Note: Descriptions are shown in the official language in which they were submitted.
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LIQUID LAUNDRY DETERGENT COMPOSITIONS
- COMPRISING COTTON SOIL ~ELEASE POLYMERS
- FIELD OF THE INVENTION
The present invention relates to liquid laundry detergent compositions
comprising water soluble and/or dispersible, modified polyamines having functionalized
backbone moieties which provide cotton soil release benefits in combination withselected non-cotton soil release agents.
BACKGROUND OF THE INVENTION
A wide variety of soil release agents for use in domestic and industrial fabric
treatment processes such as laundering, fabric drying in hot air clothes dryers, and the
like are known in the art. Various soil release agents have been commercialized and are
currently used in detergent compositions and fabric softener/~ntist~tic articles and
compositions. Such soil release polymers typically comprise an oligomeric or polymeric
ester "backbone".
Soil release polymers are generally very effective on polyester or other synthetic
fabrics where the grease, oil or similar hydrophobic stains spread out and form a att~rh~d
film and thereby are not easily removed in an aqueous laundering process. Many soil
release polymers have a less dramatic effect on "blended" fabrics, that is on fabrics that
comprise a mixture of cotton and synthetic material, and have little or no effect on cotton
articles. The reason for the affinity of many soil release agents for synthetic fabric is that
the backbone of a polyester soil release polymer typically comprises a mixture of
terephth~l~te residues and ethyleneoxy or propyleneoxy polymeric units; the same or
closely analogous to materials that comprise the polyester fibers of synthetic fabric. This
similar structure of soil release agents and synthetic fabric produce an intrinsic affinity
between these compounds.
Extensive research in this area has yielded significant improvements in the
effectiveness of polyester soil release agents yielding materials with enh~nced product
performance and formulatability. Modifications of the polymer backbone as well as the
selection of proper end-capping groups has produced a wide variety of polyester soil
release polymers. For example, end-cap modifications, such as the use of sulfoaryl
moieties and especially the low cost isethionate-derived end-capping units, haveincreased the range of solubility and adjunct ingredient compatibility of these polymers
without sacrifice of soil release effectiveness. Many polyester soil release polymers can
now be formulated into both liquid as well as solid (i.e., granular) detergents.
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In contrast to the case of polyester soil release agents, producing an oligomeric or
polymeric material that mimics the structure of cotton has not resulted in a cotton soil
release polymer. Although cotton and polyester fabric are both comprised of long chain
polymeric materials, they are chemically very different. Cotton is comprised of cellulose
fibers that consist of anhydroglucose units joined by 1-4 linkages. These glycosidic
linkages characterize the cotton cellulose as a polysaccharide whereas polyester soil
release polymers are generally a combination of terephth~l~te and
oxyethylene/oxypropylene residues. These differences in composition account for the
difference in the fabric pl o~l lies of cotton versus polyester fabric. Cotton is hydrophilic
relative to polyester. Polyester is hydrophobic and attracts oily or greasy dirt and can
easily be "dry cleaned". Importantly, the terephth~l~te and ethyleneoxy/propyleneoxy
backbone of polyester fabric does not contain reactive sites, such as the hydroxyl
moieties of cotton, that interact with stains in a different manner than synthetics. Many
cotton stains become "fixed" and can only be resolved by bleaching the fabric.
Until now the development of an effective cotton soil release agent for use in alaundry detergent has been elusive. Attempts by others to apply the paradigm of
m~tclling the structure of a soil release polymer with the structure of the fabric, a method
successful in the polyester soil release polymer field, has nevertheless yielded marginal
results when applied to cotton fabric soil release agents. The use of methylcellulose, a
cotton polysaccharide with modified oligomeric units, proved to be more effective on
polyesters than on cotton.
For example, U.K. 1,314,897, published April 26, 1973 teaches a hydroxypropyl
methyl cellulose material for the prevention of wet-soil redeposition and improving stain
release on laundered fabric. ~Vhile this material appears to be somewhat effective on
polyester and blended fabrics, the disclosure indicates these materials to be
m~ti~f~tory at producing the desired results on cotton fabric.
Other ~ ls to produce a soil release agent for cotton fabric have usually taken
the form of pe". ,~ ly modifying the chemical structure of the cotton fibers themselves
by reacting a substrate with the polysaccharide polymer backbone. For ~ ple, U. S.
Patent No. 3,897,026 issued to Kearney, discloses cellulosic textile materials having
improved soil release and stain rç~ t~n~e plOp~,. lies obtained by reaction of an ethylene-
maleic anhydride co-polymer with the hydroxyl moieties of the cotton polymers. One
perceived drawback of this method is the desirable hydrophilic properties of the cotton
fabric are subst~nti~lly modified by this process.
Non-permanent soil release treatments or finishes have also been previous}y
attempted. U.S. Patent No. 3,912,681 issued to Dickson teaches a composition for
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applying a non-permanent soil release finish comprising a polycarboxylate polymer to a
cotton fabric. ~owever, this material must be applied at a pH less than 3, a process not
suitable for consumer use nor compatible with laundry detergents which typically have a
pH greater than 7.5.
U.S. Patent No. 3,948,838 issued to Hinton, et alia describes high molecular
weight (500,000 to 1,500,000) polyacrylic polymers for soil release. These materials are
used preferably with other fabric treatments, for example, durable press textile reactants
such as formaldehyde. This process is also not readily applicable for use by consumers
in a typical washing m~-~hine.
U.S. Patent 4,559,056 issued to Leigh, et alia discloses a process for treating
cotton or synthetic fabrics with a composition comprising an organopolysiloxane
elastomer, an organosiloxaneoxyalkylene copolymer crosslinking agent and a siloxane
curing catalyst. Organosilicone oligomers are well known by those skilled in the art as
suds supressors
Other soil release agents not coln~ulising terephth~l~te and lllixlules of polyoxy
ethylene/propylene are vinyl caprolactam resins as disclosed by Rupert, et alia in U.S.
Patent Nos. 4,579,681 and 4,614,519. These disclosed vinyl caprolactam materials have
their effectiveness limited to polyester fabrics, blends of cotton and polyester, and cotton
fabrics rendered hydrophobic by fini~hing agents.
Examples of alkoxylated polyamines and qu~terni7~d alkoxylated polyamines are
disclosed in European Patent Application 206,513 as being suitable for use as soil
di~el~n~s, however their possible use as a cotton soil release agent is not disclosed. In
addition, these materials do not comprise N-oxides, a key modification made to the
polyamines of the present invention and a component of the increased bleach stability
exhibited by the presently disclosed compounds.
It has now been surprisingly discovered that effective soil release agents for
cotton articles can be prepared from certain modified polyamines. This unexpected
result has yielded compositions that are effective at providing the soil release benefits
once available to only synthetic and synthetic-cotton blended fabric. When the cotton
soil release polymers of the present invention are used in combination with non-cotton
soil release agents, the full spectrum of fabric types is provided with soil release benefits.
The present invention provides for liquid laundry detergent compositions that
comprise nonionic and anionic surfactants together with a combination of non-cotton
soil release polymers and the cotton soil release agents of the present invention. These
combinations provide a liquid laundry detergent composition that is effective for
providing soil release benefits to all fabric. The liquid detergents can have a wide range
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of viscosity and may include heavy concentrates, pourable "ready" d~lcrgellls, or light
duty fabric pre-treatments.
BACKGROUND ART
In addition to the above cited art, the following disclose various soil release
polymers or modified poly~mines; 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 4,877,896,
Maldonado, et al., issued October 31, ~989; U.S. Patent 4,891,160, Vander Meer, issued
January 2, 1990; U.S. Patent 4,976,879, Maldonado, et al., issued Decèmber 11, 1990;
U.S. Patent 5,415,807, Gosselink, issued May 16,1995; U.S. Patent 4,235,735, Marco, et
al., issued November 25, 1980; U.K. Patent 1,537,288, published December 29, 1978;
U.K. Patent 1,498,520, published January 18, 1978; WO 95/32272, published November
30, 1995; German Patent DE 28 29 022, issued January 10, 1980; J~p~n~se Kokai JP06313271, published April 27, 1994.
SUMMARY OF THE INVENTION
The present invention relates to liquid laundry d~t~lgelll compositions which
provide cotton soil release benefits, comprising:
A) at least about 0.01% by weight, of an anionic detersive surfactant selected
from the group con~i.cting of alkyl s.llf~t~s, alkyl alkoxylated s.llf~t~, and
mixtures thereof;
B) at least about 0.01% by weight, of a non-cotton soil release agent selected
from the group co~i.cting of a terephth~l~te co-polymer comprising:
i) a backbone comprising:
a) at least one moiety having the formula:
1~1~311_
b) at least one moiety having the forrnula:
Rl~ IRl~
O--~9--(O--IR9)i--~
Rl~ Rl~
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-SO3-
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M+; wherein L is a side chain moiety selected from the
group consisting of alkylene, oxyalkylene,
- alkyleneoxyalkylene, arylene, oxyarylene,
alkyleneoxyarylene, poly(oxyalkylene), oxy-
- alkyleneoxyarylene, poly(oxyalkylene)oxyarlyene,
alkylene-poly(oxyalkylene), and mixtures thereof; M is
hydrogen or a salt forming cation; i has the value of 0 or 1;
c) at least one trifunctional, ester-forming, branching moiety;
d) at least one 1,2-oxyalkyleneoxy moiety; and
ii) one or more capping units comprising:
a) ethoxylated or propoxylated hydroxyeth~nesulfonate or
ethoxylated or propoxylated hydroxy~,ol)a,.e~llfonate
units of the formula (MO3S)(CH2)m(RI lO)n~~ where M is
a salt forming cation, Rl I is ethylene, propylene, and
mixtures thereof, m is 0 or 1, and n is from 1 to 20;
b) sulfoaroyl units of the formula -(O)C(C6H4)(SO3-M+),
wherein M is a salt forming cation;
c) modified poly(oxyethylene)oxy mono~lkyl ether units of
the formula Rl2O(CH2CH2O)k-, wherein R12 cont~in~
from 1 to 4 carbon atoms and k is from about 3 to about
1 00; and
d) ethoxylated or propoxylated phenolsulfonate end-capping
units of the formula Mo3S(C6H4)(oRI3)no-~ wherein n is
from 1 to 20; M is a salt-forming cation; and Rl3 is
ethylene, propylene, and mixtures thereof;
a sulronaLed oligomeric ester co~ ,osilion co,..l,. Is;l~ the sulfonated
product of a pre-formed, snbst~nti~lly linear ester oligomer, said linear
ester oligomer comprising, per mole,
i) 2 moles of terminal units wherein from about I mole to about 2
moles of said tennin~l units are derived from an olefinically
llnc~ ed component selected from the group con~i~tine of allyl
alcohol and methallyl alcohol, and any re~inine of said telTnin~l
units are other units of said linear ester oligomer;
ii) from about 1 mole to about 4 moles of nonionic hydrophile units,
said hydrophile units being derived from alkyleneoxides, said
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alkylene oxides comprising from about 50% to 100% ethylene
oxide;
iii) from about }.1 moles to about 20 moles of repeat units derived
from an aryldicarbonyl component wherein said aryldicarbonyl
component is comprised of from about 50% to 100%
dimethylterephth~l~te, whereby the repeat units derived from said
dimethylterephth~l~te are terephthaloyl; and
iv) from about 0.1 moles to about 19 moles of repeat units derived
from a diol component selected from the group consisting of C2-
C4 glycols;
wherein the extent of sulfonation of said sulfonated oligomeric ester
composition is such that said terminal units are chemically modified by
v) from about 1 mole to about 4 moles of terminal unit substituent
groups of formula -SOXM wherein x is 2 or 3, said tennin~l unit
substihlent groups being derived from a bisulfite co.llpon~"~t
selected from the group con~i~ting of HSO3M wherein M is a
conventional water-soluble cation;
a capped terephalate co-polymer having the formula
X[(OCH2CH2h,(0R5)~ [(A-Rl--A-R2)U(A-R3-A-R2)V]--
A-R4-A[(RSO)~cH2cH20)r~lx
wherein each of the A moieties is selected from the group conci~ting of
O O
--OC-- , --CO--
and combinations thereof, each of the Rl moieties is selected from the
group con.ci~ting of 1,4-phenylene and combinations thereof with 1,3-
phenylene, 1,2 phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2'-
biphenylene, 4,4'-biphenylene, Cl-Cg alkylene, Cl-Cg alkenylene and
mixtures thereof the R2 moieties are each selected from the group
con~i~tin~ of ethylene moieties, substituted ethylene moieties having C 1-
C4 alkyl, alkoxy substitiuents, and mixtures thereof; the R3 moieties are
substituted C2-C1g hydrocarbylene moieties having at least one -CO2M, -
O[(R50)m(CH2CH20)n]X or -A[(R2-A-R4
A)]W[(R5O)m(CH2CH20)n]X substituent; the R4 moieties are Rl or R3
moieties, or mixtures thereof; each R5 is C 1 -C4 alkylene, or the moiety -
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R2-A-R6- wherein R6 is a Cl-C12 alkylene, alkenylene, arylene, or
alkarylene moiety; each M is hydrogen or a water-soluble cation; each X
- is C 1 -C4 alkyl; the indices m and n have the values such that the moiety -
(CH2CH2O)- comprises at least about 50% by weight of the moiety
- [(R50)m(CH2CH20)n], provided that when R5 is the moiety -R2-A-R6-,
m is l; each n is at least about 10; the indices u and v have the value such
that the sum of u + v is from about 3 to about 25; the index w is 0 or at
least l; and when w is at least 1 u, v and w have the value such that the
sum of u + v + w is from about 3 to about 25; and mixtures thereof;
C) at least about 0.01% by weight, of a water-soluble or dispersible,
modified polyamine cotton soil release agent comprising a polyamine
backbone corresponding to the formula:
H
[H2N~R]n+l--LN~R]m~ R]n-NH2
having a modified polyamine formula V(n+l)wmynz or a polyamine
backbone corresponding to the formula:
H I R
[H2N~R]n-k+~[N~R]m--LN-R]n~N-R]k-NH2
having a modified polyarnine formula V(n-k+l )WmYnY kZ~ 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 t~rrnin~l units having the formula:
E X~ ~
E--I--R or E--Nl--R or E--I--R--
E E E
ii) W units are backbone units having the formula:
. _ ..
