Note: Descriptions are shown in the official language in which they were submitted.
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FABRIC ENHANCEMENT COMPOSITIONS
HAVING IMPROVED COLOR FIDELITY
FIELD OF THE INVENTION
The present invention relates to fabric care and laundry detergent
compositions which
comprise a fabric enhancement system in combination with a transition metal-
comprising dye
protection system, which acts to mitigate the loss of fabric color, providing
a laundry
composition which provides enhanced fabric appearance benefits.
BACKGROUND OF THE INVENTION
Formulators of fabric care and laundry detergent compositions include various
ingredients, inter alia surfactants, cationic softening actives, anti-static
agents, dye transfer
inhibitors, and bleach-damage mitigating agents, for the purpose of improving
cleaning, fabric
appearance, fabric feel, fabric color and to extend the duration of fabric
life. Ingredients which
are added to these compositions must not only provide a benefit, but must be
compatible with a
variety of product forms, i.e. high density granules, liquid dispersions,
isotropic liquids including
clear, colorless/translucent liquids which may include principal solvents
inter alia 1,2-
hexanediol, 2,2,4-trimethyl-1,3-pentanediol (TMPD).
Many adjunct ingredients which provide fabric enhancement benefits are highly
fabric
substantive and, therefore, once deposited on the fabric surface remain with
the fabric thereby
providing the intended benefit until chemically altered or until displaced by
a more fabric
substantive material. High molecular weight modified polyalkyleneimines have
been used in
granular and liquid detergent compositions as well as rinse-added fabric
conditioning
compositions to mitigate fabric damage. These highly fabric substantive
ingredients can be
deposited onto fabric at various optimal times, for example, in the alkaline
laundry wash liquor or
the near neutral pH environment of the laundry rinse cycle. Once deposited
they serve a variety
of purposes depending upon the absolute structure of the polyalkyleneamine or
polyalkyleneimine and whether the polymeric amine is modified (for example,
ethoxylated).
Color integrity is an important aspect of fabric enhancement. When certain
polyamines
are deposited onto fabric they enhance color fidelity via various mechanisms.
Other polyamines
intercept peroxygen bleaching agents at the fabric surface. However, many
polyamines which
provide fabric benefits also have a propensity to chelate heavy metals, inter
alia, copper, which
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are components of transition metal-comprising fabric dyes. The chelation, and
hence the
extraction of, these heavy metals is ruinous to the fidelity of fabric color.
Therefore, there is a long felt need to provide colored fabric with protection
against the
pejorative effects of certain laundry-added fabric integrity materials, inter
alia, polyamines which
provide fabric wear protection and fabric lubricity benefits. In addition,
there is a need for
materials which will be highly water soluble or water dispersible, while
exhibiting a high degree
of fabric substantivity. And there is also a need for a material which will
provide a high level of
fabric dye protection on an efficient per unit weight basis.
SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in that it has been
surprisingly
discovered that oligomers which are formed from the reaction of imidazoles and
a crosslinking
agent, preferably an epihalohydrin, provide transition metal-comprising dye
protection benefits.
It has now been surprisingly discovered that the combination of a dye
protection system which
comprises the imidazole derived oligomers is combined with a polyamine based
fabric
enhancement system, the pejorative effects of heavy metal ion chelation by the
fabric
enhancement system is abated.
The heavy metal-comprising dye protection systems of the present invention are
suitable
for use in high and low density granular, heavy duty and light duty liquids,
as well as laundry bar
detergent compositions to provide fabric appearance benefits inter alia
mitigation of fabric
damage, prevention of fabric mechanical damage, as well as, the protection of
color fidelity.
A first aspect of the present invention which relates to fabric care
compositions
comprising:
a) from about 0.01% by weight, of a fabric enhancement system, said fabric
enhancement system comprising one or more modified polyamine compounds,
said modified polyamine compounds are selected from:
i) (PA)W(T)X:
ii) (PA)W(L)Z;
iii) L(PA),S-('I')x]yLL]Z; and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
2
CA 02377017 2005-04-29
0.8 : 1 to 1.5 : 1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from about 0.05 to about 2
parts by weight of said L unit; for compounds of type (iii) the indices y and
z
have values such that said modified polyamine compound comprises from about
0.05 to about 2 parts by weight of said L unit;
b) from about 0.0 i °/~ by weight, of a protection system for
transition metal containing
dyes, said protection system comprising one or more oligomers formed
from the reaction of
i) 1 part by weight of an epihalohydrin; and
ii) from 0.5 to 2 parts by weight of a substituted or unsubstituted imidazole;
and
c) the balance carriers and adjunct ingredients.
The present invention further relates to laundry detergent compositions which
comprise:
a) from about 0.01 % by weight, of a detersive surfactant selected from the
group
cansistirag of anionic, cationic, nonionic, zwitterionic, ampholytic
surfactants,
and mixtures thereof;
b) from about 0.01% by weight, of a fabric enhancement system, said fabric
enhancement system comprising one or more modified polyamine compounds,
said modified polyaniine compounds are selected from:
i) (1'A),~X;
ii) (PA)w(L~;
iii) I(1'A)W(T°)~JyLL)=~ ~d
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and
L is a non-anode forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8 : 1 to 1.5 : 1; for compounds of type (ii) the indices w and z have values
such
that said modified polyarnine compound comprises from about 0.05 to about 2
parts by weight of said L unit; for compounds of type (iii) the indices y and
z
have values such that said modified polyamine compound comprises from about
0.05 to about 2 parts by weight of said L unit;
CA 02377017 2005-04-29
c) from about 0.01°/~ by weight, of a protection system for transition
metal containing
dyes, said protection system comprising one or more oligomers formed
from the reaction of:
i) 1 part by weight of an epihaiohydrin; and
ii) from 0.5 to 2 parts by weight of a substituted or unsubstituted imidazole;
and
d) the balance carriers and adjunct ingredients, said adjunct ingredients are
selected
from the group consisting of builders, optical brighteners, soil release
polymers,
dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes,
colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric
conditioners, hydrolyzable surfactants, preservatives, anti-oxidants,
chelants,
stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides,
fungicides,
anti corrosion agents, and mixtures thereof.
These and other objects, features, and advantages will become apparent to
those of
ordinary skill in the art from a reading of the following detailed description
and the appended
claims. All percentages, ratios and proportions herein are by weight, unless
otherwise specified.
All temperatures are in degrees Celsius (~ C) unless othervrrise specified.
DETAILED DESCRIPTION OF TFIEE INVENTION
The present invention relates to laundry detergent compositions which provide
fabric
care benefits, said benefits provided by the combination of a fabric
enhancement system and a
transition metal-comprising dye protection system. The laundry compositions
comprise from
about 0.01%, preferably from about 0.1%, more preferably from 0.25%, most
preferably from
about 0.5% to about 20%, preferably to about 10%, more preferably to about 5%
by weight, of a
fabric enhancement system. Said fabric enhancement system is comprised of one
or more
modified polyamine compounds. The laundry compositions also comprise from
about O.Oi%,
preferably from about 0.1%, more preferably from 0.25%, most preferably from
about 0.5% to
about 20%, preferably to about 10%, more preferably to about 5% by weight, of
a transition
metal-comprising dye protection system. Said dye protection system is
comprised of one or more
oligomeric compounds as described herein below. The enhanced fabric care
compositions may
take any form, for example, solids (i.e., powders, granules, extrudates),
gels, thixotropic liquids,
liquids (i.e., dispersions, isotropic solutions), preferably the rinse-added
fabric conditioning
compositions take the form of liquid dispersions or isotropic liquids.
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For the purposes of the present invention the terms "fabric enhancement" and
"fabric
care" are used interchangeable throughout the present specification and stand
equally well for
one another. Fabric enhancement/fabric care is achieved when the properties
inter alia color,
fiber integrity of the garment are conserved (that is no further damage is
done during the laundry
process) or the damaging process is reversed and the fabric appears more like
its original form.
