Note: Descriptions are shown in the official language in which they were submitted.
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WO 97/42291 PCT/US97/07056
DETERGENT COMPOSITIONS COMPRISING MODIFIED POLYAM1NES AS DYE TRANSFER
1NH1BTPORS
FIELD OF THE INVENTION
The present invention relates to laundry detergent compositions which can be
used to wash dye-containing colored fabrics and which contain bleach stable,
modified
polyamine additives that inhibit dye transfer between fabrics during
laundering
operations. The present invention also relates to methods for laundering dye-
containing
colored fabrics in aqueous solutions formed from laundry compositions
comprising the
fabric surface modifying polyamines of the present invention.
BACKGROUND OF THE INVENTION
One of the most persistent and troublesome problem-causing events which arises
during modern fabric laundering operations is the tendency of some colored
fabrics to
release dye into the laundering solutions. Such dye is then frequently
transferred onto
other fabrics being washed in the same aqueous washing solution.
One approach in attacking the dye transfer problem in laundering operations
has
been to complex or adsorb the fugitive dyes washed out of dyed fabrics before
such dyes
have the opportunity to become attached to other articles in the wash
solution. Certain
polymeric materials, for instance, have been suggested as being useful laundry
detergent
additives which can complex or adsorb fugitive dyes in aqueous washing
solutions. For
example Abel, U.S. Patent 4,545,919; Issued October 8, 1985 describes the use
of
carboxyl-containing polymers in fabric laundering operations. Waldhoff et al;
DE-A-2
814 329, Published October 1 l, 1979 discloses the use of N-vinyl-oxazolidone
polymers
and Cracco et al; GB 1,348,212; Published March 13, 1974 discloses the use of
15-35%
of a copolymer of polyvinylpyrrolidone and acrylic acid nitrite or malefic
anhydride
within a washing powder. Clements et al; EP-A-265 257; Published April 27,
1988
describes detergent compositions comprising an alkali-metal carboxy-metal
carboxymethylcellulose, a vinylpyrrolidone polymer and a polycarboxylate
polymer.
Notwithstanding prior art attempts to solve the dye transfer problem during
fabric
laundering, there is a continuing need to identify detergent compositions,
detergent
composition additives and fabric laundering methods which are especially
effective
against dye transfer. Accordingly, it is an object of the present invention to
provide
detergent compositions which contain selected ingredients that eliminate or at
least
minimize dye transfer between fabrics when such compositions are used in
fabric
laundering operations.
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WO 97/42291 PCT/US97/07056
2
It has now been surprisingly discovered that a combination of certain dye
transfer
inhibitors and certain modified polyamines act together to provide an
increased dye
transfer inhibition benefit. This unexpected result has yielded compositions
that provide
this benefit to a wide range of fabric type, namely cotton, synthetic, and
synthetic-cotton
blended fabric.
The present process and compositions, because of the stability of the modified
polyamines disclosed herein toward bleaching agents, now provides this dye
transfer
inhibition to fabric articles in the presence of traditional bleaching agents.
The process or method of the present invention is equally effective when the
laundry detergent compositions disclosed herein are solid or liquid. The solid
laundry
detergents may be in the form of granules, flakes or laundry bars. The liquid
detergents
can have a wide range of viscosity and may include heavy concentrates,
pourable "ready"
detergents, or light duty fabric pre-treatments.
The modified polyamines disclosed in the present method are especially
compatible with other laundry detergent additives and adjuncts.
It is a further object of the present invention to provide such especially
effective
dye transfer-inhibiting detergent compositions in either granular or liquid
form.
It is a further object of the present invention to provide a method for
laundering
colored fabrics in aqueous washing solutions which are formed from the
detergent
compositions herein and which thereby contain materials that eliminate or at
least
minimize dye transfer between fabrics being washed therein.
BACKGROUND ART
In addition to the above cited art, the following disclose modified
polyamines;
U.S. Patent 4,548,744, Connor, issued October 22, 1985; U.S. Patent 4,597,898,
Vander
Meer, issued July 1, 1986; U.S. Patent 4,891,160, Vander Meer, issued January
2, 1990;
U.S. Patent 4,235,735, Marco, et al., issued November 25, 1980; WO 95/32272,
published November 30, 1995; U.K. Patent 1,537,288, published December 29,
1978;
U.K. Patent 1,498,520, published January 18, 1978; German Patent DE 28 29 022,
issued
January 10, 1980; Japanese Kokai JP 06313271, published April 27, 1994; and EP
634,486, published January 18, 1995.
SUMMARY OF THE INVENTION
The present invention relates to laundry detergent compositions which provide
especially effective inhibition of dye transfer between fabrics being
laundered in aqueous
washing solutions that are formed from these detergent compositions.
CA 02252941 2004-11-15
3
The laundry detergent compositions of the present invention comprise:
a) at least about 0.01% by weight, of a dye transfer inhibition agent;
b) at least about 0.1 % by weight, of a water-soluble or dispersible, modified
polyamine fabric surface rnodifjnng agent, said agent wising a polyarnir~e
bacltbone prior to rnodific~on
oo~sponding to the formula:
H
(HZN'RJn+1-(1'I'Rhn (1'1-RJn NHZ
having a modified polyamine formula V~~1)WmYnZ or a polyatnine backbone
prior to modification corresponding to the formula:
H I R
IHZN'RJn-k+t-[N-RJm (N-RJn-[N-R]k-NHZ
having a modified polyamine formula V~Mk+1)WmYnY~k~ ~~~ k is less than or
equal to n, said polyamine backbone prior to modification has a molecular
weight greater
than about 200 daitons, wherein
i) V units are terminal units having the formula:
+X
E-N-R- or E-N-R- or E-N-R-
E E E
ii) W units are backbone units having the formula:
E
X-
-N-R- or -N~ R- or -N-R-'
E E E
iii) Y units are branching units having the formula:
E O
X
-N-R_ or -N~ R- or -N-Rr
iv) Y~ units having the formula:
1
R
~_Rl-
and
CA 02252941 2004-11-15
4
v) Z units are terminal units having the formula:
E O
X-
_N-E or '-N~ E or -N-E
I i I
E E E
wherein backbone linking R units are selected from the group consisting of C2-
C 12
alkylene, C4-C 12 alkenylene, C3-C 12 hYdroXYalkYlene, C4-C 12 dihydroxy-
alkylene,
Cg-C12 dialkylaryler~, -(R1O~R1-, -(R10~R5(ORI~-, -(CH2CH(OR2~H20~z
-(Rlp~R1(OCH2CH(OR2~H2h,,r, -C(OxR4kC(O~, -CH2CH(OR2)CHZ- ;
wherein R1 is C2-C6 alkylene ; R2 is hydrogen, - (R1 OMB;
R3 is C1-C 1 g alkyl, C~-C12 aTYlaikYl, C7-C 12 ~kY1
substituted aryl, C6-C 12 aryl; R4 is C 1-C 12 alkylene. C ~-C I 2
alkenylene, Cg-C 12 arylalkylene, C6~C l p arylene; . - RS is C 1-C 12
alkylene, C3-C12 hY~xY-~kYlene. C4-C12 dihYdroxY-alkYler~, Cg~C12
dialkylaiylene, -C(O~, -C(O)NHR6IVHC(O)-, -RI(ORl) Y-, -C(OXR't)rC(O~,
-CH2CH(OH~H2-, -CH2CH(OH)CH20(R1 O)yRl-OCH2CH(OHxH2--
R6 is C2-C 12 alkylene or C6-C 12 arylene; E units are selected from the group
consisting of hydrogen, C1-C22 ~kYh C3-C22 ~kenyl, C~-C22 arylalkyl, C2-C22
hydroxyalkyl, -(CH2~C02M, -(CHZ)qS03M, -CH(CH2C02M)-C02M,
_ (CH2M, -(R O~B, -C(O)R3; B is hydrogen, C1-C6
alkyl, -(CH2)q-S03M, -(CH2~C02M, -(CH2)q(CHS03MxH2S03M, -(CH2)q-
(CHS02Ivl]ChI2SO3M, -(CH2~P03M, -P03M; - M is
hydrogen or a water soluble cation in sufFcient amount to satisfy charge
balance; X is a
water soh~ble anion; m has the value from 4 to about 400; n has the value from
0 to about
200; p:~irs the value from 1 to 6, q has the value from 0 to 6; r has the
value of 0 or 1; w
has the vttdue 0 or 1; x has the value from 1 to 100; y has the value from 0
to t 00; z has
the value of 0 or 1; wherein the polyamine comprises nitrogens totally or
partially oxidized
to N-oxides; and
d) the balance carrier and adjunct ingredients.
It is a further object of the present invention to provide a bleach stable
modified
polyamine dye transfer inhibitor and methods for preventing the transfer of
dyes from the
laundry liquor to tlu fabric being laundered.
All percentages, ratios and proportions herein are by weight, unless otherwise
specified. All tempaature$ are in degrees Celsius (o C) unless otherwise
specified. .
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WO 97/42291 PCT/US97/07056
DETAILED DESCRIPTION OF THE INVENTION
The laundry detergent compositions of the present invention comprise:
a) at least about 5% by weight, of a detersive surfactant;
b) at least about 0.01 % by weight, of a dye transfer inhibition agent;
c) at least about 0.1 % by weight, of a water-soluble or dispersible, modified
polyamine fabric surface modifying agent according to the present
invention; and
d) the balance carriers and adjunct ingredients.
Preferred laundry detergent compositions of the present invention comprise:
a) at least about 5% by weight, of an anionic detersive surfactant;
b) at least about 1 % by weight, of a nonionic detersive surfactant;
c) at least about 0.01 % by weight, of a dye transfer inhibition agent;
d) at least about 0.5% by weight, of a water-soluble or dispersible, modified
polyamine fabric surface modifying agent according to the present
invention; and
e) the balance carriers and adjunct ingredients.
Further preferred laundry detergent compositions of the present invention
comprise:
a) at least about 5% by weight, of an anionic detersive surfactant;
b) at least about 1 % by weight, of a nonionic detersive surfactant;
c) at least about 0.01 % by weight, of a dye transfer inhibition agent;
d) optionally at least about 1% by weight, of a bleach;
e) at least about 0.5 % by weight, of a water-soluble or dispersible, modified
polyamine fabric surface modifying agent according to the present
invention; and
f) the balance carriers and adjunct ingredients.
A more preferred laundry detergent compositions of the present invention
comprise:
a) at least about S% by weight, of an anionic detersive surfactant;
b) at least about 1 % by weight, of a nonionic detersive surfactant;
c) at least about 0.01 % by weight, of a dye transfer inhibition agent;
d) optionally at least about 1 % by weight, of a bleach;
e) at least about 0.1 % by weight, of a soil release polymer;
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WO 97/42291 PCT/US97/07056
6
f) at least about 0.5 % by weight, of a water-soluble or dispersible, modified
polyamine fabric surface modifying agent according to the present
invention; and
g) the balance Garners and adjunct ingredients.
A further more preferred laundry detergent compositions of the present
invention
comprise:
a) at least about 5% by weight, of an anionic detersive surfactant selected
from the group consisting of alkyl sulfate, alkyl alkoxy sulfate, and
mixtures thereof
b) at least about 5% by weight, of a nonionic detersive surfactant selected
from the group consisting of polyhydroxy fatty acid amides, alcohol
ethoxylates, and mixtures thereof;
c) at least about 0.01% by weight, of a dye transfer inhibition agent;
d) optionally at least about 1 % by weight, of a bleach;
e) at least about 0.5% by weight, of a water-soluble or dispersible, modified
polyamine fabric surface modifying agent according to the present
invention; and
the balance carriers and adjunct ingredients.
The preferred laundry detergent compositions of the present invention comprise
the following preferred materials.
Polymeric Die Transfer Inhibiting Agents
The detergent compositions herein must comprise from about 0.01 % to 10% by
weight of certain types of polymeric dye transfer inhibiting agents.
Preferably the
detergent compositions herein comprise from about 0.05% to 0.5% by weight of
these
polymeric dye transfer inhibiting materials.
The selected dye transfer inhibiting polymeric materials can be certain
polyamine
N-oxide polymers, certain copolymers of N-vinylpyrrolidone, N-vinylimidazole,
polyethoxylated urethanes, acrylamide containing polymers, polyamino acids,
and
combinations of these materials. Each of these polymer/copolymer types is
described in
greater detail as follows:
Polyamine N-oxide Polymers
The polyamine N-oxide polymers suitable for use herein contain units having
the
structural formula:
P
Ax
R
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WO 97/42291 PCT/US97/07056
7
wherein P is a polymerizable unit to which a N-O group can be attached or the
N-O
group can form part of the polymerizable unit or the N-O group can be attached
to both
units; A is one of the following structures:
II II -s~ -o- -
N-C - -C-O
x is 0 or 1; and, R comprises aliphatic, ethoxylated aliphatic, aromatic,
heterocyclic or
alicyclic groups or any combination thereof to which the nitrogen of the N-O
group can
be attached or the N-O group is part of these groups.
The N-O group can be represented by the following general structures:
O
O
(RJX- i -(R2h' =N-(RJx
(R3>Z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or,
combinations thereof; x, y and z are 0 or 1; and, the nitrogen of the N-O
group can be
attached or form part of any of the aforementioned groups. Further, the N-O
group can
be part of the polymerizable unit (P) or can be attached to the polymeric
backbone or a
combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerizable unit comprise polyamine N-oxides wherein R is selected from
aliphatic,
aromatic, alicyclic or heterocyclic groups. One class of such polyamine N-
oxides
comprises the group of polyamine N-oxides wherein the nitrogen of the N-O
group
forms part of the R group. Preferred polyamine N-oxides are those wherein R is
a
heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine,
piperidine and
derivatives thereof.
Another class of the polyamine N-oxides comprises the group of polyamine N-
oxides wherein the nitrogen of the N-O group is attached to the R-group. Other
suitable
polyamine N-oxides are the polyamine oxides in which the N-O group is attached
to the
polymerizable unit. A preferred class of these polyamine N-oxides are the
polyamine N-
oxides having the general formula presented above wherein R is an aromatic,
heterocyclic or an alicyclic group and the nitrogen of the N-O functional
group is part of
the R group. Examples of these classes are polyamine oxides wherein R is a
heterocyclic
compound such as pyridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having
the general formula presented above wherein R is an aromatic, heterocyclic or
alicyclic
group and the nitrogen of the N-O functional group is attached to the R
group(s).
CA 02252941 2003-12-17
Examples of these classes are polyamine oxides wherein R groups can be
aromatic such
as phenyl. Any polymer backbone can be used as long as the amine oxide polymer
formed is water-soluble and has dye transfer inhibiting properties. Examples
of suitable
polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers,
polyamide,
polyimides, polyacrylates and mixtures thereof.
The amine N-oxide polymers useful in the detergent compositions of the present
invention typically have a ratio of amine to the amine N-oxide of 10:1 to
1:1,000,000.
However, the number of amine oxide groups present in the polyamine oxide
polymer can
be varied by appropriate copolyrnerization or by an appropriate degree of N-
oxidation.
Preferably, the ratio of amine to amine N-oxide is from 3:1 to 1:1000000. The
polymers
useful in the detergent compositions of the present invention actually
encompass random
or block copolymers where one monomer type is an amine N-oxide and the other
monomer type is an N-oxide.
The amine oxide unit of the polyamine N-oxides has a pKa ~ 10, preferably pKa
7, more preferred pKa ~ 6. The poiyamine oxides can be obtained in almost any
degree of polymerization. The degree of polymerization is not critical
provided the
material has the desired water-solubility and dye-suspending power. Typically,
the
average molecular weight is within the range of 500 to 1,000,000; more
preferred 1,000
to 500,000; most preferred 5,000 to 100,000.
The most preferred polyamine N-oxide useful in the detergent compositions
herein is poly{4-vinylpyridine-N-oxide) which has an average molecular weight
of about
50,000 and an amine to amine N-oxide ratio of about 1:4. This preferred
material can be
abbreviated as "PVNO".
The polyamine N-oxides useful in the present invention can be synthesized by
polymerizing the amine monomer and oxidizing the resulting polymer with a
suitable
oxidizing agent or the amine oxide monomer may itself be polymerized to obtain
the
desired polyamine N-oxide. Such reaction schemes are well known and within the
scope
of those persons skilled in the art.
Copolymers of N-vi~rlpvrrolidone and N-vinvlimidazole
The detergent compositions of the present invention may also utilize a
copolymer
of N-vinylpyrrolidone and N-vinylimidazole (also abbreviated herein as
"PVPVI"). It
has been found that copolymers of N-vinylpyrrolidone and N-vinylimidazole can
provide
excellent dye transfer inhibiting performance when utilized in the
compositions of this
mvent~on.
In a preferred embodiment, the copolymer of N-vinylpyrrolidone and N-
vinylimidazoie polymers has an average molecular weight range from 5,000 to
CA 02252941 2003-12-17
9
1,000,000, more preferably from 5,000 to 200,000. A highly preferred copolymer
for
use in detergent compositions according to the present invention has an
average
molecular weight range from 5,000 to 50,000, more preferably from 8,000 to
30,000 and,
most preferably from 10,000 to 20,000. The average molecular weight range is
determined by light scattering as described in Barth J. H. G. and Mays J. W.
Chemical
Analysis Vol 113. "Modern Methods of Polymer Characterization" .
The copolymers of N-vinylpyrrolidone and N-vinylimidazole useful in the
present invention can have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from
1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1
to 0.4:1. It
should be understood that the copolymer of N-vinylpyrrolidone and N-
vinylimidazole
can be either linear or branched.
Po~ethoxylated Urethanes
Polyethoxylated urethanes which are known for use as associative thickeners in
latex compositions are condensation poiymers of polyether polyols and
isocyanates.
U.S. Patents 4,079,028 and 4,155,982, describe in detail these polyurethane
thickeners, which have been found useful as dye transfer agents
when formulated into the present invention in combination with the modified
poiyamines
described herein below.
The polyethoxylated urethane is prepared in a non-aqueous medium and is the
reaction product of at least reactants (a) and (c), but the polymer optionally
may include
reactants (b) and (d) shown below:
(a) at least one water-soluble polyether alcohol containing one or more
hydroxyl groups;
(b) at least one water-insoluble organic polyisocyanate;
(c) at least one monofunctional hydrophobic organic compound selected from
a monofunctional active hydrogen compound and an organic
monoisocyanate; and
(d) at least one polyhydric alcohol or polyhydric alcohol ether.
The polyether alcohol containing one or more functional hydroxyl groups
reactant (a), is typically an adduct of an aliphatic, cycloaliphatic, or
aromatic
polyhydroxy compound such as an adduct of an alkylene oxide and a polyhydric
alcohol
or polyhydric alcohol ether, a hydroxyl-terminated prepolymer of such adduct
and an
organic polyisocyanate, or a mixture of such adducts with such prepolymers.
Optionally,
the polyether alcohol may contain just one hydroxyl group such as an alkyl
polyethylene
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WO 97/42291 PCTIUS97/07056
IO
glycol, an alkylaryl polyethylene glycol, or a polycyclic alkyl polyethylene
glycol where
the alkyl group contains 1 to about 20 carbon atoms.
A convenient source of the hydrophilic polyether polyol adducts is a
polyalkylene
glycol (also known as a polyoxyalkylene diol) such as polyethylene glycol,
polypropylene glycol, or polybutylene glycol of about 200 to about 20,000
molecular
weight. However, adducts of an alkylene oxide and a monofunctional reactant
such as a
fatty alcohol, a phenol or an amine, or adducts of an alkylene oxide and a
difunctional
reactant such as an alkanolamine (e.g., ethanolamine) are also useful. Such
adducts are
also known as diol ethers and aIkanolamine ethers.
Suitable compounds providing polyether segments also include amino-
terminated polyoxyethylenes of the formula
NH2(CH2CH20)xH
where x has the value from about 10 to about 200.
Reactant (c), a monofunctional hydrophobic organic compound, reacts with one
or both terminal functional groups of the reaction product of reactants (a)
and (b). A
monofunctional hydrophobic organic compound includes both a monofunctional
active
hydrogen compound and an organic monoisocyanate.