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E X~ O
--I--R or --I--R-- or --I--R--
E E E
iii) Y units are br~n~hing units having the formula:
E X~ O
_7 R or --I--R or 7 R
; and
iv) Z units are tennin~l units having the formula:
E X~ O
--Nl--E or --Nl--E or --I--E
E E E
wh~,lein backbone linking R units are selected from the group consisting
of C2-C 12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-
C12 dihydroxy-alkylene, Cg-C12 dialkylarylene, -(R10)XR1-, -
(Rlo)xR5(oRl)X-,-(CH2CH(OR2)CH20)z-
(Rl O)yRl (OCH2CH(OR2)CH2)W-, -C(o)(R4)rC(o)-,
CH2CH(OR2)CH2-, and mixtures thereof; wherein Rl is C2-C3 alkylene
and mixtures thereof; R2 is hydrogen, (Rl O)xB, and mixtures thereof;
R3 is Cl-Clg alkyl, C7-C12 arylalkyl, C7-C12 alkyl substituted aryl, C6-
C12 aryl, and mixtures thereof; R4 is C1-C12 alkylene, C4-C12
alkenylene, Cg-C12 arylalkylene, C6-Clo arylene, and mixtures thereof;
RS is Cl-C12 alkylene, C3-C12 hydroxy-alkylene, C4-C12
dihydroxyalkylene, Cg-C 1 2 dialkylarylene, -C(O)-,
C(O)NHR6NHC(O)-, -R 1 (oR1)-, -C(o)(R4)rC(o)-,
CH2CH(OH)CH2-,-CH2CH(OH)CH20(RlO)yRl-OCH2CH(OH)CH2-,
and mixtures thereof; R6 is C2-C12 alkylene or C6-C12 arylene; E units
are selected from the group con~i~tin~ of hydrogen, C1-C22 alkyl, C3-
C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pC02M, -
(CH2)qS03M, -CH(CH2C02M)-C02M, -(CH2)pP03M, (R1 O)xB, -
C(o)R3, and mixtures thereof; provided that when any ~ 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, -
.
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(CH2)q(CHS03M)CH2S03M~ ~(CH2)q~(CHS02M)CH2S03M~ ~
(CH2)pPO3M, -PO3M, 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 l 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 l to
100; y has the value from 0 to 100; z has the value 0 or l; and
D) the balance carrier and adjunct ingredients wherein said composition has a
pH of about 7.2 to about 8.9 when measured as a 10% solution in water.
All percentages, ratios and proportions herein are by weight, unless otherwise
specified. All t~ dl~lres are in degrees Celsius (~ C) unless otherwise specified. All
docurnents cited are in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises liquid laundry detergent compositions suitable
for use with cotton, non-cotton, or lllix.lules of cotton and non-cotton fabric. The liquid
laundry de~e.~elll compositions may optionally comprise blearl~ing materials.
The preferred liquid laundry detergent compositions of the present invention
comprise certain anionic surf~t~t~ (preferably in combination with nonionic
surfactants), and selected non-cotton soil release agents that when used in combination
with the cotton soil release polymers of the present invention, provides improved
cleaning and soil release benefits for all fabric. The preferred liquid laundry detergent
compositions of the present invention comprise the following ingredients.
Anionic Detersive Surfactants
The colnposilions of the present invention comprise at least about 0.01%,
preferably at least 0.1%, more preferably from about 1% to about 95%, most preferably
from about 1% to about 80% by weight, of an anionic detersive surfactant selected from
the group con~ tin~ of alkyl sulfates, alkyl alkoxylated sulfates, and mixtures thereof.
Alkyl su!fate s~ rt~nt.c, either primary or secondary, are a type of anionic surfactant of
hllpollance for use herein. Alkyl sulfates have the general formula ROSO3M wherein R
preferably is a C 1 o-C24 hydrocarbyl, preferably an alkyl straight or branched chain or
hydroxyalkyl having a C1o-C20 alkyl component, more preferably a C12-CIg alkyl or
hydroxyalkyl, and M is hydrogen or a water soluble cation, e.g., an alkali metal cation
(e.g., sodiurn potassiurn, lithium), substituted or unsubstituted ammonium cations such as
methyl-, dimethyl-, and trimethyl ammonium and qU~te~n~ry arnmonium cations, e.g.,
tetramethyl-amrnonium and dimethyl piperdinium, and cations derived from alkanolamines
such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like.
~ . _
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Typically, alkyl chains of C 1 2-C 16 are preferred for lower wash temperatures (e.g., below
about 50~C) and C16-CIg alkyl chains are preferred for higher wash temperatures (e.g.,
about 50~C).
Alkyl alkoxylated sulfate surfactants are another category of preferred anionic
surfactant. These surfactants are water soluble salts or acids typically of the formula
RO(A)mSO3M wherein R is an unsubstituted C 1 o-C24 alkyl or hydroxyalkyl group
having a C 1 o-C24 alkyl component, preferably a C 1 2-C20 alkyl or hydroxyalkyl, more
preferably C 12-C 1 8 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater
than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and
about 3, and M is hydrogen or a water soluble cation which can be, for example, a metal
cation (e.g., sodium, potassium, lithium, calcium, m~necium, etc.), arnrnonium or
substituted-amrnonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated
sulfates are contemplated herein. Specific exarnples of substituted arnmonium cations
include methyl-, dimethyl-, trimethyl-ammonium and q~l~tf m~ry ammonium cations, such
ac tetrarnethyl-ammonium, dimethyl piperdinium and cations derived from alkanol~minPc,
e.g., monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
Exemplary surf~ct~ntc are C12Clg alkyl polyethoxylate (1.0) sulfate, C12-CIg alkyl
polyethoxylate (2.25) sulfate, C12-Clg alkyl polyethoxylate (3.0) sulfate, and C12-Clg
alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and
potassium.
Nonionic Detersive Surfactants
The compositions of the present invention preferably also comprise at least about
0.01%, preferably at least 0.1%, more preferably from about 1% to about 95%, most
preferably from about 1% to about 80% by weight, of an nonionic detersive surfactant.
Preferred nonionic s.~ rt~ntc such as C12-Clg alkyl ethoxylates ("AE") including the so-
called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially
ethoxylates and mixed ethoxy/propoxy), block alkylene oxide contlen.c~te of C6 to C12
alkyl phenols, alkylene oxide con-llonc~tes of Cg-C22 alkanols and ethylene
oxide/propylene oxide block polymers (PluronicTM-BASF Corp.), as well as semi polar
nonionics (e.g., amine oxides and phosphine oxides) can be used in the present
compositions. An extensive disclosure of these types of surfactants is found in U.S. Pat.
3,929,678,1 ~n~hlin et al., issued December 30, 1975, incol~oldted herein by reference.
Alkylpolysaccharides such as disclosed in U.S. Pat. 4,S65,647 Llenado
(incorporated herein by reference) are also pleÇ .Ied nonionic surfactants in the
compositions of the invention.
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W O 97/42286 PCTnUS97/06918
11
Further preferred nonionic surfactants are the polyhydroxy fatty acid amides having
the formula:
- O R8
R7--C--N--Q
wherein R7 is C5-C3 1 alkyl, preferably straight chain C7-C 19 alkyl or alkenyl, more
preferably straight chain Cg-C 1 7 alkyl or alkenyl, most preferably straight chain C I I -C 1 5
alkyl or alkenyl, or mixtures thereof; R8 is selected from the group consisting of hydrogen,
Cl -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 int~n~e~ to
exclude other suitable raw materials. Q is more preferably selected from the group
consistingof-CH2(CHOH)nCH20H,-CH(CH20H)(CHOH)n 1CH20H,-CH2(CHOH)2-
(CHOR')(CHOH)CH20H, and alkoxylated derivatives thereof, wherein n is an integerfrom 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 .
R7Co-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capric~mitle, palmitamide, tallowarnide, etc.
RB can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl, or
2-hydroxy propyl.
Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, l-deoxymannityl, 1-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 R7 is alkyl
(preferably Cl 1-Cl3), R8, is methyl and Q is l-deoxyglucityl.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid
amides, such as C 1 o-C 18 N-(3-methoxypropyl) glucamide. The N-propyl through N-
hexyl C12-Clg glllc~mides can be used for low sudsing. Clo-C20 conventional soaps
may also be used. If high sudsing is desired, the branched-chain C 1 o-C 16 soaps may be
used. Other conventional useful surfact~n~ are listed in standard texts.
I
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For the purposes of the present invention other detersive surfactants, describedherein below, may be used in the liquid laundry detergent compositions.
Non-cotton Soil Release Polvmers
The non-cotton soil release polymers to be used in the laundry detergent
compositions of the present invention are the following.
Preferred non-cotton soil release a~ent - A. Suitable for use in the laundry
detergent compositions of the present invention are preferred non-cotton soil release
polymers comprising:
a) a backbone comprising:
i) at least one moiety having the formula:
1~l_~_1~C--;
ii) at least one moiety having the forrnula:
Rl~ IRI~
--O--F.~(O--Rl 9)i--~--
Rl~ Rl~
wherein R9 is C2-C6 linear alkylene, C3-C6 branched alkylene,
Cs-C7 cyclic alkylene, and mixtures thereof; R10
is indeper~lçntly selected from hydrogen or -L-S03-M+; wherein
L is a side chain moiety selected from the group con~icting of
alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene,
alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene,
poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and
mixtures thereof; M is hydrogen or a salt forrning cation; i has the
value of O or l;
iii) at least one trifunctional, ester-forming, I,lA ~rhil~g moiety;
iv) at least one 1,2-oxyalkyleneoxy moiety; and
b) one or more capping units comprising:
i) ethoxylated or propoxylated hydroxyeth~n~sulfonate or
ethoxylated or propoxylated hydroxypropanesulfonate units of the
formula (M03S)(CH2)m(Rl 10)n-, where M is a salt forming
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13
cation such as sodium or tetralkylammonium, R I 1 is ethylene or
propylene or a mixture thereof, m is 0 or l, and n is from 1 to 20;
ii) sulfoaroyl units of the formula -(O)C(C6H4)(SO3-M+), wherein
M is a salt forming cation;
- iii) modified poly(oxyethylene)oxy monoalkyl ether units of the
fo~nula Rl20(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 Mo3S(C6H4)(oR13)no-, 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 non-cotton soil release polymer of the present invention
may be described as having the formula
[(Cap)(R4)t][(A-Rl-A-R2)U(A-Rl-A-R3)V(A-Rl-A-R5)W
-A-R 1 -A-] [(R4)t(Cap)]
wherein A is a carboxy linking moiety having the formula
R1 is arylene, preferably a 1,4-phenylene moiety having the formula
such that when A units and Rl units are taken together in the formula A-Rl-A they form
a terephth~l~te unit having the forrnula
C~C
R2 units are ethyleneoxy or 1,2-propyleneoxy. R2 units are combined with
terephth~ te moieties to forrn (A-Rl-A-R2) units having the formula
c~ O CHR'CHR"--
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14
wherein R' and R" are either hydrogen or methyl provided that R' and R" are not both
methyl at the sarne time.