Fabric Enhancement System
The fabric enhancement system of the present invention is comprised of one or
more
modified polyamines according to the present invention. The modified
polyamines of the present
invention which comprise the fabric enhancement system may be formulated as an
admixture
wherein a proportional amount of two or more compounds are combined to make up
the fabric
enhancement system. Alternatively, the formulator may adjust the reaction
conditions which
form the modified polyamines of the present invention in order to create an
admixture of suitable
ingredients inter alia an admixture of polyamine fragments and/or partially
crosslinked modified
polyamines. Whether a formulated admixture or a product by process is used, or
a mixture of
both, the compounds which comprise the fabric enhancement compositions of the
present
invention have the formula:
i) (PA)W(T)X;
ii) (PA)W(L)Z;
iii) L(PA)W('I')X~yLi-lZ~
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an
amide-forming polycarboxylic acid crosslinking unit, and L is a non-amide
forming crosslinking
unit. For compounds of type (i) and (iii) the relative amounts of PA units and
T units which are
present are such that the molar ratio of PA units to T units is from 0.8 : 1
to 1.5 : 1. For
compounds of type (ii) the relative amounts of PA units and L units which are
present are such
that the (PA)W(L)Z comprises from about 0.05, preferably from about 0.3 to 2
parts by weight of
said L units. Therefore, 1 part of a grafted or non-grafted, modified or
unmodified polyamine
backbone unit may be combined with from about 0.05, preferably from about 0.3
parts by weight
of an L unit to about 2 parts by weight of an L unit to form a suitable
modified polyamine
compound. Likewise, for compounds of type (iii), crosslinked polyamines having
the formula
(PA)W(T)X may be combined with from about 0.05, preferably from about 0.3
parts by weight of
an L unit to about 2 parts by weight of an L unit to form a suitable modified
polyamine
compound having the formula [(PA)W(T)X]y[L]Z.
Polyamine Backbone (PA units)
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The modified polyamine compounds of the present invention comprise a Polyamine
Backbone, PA unit, which can be optionally, but preferably grafted. The
following are non-
limiting examples of suitable PA units according to the present invention.
Polyalk~eneimine
A preferred PA unit according to the present invention are polyalkyleneimines
and
polyalkyleneamines having the general formula:
H B
I I
[H2N- Rl W [Z'I- RlX [1'1- Ray ~z
wherein R is C~-C>? linear alkylene, C3-C,Z branched alkylene, and mixtures
thereof; B
representing a continuation of the chain structure by branching. The indices
w, x, and y have
various values depending upon such factors as molecular weight and relative
degree of branching.
The polyalkyleneimines and polyalkyleneamines which comprise PA units of the
present
invention are divided into three categories based upon relative molecular
weight. The terms
polyalkyleneimine and polyalkyleneamine are used interchangeably throughout
the present
specification and are taken to mean polyamines having the general formula
indicated above
regardless of method of preparation.
Low Molecular Wei hg t Polyalkyleneimines
For low molecular weight polyalkyleneimines having the formula:
H B
I
[H2N-RAW [Z'1-R~X[1'I-R~y~2
R is CZ-C,Z linear alkylene, C3-C,z branched alkylene, and mixtures thereof;
preferably R is
ethylene, 1,3-propylene, and 1,6-hexylene, more preferred is ethylene. The
indices w, x, and y
are such that the molecular weight of said polyamines does not exceed about
600 daltons. For
example, for an entirely linear polyethyleneimine having a molecular weight of
about 600
daltons, the index w = 1, x = 13, and y = 0. For an entirely branched
polyethyleneimine having a
molecular weight of approximately 600 daltons, w = 8, x = 0 and y =7. (This
combination of
indices results in a material having an average molecular weight of about 646
daltons, which, for
the purposes of the present invention is a low molecular weight
polyalkyleneimine.) The index w
typically has the value of y + 1. The simplest of the low molecular weight
polyamines of this
type is ethylene diamine which may be present up to about 10% by weight of the
PA unit
mixture. Non-limiting examples of low molecular weight polyalkyleneimine PA
units include
diethylene triamine, triethylene tetramine, tetraethylene pentamine,
dipropylene triamine,
tripropylene tetramine, and dihexamethylene triamine. PA units may be used as
crude products
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or mixtures, and if desired by the formulator, these PA units may be used in
the presence of small
amounts of diamines as described herein above, wherein the amount of diamines,
inter alia,
ethylene diamine, hexamethylene diamine may be present up to about 10% by
weight, of the PA
unit mixture.
Medium Range Molecular Weight Polyalkyleneimines
For medium range molecular weight polyalkyleneimines having the formula:
H B
[HzN-RlW [Z'I-R)X[N-Rly~2
R is C~-C4 linear alkylene, C3-C4 branched alkylene, and mixtures thereof;
preferably R is
ethylene, 1,3-propylene, and mixtures thereof, more preferred is ethylene
wherein said
polyamines are polyethyleneimines (PEI's). The indices w, x, and y are such
that the molecular
weight of said polyamines is from about 600 daltons to about 50,000 daltons.
The indices w, x,
and y will indicate not only the molecular weight of the polyalkyleneimines
but also the degree of
branching present in the PA unit backbone.
High Molecular Weight Polyalkyleneimines
For high molecular weight polyalkyleneimines having the formula:
H B
[HzN- R~ W LI'1- R~X [N- Ray ~z
R is CZ-C3 linear alkylene, preferably R is ethylene. The indices w, x, and y
are such that the
molecular weight of said polyamines is from about 50,000 daltons to about
30,000,000 (30
million) daltons, preferably to about 1,000,000 (1 million) daltons. The
indices w, x, and y will
indicate not only the molecular weight of the polyalkyleneimines but also the
degree of branching
present in the PA unit backbone.
Co-polymeric Polyamines
Another example of a preferred PA unit according to the present invention are
the
polyvinyl amine homo-polymers or co-polymers having the formula:
~2
---EV CHZCH
m n
wherein V is a co-monomer, non-limiting examples of which include vinyl
amides, vinyl
pyrrolidone, vinyl imidazole, vinyl esters, vinyl alcohols, and mixtures
thereof, all of which can
be taken together or in combination with polyvinyl amine to form suitable co-
polymerization
products suitable for use in the fabric enhancement systems of the present
invention. The indices
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m and n are such that the copolymers comprise at least 10%, more preferably at
least about 30%
of units derived from vinyl amine and wherein further the molecular weight of
said copolymers if
from about 500 daltons, preferably from about 5,000 daltons to about 50,000
daltons, preferably
to about 20,000 daltons.
Polyamine Backbone Modifications
Optionally but preferably the PA units of the present invention are modified
either before
or after reaction with a T unit or L unit crosslinking agent. The two
preferred types of
modifications are grafting and capping.
Preferably the PA units of the present invention are grafted, that is the PA
unit is further
reacted with a reagent which elongates said PA unit chain, preferably by
reaction of the nitrogens
of the PA backbone unit with one or more equivalents of aziridine
(ethyleneimine), caprolactam,
and mixtures thereof. Grafting units, in contrast to the "capping" units
described herein below,
can further react on themselves to provide PA unit chain propagation. An
example of a preferred
grafted PA unit of the present invention has the formula:
G B
[GZN-R]W [N-R]X[N-R]yNG2
wherein R, B, w, x, and y are the same as defined herein above and G is
hydrogen or an extension
of the PA unit backbone by grafting. Non-limiting examples of preferred
grafting agents are
aziridine (ethyleneimine), caprolactam, and mixtures thereof. A preferred
grafting agent is
aziridine wherein the backbone is extended by units having the formula:
B'
I
- [CH2CHZNH]p [CHZCHZN] qCHZCHzNH2
wherein B' is a continuation by branching wherein the graft does not exceed
about 8 units,
preferably -CHZCHZNHZ and the value of the indices p + q have the value from
0, preferably from
about 1, more preferably from about 2 to about 7, preferably to about 5.
Another preferred
grafting unit is caprolactam.
The PA units of the present invention can be grafted prior to or after
crosslinking with
one or more T units described herein below, preferably the grafting is
accomplished after
crosslinking with said T unit. This allows the formulator to take advantage of
the differential
reactivity between the primary and secondary amino units of the PA unit
backbone thereby
allowing the formulator to controllably link said PA units and to also control
the amount of
subsequent branching which results from the grafting step.
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Another optional but preferred PA unit modification is the presence of
"capping" units.
For example, a PA unit is reacted with an amount of a monocarboxylic acid, non-
limiting
examples of which are C,-CZZ linear or branched alkyl, preferably C,o-C,8
linear alkyl inter alia
lauric acid, myristic acid. The amount of capping unit which is reacted with
the PA unit is an
amount which is sufficient to achieve the desired properties of the formula.
However, the amount
of capping unit used is not sufficient to abate any further crosslinking or
grafting which the
formulator may choose to perform.