For the purposes of the present invention, the term "monofunctional active
hydrogen compound" is defined as an organic compound having only one group
which is
reactive with isocyanate, such group containing an active hydrogen atom, where
any
other functional groups, if present, being substantially unreactive to
isocyanate. Such
compounds include monohydroxy compounds such as alcohols, alcohol ethers; and
monoamines; as well as polyfunctional compounds providing the compound is only
monofunctional to isocyanates. Representative of monofunctional active
hydrogen
compounds may include for example, the fatty (C I-C24) alcohols such as
methanol,
ethanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, and
cyclohexanol;
phenolics such as phenol, cresol, octylphenol, nonyl, and dodecyl phenol;
alcohol ethers
such as the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, and
the
analogous ethers of diethylene glycol; alkyl and alkaryl polyether alcohols
such as
straight or branched (C 1-C22) alkanol/ethylene oxide and alkyl
phenol/ethylene oxide
adducts.
Amino compounds may be used in place of all or a portion of the monohydroxy
compounds as hydrophobic monofunctional active hydrogen compounds. Amino
compounds include primary or secondary aliphatic, cycloaliphatic, or aromatic
amines
such as the straight or branched chain alkyl amines, or mixtures thereof,
containing about
1 to about 20 carbon atoms in the alkyl group. Suitable amines include n- and
t-octyl
CA 02252941 2003-12-17
amine, n-dodecyl amines, C 12-C 14 or C 1 g-C2p t-alkyl amine mixtwes, and
secondary
amines such as N,N-dibenzyl amine. N,N-dicyclohexyl amine and N,N-diphenyl
amine.
The amino compounds may contain more than one active hydrogen atom provided
that
under normal reaction conditions it is only monofunctional towards an
isocyanate group.
A primary amine is an example of such a compound.
In addition to a monofunctional active hydrogen compound, reactant (c) may be
a
monoisocyanate. The monoisocyanate may include C6-C I g straight chain,
branched
chain, and cyclic isocyanates such as fro example, butyl isocyanate, octyl
isocyanate,
dodecyl isocyanate, octadecyl isocyanate, and cyclohexyl isocyanate. These
isocyanates
may be used singly or in mixtures of two or more thereof,
The orgnaic polyisocyanate, reactant (b), inclide di- and triisocyanates,
isocyanate-terminated adducts of such polyhydric alcohols and organic di- or
triisocyanates, as well as isocyanate-terminated prepolymers of polyaikylene
ether
glycols and organic di- or triisocyanates. While it is preferred that reactant
(b) be an
organic polyisocyanate reactants containing one or more functional groups
other than
isocyanate are also suitable. The following are examples of monomers which can
be
used as reactant (b). These monomers may be used singly or in combination with
one or
more of the reactant (b) monomers:
1,6-hexamethylene diisocyanate (HDI)
1,6- and 2,4-tolylene diisocyanate (TDI)
4,4'- methylene diphenylisocyanate (MDI)
aliphatic triisocyante product of the hydrolytic trimerization of 1,6-
hexamethylene diisocyanate, sold under the trade mark DESMODUR N.
The polyisocyanates also include any polyfunctional isocyanate derived from
reaction of any of the foregoing isocyanates and an active hydrogen compound
having a
functionality of at least two, such that at least one isocyanate group remains
unreacted,
Such isocyanates are equivalent to chain-extending an isocyanate terminated
isocyanate/diol reaction product with a reactant containing at least two
active hydrogen
atoms in a manner well known in polyurethane synthesis.
The isocyanates may contain any number of carbon atoms effective to provide
the
required degree of hydrophobic character. Generally, about 4 to bout 30 carbon
atoms
are sufficient, the selection depending on the proportion of the other
hydrophobic groups
and hydrophilic poiyether in the product.
Reactant (d), a polyhydric alcohol or polyhydric alcohol ether, may be used to
terminate isocyanate functionality or to link isocyanate-terminated reaction
intermediates. The polyhydric alcohol or polyhydric alcohol ether may be
aliphatic,
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WO 97/42291 PCT/US97/07056
12
cycloaliphatic or aromatic and may be used singly or in a mixtures of either
type or
mixtures of the two types.
by appropriate selection of reactants and reaction conditions, including
proportions and molecular weights of reactants, a variety of polymeric
products may be
obtained that may be linear or complex in structure. In summary, the reaction
products
formed include the following:
i) reaction product of at least one water soluble polyether alcohol
containing at least one functional hydroxyl group reactant (a), a water
insoluble organic polyisocyanate reactant (b) and organic monoisocyanate
reactant (c);
ii) a reaction product of the reaction (a), wherein the water soluble
polyether
alcohol contains at least one functional hydroxyl group, and the organic
monoisocyanate reactant (c);
iii) a reaction product of the reactant (a), the reactant (b) , the organic
monoisocyanate reactant (c) and a reactant (d) selected from at least one
polyhydric alcohol and polyhydric alcohol ether;
iv) a reaction product of the reactant (a) , the water insoluble organic
polyisocyanate reactant (b) containing two isocyanate groups, and a
monofunctional active hydrogen containing compound; and
v) a reaction product of the reactant (a), the water insoluble organic
polyisocyanate reactant (b) containing at least three isocyanate groups,
and the monofunctional active hydrogen containing compound.
Polyethoxylated urethane useful as dye transfer inhibiting agents, generally
will
inhibit the transfer of dye during laundry process if
i) the polyether segment has a molecular weight of at least 200;
ii) the polyethoxylated urethane contains at least one hydrophobic group and
at least one water soluble polyether segment;
iii) the sum of the carbon atoms in the hydrophobic groups are at least 4; and
iv) the total molecular weight is at least 300 to about 60,000.
The polymers are prepared according to techniques generally known for the
synthesis of urethanes preferably such that no isocyanate remains unreacted.
Water
should be excluded from the reaction since it will consume isocyanate
functionality.
If desired the reaction may be run in a solvent medium in order to reduce
viscosity in those reactions leading to higher molecular weight products.
Generally, a
solvent is useful when molecular weights of 30,000 or higher are encountered.
The
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WO 97/42291 PCT/US97/07056
13
solvent should be inert to isocyanate and capable of dissolving the
polyoxyalkylene
reactant and the urethane product at reaction temperature.
Order of addition, reactant proportions and other conditions of reaction such
as
the selection of the catalyst may be varied to control the geometry, molecular
weight and
other characteristics of the products, in accordance with will-known
principles of
polyurethane synthesis.
Acrvlamide Containing Polymers
Water soluble or water dispersible acrylamide containing polymers, useful for
preventing dye deposition, are known for use as thickeners, rheology
modifiers, and
dispersants.
Generally, the acrylamide containing polymers are prepared by a free radical
initiated polymerization process in the presence of a chain transfer agent.
The
acrylamide containing polymers are formed from (i) at least one acrylamide of
N-
substituted acrylamide monomer, and optionally (ii) one or more vinyl monomers
described as follows:
(i) an acrylamide or N-substituted acrylamide having the following structural
formula:
R2
CHIC-C-N
R1 R3
wherein R1 is hydrogen or C1-C6 alkyl, preferably hydrogen and methyl;
R2 and R3 are independently selected from the group consisting of
hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and isobutyl; or
R2 and R3 together with the nitrogen, to which R2 and R3 are attached, to
form three to seven membered monoaromatic nitrogen heterocycles.
ii) A vinyl monomer such as a C1-C6 alkyl (meth)acrylate, hydroxyalkyl
(meth)acrylate, hydroxyaryl (meth)acrylate, alkoxyalkyl (meth)acrylate,
polyalkoxyalkyl (meth)acrylate, styrene, vinyltoluene, alkyl vin ethers,
such as butyl vinyl ether, amino monomers such as amino-substituted
alkyl (meth)acrylates amino-alkyl vinyl ethers, and malefic anhydride.
Also, vinyl monomers substituted with carboxylic acid may be used, such
as for example, malefic acid, fumaric acid, itaconic acid, (meth)acrylic
acid or the salts thereof.
For the purposes of the present invention the term "(meth)acrylate" is defined
as
meaning acrylic or methacrylic acid or ester. Salts of the carboxylic acid
substituted
CA 02252941 1998-10-29
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14
vinyl monomer may be formed by partially or completely neutralizing the
carboxylic
acid substituted vinyl monomers with one or more common base alkali metal or
alkaline
earth metal, ammonia, low molecular weight amine, or low quaternary salt
hydroxides.
The preparation of acrylamide polymers useful in this invention can be
prepared
by any number of techniques, well known to those skilled in the art. The
preferred
method is a radical initiated solution polymerization in water or a water and
c0-solvent
mixtures. The co-solvent may be, for example, ten-butanol, monobutyl ether of
ethylene
glycol, or diethylene glycol. A less preferred method is precipitation
polymerization in a
polar organic solvent such as methanol, ethanol, n-propanol, isopropanol, n-
butanol, sec-
butanol, isobutanol, tert-butanol, ethylene glycol monoalkyl ether, diethylene
glycol
ethers, acetone, methyl ethyl ketone, ethyl acetone, acetonitrile,
dimethylsulfoxide, or
tetrahydrofuran, as well as mixtures of these solvents with or without water.
Some of the
afore listed solvents function as efficient chain transfer agents and will
lower the
molecular weight of the product polymer.
Chain transfer agents may be added in an amount of from about 0.5 to about 12
percent by weight, based on the total weight of reactants added, to the
polymerization
process to lower the molecular weight of the polymer, or to add hydrophobic
groups to
the polymer to produce an associative thickener. Chain transfer agents useful
for
lowering the molecular weight may include for example mercaptans, such as
ethyl
mercaptan, n-propyl mercaptan, n-amyl mercaptan, hydroxy ethyl mercaptan,
mercaptopropionic acid, and mecaptoacetic acid; halogen compounds such as
carbon
tetrachloride, tetrachloroethylene; some primary alkanols such as benzyl
alcohol,
ethylene glycol, and diethylene glycol; some secondary alcohols such as
isopropanol;
and bisulfate such as sodium bisulfate. Chain transfer agents useful in
producing an
associative thickener are water insoluble, and are preferably a long chain
alkyl
mercaptan, such as n-dodecyl mercaptan, t-dodecyl mercaptan, octyl mercaptan,
tetradecyl mercaptan, and hexadecyl mercaptan. The total amount of chain
transfer agent
added to the polymerization process depends on the efficiency of the chain
transfer
agent. For example, if a less efficient chain transfer agent is used, such as
sodium
bisulfate, from about 5 to about 12 percent by weight of chain transfer agent
may have to
be used, where as if an effcient chain transfer agent is used, such as a
mercaptan, only
about 0.5 to about 5 weight percent chain transfer agent may have to be used.
The molecular weight range of these polymers are from about 2,000 to about
300,000. Preferably, the molecular weight is from about 20,000 to 60,000. The
acrylamide containing polymer is formed from about 50 to 100 weight percent of
the
acrylamide or N-substituted acrylamide monomer (i), and 0 to about 50 weight
percent
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of the vinyl monomer (ii). Acrylamide containing polymers particularly useful
in
preventing dye deposition are polymers formed where the acrylamide or N-
substituted
acrylamide monomers is dimetylacrylamide, methylacrylamide, and acrylamide,
and
mixtures thereof, and the vinyl monomer is nonionic, such as for example the
hydroxyalkyl (meth)acrylate or alkyl (meth)acrylate.
Polyamino Acids
Polyamino acids such as poly aspartic acid, polysuccinimide, and copolymers of
polyamino acids are useful in combination with the modified polyimines of the
present
invention as dye transfer inhibitors. Polyamino acids useful in the present
invention can
be prepared by techniques well know to those skilled in the art.
Modified Polyamines: Surface Modifiers Having Dye Transfer Inhibition
Enhancement Benefits -
The modified poiyamines of the present invention are materials having surface
modification properties. A result of this surprising property is the ability
of these
materials to act in conjunction with dye transfer inhibition agents to
provided for
significantly increased dye transfer inhibition. The dye transfer inhibition
enhancing
surface modification agents of the present invention are water-soluble or
dispersible,
bleach stable, modified polyamines comprising polyamine backbones that can be
either
linear or cyclic. The polyamine backbones can also comprise polyamine
branching
chains to a greater or lesser degree. In general, the polyamine backbones
described
herein are modified in such a manner that each nitrogen of the polyamine chain
is
thereafter described in terms of a unit that is substituted, quaternized,
oxidized, or
combinations thereof.
For the purposes of the present invention the term "modification" is defined
as
replacing a backbone -NH hydrogen atom by an E unit (substitution),
quaternizing a
backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-
oxide
(oxidized). The terms "modification" and "substitution" are used
interchangeably when
referring to the process of replacing a hydrogen atom attached to a backbone
nitrogen
with an E unit. Quaternization or oxidation may take place in some
circumstances
without substitution, but preferably substitution is accompanied by oxidation
or
quaternization of at least one backbone nitrogen.
The linear or non-cyclic polyamine backbones that comprise the cotton soil
release agents of the present invention have the general formula:
H
~2N'R~n+1-~-R~lri ~-R~ri NH2
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I6
said backbones prior to subsequent modification, comprise primary, secondary
and
tertiary amine nitrogens connected by R "linking" units. The cyclic polyamine
backbones comprising the cotton soil release agents of the present invention
have the
general formula:
LH2N'R]n-k+~~'R]m ~-R]nWR]k'NH2
said backbones prior to subsequent modification, comprise primary, secondary
and
tertiary amine nitrogens connected by R "linking" units
For the purpose of the present invention, primary amine nitrogens comprising
the
backbone or branching chain once modified are defined as V or Z "terminal"
units. For
example, when a primary amine moiety, located at the end of the main polyamine
backbone or branching chain having the structure
H2N-R]-
is modified according to the present invention, it is thereafter defined as a
V "terminal"
unit, or simply a V unit. However, for the purposes of the present invention,
some or all
of the primary amine moieties can remain unmodified subject to the
restrictions further
described herein below. These unmodified primary amine moieties by virtue of
their
position in the backbone chain remain "terminal" units. Likewise, when a
primary amine
moiety, located at the end of the main polyamine backbone having the structure
-NH2
is modified according to the present invention, it is thereafter defined as a
Z "terminal"
unit, or simply a Z unit. This unit can remain unmodified subject to the
restrictions
further described herein below.
In a similar manner, secondary amine nitrogens comprising the backbone or
branching chain once modified are defined as W "backbone" units. For example,
when a
secondary amine moiety, the major constituent of the backbones and branching
chains of
the present invention, having the structure
H
_~ _ R].-
is modified according to the present invention, it is thereafter defined as a
W "backbone"
unit, or simply a W unit. However, for the purposes of the present invention,
some or all
of the secondary amine moieties can remain unmodified. These unmodified
secondary
amine moieties by virtue of their position in the backbone chain remain
"backbone"
units.
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17
In a further similar manner, tertiary amine nitrogens comprising the backbone
or
branching chain once modified are further referred to as Y "branching" units.
For
example, when a tertiary amine moiety, which is a chain branch point of either
the
polyamine backbone or other branching chains or rings, having the structure
-LN _ RJ-
is modified according to the present invention, it is thereafter defined as a
Y "branching"
unit, or simply a Y unit. However, for the purposes of the present invention,
some or all
or the tertiary amine moieties can remain unmodified. These unmodified
tertiary amine
moieties by virtue of their position in the backbone chain remain "branching"
units. The
R units associated with the V, W and Y unit nitrogens which serve to connect
the
polyamine nitrogens, are described herein below.
The final modified structure of the polyamines of the present invention can be
therefore represented by the general formula
V(n+I )Wm1'nZ
for Linear polyamine cotton soil release polymers and by the general formula
V(n-k+I)WmynY~kZ
for cyclic polyamine cotton soil release polymers. For the case of poIyamines
comprising rings, a Y' unit of the formula
I'
R
,(N _RJ-
serves as a branch point for a backbone or branch ring. For every Y' unit
there is a Y
unit having the formula
-(N_RJ-
that will form the connection point of the ring to the main polymer chain or
branch. In
the unique case where the backbone is a complete ring, the polyamine backbone
has the
formula
H
fH2N-RJri (N'RJrri fN-RJri
therefore comprising no Z terminal unit and having the formula
Vn-kwmYnY~k
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18
wherein k is the number of ring forming branching units. Preferably the
polyamine
backbones of the present invention comprise no rings.
In the case of non-cyclic polyamines, the ratio of the index n to the index m
relates to the relative degree of branching. A fully non-branched linear
modified
polyamine according to the present invention has the formula
V WmZ
that is, n is equal to 0. The greater the value of n (the lower the ratio of m
to n), the
greater the degree of branching in the molecule. Typically the value for m
ranges from a
minimum value of 4 to about 400, however larger values of m, especially when
the value
of the index n is very low or nearly 0, are also preferred.
Each polyamine nitrogen whether primary, secondary or tertiary, once modified
according to the present invention, is further defined as being a member of
one of three
general classes; simple substituted, quaternized or oxidized. Those polyamine
nitrogen
units not modified are classed into V, W, Y, or Z units depending on whether
they are
primary, secondary or tertiary nitrogens. That is unmodified primary amine
nitrogens
are V or Z units, unmodified secondary amine nitrogens are W units and
unmodified
tertiary amine nitrogens are Y units for the purposes of the present
invention.
Modified primary amine moieties are defined as V "terminal" units having one
of
three forms:
a) simple substituted units having the structure:
E-N-R-
I
E
b) quaternized units having the structure:
E
X
E-N~ R-
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
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19
O
E-N-R-
I
E
Modified secondary amine moieties are defined as W "backbone" units having
one of three forms:
a) simple substituted units having the structure:
-N-R-
E
b) quaternized units having the structure:
E
-N~ R-
I
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
O
-N-R-
i
E
Modified tertiary amine moieties are defined as Y "branching" units having one
of three forms:
a) unmodified units having the structure:
-N-R-
b) quaternized units having the structure:
E
-N~ R-
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
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O
-N-R-
Certain modified primary amine moieties are defined as Z "terminal" units
having
one of three forms:
a) simple substituted units having the structure:
-N-E
E
b) quaternized units having the structure:
E
E_
1
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
O
-N-E
I
E
When any position on a nitrogen is unsubstituted of unmodified, it is
understood
that hydrogen will substitute for E. For example, a primary amine unit
comprising one E
unit in the form of a hydroxyethyl moiety is a V terminal unit having the
formula
(HOCH2CH2)HN-.
For the purposes of the present invention there are two types of chain
terminating
units, the V and Z units. The Z "terminal" unit derives from a terminal
primary amino
moiety of the structure -NH2. Non-cyclic polyamine backbones according to the
present
invention comprise only one Z unit whereas cyclic polyamines can comprise no Z
units.
The Z "terminal" unit can be substituted with any of the E units described
further herein
below, except when the Z unit is modified to form an N-oxide. In the case
where the Z
unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and
therefore E
cannot be a hydrogen.
CA 02252941 2003-12-17
21
The polyamines of the present invention comprise backbone R "linking" units
that serve to connect the nitrogen atoms of the backbone. R units comprise
units that for
the purposes of the present invention are referred to as "hydrocarbyl R" units
and "oxy
R" units. The "hydrocarbyl" R units are C2-C 12 alkylene, C4-C 12 alkenylene,
C3-C 12
hydroxyalkylene wherein the hydroxyl moiety may take any position on the R
unit chain
except the carbon atoms directly connected to the polyamine backbone
nitrogens; C4-
C 12 dihydroxyalkylene wherein the hydroxyl moieties may occupy any two of the
carbon atoms of the R unit chain except those carbon atoms directly connected
to the
polyamine backbone nitrogens; Cg-C12 dialkylarylene which for the purpose of
the
present invention are arylene moieties having two alkyl substituent groups as
part of the
linking chain. For example, a dialkylarylene unit has the formula
-(CH2)2 ~ ' CH2- -'(CH2)a / \ (CH2~-
or
although the unit need not be 1,4-substituted, but can also be 1,2 or 1,3
substituted C2-
C~2 alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more
preferably
ethylene. The "oxy" R units comprise -(R~O)XRS(OR~)x-,
-CH2CH(ORZ)CH20)Z(R~O)yRt(OCH2CH(ORZ)CH2)W-, -CH2CH(OR2)CH2-,
-(R'O)xR'-, and mixtures thereof. Preferred R units are C2-C 12 alkylene, C3-C
12
hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, -(R10~R1-,
-CHZCH(OR2~H2-, -(CH2CH(OH)CH20)Z(R10)yRl(OCH2CH-(OH)CH2)"~.,
-(R'O~RS(OR'~-, more preferred R units are C2-C 12 alkylene, C3-C 12 hydroxy-
alkylene, Cg-C12 dihydroxyalkylene, -(R10)xRl-, -(R10)xRS(OR1)x-,
-(CHZCH(OH)CH20)Z(R'O) ~yRl(OCH2CH-(OH)CH2)~,~,-, and mixtures thereof, even
more preferred R units are C2-C12 alkylene, C3 hydroxyalkylene, and mixtures
thereof,
most preferred are C2-C6 alkylene. The most preferred backbones of the present
invention comprise at least 50% R units that are ethylene.
