CA1331680C - Laundry compositions - Google Patents

Abstract

LAUNDRY COMPOSITIONS
ABSTRACT
Fabric softening is provided by water-soluble di-C6-10 alkyl quaternary 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

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Alfred BUSCH

Technical Field The present invention relates to means of softening fabrics, wherein water-soluble quaternary ammonium salts are used to provide~fabric so~tness and anti-static benefits.
Detergent compositions in spray-dried form contalning said ~ salts and a smectite clay softener are disclosed. The ,~ quaternaries herein may also be used in sheet form.

.; . , BACKGROUND
The~use oE softeners to treat fabrlcs~subsequent to a~washing oper~ation~is~a well-known laundering practice.
Fabric softener~s~are~,~in~the~main, water-insoluble cationic materials;~tha`t~are incompatible with~anionic detersive surfactànts used in most fabric washing compo-sitions. For that reasonl, the softening operation lls generally carried out in the laundry rinse bath after the~surfactant~has been removed from the washing machine.
This~èntails~add~itional~work for the user.
Formulators~of~fabr~ic~laundering compositions have long sought~means~whereby the fabric washing and softening oould be~done concurrently. Methods employing clay softeners, mixtures of clays and various amine materials and~the like, are~described in the following patents:

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, 133l68o U.S. Patents 4,375,416; 4,321,165; 3,966,629; 4,294,710;
4,338,204 and 4,321,157. The use of mixtures of amines and soaps (salts of fatty ~c-ids) as through-the-wash softeners is disclosed in U.K. Patent l 514 276.
T~e 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 ~ater soluble quaternary am~onium salt ~n an otherwise conventional spray-dr~ed detergent comp~sition matrix, and clay, to provide concurrently cleaning and softening, through-the-wash benefits. The quaternary ammoni~m salts used herein provide lmproved 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 Ieast 0.l ~(preferably l.0 % to lS %) of a water-soluble di-C6 l0 alkyl quaternary ammonium salt. The compositions are formulated to contain not more than 3 % (preferably!not more than l % - 2 %) of a nonionic detersive surfactant.
-` The invention also encompasses methods for softening fabrics by contacting same with a water-soluble di-C6 l0 alkyl quaternary ammonium salt and a smectite clay.
The invention also encompasses an article for use in a laundry bath or rinse bath, or in a laundry dryer, .;~, -~i : ~
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- 133.1680 compris~ng sa~d quaternary salts, and preferably used in a laundry bath in comhinatlon w~th a bleach activator.
The ingredients and means for preparing the compositions are disclosed more fully he~einafter, A11 weights and proportions are by weight, unless other~ise specif~ed.

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 ma~or advantages of the water-soluble quaternary ammonium salts used herein is that they are entirely compatible with such conventional detergent i~gredients, used at conventional concentrations ~with the exception of the nonionic detersive surfactants).

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WATER-COLUBLE QUATERNARY AMMONIUM SALTS
~ he water-soluble quaternaries employed herein are the di-C ~lO materials, such as the dimethyl di-C6-Clo alkyl ammonium bromides, chlorides and methylsulfates. An article appearing in "SEIFEN-OLE 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 Or ~
these quaternaries and mentions (page 275) their use with ~ -anionic and nonionic detergents.
However, this article does not disclose the use Or these quaternaries in compositions Or the present type, with restricted amounts of nonionic surfactants, nor with sortener clays, to soften fabrics in the manner Or the present invention.
e oo~x~nds prefen~ for use herein (at preferred lS-5% le~elc) are dl-octyl dlmethyl-, d1bxyl d~thyl-, octyl decyl d~ yl- and d~Y~yldi-methyl ammonium salto, e.g., chlorides and bromides, or mixtures therebf.: ~Ethyl, propyl or butyl~may be substituted for methyl, --~
so long~as the olIx~ds~are wat~er-soluble. Methyl is preferred.
;The~quaternaries~are used~in combinQtion with~a smectite clay~softener,~most~preferably,~at a wei6ht ratio ~Or quaternary:
clay~Ln~the~range of~l l00 to l00;:l, p~ferably 0.5:l to l:}.
So~tener Clay : The above-disclosed quaternaries are mo~st preferably used i~n gr~nular detergent compositions, ~here they a.e used in combination with a detergent-compatible clay B
~ . `~ . -~ 331 680 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 softe-ners 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, C~-sulfonates o~ fatty acids and of fatty acid ester$, 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 Or 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. e. the common sodium and potassium coconut or tallow soaps well-known in the art.
It is to be understood that the use OL typical alkoxylated nonionic surfactants (e.g. the Cg-Cl8 alkyl alcohols and alkyl phenols with 5 to 20 ethoxyl groups) should be limited in the practice of this invention to levels of not .