Crosslinking Units
Amide-forming T Crosslinkin~ Units
T crosslinking units are preferably carbonyl comprising polyamido forming
units. The T
units are taken together with PA units to form crosslinked modified polyamine
compounds
having the formula (PA)W(T)X or [(PA)W(T)X]Y[L]Z.
A preferred embodiment of the present invention includes crosslinked PA units
wherein a
T unit provides crosslinking between two or more PA units to form a (PA)W(T)X
polyamido
crosslinked section. A preferred crosslinking T unit has the general formula:
O O
-C-~2)1-(RI)k-(R2).l-C
wherein R' is methylene, phenylene, and mixtures thereof; preferably
methylene. The index k has
the value from 2 to about 8, preferably to about 4. Preferred values of k are
2, 3, and 4. RZ is -
NH- thereby forming a urethane amide linkage when said RZ comprising T units
react with the
backbone nitrogens of the PA units. The value of the index j is independently
0 or 1. The
presence of RZ units can result, for example, from the use of diisocyanates as
crosslinking agents.
Non-limiting examples of dibasic acids which are used as a source for T units
in the above
formula include succinic acid, malefic acid, adipic acid, glutaric acid,
suberic acid, sebacic acid,
and terephthalic acid. However, the formulator is not limited to crosslinking
T units deriving
from dibasic acids, for example, tribasic crosslinking T units, inter alia,
citrate, may be used to
link the PA units of the present invention.
Examples of (PA)W(T)x compounds according to the present invention are
obtained by
condensation of dicarboxylic acids inter alia succinic acid, malefic acid,
adipic acid, terephthalic
acid, with polyalkylene polyamines inter alia diethylenetriamine,
triethylenetetramine,
dipropylenetriamine, tripropylenetetramine wherein the ratio of the
dicarboxylic acid to
polyalkyleneamine is from 1:0.8 to 1:1.5 moles, preferably a ratio of from
1:0.9 to 1:1.2 moles
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wherein the resulting crosslinked material has a viscosity in a 50% by weight,
aqueous solution
of more than 100 centipoise at 25 °C.
Non-amide Forming L Crosslinking Units
Another preferred embodiment of the polyamines of the present invention are
(PA)W(T)X
units which are further crosslinked by L units to form polyamido amines having
the formula
[(PA)W(T)x]Y[L]Z or are reacted with PA units to form non-amide polyamines
having the formula
(PA)W(L)Z.
The L units of the present invention are any unit which suitably crosslinks PA
units or
(PA)W(T)x units. Preferred L linking units comprise units which are derived
from the use of
epihalohydrins, preferably epichlorohydrin, as a crosslinking agent. The
epihalohydrins can be
used directly with the PA units or suitably combined with other crosslinking
adjuncts non-
limiting examples of which include alkyleneglycols, and polyalkylene
polyglycols inter alia
ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol,
dipropylene glycol,
polypropylene glycol, butylene glycol, hexanediol-1,6-glycerol, oligoglycerol,
pentaerythrites,
polyols which are obtained by the reduction of carbohydrates (sorbitol,
mannitol),
monosaccharides, disaccharides, oligosaccharides, polysaccharides, polyvinyl
alcohols, and
mixtures thereof.
For example, a suitable L unit is a dodecylene unit having the formula:
-(CHZ)iz-
wherein an equivalent of 1,12-dichlorododecane is reacted, for example, with a
suitable amount
of a PA unit to produce a polyamine which is crosslinked via dodecylene units.
For the purposes
of the present invention, L crosslinking units which comprise only carbon and
hydrogen are
considered to be "hydrocarbyl" L units. Preferred hydrocarbyl units are
polyalkylene units have
the formula:
- (CHZ)n-
wherein n is from 1 to about 50.
Hydrocarbyl L units may be derived from hydrocarbons having two units which
are
capable of reacting with the nitrogen of the PA units. Non-limiting examples
of precursors which
result in the formation of hydrocarbyl L units include 1,6-dibromohexane, 1,8-
ditosyloctane, and
1,14-dichlorotetradecane.
Further examples of preferred non-amide forming crosslinking L units are the
units
which derive from crosslinking units wherein epihalohydrin is used as the
connecting unit. For
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example, 1,12-dihydroxydodecane is reacted with epichlorohydrin to form the
bis-epoxide non-
amide forming L unit precursor having the formula:
OI>-CHZO-(CH2O2-OCHZ--<IO
which when reacted with one or more PA units or (PA)W(T)X units results in an
L crosslinking
unit having the formula:
CHZ-CH-CH20-(CHZ)iz-OCHZ- i H-CH2-
OH OH
however, it is not necessary to pre-form and isolate the bis-epoxide, instead
the crosslinking unit
precursor may be formed in situ by reaction of 1,12-dihydroxydodecane or other
suitable
precursor unit with epihalohydrin in the presence of grafted or ungrafted PA
units or (PA)W(T)X
units.
Other crosslinking L units which utilize one or more epihalohydrin connecting
units
include polyalkyleneoxy L units having the formula:
-CHZ- i H-CHZ O(R10)~(R20)y-CHI- i H-CHZ
OH OH
wherein R' is ethylene, RZ is 1,2-propylene, x is from 0 to 100 and y is from
0 to 100.
Another preferred unit which can comprise an L unit and which can be suitably
combined with
epihalohydrin connecting units include polyhydroxy units having the formula:
OH
CHZ CH-CH2-O(CHZ)t(CH)u0-CHZ i H-CHZ-
OH OH
wherein the index t is from at least 2 to about 20 and the index a is from 1
to about 6. The
formulator may also combine units to form hybrid L crosslinking units, for
example, units having
the formula:
OH
CHZ CH-CHZ O(CH2)t(CH)"O O(R~O)X(R20)y CHZ- i H-CHZ
OH W yL OH
wherein the indexes w and y are each independently from 1 to 50, z is units
are present in a
sufficient to suitably connect the polyhydroxy units and the polyalkyleneoxy
units into the
backbone without the formation of ether linkages.
11
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The following is an example of an L linking group which comprises both a
polyalkyleneoxy and a polyhydroxy unit.
OH CHzOH
-CHZCHCHZ-OCHZCHCHCHCHO-CHZCHCHZ-O(CHzCH20)4-CH2CHCH~-
OH OH OH OH
A further example of a preferred crosslinking L units are units which
comprises at least
two aziridine groups as connecting groups, for example an L unit having the
formula:
O O
C N-CHZCH2-NH---C-(CH~o-~-C-NH-CH2CH2-N
which can be used to Link two (PA)W units, two (PA)W(T)x units, or mixtures
thereof.
The polyamines of the present invention may have varying final compositions,
for
example, (PA)W(T)X, [(PA)W(T)%]Y[L]Z, [(PA)]WjL]~, and mixtures thereof,
wherein each PA unit
may be grafted or ungrafted. The indices w and x have values such that the
ratio of w to x is
from 0.8 : 1 to 1.5 : 1; y and z have values such that said polyamido compound
comprises from
about 0.3 to 2 parts by weight of said 1:., unit. 1n the cases wherein no
crosslinking takes place the
indices w and y will be equal to 1 and x and z will be equal to 0. In the case
wherein no
crosslinking occurs using L units, the index y is equal to 1 and z is equal to
0. In the case
wherein no crosslinking occurs using 'T units, the indices w and y are equal
to I and x is equal to
0.
An preferred embodiment of the present invention which comprises PA units, T
units,
and L units includes the reaction product of:
a} 1 part by weight, of a polyamine obtained by condensation of 1 mole of a
dicatbO~cylic acid with p~efaablyfrum 0.8 to 1.5 moles of a polyalkylene
polyamir~e
('Le.,di~hyle~~riam~e)totheexb~tw)~reinatleastaboutl0%ofthe~Iehydsare
unmodified by reaction with said dicarboxylic acid, then optionally reacting
the
obtained polyamidoamine condensation product with up to 8 ethyleneimine units
(i.e.,
grafting of the backbone using aziridine) per basic nitrogen atom; and
b) further reacting the product obtained in (a) with from 0.05 to 2 parts by
weight, preferably,
0.3 to 2 parts by weight, of an L units, inter alia the reaction product of a
polyalkylene oxide
having from 8 to 100 alkylene oxide units with epichlorohydrin at a
temperature of from about
20°C to about 100°C.