R3 units are trifunctional, ester-forming, branching moieties having the formula
--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
terephth~l~t~ moieties to form units of the polymer backbone, for example, (A-Rl-A-
R3)-A-RI-A units, these units have the formula
--,C, ~,C, -O-CH2--CH-CH2--O-C ~ IC,--
O O O O
or the formula
--~C~ ~3,C,-o-CH2--~CH--O-C~IC,--
O O O O
wherein one terephth~l~te residue is taken to be a part of the (A-R1-A-R3) unit while the
second terephth~l~te comprises a part of another backbone unit, such as a (A-R1-A-R2)
unit, a (A-R1-A-R5) unit, a -A-R1-A-[(R4)t(Cap)~ unit or a second (A-R1-A-R3) unit.
The third functional group, which is the beginning of the br~nrhing chain, is also
typically bonded to a terephth~l~te residue also a part of a (A-R1-A-R2) unit, a (A-R1-A-
R5) unit; a -A-R1-A-[(R4)t(Cap)] unit or another (A-R1-A-R3) unit.
An exarnple of a section of a soil release polymer cont~inin~ a "trifunctional,
ester-forming, br~nl~hing moiety" R3 unit which comprises a glycerol unit, has the
formula
CA 022~28~l l998-l0-29
WO 97t42286 PCT/US97/06918
~"C'~--(CH(CH3)CH20)--
--(CH2CH20)3--C~C-O~,O-C~C-O O--C~C--
R4 units are R2, R3 or RS units.
R5 units are units having the formula
Rl~ IRl~
o~ (0--IR9)i--~
Rl~ Rl~
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 forrning cation; i has the value of 0 or 1;
Each carbon atom of the R9 units is substituted by Rl ~ units that are
independently selected from hydrogen or -L-S03-M+, provided no more than one -L-S03-M+ units is ~tt~chPd to an R9 unit; L is a side chain connPctine moiety selected
from the group cotl~ictinE 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 concictin~ of lithium, sodium,
potassium, calcium, and m~gnesium, preferably sodium and po~ssiull-.
Preferred R5 moieties are essPnti~lly R10 substituted C2-C6 alkylene chains.
The R5 units comprise either one C2-C6 alkylene chain substituted by one or moreindependently selected Rl ~ 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 Rl ~ moieties, that is R5 may comprise two separate
R9 units, each of which is substituted by one or more independently selected R10moieties. Preferably only one carbon atom of each R9 moiety is substituted by an -L-
S03-M+ unit with the rem~ining R10 substituents comprising a hydrogen atom. When
. I
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16
the value of the index i is equal to I (two R9 units comprise the R5 unit), a preferred
formula is
Rlo Rl~ Rl~ Rl~
--O-C C O C C--O--
Rl~ Rlo Rl~ Rl~
wherein each R9 comprises a C2 alkylene moiety. Preferably one R10 moiety is -L-SO3-M+, preferably the C2 carbon is substituted by the -L-SO3-M+ moiety, and thebalance are hydrogen atoms, having therefore a formula:
CHCH2-O-CH2CH2--
CH2(OCH2CH2)XSO3 M
wherein L is a polyethyleneoxymethyl substituent, x is from 0 to about 20.
As used herein, the term "R5 moieties consist ess~nti~lly of units
Rl~ IRl~
O--R~(O--IR9)i--~--
Rl~ Rl~
having the index i equal to 0 wherein R10 units are hydrogen and one R10 units is equal
to -L-SO3-M+, wherein L is a side chain connecting moiety selected from the group
coneieting of alkylene, alkenylene, alkoxyalkylene, oxyalkylene, arylene, alkylarylene,
alkoxyarylene and mixtures thereof", refers to the plerell~d compounds of the present
invention wherein the Rl ~ moieties consist of one -L-SO3-M+ moiety and the rest of the
Rl ~ moieties are hydrogen atoms, for example a
--O CH2 Cl H--O--
CH2(OCH2CH2)XSO3- Na
which is~capable of inclusion into the polymeric backbone of the soil release polymers of
the present invention as an -A-R5-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)XSO3 Na
wherein x, for the purposes of the L moiety of the present invention, is from 0 to 20.
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Other suitable monomers capable of inclusion into the backbone of the type A
preferred non-cotton soil release polymers of the present invention as R5 moieties
includes the alkylene poly(oxyalkylene)oxyarylene cont~ining monomer having the
general formula
HO--CH2--CH--OH
CH2(0CH~CH2)xO~SO3 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(0CH2CH2h~SO3'Na
wherein x is from 0 to about 20; more preferred are the monomers
HO--CH2--I H--CH2--OH or HO--CH2--CH--I H2
OCH2CH2SO3 Na OCH2CH2SO3~Na
The preferred non-cotton 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
(MO3S)(CH2)m(Rl lO)n-, where M is a salt forming cation such as sodium or
tetralkylammonium as described herein above, Rl 1 is ethylene or propylene or a mixture
thereof, m is 0 or 1, and n is from 1 to 20, preferably n is from I to about 4; sulfoaroyl
units of the formula -(O)C(C6H4)(SO3-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 l to 4 carbon atoms, Rl2 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 MO3S(C6H4)(OR1 3)n~-, wherein n is from to 20; M is a
salt-forming cation; and R1 3 is ethylene, propylene and mixtures thereof.
Most preferred end capping unit is the isethionate-type end capping unit which is
a hydroxyethane moiety, (MO3S)(CH2)m(R1 lO)n-, preferably Rl I is ethyl, m is equal
toO,andnisfrom2to4.
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18
The value of t is 0 or 1; the value of u 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 non-cotton soil release polymers of the present invention having the
formula
[(Cap)(R4)t~[(A-Rl -A-R2)U(A-Rl -A-R3)V(A-Rl -A-RS)W
-A-R1 -A-] [(R4)t(Cap)]
can be conveniently expressed as the following generic structural formula
NaO3S(CH2CH20~2 sCH2CH2--O--C~C--OCH2CH--O--C ~C--OCH2 ICH--
--u -- I _ w
OCH2CH2SO3Na
--O--C ~ O ICH2-- o C--OCHlCH(OCH2CH2)2.sSO3Na
v v+l
The following structure is an example of the preferred non-cotton soil release
polymers of the present invention.
NaO3S(CH2CH20)2 5CH2CH2--O--C~C--OCH2CII 1OI~3C--OCH2 ICH--
- 1.7-2., OcH2cH2so3Na
--O--C~C--OCH2CH-- 1OI~>--C--OCH2CH(OCH2CH2)2.sSO3Na
-- --0.15 -- 1 ~5
The above-described p~efelled non-cotton soil release agents are fully described in
U.S. Patent Application Serial No. 08/545,351 filed November 22, 1995 which is acontinuation-in-part of U.S. Patent Application Serial No. 08/355,938 filed December
14, 1994, both of which are incorporated herein by reference. Other non-cotton soil
release polymers suitable for use in the compositions of the present invention are further
described herein below.
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19
The preferred non-cotton SRA's can be further described as oligomeric esters
comprising: (1) a backbone comprising (a) at least one unit selected from the group
consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least
trifunctional whereby ester linkages are formed resulting in a branched oligomerbackbone, 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)eth~nesulfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy}
eth~nes-.lfonate ("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 tr~n~çsterifying and oligomeri~ing sodium 2-{2-(2-hydroxy-
ethoxy)ethoxy } ethanesulfonate and/or sodium 2 - [2 - { 2-(2-hydroxyethoxy)ethoxy } -
ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG,
and PG using an ap~lop.iate 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+-03S[CH~CH20]3.5)-
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.
~ ,
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Preferred non-cotton soil release a~ent - B. A second preferred class of suitable
SRA's include a sulfonated product of a substantially linear ester oligomer comprised of
an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-
derived sulfonated terminal moieties covalently att~ ed to the backbone Such ester
oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of
(a) with dimethyl terephth~l~te ("DMT") and 1,2-propylene glycol ("PG") in a two-stage
tr~n~esterification/oligomerization procedure; and (c) reacting the product of (b) with
sodium metabisulfite in water.
Suitable for use in the laundry detergent compositions of the present invention
are preferred non-cotton soil release polymers comprising:
a) one or two tennin~l units selected from the group con~ictin~ of
i) ~(CH2)q(CHS03M)CH2S03M~
ii) -(cH2)q(cHso2M)cH2so3
iii) -CH2CH2S03M,
iv) and mixtures thereof; wherein q has the value from I to about 4,
M is a water soluble cation, preferably sodium;
b) a backbone comprising:
i) arylene units, preferably terephth~l~te units having the forrnula:
c~l ~3~~1
ii) ethyleneoxy units having the formula:
--O(cH2cH2o)ncH2cH2o--
wherein the value of n is from about 1 to about 20; and
iii) 1,2-propyleneoxy units having the formula:
--O(CH2CH(CH3)0)nCH2CH(CH3)0--
wherein the value of n is from about 1 to about 20, and wherein further the preferred
backbone of this preferred non-cotton soil release polymer has a backbone comprising
arylene repeat units which alternate with the ethyleneoxy and 1,2-propyleneoxy units,
such that the mole ratio of ethyleneoxy to l,2-propyleneoxy units is from 0:1 to about
0.9:0.1, preferably from about 0:1 to about 0.4:0.6, more preferably the arylene units
alternate with essentially 1,2-propyleneoxy units.
.
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However, other combinations of the above-identified units may be used to form
non-cotton soil release polymers suitable for use in the compositions of the present
invention. These combinations are more thoroughly described in U.S. Patent 4,968,451,
Scheibel et al., issued November 6, 1990 and incoll,orated herein by reference.
Preferred non-cotton soil release a~ent - C. Suitable for use in the laundry
detergent compositions of the present invention are plef~lled non-cotton soil release
polymers having the formula
(Cap)[(A-RI -A-R2)u(A-R3-A-R2)v-A-R4-A-](Cap)
wherein A is a carboxy linking moiety, preferably A is a carboxy linking moiety having
the formula
o o
Il 11
--~c-- or --c ~,
Rl is an arylene moiety, preferably 1,4-phenylene moiety having the formula
wherein for Rl moieties, the degree of partial substitution with arylene moieties other
than 1 ,4-phenylene should be such that the soil release properties of the compound are
not adversely affected to any great extent. Generally, the partial substitution which can
be tolerated will depend upon the backbone length of the compound.
R2 moieties are ethylene moieties or substituted ethylene moieties having C I -C4
alkyl or alkoxy sub~ As used herein, the term "the R2 moieties are essPnti~lly
ethylene moieties or substituted ethylene moieties having C 1 -C4 alkyl or alkoxy
substituents" refers to compounds of the present invention where the R2 moieties consist
entirely of ethylene or substituted ethylene moieties or a partially substituted with other
compatiBle moieties. Examples of these other moieties include 1 ,3-propylene, 1,4-
butylene, 1,5-pentylene, or 1,6-hexylene, 1,2-hydroxyalkylenes and oxyalkylenes.For the R2 moieties, the degree of partial substitution with these other moieties
should be such that the soil release properties of the compounds are not adversely
affected to any great extent. For example, for polyesters made according to the present
invention with a 75:25 mole ratio of diethylene glycol (-CH2CH20CH2CH2-) to
ethylene glycol (ethylene) have adequate soil release activity.
For the R3 moieties, suitable substituted C2-C 18 hydrocarbylene moieties can
include substituted C2-C 12 alkylene, alkenylene, arylene, alkarylene and like moieties,
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The substituted alkylene or alkenylene moieties can be linear, branched or cyclic. Also,
the R3 can all be the same (e.g. all substituted arylene) or a mixture (e.g. a mixture of
substituted arylenes and substituted alkylenes). Preferred R3 moieties are those which
are substituted 1,3-phenylene, preferably 5-sulfo-1,3-phenylene. R3 moieties are also -
A-[(R2-A-R4)]-Cap wherein R4 is Rl, R3, and mixtures thereof.
The preferred (Cap) moieties comprise units having the formula
--[(R5O)n~cH2c~2o)r~x
wherein R5 is C l-C4 alkylene, or the moiety -R2-A-R6- wherein R6 is C2-C12 alkylene,
alkenylene, arylene or alkarylene moiety, X is Cl-C4 alkyl, preferably methyl; the
indices m and n are such that the moiety -CH2CH2O- comprises at least 50% by weight
of the moiety
--[(R5o)m(cH2cH2o)rJlx
provided that when R5 is the moiety -R2-A-R6-, m is at least 1; each n is at least about
10, the indices u and v are such that the sum of u + v is from about 3 to about 25; the
index w is 0 or at least 1; and when w is at least 1, the indices u, v and w have the values
such that the sum of u + v + w is from about 3 to about 25.