R1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
R2 is hydrogen, and -(R10)xB, preferably hydrogen.
R3 is C 1-C 1 g alkyl, C~-C 12 arylalkylene, C7-C 12 alkyl substituted aryl,
C6-C 12
aryl, and mixtures thereof , preferably C 1-C 12 alkyl, C~-C 12 arylalkylene,
more
preferably C 1-C 12 alkyl, most preferably methyl. R3 units serve as part of E
units
described herein beiow.
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22
R4 is C 1-C 12 alkylene, C4-C 12 alkenylene, Cg-C 12 aryialkylene, C6-C 10
arylene, preferably C 1-C 1 p alkylene, Cg-C 12 arylalkylene, more preferably
C2-Cg
alkylene, most preferably ethylene or butylene.
RS is C i -C 12 alkylene, C3-C 12 hydroxyalkylene, C4-C 12 dihydroxyalkylene,
Cg-C 12 dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -C(O)(R4)rC(O)-,
-Rl(ORl)-, -CH2CH(OH)CH20(R10)yR10CH2CH(OH)CH2-, -C(O)(R4)rC(O)-,
-CH2CH(OH)CH2-, RS is preferably ethylene, -C(O)-, -C(O)NHR6NHC(O)-,
-R1(ORl)-, -CH2CH(OH)CH2-, -CH2CH(OH)CH20(R10)yR10CH2CH-(OH)CH2-,
more preferably -CH2CH{OH)CH2-.
R6 is C2-C 12 aikylene or C6-C 12 arylene.
The preferred "oxy" R units are further defined in terms of the R1, R2, and RS
units. Preferred "oxy" R units comprise the preferred R1, R2, and RS units.
The
preferred cotton soil release agents of the present invention comprise at
least 50% R1
units that are ethylene. Preferred R l , R2, and RS units are combined with
the "oxy" R
units to yield the preferred "oxy" R units in the following manner.
i) Substituting more preferred RS into -(CH2CH20)xRS(OCH2CH2)x-
yields -(CH2CH20)xCH2CHOHCH2(OCH2CH2)x-.
ii) Substituting preferred R~ and R2 into -(CH2CH(OR2)CH20)Z
(R~O)yRIO(CH2CH(OR2)CH2)W- yields -(CH2CH(OH)CH20)Z
(CH2CH20)yCH2CH20(CH2CH(OH)CH2)W-.
iii) Substituting preferred R2 into -CH2CH(OR2)CH2- yields
-CH2CH(OH)CHZ-.
E units are selected from the group consisting of hydrogen, CI-C22 alkyl, C3-
C22 alkenyl, C~-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pC02M, -(CH2)gS03M, -
CH(CH2C02M)C02M, -(CH2)pP03M, -(R10)mB, -C(O)R3, preferably hydrogen, C2-
C22_ hydroxyalkylene, benzyl, C 1-C22 aikylene, -(R1 O)mB, -C(O)R3, -
(CH2)pC02M, -
(CH2)qS03M, -CH(CH2C02M)C02M, more preferably Cl-C22 alkylene, -(R10)xB,
-C(O)R3, -(CH2)pC02M, -(CH2)9S03M, -CH(CH2C02M)C02M, most
preferably Cl-C22 alkylene, -(R10)xB, and -C{O)R3. When no
modification or substitution is made on a nitrogen then hydrogen atom will
remain as the
moiety representing E.
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23
E units do not comprise hydrogen atom when the V, W or Z units are oxidized,
that is the nitrogens are N-oxides. For example, the backbone chain or
branching chains
do not comprise units of the following structure:
-N-R or H-N-R or -"'N-H
H H H
Additionally, E units do not comprise carbonyl moieties directly bonded to a
nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens
are N-oxides.
According to the present invention, the E unit -C(O)R3 moiety is not bonded to
an N-
oxide modified nitrogen, that is, there are no N-oxide amides having the
structure
O O
O
-N-R or R3-C-N-R or -N-C-R3
C=O E E
R3
or combinations thereof.
B is hydrogen, Cl-C6 alkyl, -(CH2)qS03M, -(CH2)pC02M, -(CH2)q-
(CHS03M)CH2S03M, -(CH2)q(CHS02M)CH2S03M, -(CH2)pP03M, -P03M,
preferably hydrogen, -(CH2)qS03M, -(CH2)q(CHS03M)CH2S03M, -(CH2)q-
(CHS02M)CH2S03M, more preferably hydrogen or -(CH2)qS03M.
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge
balance. For example, a sodium cation equally satisfies -(CH2)pC02M, and -
(CH2)qS03M, thereby resulting in -(CH2)pC02Na, and -(CH2)qS03Na moieties.
More than one monovalent cation, (sodium, potassium, etc.) can be combined to
satisfy
the required chemical charge balance. However, more than one anionic group may
be
charge balanced by a divalent cation, or more than one mono-valent cation may
be
necessary to satisfy the charge requirements of a poly-anionic radical. For
example, a -
(CH2)pP03M moiety substituted with sodium atoms has the formula -(CH2)pP03Na3.
Divalent cations such as calcium (Ca2+) or magnesium (Mg2+) may be substituted
for or
combined with other suitable mono-valent water soluble cations. Preferred
cations are
sodium and potassium, more preferred is sodium.
X is a water soluble anion such as chlorine (C1-), bromine (Br-) and iodine
CA 02252941 1998-10-29
WO 97142291 PCT/US97/07056
24
(I-) or X can be any negatively charged radical such as sulfate (5042-) and
methosulfate
(CH3S03-).
The formula indices have the following values: p has the value from I to 6, q
has
the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1, x has
the value from
1 to 100; y has the value from 0 to 100; z has the value 0 or I ; k has a
value less than n,
typically the value of k is less than 20; m has the value from 4 to about 400,
n has the
value from 0 to about 200; m + n has the value of at least 5.
The preferred dye transfer inhibition enhancers of the present invention
comprise
polyamine backbones wherein less than about 50% of the R groups comprise "oxy"
R
units, preferably less than about 20% , more preferably less than 5%, most
preferably the
R units comprise no "oxy" R units.
The most preferred dye transfer inhibition enhancers which comprise no "oxy" R
units comprise polyamine backbones wherein less than 50% of the R groups
comprise
more than 3 carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-
propylene
comprise 3 or less carbon atoms and are the preferred "hydrocarbyl" R units.
That is
when backbone R units are CZ-C 12 alkylene, preferred is C2-C3 alkylene, most
preferred
is ethylene.
The dye transfer inhibition enhancers of the present invention comprise
modified
homogeneous and non-homogeneous polyamine backbones, wherein 100% or less of
the
-NH units are modified. For the purpose of the present invention the term
"homogeneous polyamine backbone" is defined as a polyamine backbone having R
units
that are the same (i.e., all ethylene). However, this sameness definition does
not exclude
polyamines that comprise other extraneous units comprising the polymer
backbone
which are present due to an artifact of the chosen method of chemical
synthesis. For
example, it is known to those skilled in the art that ethanolamine may be used
as an
"initiator" in the synthesis of polyethyleneimines, therefore a sample of
polyethyleneimine that comprises one hydroxyethyl moiety resulting from the
polymerization "initiator" would be considered to comprise a homogeneous
polyamine
backbone for the purposes of the present invention. A polyamine backbone
comprising
all ethylene R units wherein no branching Y units are present is a homogeneous
backbone. A polyamine backbone comprising all ethylene R units is a
homogeneous
backbone regardless of the degree of branching or the number of cyclic
branches present.
For the purposes of the present invention the term "non-homogeneous polymer
backbone" refers to polyamine backbones that are a composite of various R unit
lengths
and R unit types. For example, a non-homogeneous backbone comprises R units
that are
a mixture of ethylene and 1,2-propylene units. For the purposes of the present
invention
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a mixture of "hydrocarbyl" and "oxy" R units is not necessary to provide a non-
homogeneous backbone. The proper manipulation of these "R unit chain lengths"
provides the formulator with the ability to modify the solubility and fabric
substantivity
of the cotton soil release agents of the present invention.
Preferred dye transfer inhibition enhancers of the present invention comprise
homogeneous polyamine backbones that are totally or partially substituted by
polyethyleneoxy moieties, totally or partially quaternized amines, nitrogens
totally or
partially oxidized to N-oxides, and mixtures thereof. However, not all
backbone amine
nitrogens must be modified in the same manner, the choice of modification
being left to
the specific needs of the formulator. The degree of ethoxylation is also
determined by
the specific requirements of the formulator.
The preferred polyamines that comprise the backbone of the compounds of the
present invention are generally polyalkyleneamines (PAA's), polyalkyleneimines
(PAI's),
preferably polyethyleneamine (PEA'S), polyethyleneimines (PEI's), or PEA's or
PEI's
connected by moieties having longer R units than the parent PAA's, PAI's,
PEA's or
PEI's. A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are
obtained by reactions involving ammonia and ethylene dichloride, followed by
fractional
distillation. The common PEA's obtained are triethylenetetramine (TETA) and
teraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines,
heptamines,
octamines and possibly nonamines, the cogenerically derived mixture does not
appear to
separate by distillation and can include other materials such as cyclic amines
and
particularly piperazines. There can also be present cyclic amines with side
chains in
which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May
14,
1957, which describes the preparation of PEA's.
Preferred amine polymer backbones comprise R units that are C2 alkylene
(ethylene) units, also known as polyethylenimines (PEI's). Preferred PEI's
have at least
moderate branching, that is the ratio of m to n is less than 4:1, however
PEI's having a
ratio of m to n of about 2:1 are most preferred. Preferred backbones, prior to
modification have the general formula:
H
~2NCHzCHZ~n ~CH2CH2~rri ~CH2CH2lri NH2
wherein m and n are the same as defined herein above. Preferred PEI's, prior
to
modification, will have a molecular weight greater than about 200 daltons.
The relative proportions of primary, secondary and tertiary amine units in the
polyamine backbone, especially in the case of PEI's, will vary, depending on
the manner
CA 02252941 2003-12-17
26
of preparation. Each hydrogen atom attached to each nitrogen atom of the
polyamine
backbone chain represents a potential site for subsequent substitution,
quatemization or
oxidation.
These polyamines can be prepared, for example, by polymerizing ethyleneimine
in the presence of a catalyst such as carbon dioxide, sodium bisuifite,
sulfuric acid,
hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for
preparing
these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et
al., issued
December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962;
U.S. Parent
2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839,
Crowther,
issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 2I,
1951.
Examples of dye transfer inhibition enhancers of the present invention
comprising PEI's, are illustrated in Formulas I - IV:
Formula I depicts a dye transfer inhibition enhancement agent comprising a PEI
backbone wherein all substitutable nitrogens are modified by replacement of
hydrogen
with a polyoxyalkyleneoxy unit, -(CH2CH20)7H, having the formula
IH(lzN NI(~1'lx~ho~~
.. :~t:o~~'1h
(CHxphohH ~ (CHzc~iiohH
[H(OCti_CH=hhN~N~N~N~ N~1J~N~(~'~x~z~?rHls
(~~h~hH (~2~z~~H
N~ 1rl(ctt:ctt~oy,i'ilz
~Nt(~~sOY~~'~lt
Formula I
This is an example of a cotton soil release polymer that is fully modified by
one type of
moiety.
Formula II depicts a dye transfer inhibition enhancement agent comprising a
PEI
backbone wherein all substitutable primary amine nitrogens are modified by
replacement
of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH20)7H, the molecule is then
modified by subsequent oxidation of all oxidi2able primary and secondary
nitrogens to
N-oxides, said dye transfer inhibition enhancement agent having the formula
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
27
[H(OCHzCHzhIzN ~I(CHzCH,OhHIz «~ ~ zO~H
N O~ ~~N((CHz~zOh~z
H(~z~z)6 ~O O(CHz~zO)s~ O(CHzCHzO H
O ~ I/ )
O O
O f t N~(CHz~zO)Wlz
[H(OCHzCH y,] N~N~N~N~~ ~N~N~Nw/'~
2 2
O(CHzCHzO)6H ~ 0(CHzCH20~H
O O
~ N~(~z~z01~r~z
f~(ocH,cl~hlzN o~ ~ i I(~h~,oy,~h
0
Formula II
Formula III depicts a dye transfer inhibition enhancement agent comprising a
PEI
backbone wherein all backbone hydrogen atoms are substituted and some backbone
amine units are quaternized. The substituents are polyoxyalkyleneoxy units, -
(CH2CH20)7H, or methyl groups. The modified PEI dye transfer inhibition
enhancement agent has the formula
IH(OCI-IzCH2~rl2N N(CIi2CHz0}~H
+ _ 3
CI ~3. ~ N(l'I
cH, cH, 1 ~ ~3, cH,
II'i(oc~-i,CH,y,IzN~I+~N~N~N~N~rr~T+~
Cl- ~3 ~3 ~ Cy
CI-
Formula III
+ CI_
N(~3h
N(CH3)z
Formula IV depicts a dye transfer inhibition enhancement agent comprising a
PEI
backbone wherein the backbone nitrogens are modified by substitution (i.e. by -
(CH2CH20)7H or methyl), quaternized, oxidized to N-oxides or combinations
thereof.
The resulting dye transfer inhibition enhancement agent has the formula
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
28
~3
I
fH(~z~zhlzN N(Cf-I,CH,O)~H
N ~s,N~N(CHZCHzOhH
O
Cl'
(J O
O ~ CH3 I ~3. ~3
fI-i(~z~zhlzN~+~C~N~ i ~ i ~N~N~ C~t~I~N(~3h
CH3 O O CH3
CI +~ < <...
+ Cl'
N~N(CH3h
~N(CH3h
Formula IV
In the above examples, not all nitrogens of a unit class comprise the same
modification. The present invention allows the formulator to have a portion of
the
secondary amine nitrogens ethoxylated while having other secondary amine
nitrogens
oxidized to N-oxides. This also applies to the primary amine nitrogens, in
that the
formulator may choose to modify all or a portion of the primary amine
nitrogens with
one or more substituents prior to oxidation or quaternization. Any possible
combination
of E groups can be substituted on the primary and secondary amine nitrogens,
except for
the restrictions described herein above.
METHOD OF USE
Present invention relates to methods of providing dye transfer inhibition
benefits
to dyed or colored fabric. The method comprises the step of contacting said
dyed or
colored fabric with a water-soluble or dispersible, bleach stable, modified
polyamine
fabric surface modifying agent, said agent comprising a polyamine backbone
corresponding to the formula:
H
fH2N-RJn+1-(N-RJrri fN'RJri NH2
having a modified polyamine formula Vin+1)WmYnZ or a poiyamine backbone
corresponding to the formula:
H I R
[H2N-RJn-k+t-[N-RJrri (N-RJn-~'RJk'NH2
CA 02252941 2003-12-17
29
having a modified polyamine fonmula V(n_k+1 )'lVmYnY k2~ wherein k is less
than or
equal to n, said polyamine backbone prior to modification has a molecular
weight greater
than about 200 daltons, wherein
i) V units are terminal units having the formula:
E O
X
E"N-_R'_ or E-N~ R-' or E-N-R.-
I I
E E E
ii) W units are backbone units having the formula:
E O
X-
'N-R- or -N~ R-' or 'N-R-
I I I
E E E
iii) Y units are branching units having the formula:
O
X-
-N-R- -N~ R- -N-R
or ( or
and
iv) Z units are terminal units having the formula:
E O
X
-'N-E or -N~ E or -N-E
I I I
E E E
wherein backbone linking R units are selected from the group consisting of C2-
C12
alkylene, C4-C 12 alkenylene, C3-C 12 hydroxyalkylene, C4-C 12 dihydroxy-
alkylene,
~Cg-C12 dialkylarylene, -(R10)xRl-, -(R1 O)xRS(OR1)x-, -(CH2CH(OR2)CH20)z
(R10)yRl(OCH2CH(OR2)CH2~,~,-, -C(O)(R4)rC(O)-, -CH2CH(OR2)CH2-, and
mixtures thereof; wherein R1 is C2-C6 alkylene and mixtures thereof; R2 is
hydrogen,
-(R10~B, and mixtures thereof; R3 is C1-Clg alkyl, C~-C12 arylalkyl, C?-C12
alkyl
substituted aryl, C6-C 12 aryl, and mixtures thereof; R4 is C 1-C 12 alkylene,
C4-C 12
alkenyiene, Cg-C 12 arylalkylene, C6-C 10 arylene, and mixtures thereof; RS is
C l -C 12
alkylene, C3-C 12 hydroxy-alkylene, C4-C 12 dihydroxy-alkylene, Cg-C 12
CA 02252941 2003-12-17
dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -R1{ORl)-, -C(O)(R4)rC(O)-,
-CHzCH(OH~H2-, -CHZCH(OH)CH20(R10)yRl-OCHZCH(OH)CH2-, and mixtures
thereof; R6 is C2-C 12 alkylene or C6-C 12 arylene; E units are selected from
the group
consisting of hydrogen, C1-C2~ alkyl, C3-C22 alkenyl, C~-C22 arylalkyl, C~-C~~
hydroxyalkyl, -(CH2)pC02M, -(CH2)qS03M, -CH(CH2C02M)-CO~M,
-(CH2)pP03M, -(R 1 O)xB, -C(O)R3, and mixtures thereof; provided that when any
E unit
of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is
hydrogen, C1-C6
alkyl, -(CH2)q-S03M, -(CH2)pC02M, -(CH2)q(CHS03M)CH2S03M, -(CH2)q-
(CHSO~M)CH2S03M, -(CH2)pP03M, -P03M, and mixtures thereof; M is
hydrogen or a water soluble cation in sufficient amount to satisfy charge
balance; X is a
water soluble anion; m has the value from 4 to about 400; n has the value from
0 to about
200; p has the value from 1 to 6, q has the value from 0 to 6; r has the value
of 0 or 1; w
has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to
100; z has
the value 0 or 1. These methods may also utilize an aqueous solution of a
laundry
composition according to the present invention.
The methods of the present invention are suitable for use when the fabric
being
treated for soil release is also in need of bleaching. Compositions comprising
bleaching
agents commonly used to clean white fabrics are compatible with the fabric
surface
modifying agents of the present invention.
The present invention also provides a method for laundering colored fabrics
with
little or no dye transfer taking place. Such a method employs contacting these
fabrics
with an aqueous washing solution formed from an effective amount of the
detergent
compositions hereinbefore described. Contacting of fabrics with washing
solution will
generally occur under conditions of agitation.
Detersive surfactants
The detersive surfactants suitable for use in the present invention are
cationic,
anionic, nonionic, ampholytic, zwitterionic, and mixtures thereof, further
described
herein below. The laundry detergent composition may be in any suitable form,
for
example, high density liquids; light liquids or other pourable forms in
addition to
granules or laundry bars. The cotton soil release polymers of the present
invention can
be formulated into any detersive matrix chosen by the formulator.
The laundry detergent compositions according to the present invention may
additionally comprise at least about 0.01%, preferably at least about 0.1%;
more
preferably at least about 1% by weight, of the following detersive
surfactants.
