Technical Field
[0001] The present invention relates to cleaning compositions which contain low levels of
certain alkoxylated polyamines. Optionally, the compositions further contain C
12-C
18 fatty acids; alkyl- or alkenyl- carboxylate materials, especially alkyl- or alkenyl-
succinates; citric acid or citrate; polyester soil release agents; or mixtures of
these optional ingredients.
Background
[0002] EP-PA 0 112 593, published July 4,1984, describes alkoxylated amines having clay-soil
removal/anti-redeposition properties when used in detergent compositions.
[0003] EP-PA 0 137 615, published April 17,1985 describes solvent-based liquid detergent
compositions containing alkoxylated polyamines. It has now been discovered that, when
used at the levels exemplified in the patent literature, the alkoxylated amines may
negatively affect overall cleaning performance.
[0004] It is, therefore, an object of the present invention to provide cleaning compositions
which contain alkoxylated polyamine clay soil removal/anti-redeposition agents at
levels high enough to provide the desired benefit, while not having or significant
negative effect on other performance parameters.
Summary of the Invention
[0005] The present invention relates to detergent compositions designed especially for laundering
fabrics. Said compositions may be formulated in liquid, solid, or granular form; the
liquid form is preferred and such liquid-form compositions are hereinafter referred
to as "heavy-duty liquids" or "HDL's" since they are designed to remove even the "heaviest"
soil loads from fabrics when used in a conventional laundering operation.
[0006] Specifically, this invention relates to laundry detergent compositions comprising
conventional detersive surfactants and, optionally, conventional detersive adjuncts,
characterized in that they contain from 0.1% to 0.9 %, preferably from 0.3 % to 0.7
%, of an alkoxylated polyamine of the formula:

wherein R is hydrocarbyl having from 2 to 6 carbon atoms, R' is C
1 to C
20 hydrobarbon, alkoxy is selected from ethoxy, propoxy, butoxy, or mixtures thereof,
wherein y is 2-30, n is an integer of at least 2, and X⊖ is an anion.
Detailed description of the Invention
[0007] The present invention is based on the discovery that art-disclosed alkoxylated amine
compounds, when used in detergent compositions at levels exemplified in the art, tend
to negatively affect the overall cleaning performance of such compositions. The negative
effects tend to occur when the detergent compositions are used under "stress" conditions,
e.g. high water hardness (more than 20 gpg, or more than about 3.4 mnol Ca per liter),
and/or high fabric softener load of the fabric, and/or low clay soil load.
[0008] It has now been discovered that detergent compositions can be formulated which contain
the alkoxy polyamine compounds at relatively low levels, whereby the intended performance
benefit is obtained without causing undesirable side effects, even under "stress"
conditions.
[0009] The detergent compositions are described in more detail hereinafter. All percentages
and ratios mentioned in this specification are by weight, unless otherwise specified.
Polyamines
[0010] Alkoxylated polyamines suitable as clay-soil removal/anti-redeposition agents, as
well as their preparation, are disclosed in EP-PA 0 112 593, the disclosures of which
are incorporated herein by reference.
[0011] It is to be understood that the term "polyamines" as used herein represents generically
the alkoxylated polyamines, both in their amine form and in their quaternarized form.
Such materials can conveniently be represented as molecules of the empirical structures
with repeating units:

and

Wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R
1 may be a C
l-C
20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30,
most preferably 10-20; n is an integer of at least 2, preferably from 2-20, most preferably
3-5; and X is an anion such as halide or methylsulfate, resulting from the quaternization
reaction.
[0012] The most highly preferred polyamines for use herein are the so-called ethoxylated
polyethylene imines, i.e., the polymerized reaction product of ethylene oxide with
ethylene-imine, having the general formula:

wherein n is an integer of 3 to 5 and y is an integer of 10 to 20.
[0013] Surfactants - In addition to the polyamine, the compositions herein contain organic
surface-active agents ("surfactants") to provide the usual cleaning benefits associated
with the use of such materials.
[0014] Water-soluble detersive surfactants useful herein include well-known synthetic anionic,
nonionic, anphoteric and zwitterionic surfactants. Typical of these are the alkyl
benzene sulfonates, alkyl- and alkylether- sulfates, paraffin sulfonates, olefin sulfonates,
alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, alpha-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
C
9-C
18 range; the anionic detersive surfactants are most commonly used in the form of their
sodium, potassium or triethanolammonium salts; the nonionics generally contain from
about 5 to about 17 ethylene oxide groups. U.S. Patent 4.111.855 contains detailed
listings of such typical detersive surfactants. C
11-C
16 alkyl benzene sulfonates, C12-C18 paraffin-sulfonates and alkyl sulfates, and the
ethoxylated alcohols and alkyl phenols are especially preferred in the compositions
of the present type.
[0015] The surfactant component can comprise as little as 1 % of the compositions herein,
but preferably the compositions will contain 1 % to 40 %, preferably 5 % to 30 %,
of surfactant. Mixtures of the ethoxylated nonionics with 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 fabrics.
[0016] Fatty Acid/Soap Ingredient - Fatty acids (generally C12-C18 chain length) and their
water-soluble salts (i.e., common "soaps", especially alkali metal soaps) can be used
in the present compositions not only for their detersive surfactant properties, but
also to provide an additional detergency builder function by virtue of their ability
to interact with water hardness cations. For these reasons, the fatty acids are highly
desirable components of the compositions herein. They are typically used at 5-30 %
by weight of the composition.
[0017] Optional Ingredients - The compositions herein can contain other ingredients which
aid in their cleaning performance. For example, it is highly preferred that 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 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 general,
the builder/sequestrant will comprise about 0.5 % to 15 % of the composition. Citrate
is one of the most preferred builders since it is readily soluble in the aqueous phase
of heavy-duty liquid detergent compositions.
[0018] Other examples of suitable builders are those of the general formula R-CH(COOH)CH
2(COOH) i.e. derivatives of succinic acid, wherein R is C10-C20 alkyl or alkenyl, preferably
C
12-C
16' or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents.
[0019] The succinate builders are preferably used in the form of their water-soluble salts,
including the sodium, potassium, ammonium and alkanolammonium salts.
[0020] Specific examples of succinate builders include: lauryl succinate, myristyl succinate,
palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and
the like.
[0021] The 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. Ingredients such as propane diol and/or formate, calcium
and boric acid, can be added to help stabilize the enzymes in well-known fashion,
according to the desires of the formulator.
[0022] The compositions herein also preferably contain soil release polymers having the
generic formula :