An example of this type of non-cotton soil release block polyester has the
formula
o fi~ o o o o o
X--(OCH2CH2)n--(0C~CO-R2)U--(oC-R3-Co-R2)V-oc-R4--co--(CH2CH20)r,-X
wherein the R2 moieties are essenti~lly ethylene moieties, 1,2-propylene moieties, and
mixtures thereof; the R3 moieties are all potassium or preferably sodium 5-sulfo- 1,3-
phenylene moieties; the R4 moieties are Rl or R3 moieties, or mixtures thereof; each X
is ethyl, methyl, preferably methyl; each n is from about 12 to about 43; when w is 0, u +
v is from about 3 to about 10; when w is at least 1, u + v + w is from about 3 to about 10.
The above non-cotton soil release polymers of the formula
(Cap)[(A-R~ -A-R2)u(A-R3-A-R2)v-A-R4-A-](Cap)
are further described in detail in U.S. Patent 4,702,857, Gosselink, issued October 27,
1987 and incorporated herein by lef~.ellce.
In addition to the above-described non-cotton soil release polymers, other soil
release polymers suitable for use in the liquid laundry detergent compositions of the
present invention are further described herein below.
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23
Any other anionic non-cotton soil release agent is suitable for use in the
compositions of the present invention alone or in combination except for carboxy-
methylcellulose (CMC) which cannot be used alone. If the formulator selects CMC for
use as an anionic soil release agent in the laundry detergent compositions of the present
invention, carboxymethylcellulose must be present in an amount greater than 0.2% by
weight, of the composition.
Cotton Soil Release Pol~lmers
The cotton soil release agents useful in the present invention liquid detergent
compositions are water-soluble or dispersible, modified polyamines. These polyamines
comprise backbones that can be either linear or cyclic. The polyamine backbones can
also comprise polyamine br~nching 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 interchangably 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 circ~.m~t~nces
without substitution, but substitution is preferably accompanied by oxidation orquaternization 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
[H2N~R]n+l--[N-R]m--[N-R]r,-NH2
said backbones prior to subsequent modification, comprise primary, secondary andtertiary 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:
H I ,R
[H2N ~R]n-k+ ~N-R]m--[N ~R]n{N -R]k-NH2
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24
said backbones prior to subsequent modification, comprise primary, secondary andtertiary amine nitrogens connected by R "linking" units
For the purpose of the present invention, primary amine nitrogens comprising thebackbone 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.
ln 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
[N-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.
In a further similar manner, tertiary amine nitrogens comprising the backbone orbr~nshing chain once modified are further referred to as Y "br~n~hing" 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
I
~N-R]--
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
CA 022~28~1 1998-10-29
WO 97/42286 PCT/US97/06918
or the tertiary amine moieties can remain unrnodified. 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 thepolyamine 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+l )WmYnZ
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 polyarnines
comprising rings, a Y' unit of the formula
R
~ R]--
serves as a branch point for a backbone or branch ring. For every Y' unit there is a Y
unit having the formula
I
[N-R~--
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 polyarnine backbone has the
formula
H
[H2N ~R]n--[N-R]rn--[N -R~n--
therefore comprising no Z terminal unit and having the formula
Vn-kwmyny k
wherein k is the number of ring forming br~nrhing units. Preferably the polyamine
backbones of the present invention comprise no rings.
In the case of non-cyclic poly~rnines~ the ratio of the index n to the index m
relates to the relative degree of br~nching. A fully non-branched linear modified
polyamine according to the present invention has the formula
VWmZ
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 br~nching in the molecule. Typically the value for m ranges from a
CA 022~28~1 1998-10-29
WO 97142286 PCT/US97/06918
26
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 polyarnine 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 arnine nitrogens
are V or Z units, unmodified secondary arnine nitrogens are W units and unrnodified
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--I--R
E
b) qu~terni7~1 units having the structure:
IE X-
E--N--R
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
E--I--R--
E
Modified secondary amine moieties are defined as W "b~kbone" units having
one of three forms:
a) simple substituted units having the structure:
--N-R--
E
b) quaternized units having the structure:
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WO 97/42286 PCT/US97/06918
27
IE X-
--N--R
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
--I--R--
Modified tertiary amine moieties are defined as Y "branching" units having one
of three forms:
a) unmodified units having the structure:
--I -R--
b) quaternized units having the structure:
I X
--N--R
I
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
--N--R
Certain modified primary amine moieties are defined as Z "terminal" units havingone of three forms:
a) simple substituted units having the structure:
--N, -E
E
b) ~u~terni7ecl units having the structure:
~, I ,
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WO 97/42286 PCT/US97/06918
28
I X
--N--E
E
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
When any position on a nitrogen is unsubstituted of unmodified, it is understoodthat hydrogen will substitute for E. For exarnple, a primary amine unit comprising one E
unit in the form of a hydroxyethyl moiety is a V t~nnin~l unit having the formula
(HOCH2CH2)HN-.
For the purposes of the present invention there are two types of chain termin~ting
units, the V and Z units. The Z "tçrrnin~l" unit derives from a termin~l 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.
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-C12 alkylene, C4-C12 alkenylene, C3-C12
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-C 12 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
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29
--(CH2)2~CH2 - --(cH2)4~(cH2k--
although the unit need not be 1,4-substituted, but can also be 1,2 or 1,3 substituted C2-
C 12 alkylene, preferably ethylene, I ,2-propylene, and mixtures thereof, more preferably
ethylene. The "oxy" R units comprise -(RlO)XR5(oRl)x-~ -
CH2CH(OR2)CH20)z(RlO)yRI(OCH2CH(OR2)CH2)~,-CH2CH(OR2)CH2-,
(R10)XRl-, and mixtures thereof. Preferred R units are C2-C12 alkylene, C3-C12
hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, -(R10)XRl-,
CH2CH(OR2)CH2-,-(CH2CH(OH)CH20)z(RlO)yRl(OCH2CH-(OH)CH2)W-,
(Rlo)xR5(oRl)x-~ more p~ ed R units are C2-C12 alkylene, C3-C12 hydroxy-
alkylene, C4-C 12 dihydroxyalkylene, -(R10)xRl-,-(Rlo)xRs(oRl)x-~ -
(CH2CH(OH)CH20)z(RIO)yRl(OCH2CH-(OH)CH2)~, and mixtures thereof, even
more prefe.l~,d 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.
Rl units are C2-C6 alkylene, and mixtures thereof, preferably ethylene. R2 is
hydrogen, and -(R10)xB, preferably hydrogen.
R3is Cl-Clg alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, C6-C12
aryl, and mixtures thereof, preferably C 1 -C 12 alkyl, C7-C 12 arylalkylene, more
preferably C 1 -C 12 alkyl, most preferably methyl. R3 units serve as part of E units
described herein below.
R4is Cl-C12 alkylene, C4-C12 alkenylene, Cg-C12 arylalkylene, C6-Clo
arylene, preferably Cl-Clo alkylene, Cg-C12 arylalkylene, more preferably C2-Cg
alkylene, most preferably ethylene or butylene.
R5is Cl-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene,
Cg-C12 dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -C(o)(R4)rC(o)-,
-Rl(ORl)-,-CH2CH(OH)CH20(RlO)yRlOCH2CH(OH)CH2~~-C(o)(R4)rC(o)-,
-CH2CH(oH)CH2-,R5is preferably ethylene, -C(O)-, -C(O)NHR6NHC(O)-,
-Rl(ORl)~~~CH2CH(OH)CH2~~~CH2CH(OH)CH20(RlO)yRlOCH2CH~(OH)CH2~~
more preferably -CH2CH(OH)CH2-.
R6is C2-C 12 alkylene or C6-C 12 arylene.
The preferred "oxy" R units are further defined in terms of the Rl, R2, and R5
units. P~felled "oxy" R units comprise the preferred Rl, R2, and RS units. The
preferred cotton soil release agents of the present invention comprise at least 50% Rl
CA 022~28~1 1998-10-29
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units that are ethylene. Preferred Rl, R~, and R5 units are combined with the "oxy" R
units to yield the preferred "oxy" R units in the following manner.
i) Substituting more preferred R5 into -(CH2CH2o)XR5(oCH2CH2)x-
yields -(CH2CH20)XCH2CHOHCH2(0CH2CH2)x-.
ii) Substituting l~lef~ cd Rl and R2 into -(CH2CH(OR2)CH20)z-
l o)yRl O(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)CH2-
E units are selected from the group consisting of hydrogen, C 1 -C22 alkyl, C3-
C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pC02M, -(CH2)qS03M, -
CH(CH2C02M)C02M, -(CH2)pP03M, -(RlO)mB, -C(o)R3, preferably hydrogen, C2-
C22 hydroxyalkylene, benzyl, Cl-C22 alkylene, -(RIO)mB, -C(o)R3, -(CH2)pC02M, -
(CH2)qS03M, -CH(CH2C02M)C02M, more preferably Cl-C22 alkylene, -(R10)XB,
-C(O)R3,-(CH2)pCO2M,~(cH2)qs03M~ -CH(CH2C02M)C02M, most
preferably C1-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.
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 br~nching chains
do not comprise units of the following structure:
O O O
t t t
N--R orH--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
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WO 97142286 PCT/US97/06918
O O O
~--R or R3--C--N--R or ~ '~
C=O E E
R3
nor combinations thereof.
B is hydrogen, Cl-C6 alkyl, ~(CH2)qSO3M~ -(CH2)pCO2M, ~(CH2)q~
(CHSO3M)CH2SO3M, ~(CH2)q(CHSO2M)CH2SO3M, -(CH2)pPO3M, -PO3M,
preferably hydrogen, -(CH2)qSO3M~ -(CH2)q(cHsO3M)cH2so3M~ -(CH2)
(CHSO2M)CH2SO3M, more preferably hydrogen or ~(CH2)qSO3M.
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge
balance. For example, a sodium cation equally satisfies -(CH2)pCO2M, and
(CH2)qSO3M~ thereby resulting in -(CH2)pCO2Na, and -(CH2)qSO3Na 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 benecessary to satisfy the charge requirements of a poly-anionic radical. For example, a -
(CH2)pPO3M moiety substituted with sodium atoms has the formula -(CH2)pPO3Na3.
Divalent cations such as calcium (Ca2+) or m~gnp~ium (Mg2+) may be substituted for or
combined with other suitable mono-valent water soluble cations. Preferred cations are
sodium and potassium, more pler~lled is sodium.
X is a water soluble anion such as chlorine (Cl~), bromine (Br~) and iodine
(I-) or X can be any negatively charged radical such as sulfate (S042-) and methosulfate
(CH3sO3-)
The formula indices have the following values: p has the value from 1 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
I to 100; y has the value from 0 to 100; z has the value 0 or 1; 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 S.
The p,ef~lled cotton soil release agents of the present invention comprise
polyamine backbones wherein less than about 50% of the R groups comprise "oxy" Runits, preferably less than about 20%, more preferably less than 5%, most preferably the
R units comprise no "oxy" R units.
The most preferred cotton soil release agents which comprise no "oxy" R units
comprise polyamine backbones wherein less than 50% of the R groups comprise morethan 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
I
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WO 97142286 PCT/US97/06918
32
backbone R units are C2-C12 alkylene, preferred is C2-C3 alkylene, most preferred is
ethylene.
The cotton soil release agents 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 terrn
"homogeneous polyamine backbone" is defined as a polyarnine backbone having R units
that are the sarne (i.e., all ethylene). However, this s~meness 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 ch~mical synthesis. For
example, it is known to those skilled in the art that ethanolarnine may be used as an
"initiator" in the synthesis of polyethyleneimines, therefore a sarnple of
polyethyleneimin~ that comprises one hydroxyethyl moiety resulting from the
polymerization "initiator" would be considered to comprise a homogeneous polyarnine
backbone for the purposes of the present invention. A polyamine backbone comprising
a}l ethylene R units wherein no br~nrl-ing Y units are present is a homogeneous
backbone. A polyarnine backbone comprising all ethylene R units is a homogeneousbackbone regardless of the degree of br~nçhinE or the nurnber of cyclic branches present.
For the purposes of the present invention the terrn "non-homogeneous polymer
backbone" refers to polyamine backbones that are a composite of various R unit lengths
and R unit types. For exarnple, 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
a mixture of "hydrocarbyl" and "oxy" R units is not necess~ry 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.