Nonlimiting examples of surfactants useful herein typically at levels from
about 1% to
about 55%, by weight, include the conventional C11-Clg alkyl benzene
sulfonates
CA 02252941 1998-10-29
WO 97/42291 PCT/US97107056
31
("LAS") and primary, branched-chain and random C 10-C20 alkyl sulfates ("AS"),
the
C 1 p-C 1 g secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOS03-M+)
CH3
and CH3 (CH2)y(CHOS03-M+) CH2CH3 where x and (y + 1) are integers of at least
about 7, preferably at least about 9, and M is a water-solubilizing canon,
especially
sodium, unsaturated sulfates such as oleyl sulfate, the C 10-C 1 g alkyl
alkoxy sulfates
("AEXS"; especially EO 1-7 ethoxy sulfates), C 10-C 1 g alkyl alkoxy
carboxyiates
(especially the EO 1-5 ethoxycarboxylates), the C 10-18 glycerol ethers, the C
10-C 18
alkyl polyglycosides and their corresponding sulfated polyglycosides, and C 12-
C 18
alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and
amphoteric
surfactants such as the C 12-C 1 g alkyl ethoxylates ("AE") including the so-
called narrow
peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially
ethoxylates
and mixed ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines
("sultaines"}, C 10-C 18
amine oxides, and the like, can also be included in the overall compositions.
The C 10-
C 1 g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples
include
the C 12-C 1 g N-methylglucamides. See WO 9,206,154. Other sugar-derived
surfactants
include the N-alkoxy polyhydroxy fatty acid amides, such as C 1 p-C 1 g N-(3-
methoxypropyl) glucamide. The N-propyl through N-hexyl C 12-C 1 g giucamides
can be
used for low sudsing. C 10-C2p conventional soaps may also be used. If high
sudsing is
desired, the branched-chain C 10-C 16 soaps may be used. Mixtures of anionic
and
nonionic surfactants are especially useful. Other conventional useful
surfactants are
listed in standard texts.
Anionic Surfactant Component
The detergent compositions herein preferably comprise at least about 5% by
weight, of an anionic surfactant, preferably from about S% to 60% by weight of
an
anionic surfactant component. More preferably such compositions comprise from
about
10% to 40% by weight of this anionic surfactant component.
A substantial portion, i.e., at least 50%, and more preferably at least 75%,
of the
anionic surfactant component will comprise ethoxylated alkyl sulfate
surfactants. Such
ethoxylated alkyl sulfates are those which correspond to the formula:
R2-O-(C2H40)n-S03M
wherein R2 is a C 10-C22 alkyl group, n is from about 1 to 20, and M is a salt-
forming
cation. Preferably, R2 is C 12-C 1 g alkyl, n is from about 1 to 15, and M is
sodium,
potassium, ammonium, alkylammonium or alkanolammonium. Most preferably, R2 is
C 12-C 16 n is from about 1 to 6 and M is sodium. These materials, also known
as alkyl
ether sulfates, can provide especially desirable dye transfer inhibition
benefits when used
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
32
in combination with the specific polymeric dye transfer inhibiting agents
hereinafter
described.
The alkyl ether sulfates will generally be used in the form of mixtures
comprising
varying R2 chain lengths and varying degrees of ethoxylation. Frequently such
mixtures
will inevitably also contain some unethoxylated alkyl sulfate materials, i.e.
surfactants of
the above ethoxylated alkyl sulfate formula wherein n is equal to 0. Such
unethoxylated
alkyl sulfate anionic surfactants tend to be less effective than are
ethoxylated alkyl
sulfates at inhibiting dye transfer in the context of the compositions of the
present
invention. Accordingly, it is important that anionic surfactant component
herein contain
no more than about SO% by weight of such component of unethoxylated alkyl
sulfate
materials. Preferably no more than about 25% by weight of the anionic
surfactant
component will comprise unethoxylated alkyl sulfates.
In addition to the essentially utilized ethoxylated alkyl sulfate surfactants,
the
anionic surfactant component of the compositions herein may also contain
additional
optional anionic surfactants so long as such additional optional materials are
compatible
with other composition components and do not substantially adversely effect
composition performance, e.g., dye transfer inhibition or composition
stability. Optional
anionic surfactants which may be employed include in general the carboxylate-
type
anionics. Carboxylate-type anionics include fatty acid, e.g. C 10-C 1 g,
soaps, the C 10-
C 1 g alkyl alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates)
and the
C 10-C 1 g sarcosinates, especially oleoyi sarcosinate.
One common type of anionic surfactant which should not be utilized in the
anionic
surfactant component of the compositions herein comprises the sulfonated
anionics
which are alkyl benzene sulfonates. It has been found that non-bleach
activating
sulfonated anionic surfactants like linear alkyl benzene sulfonate (LAS) tend
to interfere
with the effectiveness of the polymeric dye transfer inhibiting agents used
herein to
reduce transfer of dyes between fabrics during fabric laundering operations.
Accordingly, the anionic surfactant component of the detergent compositions
herein
should be substantially free of such alkyl benzene sulfonate anionic
surfactant materials.
Nonionic Surfactant Component
The detergent compositions herein also preferably comprise from about S% by
weight of a non-ionic surfactant, preferably from about 1 % to 20% by weight
of an
nonionic surfactant component. More preferably such compositions will comprise
from
about 2% to 10% by weight of this nonionic surfactant component.
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
33
The nonionic surfactant component essentially comprises one, and preferably
both, of two specific types of nonionic surfactant materials. These are
polyhydroxy fatty
acid amides and alcohol ethoxylates.
I ) Polyhydrox~Fatty Acid Amides
Further preferred nonionic surfactants are the polyhydroxy fatty acid amides
having
the formula:
O Rg
R~-C-N-Q
wherein R~ is CS-C31 alkyl, preferably straight chain C~-C 19 alkyl or
alkenyl, more
preferably straight chain Cg-C I ~ alkyl or alkenyl, most preferably straight
chain C I I -C I 5
alkyl or alkenyl, or mixtures thereof; Rg is selected from the group
consisting of hydrogen,
C I -C4 alkyl, C I -C4 hydroxyalkyl, preferably methyl or ethyl, more
preferably methyl. Q
is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3
hydroxyls directly
connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy
is ethoxy or
propoxy, and mixtures thereof. Preferred Q is derived from a reducing sugar in
a reductive
amination reaction. More preferably Q is a glycityl moiety. Suitable reducing
sugars
include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
As raw
materials, high dextrose corn syrup, high fructose corn syrup, and high
maltose corn syrup
can be utilized as well as the individual sugars listed above. These corn
syrups may yield a
mix of sugar components for Q. It should be understood that it is by no means
intended to
exclude other suitable raw materials. Q is more preferably selected from the
group
consisting of -CH2(CHOH)nCH20H,-CH(CH20H)(CHOH)n-I CH20H, -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. Most
preferred substituents for the Q moiety are glycityls wherein n is 4,
particularly
-CH2(CHOH)4CH20H.
RICO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc.
Rg can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy
ethyl, or
~-hydroxy propyl.
Q can be I-deoxyglucityl, 2-deoxyfructityl, I-deoxymaltityl, I-deoxylactityl,
I-
deoxygalactityl, 1-deoxymannityl, I-deoxymaltotriotityl, etc.
A particularly desirable surfactant of this type for use in the compositions
herein is
alkyl-N-methyl glucomide, a compound of the above formula wherein R~ is alkyl
(preferably CI I-C13), Rg, is methyl and Q is 1-deoxyglucityl.
CA 02252941 2003-12-17
34
Processes for making polyhydroxy fatty acid amides are known and can be found,
for
example, in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798
.
The materials themselves and their preparation are also described in greater
detail in
Honsa, U.S. Patent 5,174,937, issued December 26, 1992.
When polyhydroxy fatty acid amide nonionic is used in the nonionic surfactant
component of the detergent compositions herein, it will generally be present
to the extent of
from about 1 % to 20% by weight of the composition. More preferably,
polyhydroxy fatty
acid amide nonionic can comprise from about 2% to 10% by weight of the
compositions
herein.
2) Alcohol Ethoxvlates
Another suitable component of the nonionic surfactant used in the compositions
herein comprises an ethoxylated fatty alcohol nonionic surfactant. Such
materials are those
which correspond to the general formula:
RI (C2H40)nOH
wherein RI is a Cg - C 16 alkyl group or a C6 - C 12 alkylphenol group and n
ranges from
about 1 to 80. Preferably R1 is an alkyl group, which may be primary or
secondary, that
contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14
carbon
atoms. Preferably the ethoxylated fatty alcohols will contain from about 2 to
12 ethylene
oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide
moieties
per molecule.
The ethoxylated fatty alcohol nonionic surfactant will frequently have a
hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More
preferably,
the HLB of this material will range from about 6 to 15, most preferably from
about 10 to
15.
Examples of fatty alcohol ethoxylates useful as the essential liquid nonionic
surfactant in the compositions herein will include those which are made from
alcohols of
12 to 1 S carbon atoms and which contain about 7 moles of ethylene oxide. Such
materials have been commercially marketed under the trade marks Neodol 25-7
and
Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-
S,
an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with
about 5
moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C 12 - C 13
alcohol having
about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated Cg - C 11
primary
alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this
type have
also been marketed by Shell Chemical Company under the Dobanol trademark.
Dobanol
CA 02252941 2003-12-17
35
91-5 is an ethoxylated Cg-C 11 fatty alcohol with an average of S moles
ethylene oxide
and Dobanol 25-7 is an ethoxylated C 12-C 15 fatty alcohol with an average of
7 moles of
ethylene oxide per mole of fatty alcohol.
Other examples of suitable ethoxylated alcohol nonionic swfactants include
TM
Tergitol 15-S-7 and Tergitol 1 S-S-9 both of which are linear secondary
alcohol
ethoxylates that have been commercially marketed by Union Carbide Corporation.
The
former is a mixed ethoxylation product of C I 1 to C 15 linear secondary
alkanol with 7
moles of ethylene oxide and the latter is a similar product but with 9 moles
of ethylene
oxide being reacted.
Other types of alcohol ethoxylate nonionics useful in the present compositions
are higher molecular weight nonionics, such as Neodol 45-11, which are similar
ethylene
oxide condensation products of higher fatty alcohols, with the higher fatty
alcohol being
of 14-15 carbon atoms and the number of ethylene oxide groups per mole being
about
11. Such products have also been commercially marketed by Shell Chemical
Company.
When alcohol ethoxylate nonionic is used in the nonionic surfactant component
of the detergent compositions herein, it will generally be present to the
extent of from
about 0.5% to 10% by weight of the composition. More preferably, alcohol
ethoxylate
nonionic will comprise from about 1 % to 5% by weight of the compositions
herein.
Non-cotton Soil Release Agent
Known polymeric soil release agents, hereinafter "SRA", can optionally be
employed in the present detergent compositions. If utilized, SRA's will
generally
comprise from 0.01 % to 10.0%, typically from 0.1 % to 5%, preferably from
0.2% to
3.0% by weight, of the compositions.
Preferred SRA's typically have hydrophilic segments to hydrophiiize the swface
of
hydrophobic fibers such as polyester and nylon, and hydrophobic segments to
deposit
upon hydrophobic fibers and remain adhered thereto through completion of
washing and
rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
This can
enable stains occurring subsequent to treatment with the SRA to be more easily
cleaned
in later washing procedures.
SRA's can include a variety of charged, e.g., anionic or even cationic
species, see
U.S. 4,956,447, issued September 11, 1990 to Gosselink, et al., as well as
noncharged
monomer units, and their structures may be linear, branched or even star-
shaped. They
may include capping moieties which are especially effective in controlling
molecular
weight or altering the physical or surface-active properties. Structures and
charge
distributions may be tailored for application to different fiber or textile
types and for
varied detergent or detergent additive products.
CA 02252941 2003-12-17
36
Preferred SRA's include oligomeric terephthalate esters, typically prepared by
processes involving at least one transesterification/oligomerization, often
with a metal
catalyst such as a titanium(IV) alkoxide. Such esters may be made using
additional
monomers capable of being incorporated into the ester structure through one,
two, three,
four or more positions, without, of course, forming a densely crosslinked
overall
structure.
Other SRA's include the nonionic end-capped 1,2-propylene/polyoxyethylene
terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et
al., for
example those produced by transesterification/oligomerization of
poly(ethyleneglycol)
methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of
SRA's
include: the partly- and fully- anionic-end-capped oligomeric esters of U.S.
4,721,580,
January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"),
PG,
DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; and the anionic, especially
sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31,
1989 to
Maldonado, the latter being typical of SRA's useful in both laundry and fabric
conditioning products, an example being an ester composition made from m-
sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably
further
comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or
propylene terephthalate with polyethylene oxide or polypropylene oxide
terephthalate,
see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July
8, 1975;
cellulosic d TM atives such as the hydroxyether celIulosic polymers available
as
METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses,
see
U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose
ethers
having an average degree of substitution (methyl) per anhydroglucose unit from
about
l .6 to about 2.3 and a solution viscosity of from about 80 to about 120
centipoise
measured at 20°C as a 2% aqueous solution. Such materials are available
as
TM
METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl
cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Suitable SRA's characterised by polyvinyl ester) hydrophobe segments include
graft copolymers of polyvinyl ester), e.g., CI-C6 vinyl esters, preferably
polyvinyl
acetate), grafted onto polyalkylene oxide backbones. See European Patent
Application 0
219 048, published April 22, 1987 by Kud, et al. Commercially available
examples
TM
include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany.
Other SRA's are polyesters with repeat units containing 10-15% by weight of
ethylene
terephthalate together with 80-90% by weight of polyoxyethylene terephthalate
derived
CA 02252941 2003-12-17
37
from a polyoxyethylene glyTOl of average molecular weight 300-5,000.
Commercial
examples include ZELCON S 126 from Dupont and MILEASE T from lCi.
Another preferred SRA is an oligomer having empirical formula
(CAP)2(EG/PG)S(T)5(SIP)1 which comprises terephthaloyl {T), sulfoisophthaloyl
(SIP),
oxyethyleneoxy and oxy-1,2-propylene (EG/PG} units and which is preferably
terminated with end-caps (CAP), preferably modified isethionates, as in an
oligomer
comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy
and oxy-
1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about
10:1, and two
end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said
SRA
preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a
crystallinity-reducing stabilizer, for example an anionic surfactant such as
linear sodium
dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and
toluene-
sulfonates or mixtures thereof, these stabilizers or modifiers being
introduced into the
synthesis vessel, all as taught in U.S. 5,415,807, GosseIink, Pan, Kellett and
Hall, issued
May 16, 1995. Suitable monomers for the above SRA include Na-2-(2-
hydroxyethoxy)-
ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.
Additional classes of SRA's include: (I) nonionic terephthalates using
diisocyanate coupling agents to link polymeric ester structures, see U.S.
4,201,824,
Violland et al, and U.S. 4,240,918 Lagasse et al.; and (II} SRA's with
carboxylate
terminal groups made by adding trimellitic anhydride to known SRA's to convert
terminal hydroxyl groups to trimellitate esters. With the proper selection of
catalyst, the
trimellitic anhydride forms linkages to the terminals of the polymer through
an ester of
the isolated carboxylic acid .of trimellitic anhydride rather than by opening
of the
anhydride linkage. Either nonionic or anionic SRA's may be used as starting
materials as
long as they have hydroxyl terminal groups which may be esterified. See U.S.
4,525,524
Tung et al.. Other classes include: (III) anionic terephthalate-based SRA's of
the
urethane-linked variety, see U.S. 4,201,824, Violland et al.; (1V) polyvinyl
caprolactam)
and related co-polymers with monomers such as vinyl pytrolidone andlor
dimethylaminoethyl methacrylate, including both nonionic and cationic
polymers, see
U.S. 4,579,681, Rupperi et al.; (V) graft copolymers, in addition to the
SOKALAN types
from BASF, made by grafting acrylic monomers onto sulfonated polyesters. These
SRA's assertedly have soil release and anti-redeposition activity similar to
known
cellulose ethers: see EP 279,134 A, 1988, to Rhone-Poulenc Chemie. Still other
classes
include: {VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate
onto
proteins such as caseins, see EP 457,205 A to BASF (1991); and (VII) polyester-
polyamide SRA's prepared by condensing adipic acid, caprolactam, and
polyethylene
CA 02252941 1998-10-29
WO 97/42291 PCT/US97107056
38
glycol, especially for treating polyamide fabrics, see Bevan et al., DE
2,335,044 to
Unilever N. V., 1974. Other useful SRA's are described in U.S. Patents
4,240,918,
4,787,989 and 4,525,524.
Preferred Non-cotton Soil Release A~~ent
Suitable for use in the laundry detergent compositions of the present
invention
are the following preferred soil release polymers comprising:
a) a backbone comprising:
i) at least one moiety having the formula:
O O
-C ~ ~ C
ii) at least one moiety having the formula:
Rio Rio
I I
-O-R9-(O-R~i O
R~o Rio
wherein R9 is C2-C6 linear alkylene, C3-C6 branched alkylene,
CS-C7 cyclic alkylene, and mixtures thereof; R10
is independently selected from hydrogen or -L-S03-M+; wherein
L is a side chain moiety selected from the group consisting of
alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene,
alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene,
poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and
mixtures thereof; M is hydrogen or a salt forming cation; i has the
value of 0 or 1;
iii) at least one trifunctional, ester-forming, branching moiety;
iv) at least one 1,2-oxyalkyleneoxy moiety; and
b) one or more capping units comprising:
i) ethoxylated or propoxylated hydroxyethanesulfonate or
ethoxylated or propoxylated hydroxypropanesulfonate units of the
formula (M03S)(CH2)m(R110)n_, where M is a salt forming
cation such as sodium or tetralkylammonium, Rl 1 is ethylene or
propylene or a mixture thereof, m is 0 or 1, and n is from 1 to 20;
CA 02252941 1998-10-29
WO 97/42291 PCT/US97107056
39
ii) sulfoaroyl units of the formula -(O)C{C6H4)(S03-M+), wherein
M is a salt forming cation;
iii) modified poly(oxyethylene)oxy monoalkyl ether units of the
formula R120(CH2CH20)k-, wherein R12 contains from 1 to 4
carbon atoms and k is from about 3 to about 100; and
iv) ethoxylated or propoxylated phenolsulfonate end-capping units of
the formula M03S(C6H4)(OR13)n0-, wherein n is from 1 to 20;
M is a salt-forming cation; and R13 is ethylene, propylene and
mixtures thereof.
This type of preferred soil release polymer of the present invention may be
described as having the formula
L(CaP)(R4)tJ ~(A-R I -A-R2) u(A-R I -A-R3 )v(A-R I -A-RS )w
-A-RI-A-~~(R4)t(CaP))
wherein A is a carboxy linking moiety having the formula
o
ii
-C-
RI is arylene, preferably a 1,4-phenylene moiety having the formula
/ \
such that when A units and RI units are taken together in the formula A-RI-A
they form
a terephthalate unit having the formula
-O ~ ~ C-
R2 units are ethyleneoxy or 1,2-propyleneoxy. R2 units are combined with
terephthalate moieties to form (A-R1-A-R2) units having the formula
O O
-C / \ C-O-CHR'CHR"-
wherein R' and R" are either hydrogen or methyl provided that R' and R" are
not both
methyl at the same time.
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WO 97/42291 PCTIUS97/07056
R3 units are trifunctional, ester-forming, branching moieties having the
formula
O
I
-O-CH2-CH-CH2-O-
Preferably R3 units comprise a glycerol moiety which is placed into the soil
release
polymer backbone to provide a branch point. When R3 units are combined with
terephthalate moieties to form units of the polymer backbone, for example, (A-
Rl-A-
R3 )-A-R 1-A units, these units have the formula
O
-C ~ \ C-O-CH2-CH-CH2-O-C ~ ~ C
0 0 0 0
or the formula
O
CH2
-C ~ ~ C-O-CH2-CH-O-C ~ ~ C
O O O O
wherein one terephthalate residue is taken to be a part of the (A-Rl-A-R3)
unit while the
second terephthalate comprises a part of another backbone unit, such as a (A-
Rl-A-R2)
unit, a (A-Rl-A-RS) unit, a -A-Rl-A-[(R4)t(Cap)] unit or a second (A-Rl-A-R3)
unit.