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A preferred embodiment of the present invention are the water-soluble
condensation
products which can be obtained by the reaction of:
a) polyalkyleneimines and polyalkyleneimines grafted with ethyleneimines, and
mixtures thereof; with
b) at least bifunctional halogen-free cross-linking agents, said agents
selected from
the group consisting of:
i) ethylene carbonate, propylene carbonate, urea, and mixtures thereof;
ii) mono-carboxylic acids comprising one olefin moiety inter alia acrylic
acid, methacrylic acid, crotonic acid; and the esters, amides, and
anhydrides thereof; polycarboxylic acids inter alia oxalic acid, succinic
acid, tartaric acid, itaconic acid, malefic acid; and the esters, amides, and
anhydrides thereof;
iii) reaction products of polyetherdiamines, alkylenediamines, polyalkylene-
diamines, and mixtures thereof, with mono-carboxylic acids comprising
one olefin moiety wherein the resulting polyamine comprises a
functional units which is selected from the group consisting of at least
two ethylenically unsaturated double bonds, carbonamide, carboxyl
group, ester group, and mixtures thereof;
iv) at least two aziridine group-containing reaction products of dicarboxylic
acid esters with ethyleneimine and mixtures of the cross-linking agents.
However, prior to reaction of (PA)W(T)X units formed herein above, the
(PA)W(T)X
polyamine compound may be partially amidated ("capped" as described herein
above) by
treatment with a mono carboxylic acid or the esters of mono carboxylic acids.
The formulator
may vary the degree to which the backbone nitrogens are amidated according to
the desired
properties of the final Fabric Enhancement Polymer. Non-limiting examples of
suitable mono-
carboxylic acids include formic acid, acetic acid, propionic acid, benzoic
acid, salicylic acid,
lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic
acid, and mixtures
thereof.
The high molecular weight modified polyamine condensation products of the
present
invention (also referred to herein as "resins") are preferably formed from the
reaction of one or
more grafted, cross-linked polyethyleneimines and one or more polyethylene
and/or
polypropylene glycol copolymers, wherein the resulting crosslinked modified
polyamines (resins)
have a final viscosity of more than or equal to 300 mPa-sec., preferably from
400 to 2,500 mPa-
13
CA 02377017 2004-07-14
sec. when measured at 20° C in a 20% aqueous solution. The modified
polyamine compounds of
the present invention are suitably described in U.S. 3,642,572 Eadres et al.,
issued February 15,
1972, U.S. 4,144,123 Scharf et aL, issued March 13, 1979 and U.S. 4,371;674
Hertel et al., issued
February 1, 1983, NE 6,612,293, DT 1,946,471, DT 36386, DT 733,973, DE
1,771,814 .
Transition Metal-Comprisin~DY,e Protection System
The transition metal-comprising dye protection system of the present invention
prevents
the loss of color from fabric due to the chelation of heavy metal ions which
comprise fabric dyes
by laundry composition ingredients. The fabric care and laundry detergent
compositions of the
present invention comprise from about 0.01%, preferably from about 0.1%, more
preferably from
0,25%, most preferably from about 0.5% to about 20%, preferably to about 10%,
more preferably
to about 5% by weight, of a transition metal-comprising dye protection system.
The transition metal-comprising dye protection agents are preferably oligomers
which are
formed from the reaction of one or more substituted of unsubstituted
polymerizable imidazoles
with an epihalohydrin crosslinking agent, preferably epichlorohydrin.
The oligomers are preferably formed from the reaction of:
i) 1 part by weight of an epihalohydrin; and
ii) from 0.5, preferably from 0.75, more preferably from 1 to 2, preferably to
about
I .7 parts by weight, of a substituted or unsubstituted imidazole. Most
preferred is 1:4 parts by
weight, of a substituted or unsubstituted imidazole.
For the purposes of the present invention the term "substituted imidazole" is
defined as
"an imidazole which has the hydrogen atom at the number 2-carbon atom
substituted by a C,-C,s
alkyl unit". The imidazoles suitable for use in forming the oligomers of the
present invention
have the fonmula:
HN~N
IYR
wherein R is hydrogen, C,-C,8 alkyl, and mixtures thereof; preferably hydrogen
or C~-Ca alkyl;
more preferably hydrogen or C,-C4 alkyl; most preferably hydrogen. The
imidazoles may be as
the free compounds or the salts thereof.
Once formed, the oligomers have the formula:
14
CA 02377017 2004-07-14
OH ~ OH n
N~N N' / N N~N n X -
Y'R YIR ~~%'R
n
wherein R is defined herein above and X is a water soluble anion, preferably X
is derived from
the leaving group of the epihalohydrin, inter alia, chlorine; the index n has
a value such that the average
molecular weight of said oligomer admixture is from 500 daltons to 5000
daltons.
A further example of materials suitable for use in the transition metal-
comprising dye
protection system of the present invention are gallic acid comprising resins,
for example, gallate
ester resins derived from reducing or non-reducing sugars, inter alia, tannic
acid. However,
tannins derived from flavanol resins, are also as suitable for use as
transition metal-comprising
dye protection agents.
FABRIC CARE COMPOSITIONS
The fabric care compositions of the present invention comprise:
a) from about 0.01 % by weight, of a fabric enhancement system, said fabric
enhancement system comprising one or more modified poiyamine compounds,
said modified polyamine compounds are selected from:
i) (PA)W(T)x;
ii) (PA)W(L)Z;
iii) L(PA)w('r)x)yLLIZ~ and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
arid
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8 : 1 to 1.5 : 1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from about 0.05 to about 2
parts by weight of said L unit; for compounds of type (iii) the indices y and
z
have values such that said modified polyamine compound comprises from about
0.05 to about 2 parts by weight of said L unit;
CA 02377017 2001-12-11
WO 01/00767 PCT/US00/17649
b) from about 0.01% by weight, of a transition metal-comprising dye protection
system, said dye protection system comprising one or more oligomers formed
from the reaction of:
i) 1 part by weight of an epihalohydrin; and
ii) from 0.5 to 2 parts by weight of a substituted or unsubstituted imidazole
c) optionally from about 1 %, preferably from about 10%, more preferably from
about 20% to about 80%, preferably to about 60%, more preferably to about 45%
by weight, of a fabric softening active;
d) optionally less than about 15% by weight, of a principal solvent,
preferably said
principal solvent has a ClogP of from about 0.15 to about 1;
e) optionally from about 0.001% to about 90% by weight, of one or more dye
fixing
agents;
f) optionally from about 0.01 % to about 50% by weight, of one or more
cellulose
reactive dye fixing agents;
g) optionally from about 0.01% to about 15% by weight, of a chlorine
scavenger;
h) optionally about 0.005% to about 1% by weight, of one or more crystal
growth
inhibitors;
i) optionally from about 0.01 % to about 20% by weight, of a fabric abrasion
reducing polymer;
j) optionally from about 1% to about 12% by weight, of one or more liquid
carriers;
k) optionally from about 0.001 % to about 1 % by weight, of an enzyme;
1) optionally from about 0.01% to about 8% by weight, of a polyolefin emulsion
or
suspension;
m) optionally from about 0.01% to about 0.2% by weight, of a stabilizer;
n) optionally from about 1% to about 80% by weight, of a fabric softening
active;
o) optionally from about 0.5% to about 10% by weight, of a cationic nitrogen
compound; and
p) the balance carrier and adjunct ingredients.
LAUNDRY DETERGENT COMPOSITIONS
The laundry detergent compositions of the present invention take the form
which
comprises:
16
CA 02377017 2004-07-14
a) from about 0.01 % by weight, of a fabric enhancement system, said fabric
enhancement system comprising one or more modified polyamine compounds,
said modified polyamine compounds are selected from:
i) (PA)W(T)x;
ii) (PA)W(L)Z;
iii) ~(PA)W(T)Xl~[LIZ; and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8 : 1 to 1.5 : 1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from about 0.05, preferably
from about 0.3 to 2 parts by weight of said L unit; for compounds of type
(iii) the
indices y and z have values such that said modified polyamine compound
comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of
said
L unit;
b) from about 0.01% by weight, of a detersive surfactant selected from the
group
consisting of anionic, cationic, nonionic, zwitterionic, ampholytic
surfactants,
and mixtures thereof; and
c) from 0.01% by weight, of a transition metal-comprising dye protection
system, said dye
protection system comprising one or more oligomers formed from the reaction
of:
i) 1 part by weight of an epihalohydrin; and
ii) from 0.5 to 2 parts by weight of an unsubstituted imidazole or an
imidazole
substituted at the number 2-carbon atom by a Cl-C1$ alkyl group; and
d) the balance carriers and adjunct ingredients, wherein said adjunct
ingredients are
selected from the group consisting of builders, optical brighteners, soil
release
polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes,
perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers,
fabric
conditioners, hydrolyzable surfactants, preservatives, anti-oxidants,
chelants,
stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides,
fungicides,
anti- corrosion agents, and mixtures thereof.