Pref~lled cotton soil release polymers of the present invention comprise
homogeneous polyamine backbones that are totally or partially substituted by
polyethyleneoxy moieties, totally or partially q-~terni7Pd 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 polyalkylene~rnines (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
.
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33
PEI's. A common polyalkylenearnine (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 pçnt~minPs' i.e., the hex~n~ines, hept~mines,
- octamines and possibly non~n in~s, the cogenerically derived mixture does not appear to
separate by (li.ctill~tion and can include other materials such as cyclic amines and
particularly pipe~ es. There can also be present cyclic arnines 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 polyethylenimin~s (PEl's). Preferred PEIIs have at least
moderate br~nching, 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 plef~l.. d. Prer~ d backbones, prior to
modification have the general formula:
H
[H2NCH2CH2]n--[NcH2cH2~m--[NCH2CH2]n-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 pn~pol lions of plilll~ ~, secondary and tertiary amine units in the
polyamine backbone, especially in the case of PEI's, will vary, depending on the manner
of plepa~ation. Each hydrogen atom ~tt~rlle~l to each nitrogen atom of the polyamine
backbone chain r~resellls a potential site for subsequent substitution, q.l~terni7~tion or
oxidation.
These polyamines can be prepared, for example, by polymeri_ing ethyleneimine
in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid,
hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for ple~,~ing
these po!yamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued
December S, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent
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 21, l9Sl; all
herein incorporated by reference.
Examples of modified cotton soil release polymers of the present invention
comprising PEI's, are illustrated in Formulas I - V:
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34
Formula I depicts a preferred cotton soil release polymer comprising a PEI
backbone wherein all substitutable nitrogens are modified by replacement of hydrogen
with a polyoxyalkyleneoxy unit, -(CH2CH20)20H, having the formula:
rH(ocH2cH2)2ol2N~ N[(CH2cH20)2oHl2
N~ H(OC~12CH2)20~N~(cH-2cH2o)2oH
(CH2CH20)20H ~ ~ (CH2CH20)20H
[H(OCH2CH2)20]2N~N N~N N~N N~N N[(CHtCH20)20Hl2
(CH2CH20)20H
Nl(CH2CH20)20Hl2 Nl(CH2CH20)20Hk
Formula I
Formula II depicts a cotton soil release polymer comprising a PEI backbone
wherein all substitutable nitrogens are modified by replacement of hydrogen with a
polyoxyalkyleneoxy unit, -(CH2CH20)7H, having the formula
rH(ocH2cH2h]2N~ ~N~(CH2CH20)7Hk
NJ H(ocH2cH2h ~N~ N[(cH2cH2ohH]2
(CH2CH20)7H ~ ~ (CH2CH20)7H
[H(ocH2cH2)7l2N~N--N~N--N~N--N~N--N~N[(CH2cH20hH]2
(CH2CH20)7H (CH2CH20hH ~ (CH2CH20hH
~N
J ~ ~N[(CH2CH20)7Hl2
[H(OCH2CH2h]2N N
~,N[(CH2CH20hHk
Formula II
This is an example of a cotton soil release polymer that is fully modified by one type of
moiety.
Formula III depicts a cotton soil release polymer comprising a PEI backbone
wherein all substitutable primary amine nitrogens are modified by replacement ofhydrogen with a polyoxyalkyleneoxy unit, -(CH2CH20)7H, the molecule is then
modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to
N-oxides, said cotton soil release agent ha~ing the formula
.
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WO 97/42286 rCT/US97/06918
~0 ~0
[H(OCH2CH2h]2N N[(cH2cH2o)7Hl2 IO(CH2oCH20)6H
~ ~ 0~ ~ N[(cH2cH~o)7H]2
H(OCH2CH2)6~ ~0 (j~H2CH20)6~ o (~2cH2o)~H
rH(ocH2cH2hl2N ~--~N~ ~N o N N~( N~N[(CH2CH20)7H]2
O(CH,CH20)6H N O(cH2cH2o)6H
H(OCH2CH2)~]2N ,~N~N[(cH2cH2o)~7H]2
~, ~Nr(CH2CH20)7H]2
Formula III
Formula IV depicts a cotton soil release polymer comprising a PEI backbone
wherein all backbone hydrogen atoms are substituted and some backbone amine units are
q~ tÇ~li7ed The substituents are polyoxyalkyleneoxy units, -(CH2CH20)7H, or methyl
groups. The modified PEI cotton soil release polymer has the formula
ICH3
[H(OCH2CH2~7]2N~ ~N(CH2CH2O~7H CH3
~NJ Cl CH3 ~ ~N(CH2cH2OhH
CH3 ,CH3 ~ ~ CH3 ' CH3
rH(OCH2CH2h~2N~N--N~N N~N N~ + N~N(CH3)2
Cl CH3 CH3 ~ Cl CH3
3 Cl
H(OCH2CH2h]2N N~N(CH3)3
~,N(CH3h
Formula IV
Formula V depicts a cotton soil release polymer 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 cotton
soil release polymer has the formula
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WO 97/42286 PCT/US97/06918
36
ICH3
[H(ocH2cH2)7~2N~ ~N(CH2CH20)7H ~ CH3
~NJ Cl- CH3~N~N(cH2cH2okH
CH3 CH3 0 ~ CH3 ~ CH3~ CH3
[H(ocH~cH2)7l2N N--N~y--N~N--N~N--N~N(CH3)2
Cl CH3 0 \~ ~ Cl- CH3
~N~3 Cl-
tH(OCH2CH2)7]2N N~N(CH3)3
~,N(CH3)2
Formula V
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 arnine 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.
The laundry detergent compositions according to the present invention comprise
adjunct ingredients and carriers, said adjunct ingredients are selected from the group
con~icting of builders, optical brighteners, bleaches, bleach boosters, bleach activators,
other non-cotton soil release polymers, dye transfer agents, dispersents, enzymes,
enzyme activators, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes,
and mixtures thereof, however this list is not meant to be exhaustive or to exclude any
suitable material used by the formulator.
Detersive surfactants
In addition to the anionic and nonionic detersive surfactants described herein
above, other detersive surf~ct~nt~ that are suitable for use in the present invention are
cationic, anionic, nonionic, ampholytic, zwitterionic, and mixtures thereof, further
described herein below.
Nonlimiting examples of other surfactants useful herein typically at levels fromabout 1% to about 55%, by weight, include the conventional C1 1 -C 18 alkyl benzene
sulfonates ("LAS"), the C I o-C 18 secondary (2,3) alkyl sulfates of the fonnulaCH3(CH2)x(CHOSO3 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 cation, especially sodium, unsaturated sulfates such as oleyl sulfate,
CA 022~28~1 1998-10-29
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37
Clo-Clg alkyl alkoxy carboxylates (especially the EO l-5 ethoxycarboxylates), the Clo
18 glycerol ethers, the C I o-C 18 alkyl polyglycosides and their corresponding sulfated
polyglycosides, and C 1 2-C 18 alpha-sulfonated fatty acid esters. If desired, the
conventional nonionic and amphoteric surfactants such as the C 1 2-C 1 8 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 1 2-C 18 betaines and
sulfobetaines ("sultaines"), C I o-C 18 amine oxides, and the like, can also be included in
the overall compositions. The C I o-C 18 N-alkyl polyhydroxy fatty acid amides can also
be used. Typical exarnples include the C 1 2-C 18 N-methylglucamides. See WO
9,206,154. Other sugar-derived surf~ct~l t~ include the N-alkoxy polyhydroxy fatty acid
amides, such as Clo-cl8 N-(3-methoxypropyl) glucamide. Clo-C20 conventional
soaps may also be used. If high sudsing is desired, the branched-chain C lo-C 16 soaps
may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other
conventional useful surfactants are listed in standard texts.
Other anionic ~ul r~ useful for detersive purposes can also be included in the
compositions hereof. These can include salts (including, for example, sodium
potassium, ~mmonium, and substituted ammonium salts such a mono-, di- and
triethanolamine salts) of soap, Cg-C20 linear alkylben7~n~s~llphf nates, Cg-C22 primary
or secondary ~Ik~nl-sulphonates, Cg-C24 olefin~ulphonates, sulphonated polycarboxylic
acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfates, alkyl phenol ethylene oxide ether sulf~t~s, paraffin sulfonates, alkyl phosphates,
isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl
tauride, alkyl succin~m~tes and sulfosuccin~tPc, monoesters of sulfosuccinate (especially
saturated and unsaturated C 1 2-C 18 monoesters) diesters of sulfosuccinate (especially
saturated and unsaturated C6-C14 diesters), N-acyl sarcosin~te~, sulfates of
alkylpolys~cch~ es such as the sulfates of alkylpolyglucoside, branched primary alkyl
slllf~tes, alkyl polyethoxy carboxylates such as those of the formula
RO(CH2CH2O)kCH2COO-M+ wherein R is a Cg-C22 alkyl, k is an integer from 0 to
10, and M is a soluble salt-forming cation, and fatty acids esterified with isethionic acid
and neutralized with sodium hydroxide. Further examples are given in Surface Active
A~eents and D~l~. ,ee-,ls (Vol. I and II by Schwartz, Perry and Berch).
Non-cotton Soil Release A~ent
Known polymeric soil release agents, hereinafter "SRA", can optionally be
employed in the present detergent compositions. If utili7~ SRA's will generally
comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to3.0% by weight, of the compositions.
CA 022~28~1 1998-10-29
WO 97/42286 ~CT/US97/06918
38
Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of
hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit
upon hydrophobic fibers and remain adhered thereto through completion of 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 plop~ ies. Structures and charge
distributions may be tailored for application to different fiber or textile types and for
varied dt:lelgellt or detergent additive products.
Preferred SRA's include oligomeric terephth~l~te esters, typically prepared by
processes involving at least one tr~n~est~rificationloligomerization, often with a metal
catalyst such as a lil~li~(IV) alkoxide. Such esters may be made using additional
monomers capable of being incolyoldled into the ester structure through one, two, three,
four or more positions, without, of course, forrning a densely crosslinked overall
structure.
Other SRA's include the nonionic end~capped 1,2-propylene/polyoxyethylene
terephth~l~te polyesters of U.S. 4,711,730, December 8, 1987 to Gosselin-k et al., for
example those produced by l~ e~l~rification/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 Gossçlink, such as oligomers from ethylene glycol ("EG"), PG,
DMT and Na-3,6~dioxa-8-hydroxyoct~nPs~llfonate; and the anionic, especially
sulfoaroyl, end-capped terephth~l~te 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 ~rther
comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephth~l~te or
propylene tereph1h~l~t~ with polyethylene oxide or polypropylene oxide terephth~l~t~,
see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to R~ r, July 8, 1975;
cellulosic derivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; the C 1 -C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see
CA 022~28~1 1998-10-29
WO 97142286 PCT/US97/06918
39
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
1.6 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
METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl
cellulose ethers m~nl~f~ctured by Shin-etsu Kagaku Kogyo KK.
Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include
graft copolymers of poly(vinyl ester), e.g., C I -C6 vinyl esters, preferably poly(vinyl
acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0
219 048, published April 22, 1987 by Kud, et al. Commercially available examplesinclude SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany.
Other SRA's are polyesters with repeat units co~ 10-15% by weight of ethylene
terephth~l~te together with 80-90% by weight of polyoxyethylene terephth~l~te derived
from a polyoxyethylene glycol of average molecular weight 300-5,000. Comrnercialexamples include ZELCON 5126 from Dupont and MILEASE T from ICI.
Another plere.led SRA is an oligomer having empirical formula
(CAP)2(EG/PG)s(T)s(SIP)1 which comprises terephthaloyl (T), sulfoisophthaloyl (SIP),
oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably
tP~nin~ted with end-caps (CAP), preferably modified isethionates, as in an oligomer
comprising one sulfoisophthaloyl unit, S terephthaloyl units, oxyethyleneoxy and oxy-
1,2-propyleneoxy units in a defined ratio, p.ef~ldbly about 0.5:1 to about 10:1, and two
end-cap units derived from sodiurn 2-(2-hydroxyethoxy)-eth~nesulfonate. Said SRApreferably further comprises from 0.5% to 20%, by weight of the oligomer, of a
crystallinity-redll~ing stabilizer, for example an anionic surfactant such as linear sodium
dodecylbPn7Pn~ lfonate or a member selected from xylene-, c~-mPn~-, 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, Gosselink, Pan, Kellett and Hall, issued
May 16, l 99S. Suitable monomPrs for the above SRA include Na-2-(2-hydroxyethoxy)-
eth~nesulfonate, DMT, Na-dimethyl-S-sulfoisophsh~l~te, EG and PG.