The third functional group, which is the beginning of the branching chain, is
also
typically bonded to a terephthalate residue also a part of a (A-Rl-A-R2) unit,
a (A-Rl-A-
RS) unit, a -A-Rl-A-[(R4)t(Cap)] unit or another (A-Rl-A-R3) unit.
An example of a section of a soil release polymer containing a "trifunctional,
ester-forming, branching moiety" R3 unit which comprises a glycerol unit, has
the
formula
CA 02252941 1998-10-29
WO 97142291 PCT/LJS97/07056
41
-(CHzCH20~-C ~ ~ C
O O O O / \ O
R4 units are R2, R3 or RS units.
RS units are units having the formula
R1o Rlo
-O-R9--(O-R9)i O
Rio Rio
wherein R9 is C2-C6 linear alkylene, C3-C6 branched alkylene, and mixtures
thereof;
preferably R10 is independently selected from hydrogen or -L-S03-M+; wherein L
is a
side chain moiety selected from the group consisting of alkylene, oxyalkylene,
alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene,
poly(oxyalkylene),
oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarlyene,
alkylenepoly(oxyalkylene),and
mixtures thereof; M is hydrogen or a salt forming cation; i has the value of 0
or 1;
Each carbon atom of the R9 units is substituted by R10 units that are
independently selected from hydrogen or -L-S03-M+, provided no more than one -
L-
S03-M+ units is attached to an R9 unit; L is a side chain connecting moiety
selected
from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene,
arylene,
oxyarylene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene,
poly{oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and mixtures thereof.
M is a cationic moiety selected from the group consisting of lithium, sodium,
potassium, calcium, and magnesium, preferably sodium and potassium.
Preferred RS moieties are essentially R10 substituted C2-C6 alkylene chains.
The RS units comprise either one C2-C6 alkylene chain substituted by one or
more
independently selected R10 moieties (preferred) or two C2-C6 alkylene chains
said
alkylene chains joined by an ether oxygen linkage, each alkylene chain
substituted by
one or more independently selected R10 moieties, that is RS may comprise two
separate
R9 units, each of which is substituted by one or more independently selected
R10
moieties. Preferably only one carbon atom of each R9 moiety is substituted by
an -L-
S03-M+ unit with the remaining R10 substituents comprising a hydrogen atom.
When
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WO 97/42291 PCT/US97/07056
42
the value of the index i is equal to 1 (two R9 units comprise the RS unit), a
preferred
formula is
Rio Rio Rio Rto
-O-C C O C---~-O
Rio Rio Rlo Rio
wherein each R9 comprises a C2 alkylene moiety. Preferably one R10 moiety is -
L-
S03-M+, preferably the C2 carbon is substituted by the -L-S03-M+ moiety, and
the
balance are hydrogen atoms, having therefore a formula:
-CHCH2-O-CH2CH2-
CHZ(OCH2CH2)xS03 M+
wherein L is a polyethyleneoxymethyl substituent, x is from 0 to about 20.
As used herein, the term "RS moieties consist essentially of units
Rio Rio
I I
-O-R9-(O-R~i O
Rio Rto
having the index i equal to 0 wherein R10 units are hydrogen and one R10 units
is equal
to -L-S03-M'~, wherein L is a side chain connecting moiety selected from the
group
consisting of alkylene, alkenylene, alkoxyalkylene, oxyalkylene, arylene,
alkylarylene,
alkoxyarylene and mixtures thereof', refers to the preferred compounds of the
present
invention wherein the R10 moieties consist of one -L-S03-M+ moiety and the
rest of the
R10 moieties are hydrogen atoms, for example a
-O-CH2-CH-O-
CH2(OCHZCH2~SO3- Na+
which is capable of inclusion into the polymeric backbone of the soil release
polymers of
the present invention as an -A-RS-A- backbone segment. The units are easily
incorporated into the oligomer or polymer backbone by using starting materials
having
the general formula
HO-CH2-CH-OH
CH2(OCH2CH2~SO3- Na+
wherein x, for the purposes of the L moiety of the present invention, is from
0 to 20.
CA 02252941 1998-10-29
WO 97/42291 PCT/LTS97/07056
43
Other suitable monomers capable of inclusion into the backbone of the type A
preferred non-cotton soil release polymers of the present invention as RS
moieties
includes the alkylene poly(oxyalkylene)oxyarylene containing monomer having
the
general formula
HO-CHI-CH-OH
- CHZ(OCH2CH2~0 ~ \ S03 Na+
wherein x is 0 to 20. A further example of a preferred monomer resulting in a
preferred
RS unit wherein i is equal to 0, are the sodiosulfopoly(ethyleneoxy)methyl-1,2-
propanediols having the formula
HO-CH2-CH-OH
CH2(OCHZCH2~S03 Na+
wherein x is from 0 to about 20; more preferred are the monomers
OH
I
HO-CH2-CH-CH2-OH or HO-CH2-CH-CH2
OCH2CH2S03 Na+ OCH2CH2S03 Na+
The preferred soil release agents of the present invention in addition to the
afore-
mentioned R1, R2, R3, R4, and RS units also comprise one or more capping
groups, -
(Cap). The capping groups are independently selected from ethoxylated or
propoxylated
hydroxyethane and propanesulfonate units of the formula (M03S)(CH2~(R110)n-,
where M is a salt forming cation such as sodium or tetralkylammonium as
described
herein above, R11 is ethylene or propylene or a mixture thereof, m is 0 or 1,
and n is
from 1 to 20, preferably n is from 1 to about 4; sulfoaroyl units of the
formula -
(O)C(C6H4)(S03-M+), wherein M is a salt forming cation as described herein
above;
modified poly(oxyethylene)oxy monoalkyl ether units of the formula
R120(CH2CH20)k- wherein R12 contains from 1 to 4 carbon atoms, R12 is
preferably
methyl, and k is from about 3 to about 100, preferably about 3 to about 50,
more
preferably 3 to about 30; and ethoxylated or propoxylated phenolsulfonate end-
capping
units of the formula M03S(C6H4)(OR13)n0-, wherein n is from to 20; M is a salt-
forming cation; and R13 is ethylene, propylene and mixtures thereof.
Most preferred end capping unit is the isethionate-type end capping unit which
is
a hydroxyethane moiety, {M03S)(CH2)m{R11O)n_, preferably R11 is ethyl, m is
equal
to0,andnisfrom2to4.
CA 02252941 2003-12-17
44
The value of t is 0 or 1; the value of a is from about 0 to about 60; the
value of v
is from about 0 to about 35; the value of w is from 0 to 35.
Preferred soil release polymers of the present invention having the formula
~(CaP)(R4)t) ~~A-R 1-A-R2)u(A-R 1-A-R3 )v(A-R 1-A-RS )w
-A-R 1-A-J t(R4)t(CaP))
can be conveniently expressed as the following generic structural formula
0 0 0 0
Nao,scc~hcl-IZoh.,crlZc~z o-c / \ c-ocHzc~ o-c / \ c-ocH,~-1
R ~L
OCIizCHzSO~IJa
\ ~ ~z ~ ~o / \ O-OCHzCH(~x~zh~ssg~
v v+l
The following structure is an example of the preferred soil release polymers
of
the present invention.
NaOss(CHzCHZOh.sCHzCHz p-O / \
R I
1.7-2.~ ~ 2.5
OC9izCHz54~Na
O O
/ \ O-pp.~ I p-C / \ C-O~z~(p(~izCHz~.s~Na
0.15 1.15
The above-described preferred soil release agents are fully described in U.S.
Patent
No. 5,691,298 issued November 25, 1997. Other non-cotton soil release polymers
suitable for use in the compositions of the present invention are further
described herein
below.
The preferred SR.A's can be further described as oligomeric esters comprising:
(1)
a backbone comprising (a) at least one unit selected from the group consisting
of
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least
trifunctional
whereby ester linkages are formed resulting in a branched oligomer backbone,
and
combinations thereof; (b) at least one unit which is a terephthaloyl moiety;
and (c) at
least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one
or more
capping units selected from nonionic capping units, anionic capping units such
as
alkoxylated, preferably ethoxylated, isethionates, alkoxylated
propanesulfonates,
alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl
derivatives
and mixtures thereof. Preferred are esters of the empirical formula:
{(CAP)x(EG/PG)y'(DEG)y"(PEG)y"'(T)z(SIP)z'(SEG)q(B)m}
wherein CAP, EG/PG, PEG, T and SIP are as defined as terephthaloyl (T),
sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units,
end-caps
(CAP), poly(ethyleneglycol) (PEG), (DEG) represents di(oxyethylene)oxy units,
(SEG)
represents units derived from the sulfoethyl ether of glycerin and related
moiety units,
(B) represents branching units which are at least trifunctional whereby ester
linkages are
formed resulting in a branched oligomer backbone, x is from about 1 to about
12, y' is
from about 0.5 to about 25, y" is from 0 to about 12, y"' is from 0 to about
10, y'+y"+y~"
totals from about 0.5 to about 25, z is from about 1.5 to about 25, z' is from
0 to about
12; z + z' totals from about 1.5 to about 25, q is from about 0.05 to about
12; m is from
about 0.01 to about 10, and x, y', y", y"', z, z', q and m represent the
average number of
moles of the corresponding units per mole of said ester and said ester has a
molecular
weight ranging from about 500 to about 5,000.
Preferred SEG and CAP monomers for the above esters include Na-2-(2-,3-
dihydroxypropoxy)ethanesulfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy}
ethanesulfonate ("SE3") and its homologs and mixtures thereof and the products
of
ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class
include the
product of transesterifying and oligomerizing sodium 2-{2-(2-hydroxy-
ethoxy)ethoxy}ethanesulfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)ethoxy}-
ethoxyJethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate,
EG,
and PG using an appropriate Ti(IV) catalyst and can be designated as
(CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+-p3S[CH2CH20J3.5)-
and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as
measured by
conventional gas chromatography after complete hydrolysis.
Bleachine Compounds - Bleaching Agents and Bleach Activators
The detergent compositions herein may optionally contain bleaching agents or
bleaching compositions containing a bleaching agent and one or more bleach
activators.
When present, bleaching agents will be at levels of from about 0.05% to about
30%,
CA 02252941 2003-12-17
46
more preferably from about 1 % to about 30%, most preferably from about S% to
about
20%, of the detergent composition, especially for fabric laundering. If
present, the
amount of bleach activators will typically be from about 0.1 % to about 60%,
more
typically from about 0.5% to about 40% of the bleaching composition comprising
the
bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for
detergent compositions in textile cleaning that are now known or become known.
These
include oxygen bleaches as well as other bleaching agents. Perborate bleaches,
e.g.,
sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction
encompasses percarboxylic acid bleaching agents and salts thereof. Suitable
examples of
this class of agents include magnesium monoperoxyphthalate hexahydrate, the
magnesium salt of mete-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric
acid
and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.
Patent
4,483,781; Hartman, issued November 20,1984, U.S. Patent No. 4,634,551, Bums
et al, issued
January 6, 1987, European Patent Application 0,133,354, Banks et al, published
February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1,
1983.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid
as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching
compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate"
bleaches, sodium pyrophosphate peroxyhyd Mte, urea peroxyhydrate, and sodium
peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont)
can
also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about 1,000
micrometers, not
more than about 10% by weight of said particles being smaller than about 200
micrometers and not more than about 10% by weight of said particles being
larger than
about 1,250 micrometers. Optionally, the percarbonate can be coated with
silicate,
borate or water-soluble surfactants. Percarbonate is available from various
commercial
sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably combined with bleach activators, which lead to the in situ
production in
aqueous solution (i.e., during the washing process) of the peroxy acid
corresponding to
the bleach activator. Various nonlimiting examples of activators are disclosed
in U.S.
CA 02252941 2003-12-17
47
Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent
4,412,934. The
nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl ethylene diamine (TAED)
activators are typical, and mixtures thereof can also be used. See also U.S.
4,634,551 for
other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
RIN(RS)C(O)R2C(O)L or RIC(O)N(RS)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an
alkylene containing from 1 to about 6 carbon atoms, RS is H or alkyl, aryl, or
alkaryl
containing from about 1 to about 10 carbon atoms, and L is any suitable
leaving group.
A leaving group is any group that is displaced from the bleach activator as a
consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis
anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-
nonanamidocaproyl~xybenzenesulfonate,
(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described
in U.S.
Patent 4,634,551.
Another class of bleach activators comprises the benzoxazin-type activators
disclosed by Hodge et al in U.S. Patent 4,9b6,723, issued October 30, 1990 .
A highly preferred activator of the benzoxazin-type is:
O
II
CEO
of
~~C o
N
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
O O
I) il
O C-C H2-C H2 O C-C H2- ~ H2
Rs C N~CIi -C iCH2 Rs-C-N~
2 H2 C 2 CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to about
12 carbon atoms. Highly preferred lactam activators include benzoyl
caproiactam,
octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactam,
decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam,
3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S.
Patent
CA 02252941 2003-12-17
48
4,545,784, issued to Sanderson, October 8, 1985,
which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed
into sodium
perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art
and can be utilized herein. One type of nor.-ox;~gen bleaching agent of
particular interest
includes photoactivated bleaching agents such as the sulfonated zinc and/or
aluminum
phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et
al. If
used, detergent compositions will typically contain from about 0.025% to about
1.25%,
by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese
compound. Such compounds are well known in the art and include, for example,
the
manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S.
Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
549,271A1,
549,272A 1, 544,440A2, and 544,490A 1; Preferred examples of these catalysts
include
MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, MnIII2(u_p)1(u_
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,?-
triazacyclononane)4(C104)4, MnIII~IV4(u-O)1(u-OAc)2_(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,?-triazacyclononane)-
(OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include
those
disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,1 t4,b11. The use of
manganese with
various complex ligands to enhance bleaching is also reported in the following
United
States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;
5,274,147;
5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per ten
million of the active bleach catalyst species in the aqueous washing liquor,
and will
preferably provide from about 0.1 ppm to about 700 ppm, more preferably from
about 1
ppm to about 500 ppm, of the catalyst species in the laundry liquor.
A wide variety of other ingredients useful in detergent compositions can be
included in the compositions herein, including other active ingredients,
carriers,
hydrotropes, processing aids, dyes or pigments, solvents for liquid
formulations, solid
fillers for bar compositions, etc. If high sudsing is desired, suds boosters
such as the
C 10-C 16 alkanolamides can be incorporated into the compositions, typically
at 1 %-10%
levels. The C 1 p-C 14 monoethanoi and diethanol amides illustrate a typical
class of such
suds boosters. Use of such suds boosters with high sudsing adjunct surfactants
such as
the amine oxides, betaines and sultaines noted above is also advantageous. If
desired,
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
49
soluble magnesium salts such as MgCl2, MgS04, and the like, can be added at
levels of,
typically, 0.1 %-2%, to provide additional suds and to enhance grease removal
performance.
Various detersive ingredients employed in the present compositions optionally
can be further stabilized by absorbing said ingredients onto a porous
hydrophobic
substrate, then coating said substrate with a hydrophobic coating. Preferably,
the
detersive ingredient is admixed with a surfactant before being absorbed into
the porous
substrate. In use, the detersive ingredient is released from the substrate
into the aqueous
washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution
containing
3%-S% of C13-15 e~oxylated alcohol (EO 7) nonionic surfactant. Typically, the
enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder
is
dispersed with stirring in silicone oil (various silicone oil viscosities in
the range of 500-
12,500 can be used). The resulting silicone oil dispersion is emulsified or
otherwise
added to the final detergent matrix. By this means, ingredients such as the
aforementioned enzymes, bleaches, bleach activators, bleach catalysts,
photoactivators,
dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be
"protected" for
use in detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as
carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol,
ethanol,
propanol, and isopropanol are suitable. Monohydric alcohols are preferred for
solubilizing surfactant, but polyols such as those containing from 2 to about
6 carbon
atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene
glycol,
glycerin, and 1,2-propanediol) can also be used. The compositions may contain
from 5%
to 90%, typically 10% to 50% of such carriers.
The detergent compositions herein will preferably be formulated such that,
during
use in aqueous cleaning operations, the wash water will have a pH of between
about 6.5
and about 11, preferably between about 7.5 and 10.5. Laundry products are
typically at
pH 9-11. Techniques for controlling pH at recommended usage levels include the
use of
buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Enzymes
Enzymes can be included in the present detergent compositions for a variety of
purposes, including removal of protein-based, carbohydrate-based, or
triglyceride-based
stains from surfaces such as textiles, for the prevention of refugee dye
transfer, for
example in laundering, and for fabric restoration. Suitable enzymes include
proteases,
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WO 97/42291 PCT/US97/07056
amylases, lipases, cellulases, peroxidases, and mixtures thereof of any
suitable origin,
such as vegetable, animal, bacterial, fungal and yeast origin. Preferred
selections are
influenced by factors such as pH-activity and/or stability optima,
thermostability, and
stability to active detergents, builders and the like. In this respect
bacterial or fungal
enzymes are preferred, such as bacterial amylases and proteases, and fungal
cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain
removing or otherwise beneficial effect in a laundry, hard surface cleaning or
personal
care detergent composition. Preferred detersive enzymes are hydrolases such as
proteases, amylases and lipases. Preferred enzymes for laundry purposes
include, but are
not limited to, proteases, cellulases, lipases and peroxidases.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount".
The term
"cleaning effective amount" refers to any amount capable of producing a
cleaning, stain
removal, soil removal, whitening, deodorizing, or freshness improving effect
on
substrates such as fabrics. In practical terms for current commercial
preparations, typical
amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of
active
enzyme per gram of the detergent composition. Stated otherwise, the
compositions
herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1 % by
weight of a
commercial enzyme preparation. Protease enzymes are usually present in such
commercial preparations at levels sufficient to provide from 0.005 to 0.1
Anson units
(AU) of activity per gram of composition. For certain detergents it may be
desirable to
increase the active enzyme content of the commercial preparation in order to
minimize
the total amount of non-catalytically active materials and thereby improve
spotting/filming or other end-results. Higher active levels may also be
desirable in
highly concentrated detergent formulations.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B, licheniformis. One suitable protease
is obtained
from a strain of Bacillus, having maximum activity throughout the pH range of
8-12,
developed and sold as ESPERASE~ by Novo Industries A/S of Denmark, hereinafter
"Novo". The preparation of this enzyme and analogous enzymes is described in
GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~ and SAVINASE~
from Novo and MAXATASE~ from International Bio-Synthetics, Inc., The
Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9,
1985 and
Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A,
3anuary 9,
1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in
WO
9318140 A to Novo. Enzymatic detergents comprising protease, one or more other
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
51
enzymes, and a reversible protease inhibitor are described in WO 9203529 A to
Novo.
Other preferred proteases include those of WO 9510591 A to Procter & Gamble .
When
desired, a protease having decreased adsorption and increased hydrolysis is
available as
described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like
protease for
detergents suitable herein is described in WO 9425583 to Novo.
In more detail, an especially preferred protease, referred to as "Protease D"
is a
carbonyl hydrolase variant having an amino acid sequence not found in nature,
which is
derived from a precursor carbonyl hydrolase by substituting a different amino
acid for a
plurality of amino acid residues at a position in said carbonyl hydrolase
equivalent to
position +76, preferably also in combination with one or more amino acid
residue
positions equivalent to those selected from the group consisting of+99, +101,
+103,
+104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197,
+204,
+206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the
numbering of Bacillus amyloliquefaciens subtilisin, as described in WO
95/10615
published April 20, 1995 by Genencor International.
Useful proteases are also described in PCT publications: WO 95/30010 published
Novenber 9, 1995 by The Procter & Gamble Company; WO 95/30011 published
Novenber 9, 1995 by The Procter & Gamble Company; WO 95/29979 published
Novenber 9, 1995 by The Procter & Gamble Company.
Amylases suitable herein include, for example, a-amylases described in GB
1,296,839 to Novo; RAPIDASE~, International Bio-Synthetics, Inc. and
TERMAMYL~, Novo. FUNGAMYL~ from Novo is especially useful. Engineering of
enzymes for improved stability, e.g., oxidative stability, is known. See, for
example J.