SURFACTANT SYSTEM
The laundry detergent compositions of the present invention may comprise at
least about
0.01 % by weight, preferably from about 0.1 % to about 60%, preferably to
about 30% by weight,
of a detersive surfactant system, said system is comprised of one or more
category of surfactants
depending upon the embodiment, said categories of surfactants are selected
from the group
consisting of anionic, cationic, nonionic, zwitterionic, ampholytic
surfactants, and mixtures
17
CA 02377017 2004-07-14
thereof. Within each category of surfactant, more than one type of surfactant
of surfactant can be
selected. For example, preferably the solid (i.e. granular) and viscous semi-
solid (i.e. gelatinous,
pastes, etc.) systems of the present invention, surfactant is preferably
present to the extent of
from about 0.1% to 60 %, preferably to about 30% by weight of the composition.
Nonlimiting examples of surfactants useful herein include:
a) C"-C,8 alkyl benzene sulfonates (LAS);
b) C,o-CZ° primary, branched-chain and random alkyl sulfates (AS);
c) C,o-C,B secondary (2,3) alkyl sulfates having the formula:
OSO~ M~ OS03- M'
CH3(CT-TZ)xWH)CH3 or Cg3(CH2)y(CH)CH2CH3
wherein x and (y -'~ 1 ) are integers of at least about 7, preferably at least
about 9; said
surfactants disclosed in U.S. 3,234,258 Morris, issued February 8, 1966; U.S.
5,075,041
Lutz, issued December 24, 1991; U.S. 5,349,101 Lutz et al., issued September
20, 1994;
and U.S. 5,389,277 Prieto, issued February 14, 1995 .
d) C,o-C~a alkyl alkoxy sulfates (AExS) wherein preferably x is from 1-7;
e) C,o-C,e alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units;
fj C,z-C,$ alkyl ethoxylates, C6-C,~ alkyl phenol alkoxylates wherein the
alkoxylate units
are a mixture of ethyleneoxy and propyleneoxy units, C,z-C,8 alcohol and Cb-
C,Z alkyl
phenol condensates with ethylene oxidelpropylene oxide block polymers inter
alia
Pluronic~ ex BASF which are disclosed in U.S. 3,929,678 Laughlin et aL, issued
December 30, 1975 ;
g) Alkylpolysaccharides as disclosed in U.S. 4,565,647 Llenado, issued January
26, 1986 ;
h) Polyhydroxy fatty acid amides having the formula:
O R8
R~-C-N-Q
wherein R7 is C5-C31 alkyl; R8 is selected from the group consisting of
hydrogen, C1-
C4 alkyl, C1-C4 hydroxyalkyl, Q is a polyhydroxyalkyl moiety having a linear
alkyl
chain with at least 3 hydroxyls directly connected to the chain, or an
aIkoxylated
derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures
thereof;
18
CA 02377017 2004-07-14
preferred Q is derived from a reducing sugar in a reductive amination
reaction, more .
preferably Q is a glycityl moiety; Q is more preferably selected from the
group
consisting of -CH2(CHOH)nCH20H; -CH(CH20H)(CHOH)n_1CH20H, -
CH2(CHOH)2-(CHOR')(CHOH)CH20H, and alkoxylated derivatives thereof, wherein n
is an integer from 3 to 5, inclusive, and R' is hydrogen or a cyclic or
aliphatic
monosaccharide, which are described in U.S. 5,489,393 Connor et al., issued
February 6,
1996; and U.S. 5,45,982 Murch et al., issued October 3, 1995 ,
The laundry detergent compositions of the present invention can also comprise
from
about 0.001 % to about 100% of one or more (preferably a mixture of two or
more) mid-chain
branched surfactants, preferably mid-chain branched alkyl alkoxy alcohols
having the formula:
R R' Rz
CH3CHz(CHZ)",CH(CI-IZ)XCH(CH2)yCH(CHZ)z(EO/PO)i"OH
mid-chain branched alkyl sulfates having the formula:
R R' R2
a
CH3CH2(CHZ)~"CH(CHZ),~CH(CHZ)yCH(CHz)ZOS03M
and mid-chain branched alkyl alkoxy sulfates having the formula:
R R' RZ
CH3CH2(CHZ)v,CH(CHZ),~CH(CHZ)yCH(CHZ)Z(EO/PO)n,OS03M
wherein the total number of carbon atoms in the branched primary alkyl moiety
of these formulae
(including the R, R1, and R2 branching, but not including the carbon atoms
which comprise any
EO/PO alkoxy moiety) is from 34 to 20, and wherein further for this surfactant
mixture the
average total number of carbon atoms in the branched primary alkyl moieties
having the above
formula is within the range of greater than 14.5 to about 17.5 (preferably
from about 15 to about
17); R, R1, and R2 are each independently selected from hydrogen, C1-C3 alkyl,
and mixtures
thereof, preferably methyl; provided R, Rl, and R2 are not all hydrogen and,
when z is 1, at least
R or Rl is not hydrogen. M is a water soluble canon and may comprises more
than one type of
cation, for example, a mixture of sodium and potassium. The index w is an
integer from 0 to 13;
x is an integer from O to 13; y is an integer from 0 to 13; z is an integer of
at least l; provided w +
x + y + z is from 8 to 14. EO and PO represent ethyleneoxy units and
propyleneoxy units having
the formula:
19
CA 02377017 2001-12-11
WO 01/00767 PCT/US00/17649
H3 I H3
-CHCHZO- or -CHZCHO
respectively, however, other alkoxy units inter alia 1,3-propyleneoxy, butoxy,
and mixtures
thereof are suitable as alkoxy units appended to the mid-chain branched alkyl
moieties.
The mid-chain branched surfactants are preferably mixtures which comprise a
surfactant
system. Therefore, when the surfactant system comprises an alkoxylated
surfactant, the index m
indicates the average degree of alkoxylation within the mixture of
surfactants. As such, the index
m is at least about 0.01, preferably within the range of from about 0.1, more
preferably from
about 0.5, most preferably from about 1 to about 30, preferably to about 10,
more preferably to
about 5. When considering a mid-chain branched surfactant system which
comprises only
alkoxylated surfactants, the value of the index m represents a distribution of
the average degree
of alkoxylation corresponding to m, or it may be a single specific chain with
alkoxylation (e.g.,
ethoxylation and/or propoxylation) of exactly the number of units
corresponding to m.
The preferred mid-chain branched surfactants of the present invention which
are suitable
for use in the surfactant systems of the present invention have the formula:
i H3
CH3(CHZ)aCH(CHZ)bCHz(EO/PO)r"OS03M
or the formula:
I H3 CH3
CH3(CHZ)dCH(CH2)eCHCH2(EO/PO)i"OS03M
wherein a, b, d, and a are integers such that a + b is from 10 to 16 and d + a
is from 8 to 14; M is
selected from sodium, potassium, magnesium, ammonium and substituted ammonium,
and
mixtures thereof.
The surfactant systems of the present invention which comprise mid-chain
branched
surfactants are preferably formulated in two embodiments. A first preferred
embodiment
comprises mid-chain branched surfactants which are formed from a feedstock
which comprises
25% or less of mid-chain branched alkyl units. Therefore, prior to admixture
with any other
conventional surfactants, the mid-chain branched surfactant component will
comprise 25% or
less of surfactant molecules which are non-linear surfactants.
A second preferred embodiment comprises mid-chain branched surfactants which
are
formed from a feedstock which comprises from about 25% to about 70% of mid-
chain branched
alkyl units. Therefore, prior to admixture with any other conventional
surfactants, the mid-chain
CA 02377017 2001-12-11
WO 01/00767 PCT/US00/17649
branched surfactant component will comprise from about 25% to about 70%
surfactant molecules
which are non-linear surfactants.