Additional classes of SRA's include: (I) nonionic terephth~l~5es using
diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824,
Violland et al. and U.S. 4,240,918 T ~e~Cce 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
.. ..
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WO 97/42286 PCT/US97/06918
anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as
long as they have hydroxyl terrnin~l groups which may be esterified. See U.S. 4,525,524
Tung et al.. Other classes include: (III) anionic terephth~l~te-based SRA's of the
urethane-linked variety, see U.S. 4,201,824, Violland et al.; (IV) poly(vinyl caprolactam)
and related co-polymers with monomers such as vinyl pyrrolidone and/or
dimethylaminoethyl meth~rylate, including both nonionic and cationic polymers, see
U.S. 4,579,681, Ruppert 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 con-lçncin~ adipic acid, caprolactam, and polyethylene
glycol, especially for treating polyarnide 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.
Bleachin~ Compounds - Bleaching A~ents and Bleach Activators
The d~t~ ,.lt compositions herein may optionally contain ble~ching agents or
ble~hing con~ rl~ CO~ ,g a blea~hing agent and one or more bleach activators.
When present, bl~Achi..~ agents will be at levels of from about 0.05% to about 30%,
more preferably from about 1% to about 30%, most preferably from about 5% to about
20%, of the dt;~ 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 bleachin~ composition comprising the
ble~hing agent-plus-bleach activator.
The ble~çl~ g agents used herein can be any of the ble~ching agents useful for
detergent compositions in textile cleaning that are now known or become known. These
include oxygen bleaches as well as other ble~clling agents. Perborate bleaches, e.g.,
sodiurn perborate (e.g., mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction
encompasses pelca,bo~cylic acid bleachin~ agents and salts thereof. Suitable examples of
this class of agents include m~gnesium monoperoxyphth~l~ts hexahydrate, the
magnesium salt of metachloro pc~ lzoic acid, 4-nonylamino-4-oxoperoxybutyric acid
and diperoxydodec~n~-flioic acid. Such ble~chin~ agents are disclosed in U.S. Patent
4,483,781, II~llllan, issued November 20, 1984, U.S. Patent Application 740,446, Burns
et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published
. . .
CA 022~28~1 1998-10-29
WO 97142286 PCT/US97/06918
41
February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
Highly preferred ble~rhing 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 carl also be used. Suitable peroxygen bleaching
compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate"
bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium
peroxide. Persulfate bleach (e.g., OXONE, m~mlf~l~tllred commercially by DuPont) can
also be used.
A plef~lcd pe~c~ubollate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about 1,000 micr~."ct~,ls, 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 pelc~l,ollate can be coated with silicate,
borate or water-soluble surf~ct~nte. Percarbonate is available from various CO~ .cial
sources such as FMC, Solvay and Tokai Denka.
Mixtures of ble~chin~ agents can also be used.
Peroxygen ble~ ing agents, the perborates, the pe.c~l,onales, etc., are
preferably combined ~,vith bleach activators, which lead to the in situ production in
aqueous solution (i.e., during the washing process) of the peroxy acid col,cspollding to
the bleach activator. Various nonlimiting examples of activators are disclosed in U.S.
Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The
nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene ~i~mine (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 p~cf~ ,d amido-derived bleach activators are those of the forrn~ P:
RlN(R5)C(O)R2C(O)L or RlC(o)N(R5)R2C(o)L
wherein Rl is an alkyl group cont~ining from about 6 to about 12 carbon atoms, R2 is an
alkylene cont~ining from 1 to about 6 carbon atoms, RS is H or alkyl, aryl, or alkaryl
cont~inin~ 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 plef~,,cd leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
oct~n~mido-caproyl)oxyb~nzenesulfonate, (6-nonanamidocaproyl)oxybPn7PnPsll~fonate,
(6-~lec~n~mido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S.
Patent 4,634,551, incorporated herein by reference.
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WO 97t42286 PCT/US97/06gl8
42
Another class of bleach activators comprises the benzoxazin-type activators
disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated
herein by reference. A highly preferred activator of the benzoxazin-type is:
R
[~N"C~
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the formulae: O O
Il 11
O C--CH2--CH2 0 C--CH~--CH2
R6--C--N~ \CH2 R6--C--N~
CH2--CH2 CH2--CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group cont~inin~ from 1 to about
12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam,octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, l.n~Pcenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, llndecenoyl valerolactam, nonanoyl valerolactam,
3,5,5-trimethylhexanoyl valerolactam and n.i~ s thereof. See also U.S. Patent
4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference,
which discloses acyl caprolactams, including benzoyl caprolactam,-adsorbed into sodium
perborate.
Ble~chin~ agents other than oxygen bleaching agents are also known in the art
and can be utilized herein. One type of non-oxygen ble~chin~ agent of particular interest
includes photoactivated blç~chin~ agents such as the sulfonated zinc and/or al.-minunn
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 0.02~% to about 1.25%,
by weight, of such ble~chPs, especially sulfonate zinc phthalocyanine.
If desired, the ble~hin~ compounds can be catalyzed by means of a m~n~nese
compound. Such compounds are well known in the art and include, for example, them~n~nPse-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. 549,271A1,549,272A1, 544,440A2, and 544,490Al; Preferred examples ofthese catalysts include
MnIV2(u-O)3(1,4,7-trimethyl- 1,4,7-triazacyclononane)2(PF6)2, MnIII2(u-O) 1 (u-
OAc)2(1,4,7-trimethyl- 1,4,7-triazacyclononane~2 (ClO4)2, MnIV4(u-O)6(1,4,7-
.. ..
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43
triazacyclononane)4(C104)4, MnIIIMnIv4(u-o) 1 (u-OAc)2 (1,4,7-trimethyl- 1,4,7-
triazacyclononane)2(ClO4)3, MnIV(1,4,7-trimethyl- l ,4,7-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. 5,114,611. The use of m~ng~nese ~,vith
various complex ligands to enh~n~e bleaching is also reported in the following United
States Patents: 4,728,455; 5,284,944; 5,246,612; 5,2S6,779; 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 dete~g~llt compositions can be
included in the compositions herein, including other active ingredients, carriers,
hydrotropes, proces~ing aids, dyes or pigm~nte, solvents for liquid formulations, solid
fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the
C1o-C16 alkanol~mides can be inco~ordted into the compositions, typically at 1%-10%
levels. The C 1 o-C 14 monoethanol and diethanol amides illustrate a typical class of such
suds boosters. Use of such suds boosters with high sudsing adjunct surf~ct~nts such as
the amine oxides, betaines and sultaines noted above is also advantageous. If desired,
soluble magnesium salts such as MgCl2, MgSO4, and the like, can be added at levels of,
typically, 0.1 %-2%, to provide additional suds and to enh~nce 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 ~ulr~ t 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 int~n~led detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica (trademark
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution cont~ining
3%-5% of C 13- 15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, theenzyme/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 d1te.~ t matrix. By this means, ingredients such as the
, I
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WO 97/42286 PCT/US97/06gl8
44
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 isol,lol)al1ol are suitable. Monohydric alcohols are preferred forsolubilizing surfactant, but polyols such as those Col1tdi~ g 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 forrn~ t~c~ 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 reco...~..entlec~ 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,
amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin,
such as vegetable, animal, bacterial, fungal and yeast origin. Pl~,felled selections are
influenced by factors such as pH-activity and/or stability optima, therrnostability, and
stability to active del~,lge,.l~, builders and the like. In this respect bacterial or fungal
enzymes are plcfell~d, such as bacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain
removing or other~vise beneficial effect in a laundry, hard surface cleaning or personal
care del~,gellt composition. Preferred detersive enzymes are hydrolases such as
proteases, amylases and lipases. P~cfell~d enzymes for laundry ~ oses include, but are
not limited to, proteases, cellulases, lipases and peroxidases.
Enzymes are normally incorporated into d~L~,gell~ 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 ~l~,p~dlions, typical
amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active
CA 022~28~1 1998-10-29
WO 97142U6 PCTIUS97/06918
enzyme per gram of the detergent composition. Stated otherwise, the compositionsherein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a
commercial enzyme pl~aldLion. Protease enzymes are usually present in such
commercial plep~dlions 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 minimi7-o
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 concclllldled delclgellt forrnulations.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. Iicheniformis. 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 Dcl~ , hereinafter
"Novo". The pl~ dlion of this enzyme and analogous enzymes is described in GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~9 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, January 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
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 & Garnble. A recombinant trypsin-like protease for
detergents suitable herein is described in WO 9425583 to Novo.
The pleÇe.led liquid laundry dct~,lgcnl compositions according to the present
invention further comprise at least 0.001 % by weight, of a protease enzyme. ~Iowever,
an effective amount of ploteasc enzyme is sufficient for use in the liquid laundry
detergent compositions described herein. The term "an effective amount" refers to any
arnount capable of producing a cleaning, stain removal, soil removal, ~hit~ il-g,
deodorizing, or freshness improving effect on substrates such as fabrics. In practical
terms for current commercial ~lcp~dtions, typical amounts are up to about S 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 %- I % by weight of a co-nll.el~;ial enzyme pr~,p~tion.
The protease enzymes of the present invention are usually present in such commercial
CA 022~28~1 1998-10-29
WO 97/42286 PCT/US97/06918
46
e~alions at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of
activity per gram of composition.
Preferred liquid laundry detergent compositions of the present invention comprise
a protease enzyme, referred to as "Protease D", which 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 arnino acid residue positions equivalent to those
selected from the group concictin~ 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
amyloliqueSaciens subtilisin, as described in WO 95/10615 published April 20, 1995 by
Genencor Tntern~tional.
Useful prote~ces 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 Co~ ,~ly; WO 95/29979 published
Novenber 9, 1995 by The Procter & Gamble Company.
~ lef~ d proteolytic enzymes are also modified bacterial serine proteases, such
as those described in E~upean Patent Application Serial Number 87 303,761.8, filed
April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease
B", and in Eulopedll Patent Application 199,404, Venegas, published October 29, 1986,
which refers to a motlified bacterial serine proteolytic enzyme which is called "Protease
A" herein, Plot~ase 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, January 9, 1985
Amylases suitable herein, include, for example, a-arnylases described in GB
1,296,839 to Novo; RAPIDASE(~, Tnt~rn~tional Bio-Synthetirc, Inc. and
TERMAMYL~, Novo. FUNGAMYL g) from Novo is especially useful. Fngineering 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 prefelled
embo-lim~nte of the present compositions can make use of amylases having improved
stability in detel~,.,.lls, especially improved oxidative stability as llleaau,~d against a
reference-point of TERMAMYL(~) in conl~l,clcial use in 1993. These ~l~r~lled amylases
herein share the characteristic of being "stability-enh~nce(l" amylases, ch~ l,zed, at a
minimllm, by a measurable improvement in one or more of: oxidative stability, e.g., to
hydrogen peroxide / tetraacetylethylene-~ mine in buffered solution at pH 9-10; thermal
stability, e.g., at common wash temperatures such as about 60~C, or ~Ik~lin~ stability,
.. . .. .. . . .. .
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WO 97/42286 PCT/US97/06918
47
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
from one or more of the Baccillus arnylases, especialy the Bacillus o~-arnylases,
regardless of whether one, two or multiple amylase strains are the immediate precursors.
Oxidative stability-enh~nce~ amylases vs. the above-identified reference amylase are
preferred for use, especially in ble~ching, more preferably oxygen bleaching, as distinct
from chlorine ble~ching, detergent compositions herein. Such preferred amylases include
(a) an amylase according to the hereinbefore incorporated 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.lichenifo"nis alpha-amylase, known as TER~AMYL~), or the homologous position
variation of a similar parent amylase, such as B. amyloliquefaciens, B.subfilis, or
B.s~earothermophilus; (b) stability~enh~nce~l amylases as described by Genencor
Tntç~T ~tional in a paper entitled "Oxidatively Resict~nt 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 d~ y,ellls
inactivate alpha-amylases but that improved oxidative stability amylases have been made
by Genencor from B.licheniformis 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 mllt~ntc, particularly important being
M197L and M197T with the M197T variant being the most stable expressed variant.
Stability was measured in CASCADE~' and SUNLIGHT~; (c) particularly prefelled
amylases herein include amylase variants having additional modification in the
imrnediate parent as described in WO 9510603 A and are available from the assignee,
Novo, as DURAMYL(~'. Other particularly preferred oxidative stability enh~need
amylase include those described in WO 9418314 to Genencor Tntern~tional and WO
9402597 to Novo. Any other oxidative stability-enh~n~ed amylase can be used, forexample as derived by site-directed mutagenesis from known cnimeric, hybrid or simple
mutant parent forms of available arnylases. Other pl~ef~llc;d enzyme modifications are
accessible. See WO 9509909 A to Novo.