Biological Chem., Vol. 260, No. 11, June 1985, pp 6518-6521. Certain preferred
embodiments of the present compositions can make use of amylases having
improved
stability in detergents, especially improved oxidative stability as measured
against a
reference-point of TERMAMYL~ in commercial use in 1993. These preferred
amylases
herein share the characteristic of being "stability-enhanced" amylases,
characterized, at a
minimum, by a measurable improvement in one or more of: oxidative stability,
e.g., to
hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9-
10; thermal
stability, e.g., at common wash temperatures such as about 60oC; or alkaline
stability,
e.g., at a pH from about 8 to about 11, measured versus the above-identified
reference-
point amylase. Stability can be measured using any of the art-disclosed
technical tests.
See, for example, references disclosed in WO 9402597. Stability-enhanced
amylases can
be obtained from Novo or from Genencor International. One class of highly
preferred
amylases herein have the commonality of being derived using site-directed
mutagenesis
CA 02252941 2003-12-17
52
from one or more of the Baccillus amylases, especialy the Bacillus a-amylases,
regardless of whether one, two or multiple amylase strains are the immediate
precursors.
Oxidative stability-enhanced amylases vs, the above-identified reference
amylase are
preferred for use, especially in bleaching, more preferably oxygen bleaching,
as distinct
from chlorine bleaching, detergent compositions herein. Such preferred
amylases include
(a) an amylase according to the hereinbefore referenced WO 9402597, Novo, Feb.
3,
1994, as further illustrated by a mutant in which substitution is made, using
alanine or
threonine, preferably threonine, of the methionine residue located in position
197 of the
B.lichenijormis alpha-amylase, known as TERMAMYL~, or the homologous position
variation of a similar parent amylase, such as B. amyloliquejaciens,
B.subtilis, or
B.s~earothermophilus; (b) stability-enhanced amylases as described by Genencor
International in a paper entitled "Oxidatively Resistant alpha-Amylases"
presented at the
207th American Chemical Society National Meeting, March 13-17 1994, by C.
Mitchinson. Therein it was noted that bleaches in automatic dishwashing
detergents
inactivate alpha-amylases but that improved oxidative stability amylases have
been made
by Genencor from B.lichenijormis NCIB8061. Methionine (Met) was identified as
the
most likely residue to be modified. Met was substituted, one at a time, in
positions 8, 15,
197, 256, 304, 366 and 438 leading to specific mutants, particularly important
being
M 197L and M 197T with the M 197T variant being the most stable expressed
variant.
Stability was measured in CASCADE~ and SUNLIGHT; (c) particularly preferred
amylases herein include amylase variants having additional modification in the
immediate parent as described in WO 9510603 A and are available from the
assignee,
Novo, as DURAMYL~. Other particularly preferred oxidative stability enhanced
amylase include those described in WO 9418314 to Genencor International and WO
9402597 to Novo. Any other oxidative stability-enhanced amylase can be used,
for
example as derived by site-directed mutagenesis from known chimeric, hybrid or
simple
mutant parent forms of available amylases. Other preferred enzyme
modifications are
accessible. See WO 9509909 A to Novo.
Cellulases usable herein include both bacterial and fungal types, preferably
having
a pH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6,
1984,
discloses suitable fungal cellulases from Humicola insolens or Numicola strain
DSM 1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas,
and
cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella
Auricula
Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-
2.095.275
and DE-OS-2.247.832. CAREZYME~ (Novo) is especially useful. See also WO
9117243 to Novo.
CA 02252941 2003-12-17
53
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent
Application
53,20487, laid open Feb. 24, 1978. This lipase is available from Amano
Pharmaceutical
Co. Ltd., Nagoya, Japan, under the trade mark Lipase P "Amano," or "Amano-P."
Other
suitable commercial lipases include Amano-CES, lipases ex Chromobacter
viscosum,
e.g. Claromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,
Tagata,
Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and
Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE~
enzyme derived from Humicola lanuginosa and commercially available from Novo,
see
also EP 341,947, is a preferred lipase for use herein. Lipase and amylase
variants
stabilized against peroxidase enzymes are described in WO 9414951 A to Novo.
See
also WO 9205249 and RD 94359044.
Cutinase enzymes suitable for use herein are described in WO 8809367 A to
Genencor.
Peroxidase enzymes may be used in combination with oxygen sources, e.g.,
percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or
prevention
of transfer of dyes or pigments removed from substrates during the wash to
other
substrates present in the wash solution. Known peroxidases include horseradish
peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-
peroxidase.
Peroxidase-containing detergent compositions are disclosed in WO 89099813 A,
October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to
McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al,
July 18,
1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful
for
liquid detergent formulations, and their incorporation into such formulations,
are
disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in
detergents
can be stabilized by various techniques. Enzyme stabilization techniques are
disclosed
and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405
and EP
200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also
described,
for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases,
xylanases
and cellulases, is described in WO 9401532 A to Novo.
Enzyme StabilizingSystem
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WO 97/42291 PCT/US97/07056
54
Enzyme-containing, including but not limited to, liquid compositions, herein
may
comprise from about 0.001 % to about 10%, preferably from about 0.005% to
about 8%,
most preferably from about 0.01 % to about 6%, by weight of an enzyme
stabilizing
system. The enzyme stabilizing system can be any stabilizing system which is
compatible with the detersive enzyme. Such a system may be inherently provided
by
other formulation actives, or be added separately, e.g., by the formulator or
by a
manufacturer of detergent-ready enzymes. Such stabilizing systems can, for
example,
comprise calcium ion, boric acid, propylene glycol, short chain carboxylic
acids, boronic
acids, and mixtures thereof, and are designed to address different
stabilization problems
depending on the type and physical foam of the detergent composition.
One stabilizing approach is the use of water-soluble sources of calcium and/or
magnesium ions in the finished compositions which provide such ions to the
enzymes.
Calcium ions are generally more effective than magnesium ions and are
preferred herein
if only one type of cation is being used. Typical detergent compositions,
especially
liquids, will comprise from about 1 to about 30, preferably from about 2 to
about 20,
more preferably from about 8 to about 12 millimoles of calcium ion per liter
of finished
detergent composition, though variation is possible depending on factors
including the
multiplicity, type and levels of enzymes incorporated. Preferably water-
soluble calcium
or magnesium salts are employed, including for example calcium chloride,
calcium
hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide
and
calcium acetate; more generally, calcium sulfate or magnesium salts
corresponding to the
exemplified calcium salts may be used. Further increased levels of Calcium
and/or
Magnesium may of course be useful, for example for promoting the grease-
cutting action
of certain types of surfactant.
Another stabilizing approach is by use of borate species. See Severson, U.S.
4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or
more of the
composition though more typically, levels of up to about 3% by weight of boric
acid or
other borate compounds such as borax or orthoborate are suitable for liquid
detergent
use. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-
bromophenylboronic acid or the like can be used in place of boric acid and
reduced
levels of total boron in detergent compositions may be possible though the use
of such
substituted boron derivatives.
Stabilizing systems of certain cleaning compositions may further comprise from
0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine
bleach
scavengers, added to prevent chlorine bleach species present in many water
supplies
from attacking and inactivating the enzymes, especially under alkaline
conditions. While
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WO 97/42291 PCT/US97/07056
chlorine levels in water may be small, typically in the range from about 0.5
ppm to about
1.75 ppm, the available chlorine in the total volume of water that comes in
contact with
the enzyme, for example during fabric-washing, can be relatively large;
accordingly,
enzyme stability to chlorine in-use is sometimes problematic. Since perborate
or
percarbonate, which have the ability to react with chlorine bleach, may
present in certain
of the instant compositions in amounts accounted for separately from the
stabilizing
system, the use of additional stabilizers against chlorine, may, most
generally, not be
essential, though improved results may be obtainable from their use. Suitable
chlorine
scavenger anions are widely known and readily available, and, if used, can be
salts
containing ammonium cations with sulfite, bisulfate, thiosulfite, thiosulfate,
iodide, etc.
Antioxidants such as carbamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine
(MEA), and mixtures thereof can likewise be used. Likewise, special enzyme
inhibition
systems can be incorporated such that different enzymes have maximum
compatibility.
Other conventional scavengers such as bisulfate, nitrate, chloride, sources of
hydrogen
peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate
and
sodium percarbonate, as well as phosphate, condensed phosphate, acetate,
benzoate,
citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures
thereof can be used
if desired. In general, since the chlorine scavenger function can be performed
by
ingredients separately listed under better recognized functions, (e.g.,
hydrogen peroxide
sources), there is no absolute requirement to add a separate chlorine
scavenger unless a
compound performing that function to the desired extent is absent from an
enzyme-
containing embodiment of the invention; even then, the scavenger is added only
for
optimum results. Moreover, the formulator will exercise a chemist's normal
skill in
avoiding the use of any enzyme scavenger or stabilizer which is majorly
incompatible, as
formulated, with other reactive ingredients, if used. In relation to the use
of ammonium
salts, such salts can be simply admixed with the detergent composition but are
prone to
adsorb water and/or liberate ammonia during storage. Accordingly, such
materials, if
present, are desirably protected in a particle such as that described in US
4,652,392,
Baginski et al.
. The compositions herein can optionally include one or more other detergent
adjunct materials or other materials for assisting or enhancing cleaning
performance,
treatment of the substrate to be cleaned, or to modify the aesthetics of the
detergent
composition (e.g., perfumes, colorants, dyes, etc.). The following are
illustrative
examples of such adjunct materials.
Builders
CA 02252941 2003-12-17
56
Detergent builders can optionally be included in the compositions herein to
assist
in controlling mineral hardness. Inorganic as well as organic builders can be
used.
Builders are typically used in fabric laundering compositions to assist in the
removal of
particulate soils.
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. Liquid 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 1 S% 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 mete-phosphates),
phosphonates, phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and aluminosilicates. 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: l and layered silicates,
such as the
layered sodium silicates described in U.S. Patent 4,664,839, issued May 12,
1987 to H.
P. Rieck. 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 Mcan
be us~d
herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7
and
TM
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
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
57
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-
occurnng aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange materials is disclosed in U.S. Patent 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:
Nal2~(A102)12(Si02)12l'~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 polycarboxyiate
compounds. As used
herein, "polycarboxylate" 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
materials. One important category of polycarboxylate builders encompasses the
ether
polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent
3,128,287,
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued
January 18, 1972.
CA 02252941 2003-12-17
58
See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on
May 5,
1987. Suitable ether polycarboxylates also include cyclic compounds,
particularly
alicyclic compounds, such as those described in U.S. Patents 3,923,679;
3,835,163;
4,158,635; 4,120,874 and 4,102,903.
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 nitrilotriacetic acid, as well as
polycarboxylates
such as mellitic acid, succinic acid, oxydisuccinic 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-
dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
Patent
4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders
include the CS-
C20 alkyl and alkenyl succinic acids and salts thereof. A particularly
prefen~d
compound of this type is dodecenylsuccinic 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 polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, i 979 and in U.S. Patent 3,308,067, Diehl,
issued
March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C 12-C 1 g monocarboxylic acids, can also be incorporated
into
the compositions alone, or in combination with the aforesaid builders,
especially citrate
and/or 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
formulation of bars used for hand-laundering operations, the various alkali
metal
CA 02252941 2003-12-17
59
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate
and sodium orthophosphate 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.
ChelatinyAgents
The detergent compositions herein may also optionally contain one or more iron
and/or manganese chelating agents. Such chelating agents can be selected from
the
group consisting of amino carboxylates, amino phosphonates, polyfunctionally-
substituted aromatic chelating agents and mixtures therein, all as hereinafter
defined.
Without intending to be bound by theory, it is believed that the benefit of
these materials
is due in part to their exceptional ability to remove iron and manganese ions
from
washing solutions by formation of soluble chelates:
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-
triacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,
ammonium, and
substituted ammonium salts therein and mixtures therein. Also suitable for use
as a
chelant is methylglycine di-acetic acid (MGDA).
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at lease low levels of total phosphorus are
permitted
in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates)
TM
as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or
alkenyl
groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et al.
Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-
dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233,
November
3, 1987, to Hartman and Perkins.
if utilized, these chelating agents will generally comprise from about 0.1% to
about 10% by weight of the detergent compositions herein. More preferably, if
utilized,
the chelating agents will comprise from about 0.1% to about 3.0% by weight of
such
compositions.
Clay Soil Removal/Anti-rede_position Agents
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WO 97/42291 PCT/US97/07056
The compositions of the present invention can also optionally contain water-
soluble ethoxylated amines having clay soil removal and antiredeposition
properties.
Granular detergent compositions which contain these compounds typically
contain from
about 0.01 % to about 10.0% by weight of the water-soluble ethoxylates amines;
liquid
detergent compositions typically contain about 0.01 % to about 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S.
Patent 4,597,898, VanderMeer, issued July l, 1986. Another group of preferred
clay soil
removal-antiredeposition agents are the cationic compounds disclosed in
European
Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other
clay soil
removal/antiredeposition agents which can be used include the ethoxylated
amine
polymers disclosed in European Patent Application 111,984, Gosselink,
published June
27, 1984; the zwitterionic polymers disclosed in European Patent Application
112,592,
Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
Patent
4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or
anti
redeposition agents known in the art can also be utilized in the compositions
herein.
Another type of preferred antiredeposition agent includes the carboxy methyl
cellulose
(CMC) materials. These materials are well known in the art.
Polymeric Dispersing-Agents
Polymeric dispersing agents can advantageously be utilized at levels from
about
0.1 % to about 7%, by weight, in the compositions herein, especially in the
presence of
zeolite and/or layered silicate builders. Suitable polymeric dispersing agents
include
polymeric polycarboxylates and polyethylene glycols, although others known in
the art
can also be used. It is believed, though it is not intended to be limited by
theory, that
polymeric dispersing agents enhance overall detergent builder performance,
when used
in combination with other builders (including lower molecular weight
polycarboxylates)
by crystal growth inhibition, particulate soil release peptization, and anti-
redeposition.
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
polycarboxylates 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.
CA 02252941 2003-12-17
61
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 to 100,000,
more
preferably from about 5,000 to 75,000, most preferably from about 7,000 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 maleiclacryliclvinyl alcohol terpolymers.
Such
materials are also disclosed in EP 193,360, including, for example, the
45/45/10
terpolymer of acrylic/maleic/vinyi 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.
Brig htx ever
Any optical brighteners or other brightening or whitening agents known in the
art
can be incorporated at levels typically from about 0.05% to about 1.2%, by
weight, into
the detergent compositions herein. Commercial optical brighteners which may be
useful
CA 02252941 2003-12-17
62
in the present invention can be classified into subgroups, which include, but
are not
necessarily limited to, derivatives of stilbene, pyrazoline, coumarin,
carboxylic acid,
methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring
heterocycles, and other miscellaneous agents. Examples of such brighteners are
disclosed in "The Production and Application of Fluorescent Brightening
Agents", M.
Zahradnik, Published by John Wiley & Sons, New York (1982).
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on
TM
December 13, 1988. These brighteners include the PHORWHITE series of
brighteners
TM
from Verona. Other brighteners disclosed in this reference include: Tinopal
UNPA,
Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic White CC and
Attic
White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryl-
phenyl)-2H-
napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes; 4,4'-
bis(stryl)bisphenyls;
and the aminocoumarins. Specific examples of these brighteners include 4-
methyl-7-
diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene; 1,3-diphenyl-
phrazolines;
2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-d]oxazole; and 2-
(stilbene-4-yl)-
2H-naphtho- [1,2-d]triazole. See also U.S. Patent 3,646,015, issued February
29, 1972
to Hamilton. Anionic brighteners are preferred herein.
Suds Suppressors
Compounds for reducing or suppressing the formation of suds can be
incorporated into the compositions of the present invention. Suds suppression
can be of
particular importance in the so-called "high concentration cleaning process"
as described
in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing
machines.
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well known to those skilled in the art. See, for example, Kirk
Othmer
Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447
(John
Wiley & Sons, Inc., 1979). One category of suds suppressor of particular
interest
encompasses monocarboxylic fatty acid and soluble salts therein. See U.S.
Patent
2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxyiic
fatty
acids and salts thereof used as suds suppressor typically have hydrocarbyl
chains of 10 to
about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts
include the
alkali metal salts such as sodium, potassium, and lithium salts, and ammonium
and
alkanolammonium salts.
The detergent compositions herein rnay also contain non-surfactant suds
suppressors. These include, for example: high molecular weight hydrocarbons
such as
paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid
esters of monovalent
CA 02252941 2003-12-17
63
alcohols, aliphatic C 1 g-C4p ketones (e.g., stearone), etc. Other suds
inhibitors include
N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to
tetra-
alkyldiamine chlortriazines formed as products of cyanotic chloride with two
or three
moles of a primary or secondary amine containing 1 to 24 carbon atoms,
propylene
oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester
and
monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate
esters. The
hydrocarbons. such as paraffin and haloparaffin can be utilized in liquid
form. The liquid
hydrocarbons will be liquid at room temperatwe and atmospheric pressure, and
will have
a pour point in the range of about -40°C and about 50°C, and a
minimum boiling point
not less than about 110°C (atmospheric pressure). It is also known to
utilize waxy
hydrocarbons, preferably having a melting point below about 100°C. The
hydrocarbons
constitute a preferred category of suds suppressor for detergent compositions.
Hydrocarbon suds suppressors are described, for example, in U.S. Patent
4,265,779,
issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include
aliphatic,
alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons
having from
about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds
suppressor
discussion, is intended to include mixtures of true paraffins and cyclic
hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises
silicone
suds suppressors. This category includes the use of polyorganosiloxane oils,
such as
polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or
resins, and
combinations of polyorganosiloxane with silica particles wherein the
polyorganosiloxane
is chemisorbed or fused onto the silica. Silicone suds suppressors are well
known in the
art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5,
1981 to
Gandolfo et al and European Application No. 354,016, published February 7,
1990, by
Starch, M.S.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which
relates to compositions and processes for defoaming aqueous solutions by
incorporating
therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in
German
Patent Application DOS 2,124,526. Silicone defoamers and suds controlling
agents in
granular detergent compositions are disclosed in U.S. Patent 3,933,672,
Barioiotta et al,
and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing
amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about
1,500 cs. at 25°C;
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64
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane
resin composed of (CH3)3Si01~2 units of Si02 units in a ratio of from
(CH3)3 Si01/2 units and to Si02 units of from about 0.6:1 to about 1.2:1;
and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid
silica
gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous
phase is made up of certain polyethylene glycols or polyethylene-polypropylene
glycol
copolymers or mixtures thereof (preferred), or polypropylene glycol. The
primary
silicone suds suppressor is branched/crosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions with
controlled suds will optionally comprise from about 0.001 to about 1,
preferably from
about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight
% of said
silicone suds suppressor, which comprises ( 1 ) a nonaqueous emulsion of a
primary
antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous
siloxane or
a silicone resin-producing silicone compound, {c) a finely divided filler
material, and (d)
a catalyst to promote the reaction of mixture components (a), (b) and (c), to
form
silanolates; (2) at least one nonionic silicone surfactant; and (3)
polyethylene glycol or a
copolymer of polyethylene-polypropylene glycol having a solubility in water at
room
temperature of more than about 2 weight %; and without polypropylene glycol.
Similar
amounts can be used in granular compositions, gels, etc. See also U.S. Patents
4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued
January 8,
1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents
4,639,489 and
4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol
and
a copolymer of polyethylene glycol/polypropylene glycol, all having an average
molecular weight of less than about 1,000, preferably between about 100 and
800. The
polyethylene glycol and polyethylene/polypropylene copolymers herein have a
solubility
in water at room temperature of more than about 2 weight %, preferably more
than about
weight %.
. The preferred solvent herein is polyethylene glycol having an average
molecular
weight of less than about 1,000, more preferably between about 100 and 800,
most
preferably between 200 and 400, and a copolymer of polyethylene
glycol/polypropylene
glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between
about 1:1
and 1:10, most preferably between 1:3 and 1:6, of polyethylene
glycol:copolymer of
polyethylene-polypropylene glycol.
