Technical Field
[0001] 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
[0002] 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.
[0003] 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.
[0004] The prior art also describes the use of various cationic materials in sheet form.
See U.S. Patent 4 220 562.
[0005] 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
[0006] 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.
[0007] 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
[0008] 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
[0009] 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".
[0010] The article describes the antimicrobial properties of these quaternaries and mentions
(page 275) their use with anionic and nonionic detergents.
[0011] 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.
[0012] 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.
[0013] 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.
[0014] 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 %.
[0015] 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.
[0016] 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.
[0017] 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.
[0018] 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.
[0019] 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.
[0020] 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.
[0021] 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.
[0022] 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.
[0023] 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
[0024] 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
[0025] 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 |
* Natural smectite; CaCO₃ ion exchange capacity above 50 meq/100g clay |
** U.S. Patent 3 927 967 |
[0026] The composition of Example I is free-flowing and provides excellent cleaning and
through-the-wash fabric softening.
[0027] The composition of Example I may be modified by adding 1.0 % tetraacetyl ethylenediamine
(TAED) as a perborate bleach activator.
EXAMPLE II
[0028] 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 |
* As Gelwhite GP (TM); CaC0₃ ion exchange capacity > 70 Meq/100 g. |
[0029] 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.
1. 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.
2. A composition according to claim 1 which contains from 1 % to 15 % of the quaternary
ammonium salt.
3. 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.
4. A composition according to any of the foregoing claims which contains at least 1 %
of a smectite clay softener.
5. A composition according to claim 4 which contains 1 % to 20 % of the clay softener.
6. 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.
7. A composition according to claim 6 which contains not more than 3 % of an alkoxylated
nonionic detersive surfactant.
8. 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.
9. 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.
1. Waschmittelzubereitung enthaltend Waschmitteltensid, Builder und andere übliche Waschmittelbestandteile
und Ton-Gewebeweichmacher, dadurch gekennziechnet, daß sie mindestens 0,1 % eines wasserlöslichen quaternären Di-C₆-C₁₀-alkyl-ammoniumsalzes
und nicht mehr als 3 Gew.-% alkoxyliertes, nichtionisches Waschmitteltensid enthält.
2. Zubereitung nach Anspruch 1, enthaltend 1 bis 15 % des quaternären Ammoniumsalzes.
3. Zubereitung nach Anspruch 2, worin das quaternäre Ammoniumsalz aus Dioctyl-dimethyl-,
Didecyl-dimethyl-, Octyl-decyl-dimethyl- und Dihexyl-dimethyl-ammoniumsalzen und Mischungen
davon ausgewählt ist.
4. Zubereitung nach einem der vorhergehenden Ansprüche, enthaltend mindestens 1 % eines
Smektit-Tonweichmachers.
5. Zubereitung nach Anspruch 4, enthaltend 1 bis 20 % des Tonweichmachers.
6. Zubereitung nach Anspruch 5, enthaltend 1 bis 5 % des wasserlöslichen quaternären
Ammoniumsalzes und 2 bis 7 % des Smektit-Tons.
7. Zubereitung nach Anspruch 6, enthaltend nicht mehr als 3 % eines alkoxylierten, nichtionischen
Waschmitteltensids.
8. Zubereitung nach einem der vorhergehenden Ansprüche, enthaltend einen Waschmittelbuilder,
ausgewählt aus Phosphat-, Nitrilotriacetat-, Polycarboxylat-, Citrat- und Zeolit-Buildern
oder Mischungen davon.
9. Zubereitung nach einem der vorhergehenden Ansprüche, enthaltend
a) 1 bis 5 % eines wasserlöslichen quaternären Ammoniumsalzes ausgewählt aus Dioctyl-dimethyl-ammonium-,
Didecyl-dimethyl-ammonium-, Octyl-decyl-dimethyl- und Dihexyldimethyl-ammoniumsalzen;
b) 2 bis 7 % eines Smektit-Tonweichmachers, gegebenenfalls,
c) 0 bis 1 % alkoxyliertes, nichtionisches Waschmitteltensid; und
d) übliche Waschmittelbestandteile in üblichen Mengen als Rest; welche Zubereitung
in Form von sprühgetrockneten Granulaten vorliegt.
1. Composition détergente comprenant un agent tensio-actif détersif, des adjuvants et
d'autres ingrédients détersifs classiques ainsi qu'un assouplissant de tissus à base
d'argile, caractérisée en ce qu'elle contient au moins 0,1 % d'un sel de di-C₆-C₁₀
alkyl ammonium quaternaire soluble dans l'eau et pas plus de 3 % en poids d'un agent
tensio-actif détersif non ionique alkoxylé.
2. Composition selon la revendication 1 contenant 1 à 15 % du sel d'ammonium quaternaire.
3. Composition selon la revendication 2 dans laquelle le sel d'ammonium quaternaire est
choisi parmi les sels de dioctyl diméthyl, didécyl diméthyl, octyl décyl diméthyl
et dihexyl diméthyl ammonium et leurs mélanges.
4. Composition selon l'une quelconque des revendications précédentes contenant au moins
1 % d'un assouplissant à base d'argile de type smectite.
5. Composition selon la revendication 4 contenant 1 à 20 % de l'assouplissant à base
d'argile.
6. Composition selon la revendication 5 contenant 1 à 5 % du sel d'ammonium quaternaire
soluble dans l'eau et 2 à 7 % de l'argile de type smectite.
7. Composition selon la revendication 6 ne contenant pas plus de 3 % d'un agent tensio-actif
détersif non ionique alkoxylé.
8. Composition selon l'une quelconque des revendications précédentes contenant un adjuvant
de détergence choisi parmi les adjuvants de phosphate, de nitrilotriacétate, de polycarboxylate,
de citrate et de zéolite ou leurs mélanges.
9. Composition selon l'une quelconque des revendications précédentes comprenant :
a) 1-5 % d'un sel d'ammonium quaternaire soluble dans l'eau choisi parmi les sels
de dioctyl diméthyl, didécyl diméthyl, octyl décyl diméthyl et dihexyldiméthyl ammonium;
b) 2-7 % d'un assouplissant à base d'argile de type smectite, facultativement;
c) 0-1 % d'un agent tensio-actif détersif non ionique alkoxylé; et
d) le restant comprenant des ingrédients de détergents classiques à des niveaux classiques;
ladite composition se présentant sous la forme de granulés séchés par pulvérisation.