in which X can be any suitable capping group, with each X being selected from the
group consisting of H, and alkyl or acyl groups containing from 1 to about 4 carbon
atoms, in particular methyl. n is selected for water solubility and generally is from
about 6 to about 120, preferably from about 10 to about 50. u is critical to formulation
in a liquid detergent having a relatively high ionic strength. There should be little
material, preferably, less than 5%, having u greater than 5. Furthermore, the weight
average value of u preferably is in the range of from 1 to 2.
[0023] The
R1 moieties are essentially 1,4-phenylene moieties. As used herein, the term "the R
moieties are essentially 1,4-phenylene moieties" refers to compounds where the R moieties
consist entirely of 1,4-phenylene moieties, or are partially substituted with other
arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures
thereof. Arylene and alkarylene moieties which can be partially substituted for 1,4-phenylene
include 1,3-phenylene, 1,2-phenylene, 1,8-naphtylene, 1,4-naphtylene, 2,2-biphenylene,
4,4-biphenylene and mixtures thereof. Alkylene and alkenylene moieties which can be
partially substituted include ethylene, 1,2 propylene, 1,4-butylene, 1,5-pentylene,
1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mixtures
thereof.
[0024] For the R moieties, the degree of partial substitution with moieties other than 1,4-phenylene
should be such that the soil release properties of the compound are not adversely
affected to any great extent. Generally, the degree of partial substitution which
can be tolerated will depend upon the backbone length of the compound, i.e., longer
backbones can have greater partial substitution for 1,4-phenylene moieties. Usually,
compounds where the R comprise from about 50 to 100 % 1,4-phenylene moieties (from
0 to about 50 % moieties other than 1,4-phenylene) have adequate soil release activity.
For example, polyesters made according to the present invention with a 40:60 mole
ratio of isophtalic (1,3-phenylene) to terephtalic (1,4-phenylene) acid have adequate
soil release activity. However, because most polyesters used in fiber making comprise
ethylene terephthalate units, it is usually desirable to minimize the degree of partial
substitution with moieties other than 1,4-phenylene for best soil release activity.
Preferably, the R moieties consist entirely of (i.e., comprise 100 %) 1,4-phenylene
moieties, i.e. each R
1 moiety is 1,4-phenylene. (Irrespective of the mechanism of action, it is surprising
that the soil release polymers do show excellent benefits on fabrics other than polyester
fabrics and the compositions herein are designed to clean all manner of fabrics and
textiles.)
[0025] For the
R2 moieties, suitable ethylene or substituted ethylene moieties include ethylene, 1,2-propylene,
1,2-butylene, 1,2-hexylene, 3-methoxy-l,2-propylene and mixtures thereof. Preferably,
the R
2 moieties are essentially ethylene moieties, 1,2-propylene moieties or mixtures thereof.
Inclusion of a greater percentage of ethylene moieties tends to improve the soil release
activity of the compounds. Surprisingly, inclusion of a greater percentage of 1,2-propylene
moieties tends to improve the water solubility of the compounds.
[0026] 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.
[0027] In a through-the-wash laundry mode, the compositions are typically used at a concentration
of at least 500 ppm, preferably 0.10 % to 2.5 %, in an aqueous laundry bath at pH
7-11 to launder fabrics. The laundering can be carried out by agitating fabrics with
the present compositions over the range from 5°C to the boil, with excellent results.
1. A laundry detergent composition comprising conventional detersive surfactants,
and optional, conventional detersive adjuncts, characterized in that it contains :
from 0.1 % to 0.9 % of an alkoxylated polymaine of the formula :

wherein R is hydrocarbyl having from 2 to 6 carbon atoms, R1 is C1 to C20 hydrocarbon, alkoxy is selected from ethoxy, propoxy, butoxy, or mixtures thereof,
y is 2-30, n is an integer of at least 2, and is an anion.
2. A composition according to Claim 1 wherein the alkoxylated polyamine is the polymerized
reaction product of ethylene oxide with ethylene imine.
3. A composition according to Claim 2 wherein the alkoxylated polyamine is of the
formula :

wherein n is an integer from 3 to 5 and y is an integer from 10 to 20.
4. A composition according to any of the preceding claims which further comprises
from 5 % to 30 % of C12-C18 fatty acids.
5. A composition according to any of the preceding claims which further comprises
from 0.01 % to 2.5 %, preferably from 0.1 % to 1 %, of the soil release polymer defined
herein.
6. A composition according to claim 5 wherein the soil release polymer is of the formula
:

wherein R
1 is 1,4-phenylene; R
2 is 1.2-propylene; X is methyl; n is an integer of 6 to 120; u is generally an integer
of 5, or less, the average value of u being in the range of from 1 to 2.
7. A composition according to any of the preceding claims which further comprises
from 1 % to 35 % of an alkyl-or alkenyl dicarboxylate detergency builder.
8. A composition according to Claim 7 wherein the dicarboxylate builder is a C12-C16 alkyl- or alkenyl-succinate.
9. A composition according to any of the preceding claims which further comprises
from 0.1 % to 3 % of citric acid or a salt thereof.
10. A liquid detergent composition according to any of the preceding claims.
11. A composition according to any of the preceding claims which comprises from 0.3
% to 0.7 of the polyamine.
12. A method of laundering fabrics by agitating fabrics with an aqueous bath containing
at least 500 ppm of a composition according to one of the foregoing claims.