CA 02252941 2003-12-17
The preferred silicone suds suppressors used herein do not contain
polypropylene
glycol, particularly of 4,000 molecular weight. They also preferably do not
contain
block copolymers of ethylene oxide and propylene oxide, like PLURON1C L101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-
alkyl alkanols) and mixtures of such aicohols with silicone oils, such as the
silicones
disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols
include
the C6-C 16 alkyl alcohols having a C 1-C 16 chain. A preferred alcohol is 2-
butyl
octanol, which is available from Condea under the trademark ISOFOL 12.
Mixtures of
secondary alcohols are available under the trademark ISALCHEM 123 from
Enichem.
Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a
weight
ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic laundry washing
machines, suds should not form to the extent that they overflow the washing
machine.
Suds suppressors, when utilized, are preferably present in a "suds suppressing
amount.
By "suds suppressing amount" is meant that the formulator of the composition
can select
an amount of this suds controlling agent that will sufficiently control the
suds to result in
a low-sudsing laundry detergent for use in automatic laundry washing machines.
The compositions herein will generally comprise from 0% to about 5% of suds
suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and
salts
therein, will be present typically in amounts up to about S%, by weight, of
the detergent
composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate
suds
suppressor is utilized. Silicone suds suppressors are typically utilized in
amounts up to
about 2.0%, by weight, of the detergent composition, although higher amounts
may be
used. This upper limit is practical in nature, due primarily to concern with
keeping costs
minimized and effectiveness of lower amounts for effectively controlling
sudsing.
Preferably from about 0.01 % to about 1 % of silicone suds suppressor is used,
more
preferably from about 0.25% to about 0.5%. As used herein, these weight
percentage
values include any silica that may be utilized in combination with
polyorganosiloxane, as
well as any adjunct materials that may be utilized. Monostearyl phosphate suds
suppressors are generally utilized in amounts ranging from about 0.1 % to
about 2%, by
weight, of the composition. Hydrocarbon suds suppressors are typically
utilized in
amounts ranging from about 0.01% to about 5.0%, although higher levels can be
used.
The alcohol suds suppressors are typically used at 0.2%-3% by weight of the
finished
compositions.
Fabric Softeners
CA 02252941 2003-12-17
66
Various through-the-wash fabric softeners, especially the impalpable smectite
clays of U.S. Patent 4,062,b47, Storm and Nirschl, issued December 13, 1977,
as well as
other softener clays known in the art, can optionally be used typically at
levels of from
about 0.5% to about 10% by weight in the present compositions to provide
fabric
softener benefits concurrently with fabric cleaning. Clay softeners can be
used in
combination with amine and cationic softeners as disclosed, for example, in
U.S. Patent
4,375,416, Crisp et at, March 1, 1983 and U.S. Patent 4,291,071, Hams et al,
issued
September 22, 1981.
Optical Brighteners
The detergent compositions herein may also optionally contain from about
0.005% to 5% by weight of certain types of hydrophilic optical brighteners
which also
provide a dye transfer inhibition action. If used, the compositions herein
will preferably
comprise from about 0.01% to 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
R~ RZ
N H H N
N N C C O N --~O N
~N H H N
R2 S03M S~3M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2
is selected from N-2-bis-hydroxyethyI, N-2-hydroxyethyl-N-methylamino,
motphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-
triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the trademark Tinopal-UNPA-
GX by
Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-
2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stiltienedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
trademark Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2-
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67
yl)amino~2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is
commercially marketed under the trademark Tinopal AMS-GX by Ciba Geigy
Corporation.
EXAMPLE 1
Preparation of PEI 1800 E_7
The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave
equipped for temperature measurement and control, pressure measurement, vacuum
and
inert gas purging, sampling, and for introduction of ethylene oxide as a
liquid. A ~20 lb.
net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a
liquid by a
pump to the autoclave with the cylinder placed on a scale so that the weight
change of
the cylinder could be monitored.
TM
A 750 g portion of polyethyleneimine (PEI) (Nippon Shokubai, Epomin SP-018
having a listed average molecular weight of 1800 equating to about 0.417 moles
of
polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The
autoclave
is then sealed and purged of air (by applying vacuum to minus 28" Hg followed
by
pressurization with nitrogen to 250 psia, then venting to atmospheric
pressure). The
autoclave contents are heated to 130 °C while applying vacuum. After
about one hour,
the autoclave is charged with nitrogen to about 250 psia while cooling the
autoclave to
about 105 °C. Ethylene oxide is then added to the autoclave
incrementally over time
while closely monitoring the autoclave pressure, temperature, and ethylene
oxide flow
rate. The ethylene oxide pump is turned off and cooling is applied to limit
any
temperature increase resulting from any reaction exotherm. The temperature is
maintained between 100 and 110 °C while the total pressure is allowed
to gradually
increase during the course of the reaction. After a total of 750 grams of
ethylene oxide
has been charged to the autoclave (roughly equivalent to one mole ethylene
oxide per
PE1 nitrogen function), the temperature is increased to 110 °C and the
autoclave is
allowed to stir for an additional hour. At this point, vacuum is applied to
remove any
residual unreacted ethylene oxide.
Next, vacuum is continuously applied while the autoclave is cooled to about 50
°
C while introducing 3?6 g of a 25% sodium methoxide in methanol solution (1.74
moles,
to achieve a 10% catalyst loading based upon PEI nitrogen functions). The
methoxide
solution is sucked into the autoclave under vacuum and then the autoclave
temperature
controller setpoint is increased to 130 °C. A device is used to monitor
the power
consumed by the agitator. The agitator power is monitored along with the
temperature
and pressure. Agitator power and temperature values gradually increase as
methanol is
removed from the autoclave and the viscosity of the mixture increases and
stabilizes in
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68
about 1 hour indicating that most of the methanol has been removed. The
mixture is
further heated and agitated under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it
is being
charged with nitrogen to 250 psia and then vented to ambient pressure. The
autoclave is
charged to 200 psia with nitrogen. Ethylene oxide is again added to the
autoclave
incrementally as before while closely monitoring the autoclave pressure,
temperature,
and ethylene oxide flow rate while maintaining the temperature between 100 and
110 °C
and limiting any temperature increases due to reaction exotherm. After the
addition of
4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide
per mole of
PEI nitrogen function) is achieved over several hours, the temperature is
increased to 110
°C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and
eventually
transferred into a 22 L three neck round bottomed flask equipped with heating
and
agitation. The strong alkali catalyst is neutralized by adding 167 g
methanesulfonic acid
(1.74 moles). The reaction mixture is then deodorized by passing about 100 cu.
ft. of
inert gas (argon or nitrogen) through a gas dispersion frit and through the
reaction
mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass
containers
purged with nitrogen.
In other preparations the neutralization and deodorization is accomplished in
the
reactor before discharging the product.
EXAMPLE 2
Quaternization of PEI 1800 E_7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added
polyethyleneimine having a molecular weight of 1800 which is further modified
by
ethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen
(PEI
1800, E7) (207.3g, 0.590 mol nitrogen, prepared as in Example I) and
acetonitrile (120
g). Dimethyl sulfate (28.3g, 0.224 mol) is added in one portion to the rapidly
stirring
solution, which is then stoppered and stirred at room temperature overnight.
The
acetonitrile is removed by rotary evaporation at about 60°C, followed
by further
stripping of solvent using a Kugelrohr apparatus at approximately 80°C
to afford 220 g
of the desired partially quaternized material as a dark brown viscous liquid.
The 13C-
NMR (D20) spectrum obtained on a sample of the reaction product indicates the
absence
of a carbon resonance at ~58ppm corresponding to dimethyl sulfate. The 1 H-NMR
(D20) spectrum shows a partial shifting of the resonance at about 2.5 ppm for
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69
methylenes adjacent to unquaternized nitrogen has shifted to approximately 3.0
ppm.
This is consistent with the desired quaternization of about 38% of the
nitrogens.
EXAMPLE 3
Formation of amine oxide of PEI 1800 E_7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added
polyethyleneimine having a molecular weight of 1800 and ethoxylated to a
degree of
about 7 ethoxy groups per nitrogen (PEI-1800, E7) (209 g, 0.595 mol nitrogen,
prepared
as in Example I), and hydrogen peroxide (120 g of a 30 wt % solution in water,
1.06
mol). The flask is stoppered, and after an initial exotherm the solution is
stirred at room
temperature overnight. 1 H-NMR (D20) spectrum obtained on a sample of the
reaction
mixture indicates complete conversion. The resonances ascribed to methylene
protons
adjacent to unoxidized nitrogens have shifted from the original position at
~2.5 ppm to
~3.5 ppm. To the reaction solution is added approximately 5 g of 0.5% Pd on
alumina
pellets, and the solution is allowed to stand at room temperature for
approximately 3
days. The solution is tested and found to be negative for peroxide by
indicator paper.
The material as obtained is suitably stored as a 51.1 % active solution in
water.
EXAMPLE 4
Oxidation of Ouaternized PEi 1800 E_7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added
polyethyleneimine having a molecular weight of 1800 which is further modified
by
ethoxylation to a degree of 7 ethyleneoxy residues per nitrogen (PEI 1800 E7)
subsequently quaternized with dimethyl sulfate to approximately 4.7% (121.7 g,
0.32
mol oxidizeable nitrogen), hydrogen peroxide (40 g of a 50 wt% solution in
water, 0.588
mol), and water ( 109.4 g). The flask is stoppered, and after an initial
exotherm the
solution is stirred at room temperature overnight. ~H-NMR (D20) spectrum
obtained on
a sample of the reaction mixture indicates the methylene peaks at 2.5-3.0 ppm
have
shifted to ~3.5 ppm. To the reaction solution is added ~5 g of 0.5 % Pd on
alumina
pellets, and the solution is allowed to stand at room temperature for ~3 days.
The
solution is tested and found to be negative for peroxide by indicator paper.
The desired
material with ~-4.7% of the nitrogens quaternized and 95.3% of the nitrogens
oxidized
to the amine oxide is obtained and is suitably stored as a 46.5% solution in
water.
EXAMPLE 4A
Preparation of PEI 1200 E_7
The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave
equipped for temperature measurement and control, pressure measurement, vacuum
and
inert gas purging, sampling, and for introduction of ethylene oxide as a
liquid. A ~20 lb.
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a
liquid by a
pump to the autoclave with the cylinder placed on a scale so that the weight
change of
the cylinder could be monitored.
A 750 g portion of polyethyleneimine (PEI) ( having a listed average molecular
weight of 1200 equating to about 0.625 moles of polymer and 17.4 moles of
nitrogen
functions) is added to the autoclave. The autoclave is then sealed and purged
of air (by
applying vacuum to minus 28" Hg followed by pressurization with nitrogen to
250 psia,
then venting to atmospheric pressure). The autoclave contents are heated to
130 °C
while applying vacuum. After about one hour, the autoclave is charged with
nitrogen to
about 250 psia while cooling the autoclave to about 105 °C. Ethylene
oxide is then
added to the autoclave incrementally over time while closely monitoring the
autoclave
pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump
is turned
off and cooling is applied to limit any temperature increase resulting from
any reaction
exotherm. The temperature is maintained between 100 and I 10 °C while
the total
pressure is allowed to gradually increase during the course of the reaction.
After a total
of 750 grams of ethylene oxide has been charged to the autoclave (roughly
equivalent to
one mole ethylene oxide per PEI nitrogen function), the temperature is
increased to 110 °
C and the autoclave is allowed to stir for an additional hour. At this point,
vacuum is
applied to remove any residual unreacted ethylene oxide.
Next, vacuum is continuously applied while the autoclave is cooled to about 50
°
C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74
moles,
to achieve a 10% catalyst loading based upon PEI nitrogen functions). The
methoxide
solution is sucked into the autoclave under vacuum and then the autoclave
temperature
controller setpoint is increased to 130 °C. A device is used to monitor
the power
consumed by the agitator. The agitator power is monitored along with the
temperature
and pressure. Agitator power and temperature values gradually increase as
methanol is
removed from the autoclave and the viscosity of the mixture increases and
stabilizes in
about 1 hour indicating that most of the methanol has been removed. The
mixture is
further heated and agitated under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it
is being
charged with nitrogen to 250 psia and then vented to ambient pressure. The
autoclave is
charged to 200 psia with nitrogen. Ethylene oxide is again added to the
autoclave
incrementally as before while closely monitoring the autoclave pressure,
temperature,
and ethylene oxide flow rate while maintaining the temperature between 100 and
110 °C
and limiting any temperature increases due to reaction exotherm. After the
addition of
4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide
per mole of
CA 02252941 1998-10-29
WO 97/42291 PCT/US97/07056
71
PEI nitrogen function) is achieved over several hours, the temperature is
increased to 110
°C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and
eventually
transferred into a 22 L three neck round bottomed flask equipped with heating
and
agitation. The strong alkali catalyst is neutralized by adding 167 g
methanesulfonic acid
( 1.74 moles). The reaction mixture is then deodorized by passing about 100
cu. ft. of
inert gas (argon or nitrogen) through a gas dispersion frit and through the
reaction
mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass
containers
purged with nitrogen.
In other preparations the neutralization and deodorization is accomplished in
the
reactor before discharging the product.
Other preferred examples such as PEI 1200 E 15 and PEI 1200 E20 can be
prepared by the above method by adjusting the reaction time and the relative
amount of
ethylene oxide used in the reaction.
EXAMPLE 4B
9.7% Quaternization of PEI 1200 E7
To a SOOmI erlenmeyer flask equipped with a magnetic stirring bar is added
poly(ethyleneimine), MW 1200 ethoxylated to a degree of 7 (248.48, 0.707 mol
nitrogen,
prepared as in Example S) and acetonitrile (Baker, 200 mL). Dimethyl sulfate
(Aldrich,
8.488, 0.067 mol) is added all at once to the rapidly stirring solution, which
is then
stoppered and stirred at room temperature overnight. The acetonitrile is
evaporated on
the rotary evaporator at ~60°C, followed by a Kugelrohr apparatus
(Aldrich) at ~80°C to
afford ~220g of the desired material as a dark brown viscous liquid. A 13C-NMR
(D20)
spectrum shows the absence of a peak at ~58ppm corresponding to dimethyl
sulfate. A
1 H-NMR (D20) spectrum shows the partial shifting of the peak at 2.Sppm
(methylenes
attached to unquaternized nitrogens) to ~3.Oppm.
EXAMPLE S
Preparation of Non-cotton Soil Release Polymers
. Synthesis of Sodium 2-f2 3-Dihydroxypropoxylethanesulfonate Monomer
To a SOOmI, three neck, round bottom flask equipped with a magnetic stirring
bar, modified Claisen head, condenser (set for distillation), thermometer, and
temperature controller (Therm-O-WatchTM, I2R) is added isethionic acid, sodium
salt
(Aldrich, SO.Og, 0.338 mol), sodium hydroxide (2.78, 0.0675 mol), and glycerin
(Baker,
310.98, 3.38 mol). The solution is heated at 190°C under argon
overnight as water
distills from the reaction mixture. A 13C-NMR(DMSO-d6) shows that the reaction
is
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WO 97/42291 PCT/US97/07056
72
complete by the virtual disappearance of the isethionate peaks at 53.5 ppm and
57.4
ppm, and the emergence of product peaks at 51.4 ppm (-CH2S03Na) and 67.5 ppm
(CH2CH2S03Na). The solution is cooled to 100°C and neutralized to pH 7
with
methanesulfonic acid (Aldrich). The desired, neat material is obtained by
adding 0.8
mol% of potassium phosphate, monobasic as buffer and heating on a Kugelrohr
apparatus {Aldrich) at 200°C for ~ 3 hrs. at ~1 mm Hg to afford 77g of
yellow waxy
solid. As an alternative, not all of the glycerin is removed before use in
making the
oligomers. The use of glycerin solutions of SEG can be a convenient way of
handling
this sulfonated monomer.
EXAMPLE 6
Synthesis of Sodium 2-[2-(2-Hydroxyethoxylethoxy]ethanesulfonate Monomer
To a 1 L, three neck, round bottom flask equipped with a magnetic stirring
bar,
modified Claisen head, condenser (set for distillation), thermometer, and
temperature
controller (Therm-O-WatchT"",12R) is added isethionic acid, sodium salt
(Aldrich,
I OO.Og, 0.675 mol) and distilled water {~90 ml). After dissolution, one drop
of hydrogen
peroxide {Aldrich, 30% by wt. in water) is added to oxidize traces of
bisulfate. The
solution is stirred for one hour. A peroxide indicator strip shows a very weak
positive
test. Sodium hydroxide pellets (MCB, 2.Sg, 0.0625 mol) are added, followed by
diethylene glycol (Fisher, 303.3g, 2.86 mol). The solution is heated at
190C° under
argon overnight as water distills from the reaction mixture. A 13C-NMR(DMSO-
d6)
shows that the reaction is complete by the disappearance of the isethionate
peaks at
53.5 ppm and 57.4 ppm. The solution is cooled to room temperature and
neutralized
to pH 7 with 57.4g of a 16.4% solution of p-toluenesulfonic acid monohydrate
in
diethylene glycol. (Alternatively, methanesulfonic acid may be used.) The 13C-
NMR
spectrum of the product shows resonances at ~S lppm (-CH2S03Na) , ~60ppm (-
CH20H), and at ~69 ppm, ~72 ppm, and ~77 ppm for the remaining four
methylenes.
Small resonances are also visible for the sodium p-toluenesulfonate which
formed during
neutralization. The reaction affords 451g of a 35.3% solution of sodium 2-[2-
(2-
hydroxyethoxy)ethoxy]ethanesulfonate in diethylene glycol. The excess
diethylene
glycol is removed by adding 0.8 mol% of monobasic potassium phosphate
(Aldrich) as a
buffer and heating on a Kugelrohr apparatus (Aldrich) at 1 SOC° for ~ 3
hrs. at ~ 1 mm Hg
to give the desired "SE3" (as defined herein above) as an extremely viscous
oil or glass.
EXAMPLE 7
Synthesis of Sodium 2-12-f2-(2-Hydroxvethoxy)ethoxy]ethoxvlethanesulfonate
Monomer
To a 1 L, three neck, round bottom flask equipped with a magnetic stirring
bar,
modified Claisen head, condenser (set for distillation), thermometer, and
temperature
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WO 97/42291 PCT/iJS97/07056
73
controller (Therm-O-WatchT"", I2R) is added isethionic acid, sodium salt
(Aldrich,
205.Og, 1.38 mol) and distilled water 0200 ml). After dissolution, one drop of
hydrogen
peroxide (Aldrich, 30% by wt. in water) is added to oxidize traces of
bisulfate. The
solution is stirred for one hour. A peroxide indicator strip shows a very weak
positive
test. Sodium hydroxide pellets (MCB, S.Sg, 0.138 mol) are added, followed by
triethylene glycol (Aldrich, 448.7g, 3.0 mol). Optionally, the triethylene
glycol can be
purified by heating with strong base such as NaOH until color stabilizes and
then
distilling off the purified glycol for use in the synthesis. The solution is
heated at 190C°
under argon overnight as water distills from the reaction mixture. A 13C-
NMR(DMSO-
d6) shows that the reaction is complete by the disappearance of the
isethionate peaks at
53.5 ppm and 57.4 ppm, and the emergence of product peaks at ~S l ppm (-
CH2S03Na) , ~60ppm (-CH20H), and at ~67 ppm, ~69 ppm, and ~72 ppm for the
remaining methylenes. The solution is cooled to room temperature and
neutralized to
pH 7 with methanesulfonic acid (Aldrich). The reaction affords 650g of a 59.5%
solution of sodium 2-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}ethanesulfonate in
triethylene glycol. The excess triethylene glycol is removed by adding 0.8
mol% of
monobasic potassium phosphate (Aldrich) as a buffer and heating on a Kugelrohr
apparatus (Aldrich) at 180C° for ~ 5.5 hrs. at ~1 mm Hg to give the
desired material as a
brown solid. It is found that a more soluble buffer can be more effective in
controlling
pH during the stripping of excess triethylene glycol. One example of such a
more
soluble buffer is the salt of N-methylmorpholine with methanesulfonic acid.