The surfactant systems of the laundry detergent compositions of the present
invention
can also comprise from about 0.001%, preferably from about 1%, more preferably
from about
S%, most preferably from about 10% to about 100%, preferably to about 60%,
more preferably to
about 30% by weight, of the surfactant system, of one or more (preferably a
mixture of two or
more) mid-chain branched alkyl arylsulfonate surfactants, preferably
surfactants wherein the aryl
unit is a benzene ring having the formula:
R1RZL R3
CM q+~b
S03
wherein L is an acyclic hydrocarbyl moiety comprising from 6 to 18 carbon
atoms; R', R2, and R3
are each independently hydrogen or C,-C3 alkyl, provided R' and Rz are not
attached at the
terminus of the L unit; M is a water soluble cation having charge q wherein a
and b are taken
together to satisfy charge neutrality.
ADJUNCT INGREDIENTS
The following are non-limiting examples of adjunct ingredients useful in the
laundry
compositions of the present invention, said adjunct ingredients include
cationic nitrogen
compounds, builders, optical brighteners, soil release polymers, dye transfer
agents, dispersents,
enzymes, suds suppressers, dyes, perfumes, colorants, filler salts,
hydrotropes, photoactivators,
fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives,
anti-oxidants, chelants,
stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides,
fungicides, anti corrosion
agents, and mixtures thereof.
Cationic Nitrogen Compounds - The fabric enhancement compositions of the
present
invention may optionally comprise from about 0.5%, preferably from about 1% to
about 10%,
preferably to about 5% by weight, of one or more cationic nitrogen containing
compound,
preferably a cationic compound having the formula:
CR-N(RI)3~ X
wherein R is C1o-C~8 alkyl, each R' is independently C,-C4 alkyl, X is a water
soluble anion;
preferably R is C,2-C,4, preferably R' is methyl. Preferred X is halogen, more
preferably
21
CA 02377017 2004-07-14
chlorine.
Non-limiting examples of preferred cationic nitrogen compounds are N,N-
dimethyl-{2-
hydroxyethyl)-N-dodecyl ammonium bromide, N,N-dimethyl-(2-hydroxyethyl)-N-
tetradecyl
ammonium bromide. Suitable cationic nitrogen compounds are available ex Akzo
under the
trademarks Ethomeen T115~, Secomine TAIS~, and Ethoduomeen T/20~.
Builders - The laundry detergent compositions of the present invention
preferably
comprise one or more detergent builders or builder systems. When present, the
compositions
will typically comprise at least about 1% builder, preferably from about 5%,
more preferably
from about 10% to about 80%, preferably to about 50%, more preferably to about
30% by
weight, of detergent builder.
The level of builder can vary widely depending upon the end use of the
composition and
its desired physical form. When present, the compositions will typically
comprise at least about
1% builder. Formulations typically comprise from about 5% to about 50%, more
typically about
5% to about 30%, by weight, of detergent builder. Granular formulations
typically comprise
from about 10% to about 80%, more typically from about 15% to about 50% by
weight, of the
detergent builder. Lower or higher levels of builder, however, are not meant
to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the alkali
metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by
the
tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates,
phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and
aluminosiiicates. However, non-phosphate builders are required in some
locales. Importantly,
the compositions herein function surprisingly well even in the presence of the
so-called "weak"
builders {as compared with phosphates) such as citrate, or in the so-called
"underbuilt" situation
that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly
those having a
Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the
layered sodium
silicates described in U.S. 4,664,839 Rieck, issued May 12, 198?. NaSKS-6 is
the trademark for
a crystalline layered silicate marketed by Hoechst (commonly abbreviated
herein as "SKS-6").
Unlike zeolite builders, the Na SKS-6 silicate builder does not contain
aluminum. NaSKS-6 has
the delta-Na2Si05 morphology form of layered silicate. It can be prepared by
methods such as
those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly
preferred
layered silicate for use herein, but other such layered silicates, such as
those having the general
formula NaMSix02x+1 ~yH20 wherein M is sodium or hydrogen, x is a number from
1.9 to 4,
preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
Various other
22
CA 02377017 2004-07-14
TM TM ,~,M
layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the
alpha, beta
and gamma forms. As noted above, the delta-Na2Si05 (NaSKS-6 form) is most
preferred for use
herein. Other silicates may also be useful such as for example magnesium
silicate, which can
serve as a crispening agent in granular formulations, as a stabilizing agent
for oxygen bleaches,
and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as
disclosed in German Patent Application No:2,321,001 published on November 15,
1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders
are of great importance in most currently marketed heavy duty granular
detergent compositions,
and can also be a significant builder ingredient in liquid detergent
formulations. Aluminosilicate
builders include those having the empirical formula:
[Mz(zA102)y] ~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0 to
about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring
aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange
materials is disclosed in U.S. 3,985,669, Krummel et al, issued October 12,
1976. Preferred
synthetic crystalline aluminosilicate ion exchange materials useful herein are
available under the
designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an
especially preferred
embodiment, the crystalline aluminosilicate ion exchange material has the
formula:
Nal2L(A102)12(Si02)12~'~20
wherein x is from about 20 to about 30, especially about 27. This material is
known as Zeolite
A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the
aluminosilicate has
a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but
are not restricted to, a wide variety of polycarboxylate compounds. As used
herein, "poly-
carboxylate" refers to compounds having a plurality of carboxylate groups,
preferably at least 3
carboxylates. Polycarboxylate builder can generally be added to the
composition in acid form,
but can also be added in the form of a neutralized salt. When utilized in salt
form, alkali metals,
such as sodium, potassium, and lithium, or alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are a variety of categories of
useful mate-
rials. One important category of polycarboxylate builders encompasses the
ether poIycarboxy-
lates, including oxydisuccinate, as disclosed in U.S. 3,128,287 Berg, issued
April 7, 1964, and
U.S. 3,635,830 Lamberti et al., issued January 18, 1972. See also "TMS/TDS"
builders of U.S.
23
CA 02377017 2004-07-14
4,663,071 Bush et al., issued May 5, 1987. Suitable ether polycarboxylates
also include cyclic
compounds, particularly alicyclic compounds, such as those described in U.S.
3,923,679 Rapko,
issued December 2, 1975; U.S. 4,158,635 Crutchfield et al., issued 3une 19,
1979; U.S.
4,120,874 Crutchfield et al., issued October 17, 1978; and U.S. 4,102,903
Crutchfield et al.,
issued July 25, 1978.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers
of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy
benzene-2, 4, 6-
trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali
metal, ammonium and
substituted ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic acid and
nitr-ilotriacetic acid, as well as polycarboxylates such as mellitic acid,
succinic acid, oxy-
disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic
acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt), are
polycarboxylate builders of particular importance for heavy duty liquid
detergent formulations
due to their availability from renewable resources and their biodegradability.
Citrates can also
be used in granular compositions, especially in combination with zeolite
and/or layered silicate
builders. Oxydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-dicar-
boxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
4,566,984, Bush,
issued January 28, 1986. Useful succinic acid builders include the C5-C20
alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred compound of this
type is do-
decenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-
pentadecenylsuccinate,
and the like. Laurylsuccinates are the preferred builders of this group, and
are described in
European Patent Application 0,200,263, published November 5, 1986.
Other suitable polycarboxylat~es are disclosed in U.S. 4,144,226, Crutchfield
et al., issued
March 13, 1979 and in U.S. 3,308,06%, Diehl, issued March 7, 1967. See also
Diehl U.S. Patent
3,723,322.
Fatty acids, e.g., C12-Clg monocarboxylic acids, can also be incorporated into
the
compositions alone, or in combination with the aforesaid builders, especially
citrate andlor the
succinate builders, to provide additional builder activity. Such use of fatty
acids will generally
result in a diminution of sudsing, which should be taken into account by the
formulator.
In situations where phosphorus-based builders can be used, and especially in
the for-
mulation of bars used for hand-laundering operations, the various alkali metal
phosphates such as
the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium
orthophosphate
24
CA 02377017 2004-07-14
can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate
and other
known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030;
3,422,021; 3,400,148
and 3,422,137) can also be used.
Dis~ersants
A description of other suitable polyalkyleneimine dispersants which may be
optionally
combined with the bleach stable dispersants of the present invention can be
found in U.S.
