Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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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.
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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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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,
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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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1331680
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
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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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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.
, . . . . . . . .
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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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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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
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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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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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