Alternatively, the pH can be controlled by frequent or continuous addition of
acid such
as methanesulfonic acid to maintain a pH near neutral during the stripping of
excess
glycol.
The material is believed to contain a low level of the disulfonate arising
from
reaction of both ends of the triethylene glycol with isethionate. However, the
crude
material is used without further purification as an anionic capping groups for
polymer
preparations.
Other preparations use a larger excess of triethylene glycol such as 5 to 10
moles
per mole of isethionate.
EXAMPLE 8
S_~nthesis of an Oii~omer of Sodium 2-[2-(2-H
droxyethoxy)ethoxylethanesulfonate
Dimethvl Terephthalate Sodium 2-(2 3-Dihydroxypropoxylethanesulfonate Glycerin
Ethylene Glycol and Propylene Glycol 1
- To a 250m1, three neck, round bottom flask equipped with a magnetic stirring
bar, modified Claisen head, condenser (set for distillation), thermometer, and
CA 02252941 2003-12-17
74
temperature controller (Therm-O-Watch~, I2R) is added sodium 2-[2-(2-
hydroxyethoxy)ethoxy]ethanesulfonate (7.Og, 0.030 mol), dimethyl terephthalate
(14.4g,
0.074 mol), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (3.3g, 0.015 mol),
glycerin (Baker, 1.4g, 0.015 mol), ethylene glycol (Baker, l4.Og, 0.225 mol),
propylene
glycol (Fisher, l7.Sg, 0.230 mol), and titanium (IV) propoxide (O.OIg, 0.02%
of total
reaction weight). This mixture is heated to 180°C and maintained at
that temperature
overnight under argon as methanol and water distill from the reaction vessel.
The
material is transferred to a SOOmI, single neck, round bottom flask and heated
gradually
over about 20 minutes to 240°C in a Kugelrohr apparatus (Aldrich) at
about 2 mm Hg
and maintained there for 1.5 hours. The reaction flask is then allowed to air
cool quite
rapidly to near room temperature under vacuum (~30 min.) The reaction affords
21.3g
of the desired oligomer as a brown glass. A 13C-NMR(DMSO-d6) shows a resonance
for ~(O~CH CH20(O~- at --63.2 ppm (diester) and a resonance for -
C(O)OCH CH20H at --59.4 ppm (monoester). The ratio of the diester peak height
to
the monoester peak height is about 10. Resonances at 51.5 ppm and ~S 1.6 ppm
representing the sulfoethoxy groups (-CH2S03Na) are also present. A 1 H-
NMR(DMSO-d6) shows a resonance at --7.9 ppm representing terephthalate
aromatic
hydrogens. Analysis by hydrolysis-gas chromatography shows that the mole ratio
of
incorporated ethylene glycol to incorporated propylene glycol is 1.7:1. It
also shows that
about 0.9% of the final polymer weight consists of glycerin. If all glycerin
monomer has
been incorporated as esters of glycerin, it would represent approximately 4%
of final
oligomer weight. The solubility is tested by weighing a small amount of
material into a
vial, adding enough distilled water to make a 35% by weight solution, and
agitating the
vial vigorously. The material is readily soluble under these conditions.
EXAMPLE 9
Synthesis of an Oli;~omer of Sodium 2-[2-(2-
Hydroxyethoxy)ethoxy]ethanesulfonate.
Dimethyl Terephthalate. Sodium 2-(2.3-Dih dy roxYpropoxylethanesulfonate.
Ethylene
Glycol, and Propylene Gycoll
To a 250 ml, three neck, round bottom flask equipped with a magnetic stirring
bar, modified Claisen head, condenser (set for distillation), thermometer, and
temperature controller (Therm-O-Watch~, I2R) is added sodium 2-[2-(2-
hydroxyethoxy)ethoxy]ethanesulfonate {7.Og, 0.030 mol), dimethyl terephthalate
(14.4g,
0.074 mol), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (6.6g, 0.030 mol),
ethylene glycol (Baker, l4.Og, 0.225 mol), propylene glycol (Fisher, 18.3g,
0.240 mol),
and titanium (IV) propoxide (0.01 g, 0.02% of total reaction weight). This
mixture is
heated to 180°C and maintained at that temperature overnight under
argon as methanol
CA 02252941 2003-12-17
distills from the reaction vessel. The material is transferred to a SOOmI,
single neck,
round bottom flask and heated gradually over about 20 minutes to 240°C
in a Kugelrohr
apparatus (Aldrich) at about 0.1 mm Hg and maintained there for 110 minutes.
The
reaction flask is then allowed to air cool quite rapidly to near room
temperature under
vacuum (~3G min.) The reaction affords 24.48 of the desired oligomer as a
brown glass.
A 13C-NMR{DMSO-d6) shows a resonance for -C(O~CH CH20(O~- at -r63.2 ppm
(diester) and a resonance for -C(O~CH CHZOH at 59.4 ppm (monoester). The ratio
of the diester peak to monoester peak is measured to be 8. Resonances at 51.5
ppm
and --5 I .6 ppm representing the sulfoethoxy groups (-CH2S03Na) are also
present. A
I H-NMR(DMSO-d6) shows a resonance at -?.9 ppm representing terephthalate
aromatic hydrogens. Analysis by Hydrolysis-GC shows that the mole ratio of
incorporated ethylene glycol to incorporated propylene glycol is 1.6:1. The
solubility is
tested by weighing a small amount of material into a vial, adding enough
distilled water
to make a 35% by weight solution, and agitating the vial vigorously. The
material is
readily soluble under these conditions.
EXAMPLE 10
Synthesis of an Oligomer of Sodium 2=j2-(2-
Hvdroxyethoxy)ethoxylethanesulfonate.
Dimeth 1 Terephthalate, Sodium 2-(2.3-Dihydroxypropoxy,)ethanesulfonate.
Glycerin.
Ethyler~e Glycol. and Propylene Glvcol )
To a 250 ml, three neck, round bottom flask equipped with a magnetic stirring
bar, modified Claisen head, condenser (set for distillation), thermometer, and
temperature controller (Therm-O-Watch~, I2R) is added sodium 2-[2-(2-
hydroxyethoxy)ethoxyJethanesulfonate (?.Og, 0.030 mol), dimethyl terephthalate
(9.6g,
0.049 mol), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (2.2g, 0.010 mol),
glycerin (Baker, 1.8g, 0.020 mol), ethylene glycol (Baker, 6.1 g, 0.100 mol),
propylene
glycol (Fisher, ?.Sg, 0.100 mol), and titanium (IV) propoxide (O.OIg, 0.02% of
total
reaction weight). This mixture is heated to 180°C and maintained at
that temperature
overnight under argon as methanol distills from the reaction vessel. The
material is
transferred to a 250 ml, single neck, round bottom flask and heated gradually
over about
20 minutes to 240°C in a Kugelrohr apparatus (Aldrich) at about 3 mm Hg
and
maintained there for I .5 hours. The reaction flask is then allowed to air
cool quite
rapidly to near room temperature under vacuum (--30 min.) The reaction affords
18.1 g
of the desired oligomer as a brown glass. A 13C-NMR(DMSO-d6) shows a resonance
for -C(O)OCH CHZO(O~- at -~-63.2 ppm (diester). A resonance for
-C(O~CH CH20H at 59.4 ppm (monoester) is not detectable and is at least 12
times
smaller than the diester peak. Resonances at -51.5 ppm and --51.6 ppm
representing the
CA 02252941 2003-12-17
76
sulfoethoxy groups (-CHZS03Na) ~'e also present. A 1 H-NMR(DMSO-d6) shows a
resonance at -7.9 ppm representing terephthalate aromatic hydrogens. Analysis
by
Hydrolysis-GC shows that the mole ratio of incorporated ethylene glycol to
incorporated
propylene glycol is 1.6:1. The incorporated glycerin is found to be 0.45
weight % of the
final polymer. The solubility is tested by weighing a small amount of material
into a vial,
adding enough distilled water to make a 35% by weight solution, and agitating
the vial
vigorously. The material is readily soluble under these conditions.
EXAMPLE 11
Synthesis of an Oligomer of Sodium 2-I2-(2-
Hydroxyethoxy>ethoxy]ethanesulfonate,
Dimethyl Terephthalate. Sodium 2-(2,3-Dihydroxynropoxy)ethanesulfonate. Gl
cerol,
Ethylene Glycol, and Propylene Gl3rcol)
To a 250 ml, three neck, round bottom flask equipped with a magnetic stirring
bar, modified Claisen head, condenser (set for distillation), thermometer, and
temperature
controller (Therm-O-Watch~, I2R) is added sodium 2-[2-(2-
hydroxyethoxy)ethoxy]ethanesulfonate {2.7g, 0.011 mol, as in Example 2),
dimethy(
terephthalate ( l2.Og, 0.062 mol, Aldrich), sodium 2-(2,3-
dihydroxypropoxy)ethanesulfonate (S.Og, 0.022 mol, as in Example 1 ), glycerol
(Baker,
O.SOg, 0.0055 mol), ethylene glycol (Baker, 6.8g, 0.110 mol), propylene glycol
(Baker,
8.Sg, O.I 12 mol), and titanium (IV) propoxide (0.01 g, 0.02% of total
reaction weight).
This mixture is heated to 180°C and maintained at that temperature
overnight under
argon as methanol and water distill from the reaction vessel. The material is
transferred
to a SOOmI, single neck, round bottom flask and heated gradually over about 20
minutes
to 240°C in a Kugelrohr apparatus (Aldrich) at about 0.5 mm Hg and
maintained there
for 150 minutes. The reaction flask is then allowed to air cool quite rapidly
to near room
temperature under vacuum (~30 min.) The reaction affords 16.7g of the desired
oligomer
as a brown glass. A 13C-NMR(DMSO-d6) shows a resonance for -
-C(O~CH CHZO(O)C- at ~-63.2 ppm (diester) and a resonance for -C(O)OCH CH20H
at --59.4 ppm (monoester). The ratio of the peak height for the diester
resonance to that
of the monoester resonance is measured to be 6.1. Resonances at ~S 1.5 ppm and
--51.6
ppm _representing the sulfoethoxy groups (-CHzS03Na) are also present. A IH-
NMR(DMSO-d6) shows a resonance at --7.9 ppm representing terephthalate
aromatic
hydrogens. Analysis by hydrolysis-gas chromatography shows that the mole ratio
of
incorporated ethylene glycol to incorporated propylene glycol is 1.42:1. The
solubility is
tested by weighing a small amount of material into a vial, adding enough
distilled water
to make a 35% by weight solution, and agitating the vial vigorously. The
material is
readily soluble under these conditions. A ~9g sample of this material is
further heated at
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WO 97/42291 PCT/US97/07056
77
240°C in a Kugelrohr apparatus at about 0.5 mm Hg and maintained there
for 80 minutes.
A I3C-NMR(DMSO-d6) shows no detectable peak for monoester at 59.4 ppm. The
peak for diester at 63.2 ppm is at least 11 times larger than the monoester
peak. The
solubility of this material is tested as above and it is also found to be
readily soluble
under these conditions.
The modified polyamines of the present invention useful as cotton soil release
agents are suitably prepared by the following methods.
Detergent Composition Formulation
The detergent compositions according to the present invention can be in
liquid,
paste or granular forms. Such compositions can be prepared by combining the
essential
and optional components in the requisite concentrations in any suitable order
and by an
conventional means.
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.
TABLEI
Liauid Laundry Detergent Compositions
Ingredients 12 13 14 15
C 12-C 15 Alkyl sulfate -- 19.0 21.0 --
C 12-C 15 Alkyl ethoxylated23.0 4.0 4.0 25.0
sulfate
C 12-C 14 N-methyl glucamide9.0 9.0 9.0 9.0
C I 2-C I 4 Fatty alcohol 6.0 6.0 6.0 6.0
ethoxylate
C I 2-C 16 Fatty acid 9.0 6.8 14.0 I 4.0
Citric acid (anhydrous) 6.0 4.5 3.5 3.5
Diethylene triamine pentaethyleneI .0 1.0 2.0 2.0
phoshonic acid (DPTA)
Monoethanolamine 13.2 12.7 12.8 I I
.0
Propanediol 12.7 14.5 13.1 10.0
Ethanol 1.8 1.8 4.7 5.4
Enzymes (protease, lipase)2.4 2.4 2.0 2.0
Soil Release Agent I 0.5 0.5 -- -_
Soil Release Agent 2 -- -- 0.5 0.5
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WO 97/42291 PCT/US97/07056
78
Boric acid 2.4 2.4 2.8 2.8
2-butyloctanol 2.0 2.0 2.0 2.0
DC 3421 R 3 0.3 0.4 -- --
FF 400 R 4 -- -- 0.3 0.4
Poly(4-vinylpyridine)-N-oxide-- -- 0.5 0.5
N- 0.3 0.3 -- --
vinylpyrrolidinone/vinylimidazole
copolymer - MW 10,000
PEI 1800 E7 2.0 2.0 2.0 2.0
Tinopal UNPA-GX Brightener0.075 0.21 -- --
Tinopal SBM-GX Brightener -- -- 0.21 0.075
Water & minors balance balancebalance balance
1. Soil release agent according to U.S. Patent 4,968,451, Scheibel et al.,
issued
November 6, 1990.
2. Soil release agent according to Example 11.
3. Silicone oil commercially available from Dow Corning.
4. Silicone glycol emulsifier available from Dow Corning.
The compositions described in Table I are suitable for laundering colored
fabrics
in aqueous washing solution while providing excellent dye transfer inhibition
benefits.
Dye transfer inhibition performance provide by the combination of the PVNO or
PVPI
with the selected polyamine (PEI 1800 E7) is significantly better than if the
dye transfer
inhibiting polymers or the polyamine were used alone.
TABLE II
.LicLuid Laundr~r Detereent Compositions
Ingredients 16 17 18 19
C 12-C 15 Alkyl ethoxylated18.0 16.0 18.0 16.0
sulfate
C 12-C 14 N-methyl glucamide4.5 3.1 4.5 3.1
C 12-C 14 Fatty alcohol 2.0 1.0 2.0 1.0
ethoxylate
C 12-C 16 Fatty acid 2.0 2.0 2.0 2.0
Citric acid (anhydrous) 3.0 2.5 3.0 2.5
Monoethanolamine 0.0 0.75 0.0 0.75
Propanediol 0.0 5.1 0.0 5.1
NaOH 2.93 2.9 2.93 2.9
Ethanol 3.52 2.88 3.52 2.88
Enzymes 1 1.25 0.7 1.25 0.7
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WO 97/42291 PCT/US97/07056
79
Soil release agent 2 0.2 -- 0.2 --
Soil release agent 3 -- 1.18 -- 1.18
Sodium formate 0.093 0.058 0.093 0.058
Boric acid 3.5 2.5 3.5 2.5
Silicone Suds Suppressor 0.119 0.085 0.119 0.085
Poly(4-vinylpyridine)-N-oxide0.1 0.2 -- __
N- _- __ 0.1 0.2
vinylpyrrolidinone/vinylimidazole
copolymer - MW 10,000
PEI 1800 E7 2.0 2.0 2.0 2.0
Tinopal UNPA-GX Brightener0.05 -- 0.05 --
Water & minors balance balancebalance balance
1. ttacillus amyloliquefaciens subtilisin as described in WO 95/10615
published April
20, 1995 by Genencor International.
2. Terephthalate co-polymer as disclosed in U.S. Patent 4,968,451, Scheibel et
aL,
issued November 6, 1990.
3. Soil release polymer according to U.S. Patent 4,702,857, Gosselink, issued
October
27, 1987.
Concentrated built heavy duty liquid detergent compositions are prepared
having
the formulations set forth in Table III.
TABLE III
Liauid Detergent Compositions
Ingredients ~n m
C 14-C 15 ~Yl PolYethoxylene (2.25) 23.00 12.50
sulfonic acid
C I 2'C 13 Linear alkyl benzene sulfonic-- 1 I .46
acid
1,2-Propandiol 10.50 3.97
Monoethanolamine 12.50 3.65
C 12-C 13 Alkyl polyethoxylate (6.5) 6.00 1.78
Ethanol 3.80 1.75
Polyhydroxy C 12-C 14 fatty acid amide9.00 --
C 12-C 16 Coconut fatty acid 9.00 2.60
Citric acid 6.00 6.04
DTPA 0.95 --
Sodium formate 0.14
Boric acid 2.4 1.0
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Tetraethylenepentamine ethoxylate (15-18)1.00 1.44
Soil release agent 1 0.5 0.6
PEI 1800 E7 3.00 3.1
Enzymes (protease and lipase) 2.55 2.27
Silicone antifoam composition 0.04 0.02
Poly(4-vinylpyridine)-N-oxide (PVNO) 0.10 0.10
Brightener - Tinopal UNPA-GX 0.20 0.20
Water and minors balancebalance
1. Soil release polymer according to U.S. Patent 4,702,857, Gosselink, issued
October 27, 1987.
Granular compositions, for example, 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 can be admixed in granular powder form with the spray dried
granules in a
rotary mixing drum and the liquid ingredients (e.g. 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 g/l. 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
sulfates and chlorides, typically sodium sulfate; "compact" detergents
typically comprise
not more than 10% filler salt.
TABLE IV
Granular Detergent Compositions
Ingredients 22 23 24
C 13-C 14 Linear alkyl benzene 11.40 -- --
sulfonic
acid
C 12-C 15 Alkyl ethoxylated -- 10.00 --
sulfate
C 12-C 14 N-methyl glucamide -- -- 13.00
Tallow alkyl sulfate 1.80 1.80 1.80
C46 Alkyl sulfate 3.00 3.00 3.00
C45 Alcohol E7 ethoxylate 4.00 4.00 4.00
Tallow alcohol E7 ethoxylate 1.80 1.80 1.80
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Dispersent 0.07 0.07 0.07
Silicone fluid 0.80 0.80 0.80
Trisodium citrate 14.00 14.00 14.00
Citric acid 3.00 3.00 3.00
Zeolite 32.50 32.50 32.50
Malefic acid acrylic acid copolymer5.00 5.00 5.00
Cellulose (active protein) 0.03 0.03 0.03
AlkalaseBAN 0.60 0.60 0.60
Lipase 0.36 0.36 0.36
Sodium silicate 2.00 2.00 2.00
Sodium sulfate 3.50 3.50 3.50
Poly(4-vinylpyridine)-N-oxide 0.10 0.10 --
(PVNO)
N-vinylpyrrolidone/N-vinylimidazole-- -- 0.20
copolymer MW 10,000 (PVPI)
Soil release agentl 0.5 -- --
Soil release agent2 -- 0.5 --
Soil release agent3 -- -- 0.5
PEI 1800 E7 3.0 3.0 3.0
Tinopal UNPA-GX 0.20 -- 0.20
TinopalSBM-GX -- 0.20 --
Minors balance balancebalance
1. Non-cotton soil release polymer according to U.S. Patent 4,968,451,
Scheibel et al.,
issued November 6, 1990.
2. Non-cotton soil release polymer according to U.S. Patent 5,415,807,
Gosselink, Pan,
Kellett and Hall, issued May 16, 1995.
3. Non-cotton soil release polymer according to U.S. Patent 4,702,857,
Gosselink,
issued October 27, 1987.
The compositions described in Table IV are suitable for laundering colored
fabrics in aqueous washing solution while providing excellent dye transfer
inhibition
benefits. Dye transfer inhibition performance provide by the combination of
the PVNO
or PVPI with the selected polyamine (PEI 1800 E7) is significantly better than
if the dye
transfer inhibiting polymers or the polyamine were used alone.
Method of Use
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The present invention also provides a method for laundering colored fabrics
with
little or no dye transfer taking place. Such a method employs contacting these
fabrics
with an aqueous washing solution formed from an effective amount of the
detergent
compositions hereinbefore described. Contacting of fabrics with washing
solution will
generally occur under conditions of agitation.
Agitation is preferably provided in a washing machine for good cleaning.
Washing is preferably followed by drying the wet fabric in a conventional
clothes dryer.
An effective amount of the liquid or granular detergent composition in the
aqueous wash
solution in the washing machine is preferably from about 500 to about 7000
ppm, more
preferably from about 1000 to about 3000 ppm.