Cellulases usable herein include both bacterial and fungal types, preferably having
a pH optimurn between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6, 1984,
discloses suitable fungal cellulases from Humicola insolens or Humicola strain
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48
DSM1800 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.
Suitable lipase enzymes for detergent usage include those produced by
microorg~ni~m~ of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in GB 1,372,034. See also lipases in J~p~n~se Patent Application
53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical
Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P." Other
suitable comrnercial lipases include Amano-CES, lipases ex Chromobacter viscosum,
e.g. Chromobacter viscosum var. Iipolyticum 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 co~ ,ercially available from Novo, see
also EP 341,947, is a p.efel,~d lipase for use herein. Lipase and amylase variants
stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. Seealso 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 ble~chin~" or prevention
of transfer of dyes or pigm.-nt~ removed from substrates during the wash to other
substrates present in the wash solution. Known peroxidases include horseradish
peroxidase, li~nin~e, and haloperoxidases such as chloro- or bromo-peroxidase.
Peroxidase-cont~inin~ 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 incol~olalion into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor Intern~tional, 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 forliquid 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
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49
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 Stabilizin~ System
Enzyme-cont~ining, including but not limited to, liquid compositions, herein maycomprise 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 stabilizingsystem. 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 forrnulator or by a
m~nl~f~cturer 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 ~sigrl~d to address di~e.ll stabilization problems
depending on the type and physical form of the d~l~rg~lll composition.
One stabilizing approach is the use of water-soluble sources of calcium and/or
m~gn~eium ions in the finichçd compositions which provide such ions to the enzymes.
Calcium ions are generally more effective than m~gn~sium 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 finiched
detergent composition, though variation is possible depending on factors including the
multiplicity, type and levels of enzymes incorporated. Preferably water-soluble calcium
or m~gn~sjum salts are employed, including for example calcium chloride, calciumhydroxide, calcium formate, calcium malate, calcium m~le~te, calcium hydroxide and
calcium acetate; more gençr~lly, calcium sulfate or m~gn~Sjum 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 apploacll 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.
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Stabilizing systems of certain cleaning compositions may further comprise from
O 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 ~lk~lin~ conditions. While
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 orpercarbonate, 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
essenti~l 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
cont~ining ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
Antioxidants such as carb~m~te, ascorbate, etc., organic amines such as
ethylenP~ minetetracetic 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 bi~11f~te, nitrate, chloride, sources of hydrogen
peroxide such as sodium perborate tetrahydrate, sodium pe.l,olale monohydrate and
sodium percarbonate, as well as phosphate, con~n~ed phosphate, acetate, ben70~t~,
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-
cont~ining 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,
B~gin~i et al.
Builders
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51
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 15% to about 50% by weight, of the detergent builder.
Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-cont~ining detergent builders include, but are not limited to, the
alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by
the tripolyphosph~tes7 pyrophosph~tes, and glassy polymeric meta-phosphates),
phosphon~tes, phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and aluminosilic~tçs However, non-phosphate builders are
required in some locales. Impo.~tly, 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 thosehaving a SiO2:Na2O ratio in the range 1.6: 1 to 3.2: 1 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 tr~-lern~rk for a crystalline layered silicate marketed by
Hoechst (comrnonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na
SKS-6 silicate builder does not contain all-mimlm NaSKS-6 has the delta-Na2SiOs
morphology form of layered silicate. It can be plel)~ed by methods such as thosedescribed 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 NaMSixO2x+l ~yH2O wherein M is sodium or hydrogen, x is a numberfrom 1.9 to 4, plefeldbly 2, and y is a number from 0 to 20, preferably 0 can be used
herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na~SiOs
(NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such
as for example m~gn-osium silicate, which can serve as a crispening agent in granular
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52
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 signific~nt 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 l S to about 264.
Useful aluminosilicate ion ex~h~nge materials are commercially available. These
aluminosilicates can be crystalline or amorphous in structure and can be naturally-
occurring aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel,
et al, issued October 12, 1976. P~f~ d synthetic crystalline aluminosilicate ionexchange materials useful herein are available under the ~lecign~tions Zeolite A, Zeolite
P (B), Zeolite MAP and Zeolite X. In an especially p,ef, l,ed embodiment, the
crystalline aluminosilicate ion exchange material has the formula:
Na 12 [(AIO2) 12(sio2) 12] ~XH2O
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 ~ meter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate compounds. As used
herein, "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 forrn, alkali metals, such as sodium, potassium, and lithium, or
alkanolarnmonium salts are prefe"~d.
Included among the polycarboxylate builders are a variety of categories of useful
materials. One important category of polycarboxylate builders encomp~csec the ether
polycarboxylates, including oxydi~Llccinate, 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.
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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 maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy
benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali
metal, ammoniurn and substituted ammoniurn salts of polyacetic acids such as
ethylçne.li~mine 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 li~uid
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 preferredcompound of this type is dodecenylsuccinic acid. Specific examples of succinate
builders include: laurylsuccinate, myristylsuccinate, palmityl~u~cin~te, 2-
dodecenyl.c~lccin~te (~ler~.,ed), 2-pçnt~lecenyl~lccin~te, and the like. Laurylsuccinates
are the ple~.led builders of this group, and are described in E~opedll Patent Application
86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 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 18 monocarboxylic acids, can also be incorporated intothe 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 fliminlltion of sudsing, which should be taken into account
by the form~ t-)r.
In situations where phosphorus-based builders can be used, and especially in theformulation of bars used for hand-laundering operations, the various alkali metal
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54
phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphateand sodium orthophosphate can be used. Phosphonate builders such as ethane-l-
hydroxy-l,l-diphosphonate and other known phosphonates (see, for exarnple, U.S.
Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
Chelatin~e Agents
The detergent compositions herein may also optionally contain one or more iron
and/or m~n~nPse ch~l~ting agents. Such chelating agents can be selected from thegroup con~i~ting of amino carboxylates, amino phosphonates, polyfunctionally-
substituted aromatic chelating agents and mixtures therein, all as hereinafter definP~1
Without inten-ling 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 m~ng~nese ions from
washing solutions by formation of soluble che1~tes.
Amino carboxylates useful as optional chel~ting agents include
ethylPne~i~minPtetr~cet~tPs~ N-hydroxyethylethylene~ minetriacetates, nitrilo-
tri~ret~tPs~ ethylr~.PAi~ .e ~ell~lopl;onates, triethylenet~ inphex~et~tes~diethylenetri~mil.~,pe..~ ret~tt?s, and ethanoldiglycines, alkali metal, ammonium, and
substituted ammonium salts therein and mixtures therein.
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 dclergent co~ ,osilions, and include ethylene~i~minetetrakis (methylenephosphonates)
as DEQUEST. PlcÇ~lled, these amino phosphonates to not contain alkyl or alkenyl
groups with more than about 6 carbon atoms.
Polyfunctionally-sub~liluled 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.
Plcfell. d compounds of this type in acid form are dihydroxydisulfoben_enes such as 1,2-
dihydroxy-3 ,5 -disulfobçn7PnP.
A ~ ed biodegradable chelator for use herein is ethylenP~ minP disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November
3, 1987, to Hartman and Perkins.
If l~tili7f'(~, these chPl~tin~ agents will generally comprise from about 0.1% to
about 10% by weight of the detergent compositions herein. More preferably, if utili7t~
the chelating agents will comprise from about 0.1% to about 3.0% by weight of such
compositions.
Clay Soil Removal/Anti-redeposition A~ents
The compositions of the present invention can also optionally contain water-
soluble ethoxylated amines having clay soil removal and antiredeposition p,.~p~lLies.
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Granular detergent compositions which contain these compounds typically contain from
about 0.Q1 % 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
tetraethylenepenJ~mine. Exemplary ethoxylated amines are further described in U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil
removal-antiredeposition agents are the cationic compounds disclosed in EuropeanPatent 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. Patent4,548,744, 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 A~ents
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 enh~nce overall d~le.ge.ll builder p~.Ço~ ce, 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 prepaled 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, maleic acid (or maleic anhydride), fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
The presence in the polymeric polycarboxylates herein or monomeric segmç.ltc,
cont~ining no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble salts of
polymerized acrylic acid. The average molecular weight of such polymers in the acid
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56
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 d~lelgellL 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 maleic acid. The average molecular weight of suchcopolymers 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 subslilul~d ammonium salts. Soluble acrylate/maleate copolymers of
this type are known materials which are described in ELu~opean Patent Application No.
66915, published December 15, 1982, as well as in EP 193,360, published September 3,
1986, which also describes such polymers comprising hydroxypropylacrylate. Still other
useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such
materials are also disclosed in EP 193,360, including, for example, the 45/45/10terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG can exhibit dispersing agent performance as well as act as a clay soil removal-
antiredeposition agent. Typical molecular weight ranges for these purposes range from
about 500 to about 100,000, preferably from about 1,000 to about 50,000, more
preferably from about 1,500 to about 10,000.
Poly~p~le and polygh-t~m~te dispersing agents may also be used, especially
in conjunction with zeolite builders. Dis~ ing agents such as polyaspartate preferably
have a molecular weight (avg.) of about 10,000.
Brightener
Any optical bri~ht~n~rs or other bright~ning or while~ g agents known in the artcan 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
in the present invention can be classified into subgroups, which include, but are not
n~cess~rily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid,
methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring
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57
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
December 13, 1988. These brighteners include the PHORWHITE series of bri~hl~nelsfrom Verona. Other brighteners disclosed in this reference include: Tinopal UNPA,
Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic White CC and ArticWhite 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 aminoco.lm~rin.c 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 bri~hten~rs are preferred herein.
Suds Su,~ ess."~
Compounds for reducing or su,OplG~sing 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 m~chinPs.
A wide variety of materials may be used as suds ~up~.Gssors, and suds
suppressors are well known to those skilled in the art. See, for example, Kirk Othrner
Encyclopedia of Chemical Technology, Third Edition, Volurne 7, pages 430-447 (John
Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest
enco~..p~eses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent
2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fattyacids and salts thereof used as suds SUppl~,SSOt 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
alkanolarnmonium salts.
The d~ ,elll compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight hydrocarbons such as
paraffin, fany acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic C 1 g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include
N-alkylated amino triazines such as tri- to hexa-alkylmel~ines or di- to tetra-
alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three
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moles of a primary or secondary amine cont~ining l to 24 carbon atoms, propyleneoxide, 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 temperature 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 ~ h~tic,
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 inten~ed to include mixtures of true l~arrlns and cyclic hydrocarbons.
Another l,ie~.ed category of non-surfactant suds suppressors comprises silicone
suds ~u~.p~essors. 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 Patent Application No. 89307851.9, 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 defoarning aqueous solutions by incorporating
therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and ~ n~ted silica are described, for in~t~nre, 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, Bartolotta et al,
and in U.S. Patent 4,652,392, B~gin~L i et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds ~ples~ing
arnount of a suds controlling agent con~i~ting e~enti~lly of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about
1,500 cs. at 25~C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane
resin composed of (CH3)3SiOl/2 units of SiO2 units in a ratio of from
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59
(CH3)3 siol/2 units and to SiO2 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 pler~,l.ed 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 (plefel,~d), or polypropylene glycol. The primarysilicone suds suppressor is branched/cro.sslink.?d 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 (I ) 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
tel,.p~ re of more than about 2 weight %; and without polypropylene glycol. Similar
arnounts 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 anda 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 tc.l.p~ re of more than about 2 weight %, preferably more than about
S 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, mostpreferably 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 bet~veen 1 :3 and 1 :6, of polyethylene glycol:copolymer of
polyethylene-polypropylene glycol.
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The preferred silicone suds suppressors used herein do not contain polypropyleneglycol, particularly of 4,000 molecular weight. They also preferably do not contain
block copolymers of ethylene oxide and propylene oxide, like PLURONIC L 101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-
alkyl alkanols) and mixtures of such alcohols 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 I -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 m~rhin~
Suds suppressors, when utili7P-l are preferably present in a "suds ~up~les~itlg amount.
By "suds suppressing amount" is meant that the f nmll~tor of the composition can select
an arnount 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 m~rllin~s.
The compositions herein will generally comprise from 0% to about 5% of suds
suppressor. When utilized as suds sup~,lessGls, monocarboxylic fatty acids, and salts
therein, will be present typically in amounts up to about 5%, by weight, of the detergent
composition. Preferably, from about 0.S% to about 3% of fatty monocarboxylate suds
suppressor is lltili7P~l Silicone suds ~u~p,essors are typically utilized in arnounts 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
minimi7~d and effectiveness of lower amounts for effectively controlling sudsing.
