface-active agents ("surfactants") to provide the usual cleaning benefits associated with the use of such materials. Detersive surfactants useful herein include well-known synthetic anionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl-and alkylether sulfates, paraffin sulfonates, olefin sulfonates, amine oxides, α-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art. In general, such detersive surfactants contain an alkyl group in the C₉-C₁₈ range; the anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts. U.S. Patents 4 111 855 and 3 995 669 contain detailed listings of such typical detersive surfactants. C₁₁-C₁₆ alkyl benzene sulfonates, C₁₂-C₁₈ paraffin-sulfonates and alkyl sulfates are especially preferred in the compositions of the present type. Also useful herein as the surfactant are the water-soluble soaps, e.g. the common sodium and potassium coconut or tallow soaps well-known in the art. It is to be understood that the use of typical alkoxylated nonionic surfactants (e.g. the C₉-C₁₈ alkyl alcohols and alkyl phenols with 5 to 20 ethoxyl groups) should be limited in the practice of this invention to levels of not more than about 3 %, preferably not more than 2 %, most preferably 0-1 %, of the compositions. Such alkoxylates interfere with the softening properties of the compositions. However, a limited amount (as stated) may be used to disperse optical brightener in the compositions, and to reduce dustiness, according to the desires of the formulator. The surfactant component (other than alkoxylated nonionic) can comprise as little as 1 % of the compositions herein, but preferably the compositions will contain 5 % to 40 %, preferably 6 % to 30 %, of surfactant. Mixtures of the anionics, such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred for through-the-wash cleansing of a broad spectrum of soils and stains from fabric. Detersive Adjuncts - The compositions herein can contain other ingredients which aid in their cleaning performance. For example, it is highly preferred that through-the-wash detergent compositions contain a detergent builder and/or metal ion sequestrant. Compounds classifiable and well-known in the art as detergent builders include the nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicates, and mixtures thereof. Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-polyphosphonates and phosphates (DEQUEST) and a wide variety or other poly-functional organic acids and salts too numerous to mention in detail here. See U.S. Patent 3 579 454 for typical examples of the use of such materials in various cleaning compositions. In general, the builder/sequestrant will comprise about 0.5% to 45% of the composition. The 1-10 micron size zeolite (e.g. zeolite A) builders disclose in German patent 2 422 655 are especially preferred for use in low-phosphate compositions which contain the softeners described herein. The laundry compositions herein also preferably contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains. Amylase and protease enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents. Commercial detersive enzymes (preferably a mixture of amylase and protease) are typically used at levels of 0.001 % to 2 %, and higher, in the present compositions. Moreover, the compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Typical ingredients include pH regulants, perfumes, dyes, bleaches, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides preservatives, suds control agents, bleach activators and the like. In a through-the-wash mode, the compositions are typically used at a concentration of at least 500 ppm, preferably 0.10 % to 1.5 %, in an aqueous laundry bath at pH 7-11 to launder fabrics. The laundering can be carried out over the range from 5° C to the boil, with excellent results. INDUSTRIAL APPLICATION The following examples are typical of the preferred composition of this invention, but are not intended to limit the scope of the invention. EXAMPLE I An aqueous crutcher mix comprising the following ingredients is prepared and spray-dried in standard fashion (percentages listed relate to percent ingredients in the complete formulation after spray-drying). Ingredients Percent C₁₁₋₁₂ alkyl benzene sulfonate 6.2 Tallow alcohol ethoxylate (EO11) 1.0 Sodium perborate 20.0 Sodium tripolyphosphate 24.0 Sodium sulfate 22.0 Sodium silicate 8.0 Smectite clay 2.4 Ditallow methyl amine 3.8 Dioctyl dimethyl ammonium chloride 1.6 Carboxymethyl cellulose 0.4 Maleic/acrylate polymer (soil suspender) 1.7 Enzymes 0.5 Optical brightener 0.23 Sulphonated zinc phthalocyanine 25 ppm EDTA 0.2 Perfume/copper salts/minors/brigtener 0.5 Suds suppressor 2.7 Moisture to 100 The composition of Example I is free-flowing and provides excellent cleaning and through-the-wash fabric softening. The composition of Example I may be modified by adding 1.0 % tetraacetyl ethylenediamine (TAED) as a perborate bleach activator. EXAMPLE II A nil-P spray-dried detergent formulation is as follows : Ingredient Percent Zeolite A (1-10 micrometer) 26.0 Sodium nitrilotriacetate 5.0 Smectite clay 3.0 Didecyl dimethyl ammonium chloride 2.5 C₁₁₋₁₂ alkyl benzene sulfonate (Na) 6.5 Tallow ethoxylate (EO 9-11) 0.5 Sodium perborate.4H₂O 20.0 Sodium silicate 8.0 CMC 1.0 Sodium sulfate 20.0 Enzymes (1:1 amylase/protease) 1.5 Optical brightener 0.5 TAED 1.2 Water, minors to 100 The composition of Example II is prepared by spray-drying an aqueous crutcher mix. In use, the composition gives excellent cleaning and through-the-wash fabric softening performance.

Claims: A detergent composition comprising detersive surfactant, builders and other conventional detersive ingredients, and clay fabric softener, characterized in that it contains at least 0.1 % of a water-soluble di- C₆-C₁₀ alkyl quaternary ammonium salt and not more than 3 % by weight of alkoxylated nonionic detersive surfactant. A composition according to claim 1 which contains from 1 % to 15 % of the quaternary ammonium salt. A composition according to claim 2 where the quaternary ammonium salt is selected from dioctyl dimethyl, didecyl dimethyl, octyl decyl dimethyl and dihexyldimethyl ammonium salts, and mixtures thereof. A composition according to any of the foregoing claims which contains at least 1 % of a smectite clay softener. A composition according to claim 4 which contains 1 % to 20 % of the clay softener. A composition according to claim 5 which contains from 1 % to 5 % of the water-soluble quaternary ammonium salt and from 2 % to 7 % of the smectite clay. A composition according to claim 6 which contains not more than 3 % of an alkoxylated nonionic detersive surfactant. A composition according to any of the foregoing claims which contains a detergency builder selected from phosphate, nitrilotriacetate, polycarboxylate, citrate and zeolite builders, or mixtures thereof. A composition according to any of the foregoing claims which comprises : a) 1-5 % of a water-soluble quaternary ammonium salt selected from dioctyl dimethyl ammonium, didecyl dimethyl ammonium, octyl decyl dimethyl and dihexyldimethyl ammonium salts; b) 2-7 % of a smectite clay softener, optionally, c) 0-1 % alkoxylated nonionic detersive surfactant; and d) the balance comprising conventional detergent ingredients at conventional levels; said composition being in the form of spray-dried granules.

Inventors: BURCKETT ST.LAURENT, JAMES CHARLES THEOPHILE ROGER, BUSCH, ALFRED
Applicants: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER, THE PROCTER & GAMBLE COMPANY
Application year: 1984
Main classification: C11D1
IPC codes: D06M13, C11D1, C11D3, D06M11, C11D17