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- 6 - 1 ~3 1 6 80 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 dusti-ness, according to the desires of the formulator.
The surfactant component tother 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 Or 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.
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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 ~;ide variety of 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 generalJ the builder/sequestrant will comprise about 0.5% to 45% of the composition. The 1-10 micron size zeolite (e.g. zeolite A) builders disclosed 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 .
* TrademarK

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^ _ 7 _ 1331680 suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents.
Commercial detersive enzymes (prererably a mixture of amylase and protease) are typically used at levels Or 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 benerits.
Typical ingredients include pH regulants, perfumes, dyes, bleaches, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, rreeze-thaw stabilizers, bactericides,preservati~es, suds control agents, bleach activators and the like.
In a through-the-wash mode, the compositions are typically used at a concentration Or at least 500 ppm, prererably 0.10 % to 1.5 Z, 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, wit~ excellent results.
In an alternate mode, the quaternaries herein may be releasably adsorbed or releasably coated onto a non-particulate substrate such as a non-woven or paper sheet or flexible sponge mat, or the like. Such sheet-rorm objects may be added to the laundry or~rinse bath, or to the~laundry dryer, where the quaternary is released to provide fabric sortening.
In an alternate, and highly preferred, mode the quaternary is used in sheet form in combination with a bleach activator (such as tetraacetyllethyiene diamine or a straight- or branched-chain C6-C10 oxybenzene sulfonate) as a combined perborate-activator and so~tener in a laundry li~uor. See, -~
for example, U.S. Patent 4 220 562, cited above.
Such sheet-form products will generally employ 1-20 grams the quaternary and 1-20 grams Or the bleach activator.
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1331680 ~

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). d-~
Ingredients Percent -Cll-12 alkyl benzene sulfonate 6.2 Tallow alcohol ethoxylate (EOll) 1.0 ~:
Sodium perborate 20.0 `;~
Sodium tripolyphosphate 24,0 Sodiumi sulfate 22.0 Sodium sillcate .8.0 Smectite clay ~ 2.4 .':~ .
Ditallow methyl amlne 3.8 -~
Dloctyl dimethyl ammonium chloride 1.6 .` -Carboxymethyl cellulose 0.4 ~:~
Malelc/acrylate polymer~:(soil suspender) 1.7 Enzymes 0.5 Optical brightener 0.23 Sulphonated zinc phthalocyanine ~: 25 ppm ::
EDTA , 0 2 Perfume/ocpFer salts/minors~brightener Ø5 Suds~su~l~ssor : 2.7 --:
Mbisture~ to 100 Nbtu ~ smectite; CaC03 ion exchange capacity abcve 50 meq/lCOg clay U.S. Patent 3 927 967 ~" ~
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133t68û
g 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-lO micron 26.0 Sodium nitrilotriacetate 5.0 Smectite clay ~ 3.0 Didecyl dimethyl ammonium chloride 2.5 C11_l2 alkyl benzene sulfonate (Na) 6.5 Tallow ethoxylate (EO 9-11) 0.5 Sodium perborate.4H20 20.0 Sodium silicate 8. o 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 " ' 1 ~
As Gelwhite GP (TM); CaC03 ion exchange capacity > 70 Meq/100 g.
The composition of Example II is prepared b~ spray-drying an ~queous crutcher mix. In use, the composition gives excellent cleaning and through-the-wash fabric oftening performance.
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`; :` ' ' - lO 13316~0 EXAMPLE III
A laundry additive product is prepared by warming 6.5 g of didecyl dimethyl ammonium bromide and spreading the melt onto an ordinary d;sposable paper hand-towel (20x20 cm), TAED powder (1-10 microns) is sprinkled onto, and pressed into the melt before it has the chance to solidify.
The article of Example III is added to a laundry liquor containing a commercial perborate/clay detergent composition (DASH-3; Trademark) to enhance through-the-wash softening and bleaching performance.
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Claims (9)

1. A detergent composition comprising detersive surfactant, builders and other conventional detersive ingredients, and 2-7 wt.% clay fabric softener, characterized in that it contains 1-5 wt% of a water-soluble -di-C1-C4, di- C6-C10 alkyl quaternary ammonium salt and not more than 3% by weight of alkoxylated nonionic detersive surfactant.

2. A composition according to claim 1 wherein the quaternary ammonium salt is selected from dioctyl dimethyl, didecyl, dimethyl, octyl decyl dimethyl and dihexyldimethyl ammonium salts, and mixtures thereof.

3. A composition according to claim 1 wherein the clay fabric softener is the smectite clay.

4. A composition according to claim 3 wherein the compositions contains not more than 2% of an alkoxylated nonionic detersive surfactant.

5. A composition according to claim 4 which contains a detergency builder selected from phosphate, nitrilotriacetate, polycarboxylate, citrate and zeolite builders, or mixtures thereof.

6. A composition according to claim 1 which comprises:
(a) 1-5% of a water-soluble quaternary ammonium salt selected from dioctyl dimethyl ammonium, didecyl dimethyl ammonium, octyl decyl diethyl and dihexyldimethyl ammonium salts;

(b) 2-7% of a smectite clay softener;

(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.

7. A method of softening fabrics by contacting said fabrics with an aqueous solution comprising at least 500 ppm of composition according to claim 1.

8. A composition according to claim 5 wherein the detergency builder comprises zeolite A having a particle size of from 1 to 10 microns.

9. A composition according to claim 2 wherein the quaternary ammonium salt is a dioctyldimethyl ammonium salt.