4,597,898 Vander Meer, issued July l, 1986; European Patent Application
111,965 Oh and
Gosselink, published June 27, 1984; European Patent Application 111,984
Gosselink, published
June 27, 1984; European Patent Application 112,592 Gosselink, published July
4, 1984; U.S.
4,548,744 Connor, issued October 22, 1985; and U.S. 5,565,145 Watson et al.,
issued October 15,
1996. However, any suitable clay/soil dispersant or anti-redepostion agent can
be used in the laundry
compositions of the present invention.
In addition, polymeric dispersing agents which include polymeric
polycarboxylates and
polyethylene glycols, are suitable for use in the present invention. Polymeric
polycarboxylate
materials can be prepared by polymerizing or copolymerizing suitable
unsaturated monomers,
preferably in their acid form. Unsaturated monomeric acids that can be
polymerized to form
suitable polymeric polycarboxyiates include acrylic acid, malefic acid (or
malefic anhydride),
fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid
and methylenemalonic
acid. The presence in the polymeric polycarboxylates herein or monomeric
segments, containing
no carboxylate radicals such as vinylmethyl ether.. styrene, ethylene, etc. is
suitable provided that
such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such
acrylic acid-based polymers which are useful herein are the water-soluble
salts of polymerized
acrylic acid. The average molecular weight of such polymers in the acid form
preferably ranges
from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most
preferably from
about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can
include, for example,
the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of
this type are
known materials. Use of polyacrylates of this type in detergent compositions
has been disclosed,
for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of
the
dispersing/anti-redeposition agent. Such materials include the water-soluble
salts of copolymers
of acrylic acid and malefic acid. The average molecular weight of such
copolymers in the acid
form preferably ranges from about 2,000, preferably from about 5,000, more
preferably from
CA 02377017 2004-07-14
about 7,000 to 100,000, more preferably to 75,000, most preferably to 65,000.
The ratio of
acrylate to maleate segments in such copolymers will generally range from
about 30:1 to about
1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such
acrylic acid/maleic acid
copolymers can include, for example, the alkali metal, ammonium and
substituted ammonium
salts. Soluble acrylate/maleate copolymers of this type are known materials
which are described
in European Patent Application No. 66915, published December 15, 1982; as well
as in EP
193,360, published September 3, 1986, which also describes such polymers
comprising
hydroxypropylacrylate. Still other useful dispersing agents include the
maleic/acrylic/vinyl
alcohol terpolymers. Such materials are also disclosed in EP 193,360,
including, for example, the
45/45110 terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG
can exhibit dispersing agent performance as well as act as a clay soil removal-
antiredeposition
agent. Typical molecular weight ranges for these purposes range from about 500
to about
100,000, preferably from about 1,000 to about 50,000, more preferably from
about 1,500 to about
10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially
in
conjunction with zeolite builders. Dispersing agents such as polyaspartate
preferably have a
molecular weight (avg.) of about 10,000.
Soil Release Agents
The compositions according to the present invention may optionally comprise
one or
more soil release agents. If utilized, soil release agents will generally
comprise from about
0.01 %, preferably from about 0.1 %, more preferably from about 0.2% to about
10%, preferably
to about 5%, more preferably to about 3% by weight, of the composition.
Polymeric soil release
agents are characterized by having both hydrophilic segments, to hydrophilize
the surface of
hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to
deposit upon
hydrophobic fibers and remain adhered thereto through completion of the
laundry cycle and, thus,
serve as an anchor for the hydrophilic segments. This can enable stains
occuring subsequent to
treatment with the soil release agent to be more easily cleaned in later
washing procedures.
The following describe soil release polymers suitable
for use in the present invention. U.S. 5,728,671 Rohrbaugh et al., issued
March 17, 1998; U.S.
5,691,298 Gosselink et al., issued November 25, 1997; U.S. 5,599,782 Pan et
al., issued February
4, 1997; U.S. 5,415,807 Gosselink ei aT., issued May 16, 1995; U.S. 5,182,043
Morrall et al.,
issued January 26, 1993; U.S. 4,956,447 Gosselink et al., issued September 11,
1990; U.S.
26
CA 02377017 2004-07-14
4,976,879 Maldonado et al. issued December 11, 1990; U.S. 4,968,451 Scheibel
et al., issued
November 6, 1990; U.S. 4,925,577 Borcher, Sr. et al., issued May i5, 1990;
U.S. 4,861,512
Gosselink, issued August 29, 1989; U.S. 4,877,896 Maldonado et al., issued
October 31, 1989;
U.S. 4,771,730 Gosselink et al., issued October 27, 1987; U.S. 711,730
Gosselink et al., issued
December 8, 1987; U.S. 4,721,580 Gosselink issued January 26, 1988; U.S.
4,000,093 Nicol et
al., issued December 28, 1976; U.S. 3,959,230 Hayes, issued May 25, 1976; U.S.
3,893,929
Basadur, issued July 8, 1975; and European Patent Application 0 219 048,
published April 22,
1987 by Kud et al.
Further suitable soil release agents are described in U.S. 4,201,824 Voilland
et al.; U.S.
4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al.; U.S. 4,579,681 Ruppert
et al.; U.S.
4,220,918; U.S. 4,787,989; EP 279,134 A, 1988 to Rhone-Poulenc Chemie; EP
457,205 A to
BASF (1991); and DE 2,335,044 to Unilever N.V., 1974 .
As a non-limiting example, granular compositions are generally made by
combining base
granule ingredients, e.g., surfactants, builders, water, etc., as a slurry,
and spray drying the
resulting slurry to a low level of residual moisture (5-12%). The remaining
dry ingredients, e.g.,
granules of the polyalkyleneimine dispersant, can be admixed in granular
powder form with the
spray dried granules in a rotary mixing drum. The liquid ingredients, e.g.,
solutions of the
polyalkyleneimine dispersant, enzymes, binders and perfumes, can be sprayed
onto the resulting
granules to form the finished detergent composition. Granular compositions
according to the
present invention can also be in "compact form", i.e. they may have a
relatively higher density
than conventional granular detergents, i.e. from 550 to 950 gll. In such case,
the granular
detergent compositions according to the present invention will contain a lower
amount of
"inorganic filler salt", compared to conventional granular detergents; typical
filler salts are
alkaline earth metal salts of sulphates and chlorides, typically sodium
sulphate; "compact"
detergents typically comprise not more than 10% filler salt.
Liquid detergent compositions can be prepared by admixing the essential and
optional
ingredients thereof in any desired order to provide compositions containing
components in the
requisite concentrations. Liquid compositions according to the present
invention can also be in
"compact form", in such case, the liquid detergent compositions according to
the present
invention will contain a lower amount of water, compared to conventional
liquid detergents.
Addition of the polyalkyleneimine dispersant to liquid detergent or other
aqueous compositions
of this invention may be accomplished by simply mixing into the liquid
solutions the
polyalkyleneimine dispersant.
27
CA 02377017 2004-07-14
The compositions of the present invention can be suitably prepared by any
process
chosen by the formulator, non-limiting examples of which are described in U.S.
5,691,297
Nassano et al., issued November I 1, I 997; U.S. 5;574,005 Welch et al.,
issued November 12,
1996; U.S. 5,569,645 Dinniwell et al., issued October 29, 1996; U,S. 5,565,422
Del Greco et al.,
issued October I5, 1996; U.S. 5,516,448 Capeci et al., issued May 14, 1996;
U.S. 5,489,392
Capeci et al., issued February 6, 1996; U.S. 5,486,303 Capeci et al., issued
January 23, 1996.
1VIETHOD OF USE
The present invention further relates to a method for providing protection and
enhancement of fabric, said method comprising the step of contacting a fabric
with an aqueous
solution containing a least 50 ppm, preferably at least about 100 ppm, more
preferably at least
about 200 ppm, of a fabric care composition which comprises:
a) from 0.01 % by weight, of a detersive surfactant selected from the group
consisting of anionic, cationic, nonionic, zwitterionic, ampholytic
surfactants,
and mixtures thereof;
b) from about 0.01 % by weight, of a fabric enhancement system, said fabric
enhancement system comprising one or more modified polyamine compounds,
said modified polyamine compounds are selected from:
i) (PA)w(T)x>
ii) (PA)W(L)Z;
iii) I(PA)w(T)x~rfLlz~ and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyarnine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8 : 1 to 1.5 : I; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from about 0.05, preferably
from about 0.3 to 2 parts by weight of said L unit; for compounds of type
(iii) the
indices y and z have values such that said modified polyamine compound
comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of
said
L unit;
c) from about 0.01 % by weight, of a transition metal-comprising dye
protection
system, said dye protection system comprising one or more oligomers formed
from the reaction of:
i) 1 part by weight of an epihalohydrin; and
28
CA 02377017 2004-07-14
ii) from 0.5 to 2 parts by weight of a substituted or unsubstituted imidazole;
and
d) the balance carriers and adjunct ingredients.
Preferably the method of the present invention relates to a method for
providing
protection and enhancement of fabric, said method comprising the step of
contacting a fabric with
an aqueous solution containing a least 50 ppm, preferably at least about 100
ppm, more
preferably at least about 200 ppm, of a fabric care composition which
comprises:
a) from about 0.01 % by weight, of a fabric enhancement system, said fabric
enhancement system comprising one or more modified polyamine compounds,
said modified polyamine compounds are selected from:
i) (PA)w('r)~;
ii) (PA)W(L)Z;
iii) [(PA)W(T),~y[L]Z; and
iv) mixtures thexeof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8 : 1 to 1.5 : 1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from about 0.05 to about 2
parts by weight of said L unit; for compounds of type (iii) the indices y and
z
have values such that said modified polyamine compound comprises from about
0.05 to about 2 parts by weight of said L unit;
b) from about 0.01% by weight, of a transition metal-comprising dye protection
system, said dye protection system comprising one or more oligomers formed
from the reaction of:
i) 1 part by weight of an epihalohydrin; and
ii) from 0.5 to 2 parts by weight of a substituted or unsubstituted imidazole
c) optionally from about 1 %, preferably from about 10%, more preferably from
about 20% to about 80%, preferably to about 60%, more preferably to about 45%
by weight, of a fabric softening active;
d) optionally less than about IS% by weight, of a principal solvent,
preferably said
principal solvent has a ClogP of from about 0.15 to about 1;
29
CA 02377017 2004-07-14
e) optionally from about 0.001% to about 90% by weight, of one or more dye
fixing
agents;
f) optionally from about 0.01% to about 50% by weight, of one or more
cellulose
reactive dye fixing agents;
g) optionally from about 0.01% to about IS% by weight, of a chlorine
scavenger;
h) optionally about 0.005% to about 1% by weight, of one or more crystal
growth
inhibitors;
i) optionally from about 0.01% to about 20% by weight, of a fabric abrasion
reducing polymer;
j) optionally from about 1% to about 12% by weight, of one or more liquid
carriers;
k) optionally from about 0.001% to about 1 % by weight, of an enzyme;
1) optionally from about 0.01% to about 8% by weight. of a polyolefin emulsion
or
suspension;
m) optionally from about 0.01% to about 0.2% by weight, of a stabilizer;
n) optionally from about 1% to about 80% by weight, of a fabric softening
active;
o) optionally from about 0.5% to about 10% by weight, of a cationic nitrogen
compound; and
p) the balance carrier and adjunct ingredients.
The fabric care compositions according to the present invention can be in
liquid, paste,
laundry bar, or granular form, Such compositions can be prepared by combining
the essential
and optional components in the requisite concentrations in any suitable order
and by any
conventional means.
The following are examples of fabric care compositions which comprise a fabric
enhancement system of the present invention.
TABLEI
weight
Ingredients r 1 Z 3
Dye fixative' S.0 ~.4 2.4
BayhibitTM AMZ 1.0 1.0 1.0
C~~ Trimethyl ammonium chloride2.0 2.0 2.0
Fabric enhancement polyamine3.0 3.0 3.0
3
Fabric enhancement polyamine3.5 ~ 3.5 3.5
" ~ ~
CA 02377017 2004-07-14
Heavy metal dye transfer 3.0 3.0 1.0
inhibitor 5
Water and minors 6 ~~ balance balance balance
1, Dye fixing agent ex Clariant under the trademark Cartafix CB'~.
2. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
3. Lupasoh SKA ex BASF.
4. Luviskol~' K85 ex BASF.
5. Oligomeric polyamine formed from the condensation of 1 part epichlorohydrin
and 1.4 parts
imidazole and comprising about 94% oligomer and about 6% imidazole, said
oligomer
having an average molecular weight of about 2000 daltons.
G. All formulations have a pH of from 5 to 5.5 and a viscosity of 100-180 cps.
TABLE II
weight
Ingredients 4 5 6
Dye fixative ' 2.4 4.0 5.0
Bayhibit AM'' 0.5 1.0 0.5
C,~ Trimethyl ammonium chloride2.0 3.0 5.0
Fabric enhancement polyamine I .0 3.0 5.0
3
Fabric enhancement polyamine 3.5 4.0 6.0
4
Heavy metal dye transfer inhibitor0.1 3.0 2.0
Water and minors balance balance balance
1. Dye fixing agent ex Clariant under the trademark Lartatix c:~i°.
2. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
3. Lupasoh SKA ex BASF.
4. Luviskol~ K85 ex BASF.
5. Oligomeric polyamine formed from the condensation of 1 part epichlorohydrin
and 1.4 parts
imidazole and comprising about 94% oligomer and about 6% imidazoie, said
oligomer
having an average molecular weight of about 2000 daltons.
6. All formulations have a pH of from 5 to ~.S and a viscosity of 100-180 cps.
The following is an example of laundry detergent compositions which comprise a
fabric
enhancement system of the present invention.
31
CA 02377017 2004-07-14
TABLE III
weight
Ingredients 7 8 9 10
Polyhydroxy coco-fatty acid 2.50 4.00 4.50 --
amide
NEODOLTM 24-7' -- 4.50 -- --
NEODOL 23-9 ~ 0.63 -- 4.50 2.00
C25 Alkyl ethoxylate sulphate20.15 4.40 5.50 20.50
C25 Alkyl sulfate -- 14.00 15.00 --
C 11.8 linear alkylbenzene -- -- -- 6.00
sulfonate
Cg_10 -Amidopropyl Amine -- 1.30 -- --
C 10 -Amidopropyl Amine 0.50 -- - 1.50
Citric acid 3.00 2.00 3.00 2.50
C12-18 fatty acid 2.00 6.50 5.00 5.00
Rapeseed fatty acid -- 4.10 -- 6.50
Ethanol 3.36 1.53 5.60 0.50
Propanediol 7.40 9.20 6.22 4.00
Monoethanolamine 1.00 7.90 8.68 0.50
Sodium hydroxide 2.75 I .30 0.75 4.40
Sodium p-toluene sulfonate 2.25 - 1.90
BoraxBoric acid 2.50 2.00 3.50 2.50
Protease 0.88 0.74 I.50 0.88
LipolaseTM4 -- 0.12 0.18 --
DuramylTMS 0.15 0.11 - 0.15
CAREZYMETM 0.053 0.028 0.080 0.053
Dispersant b 0.60 0.70 1.50 0.60
Ethoxylated polyalkyleneimine1.20 0.70 1.50 1.20
~
Optical Brightener 0.13 0.15 0.30 0.15
Fabric enhancement polyamine5.00 1.00 -- --
g
Fabric enhancement polyamine-- -- 0.25 0.50
y
Dye protection system 1 ~ 0.75 0.25 1.00 0.75
Suds suppressor 0.12 0.28 0.12 0.12
Minors, aesthetics, stabilizers,~ balancebalancebalancebalance
water
1. CI2-C14 alkyl ethoxylate as sold by Shell Oil Co.
32
CA 02377017 2001-12-11
WO 01/00767 PCT/US00/17649
2. C12-C13 alkyl ethoxylate as sold by Shell Oil Co.
3. Protease B variant of BPN' wherein Tyr 17 is replaced with Leu.
4. Derived from Humicola lanuginosa and commercially available from Novo.
S. Disclosed in WO 9510603 A and available from Novo.
6. Hydrophilic dispersant PEI 189 E,5-E,g according to U.S.4,597,898, Vander
Meer, issued
July 1, 1986.
7. Polyalkyleneimine dispersant PEI 600 E2o.
8. Lupasol~ SK ex BASF.
9. Lupasol~ SKA ex BASF.
10. Oligomeric polyamine formed from the condensation of 1 part
epichlorohydrin and 1.4 parts
imidazole and comprising about 94% oligomer and about 6% imidazole, said
oligomer
having an average molecular weight of about 2000 daltons.
33