Preferably from about 0.01% to about 1% of silicone suds sup~ ,sor is used, morepreferably 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 ~Itili7P.~ 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
arnounts 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 fini~hed
compositlons.
Fabric Softeners
.
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Various through-the-wash fabric softeners, especially the impalpable smectite
clays of U.S. Patent 4,062,647, 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 al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued
September 22, 1981.
Dve Transfer Inhibitin~ A~ents
The compositions of the present invention may also include one or more materialseffective for inhibiting the transfer of dyes from one fabric to another during the cleaning
process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone
polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, m~ng~n~se phthalocyanine, peroxidases, and mixtures thereof. If used,
these agents typically comprise from about 0.01% to about 10% by weight ofthe
composition, preferably from about 0.01% to about 5%, and more preferably from about
0.05% to about 2%.
More specifically, the polyamine N-oxide polymers ~,eft.led for use herein
contain units having the following structural formula: R-AX-P; wherein P is a
polymerizable unit to which an N-O group can be att~hPd or the N-O group can form
part of the polymerizable unit or the N-O group can be att~hed to both units; A is one of
the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic,
ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination
thereof to which the nitrogen of the N-O group can be ~ rhecl or the N-O group is part
of these groups. Pl~f~ ,d polyamine N-oxides are those wherein R is a heterocyclic
group such as pyridine, pyrrole, imirl~7O1e, pyrrolidine, piperidine and derivatives
thereof.
The N-O group can be represented by the following general structures:
~l ~l
(Rl)x--Nl--(R2)y; =N--(Rl)x
(R3)z
wherein Rl, 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. The amine oxide unit of the
polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
.. . ..
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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. These polymers include random or block copolymers
where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of
10: I to 1: 1,000,000. However, the number of amine oxide groups present in the
polyamine oxide polymer can be varied by app~oll~iate copolymerization or by an
appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any
degree of polymerization. Typically, the average molecular weight is within the range of
500 to 1,000,000; more prc~ ;d 1,000 to S00,000; most preferred 5,000 to 100,000.
This preferred class of materials can be referred to as "PVNO".
The most plcfclled polyamine N-oxide useful in the detergent compositions
herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about
50,000 and an amine to amine N-oxide ratio of about 1 :4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an
average molecular weight range from S,000 to 1,000,000, more preferably from S,000 to
200,000, and most preferably from 10,000 to 20,000. (The average molecular weight
range is determined by light scattering as described in Barth, et al., Chemical AnalYsis,
Vol 113. "Modern Methods of Polymer Characl~,; alion", the disclosures of which are
incorporated herein by ,~f~l~,nce.) The PVPVI copolymers typically 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. These copolymers can be either linear or
branched.
The present invention compositions also may employ a polyvinylpyrrolidone
("PVP") having an average molecular weight of from about S,000 to about 400,000,prcr~lably from about 5,000 to about 200,000, and more preferably from about 5,000 to
about 50,000. PVP's are known to persons skilled in the detergent field; see, for
example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference.
Compositions co~t~ining PVP can also contain polyethylene glycol ("PEG") having an
average molecular weight from about 500 to about 100,000, preferably from about 1,000
to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash
solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about
10:1.
.
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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 forrnula:
N~ ~C=C~ l N
R2 SO3M SO3M Rl
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2
is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassiurn.
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)arninol-2,2'-stilbenedisulfonic acid and disodium salt. This particular
brightener species is commercially marketed under the tr~den~me Tinopal-UNPA-GX by
Ciba-Geigy Corporation. Tinopal-UNPA-GX is the pler~ ,d 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-methylarnino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid
disodium salt. This particular bri~htener species is commercially marketed under the
tr~-len~me Tinopal 5BM-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 bright~n~r is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular bright.oner species is
commercially marketed under the traclen~me Tinopal AMS-GX by Ciba Geigy
Corporation.
The specific optical brightener species selected for use in the present invention
provide especially effective dye transfer inhibition performance benefits when used in
combination with the selected polymeric dye transfer inhibiting agents hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal SBM-
GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in
I
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64
aqueous wash solutions than does either of these two detergent composition components
when used alone. Without being bound by theory, it is believed that such brighteners
work this way because they have high affinity for fabrics in the wash solution and
therefore deposit relatively quick on these fabrics. The extent to which brighteners
deposit on fabrics in the wash solution can be defined by a parameter called the"exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the
brightener material deposited on fabric to b) the initial brightenPr concentration in the
wash liquor. Bri~htt ners with relatively high exhaustion coefficients are the most
suitable for inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical bright~ner types
of compounds can optionally be used in the present compositions to provide conventional
fabric "brightn~cs" benefits, rather than a true dye transfer inhibiting effect. Such usage
is conventional and well-known to detergent formulations.
Prepaldlion of Cotton Soil Release Polymers
EXAMPLE 1
PEI 1800 E7
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 Ib.
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) (Nippon Shokubai, Epomin SP-OI 8
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,r~a~ul;~lion 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, t~lllpe,~ re, 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 t~l.lpelal lre ism~int~ined 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
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PEI nitrogen function), the temperature is increased to I 10 ~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 t~ p~.dlure
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 te~llp~lalure values gradually increase as meth~nol 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 ~git~te~l under vacuum for an additional 30 min1lte~
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
incremPnt~l1y as before while closely monitoring the autoclave pressure, temperature,
and ethylene oxide flow rate while m~itl~ 1i.,ing the t~lllpcldlure between 100 and 110 ~C
and limiting any telnl)clalllre 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 tc~ ,e.~ re 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 ~e~.a~tions the neutralization and deodorization is accomplished in thereactor before discharging the product.
EXAMPLE 2
Quatemization of PEI 1800 E7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added
polyethyler~iminP having a molecular weight of 1800 which is further modified by
I
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66
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. Theacetonitrile is removed by rotary evaporation at about 60~C, followed by furtherstripping of solvent using a Kugelrohr apparatus at approximately 80~C to afford 220 g
of the desired partially ~uaternized material as a dark brown viscous liquid. The 13C-
NMR (D2O) spectrum obtained on a sample of the reaction product indicates the absence
of a carbon resonance at ~58ppm corresponding to dimethyl sulfate. The I H-NMR
(D2O) spectrum shows a partial shifting of the resonance at about 2.5 ppm for
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 E7
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, prcpared
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 (D2O) 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 tt;~ ,eldlllre 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.
In other ple~lalalions~ a lesser excess of hydrogen peroxide is used and the excess
is left in the product or optionally destroyed by addition of a re~ çing agent such as
sodium sulfite.
EXAMPLE 4
Formation of amine oxide of quaternized PEI 1800 E7
To a 500 mL Erlenmeyer flask equipped with a m~gnetic stirring bar is added
polyethyleneimine having a molecular weight of 1800 which is further modified byethoxylation to a degree of about 7 ethyleneoxy residues per nitrogen (PEI 1800 E7) and
then further modified by qu~terni7~tion to approximately 38% with dimethyl sulfate (130
g, ~0.20 mol oxidizeable nitrogen, hydrogen peroxide (48 g of a 30 wt % solution in
water, 0.423 mol), and water (~S0 g). The flask is stoppered, and after an initial
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67
exotherm the solution is stirred at room temperature overnight. IH-NMR (D2O)
spectrum obtained on a sample taken from the reaction mixture indicates completeconversion of the resonances attributed to the methylene peaks previously observed in
the range of 2.5-3.0 ppm to a material having methylenes with a chemical shift of
approximately 3.7 ppm. To the reaction solution is added approximately S g of 0.5% Pd
on alurnina pellets, and the solution is allowed to stand at room te~ .dlLlre for
approximately 3 days. The solution is tested and found to be negative for peroxide by
indicator paper. The desired material with ~38% of the nitrogens quaternized and 62%
of the nitrogens oxidized to amine oxide is obtained and is suitably stored as a 44.9%
active solution in water.
EXAMPLE 5
Ple~l.~dlion of PEI 1200 E7
The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave
equipped for tellllleldlul~ mea~ure.llent and control, ~res~ measurement, vacuum and
inert gas purging, sampling, and for introduction of ethylene oxide as a liquid. A ~20 Ib.
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 2X" Hg followed by pressurization with nitrogen to 250 psia,
then venting to atmospheric ples~ule). 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 incrrmPnt~lly over time while closely monitoring the autoclave
pressure, teml)eldl~lre, and ethylene oxide flow rate. The ethylene oxide pump is turned
off and cooling is applied to limit any t~lllp~ldl~lre increase resulting from any reaction
exotherm. The temperature is m~int~inPc~ 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 PEI nitrogen function), the tel"peld~lre 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, vacuurn 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,
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68
to achieve a 10% catalyst loading based upon PEI nitrogen functions). The methoxide
solution is sucked into the autoclave under vacuurn 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 I 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
increment~lly as before while closely monitoring the autoclave pressure, temperature,
and ethylene oxide flow rate while m:3;nt~ining the tell~peldlllre between 100 and 110 ~C
and limiting any t~ll,p~,.dl~e 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 plc~l)~dlions the neutralization and deodorization is accomplished in the
reactor before dischal~,ing the product.
Other preferred examples such as PEI 1200 E15 and PEI 1200 E20 can be
prepared by the above method by adjusting the reaction time and the relative arnount of
ethylene oxide used in the reaction.
EXAMPLE 6
9.7% Quaternization of PEI 1200 E7
To a 500ml erlenmeyer flask equipped with a magnetic stirring bar is added
poly(ethyleneimine), MW 1200 ethoxylated to a degree of 7 (248.4g, 0.707 mol nitrogen,
prepared as in Example S) and acetonitrile (Baker, 200 mL). Dimethyl sulfate (Aldrich,
8.48g, 0.067 mol) is added all at once to the rapidly stirring solution, which is then
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69
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-NM~ (D2O)
spectrum shows the absence of a peak at ~58ppm corresponding to dimethyl sulfate. A
lH-NMR (D2O) spectrum shows the partial shifting ofthe peak at 2.5ppm (methylenes
attal~hed to unqu~terni7~d nitrogens) to ~3.0ppm.
EXAMPLE 7
Plcl)~dlion of PEI 600 E?o
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 Ib.
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 250 g portion of polyethyl- -.ei~ (PEI) (Nippon Shokubai, having a listed
average molecular weight of 600 equating to about 0.417 moles of polymer and 6.25
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 in~iIe..,~ y over time while closely monitoring
the autoclave pressure, tenlpc,dlule, and ethylene oxide flow rate. The ethylene oxide
pump is turned off and cooling is applied to limit any te.l.~eldL~lre increase resulting
from any reaction exotherm. The te.llpe.dlule is m~int~ined between 100 and 110 ~C
while the total ~ , is allowed to gradually increase during the course of the reaction.
After a total of 275 grams of ethylene oxide has been charged to the autoclave (roughly
equivalent to one mole ethylene oxide per PEI nitrogen function), the temp~,ldlllre is
increased to I l O ~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 135 g of a 25% sodium methoxide in methanol solution (0.625
moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions). Themethoxide 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
CA 022~28~1 1998-10-29
WO 97142286 PCT/US97/06918
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 m~int~ining the t~l~lp~ldl lre between 100 and 110 ~C
and limiting any te~l~p~ .alllre increases due to reaction exotherrn. After the addition of
approximately 5225 g of ethylene oxide (resulting in a total of 20 moles of ethylene
oxide per mole of PEI nitrogen function) is achieved over several hours, the ~e~ ,c.dlure
is increased to 1 10 ~C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged collldh~.s 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 60 g meth~nloslllfonic acid
(0.625 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 ~git~ting and heating the llli~ to 130 ~C.
The final reaction product is cooled slightly and collected in glass containers
purged with nitrogen.
In other ~ a dlions the neutralization and deodorization is accomplished in the
reactor before discharging the product.
Pl~l,~alion of Non-cotton Soil Release Polymers
EXAMPLE 8
Synthesis of Sodium 2-(2~3-DihydroxYpropoxv)e~ lfonate Monomer
To a 500ml, three neck, round bottom flask equipped with a m~gn~tic stirring
bar, modified Claisen head, condenser (set for (1ictill~tion), thermometer, and
t~lllpcldlu~e controller (Therm-O-WatchTM, I2R) is added isethionic acid, sodium salt
(Aldrich, 50.0g, 0.338 mol), sodium hydroxide (2.7g, 0.0675 mol), and glycerin (Baker,
310.9g, 3.38 mol). The solution is heated at 190~C under argon overnight as water
distills from the reaction mixture. A 1 3C-NMR(DMSO-d6) shows that the reaction is
complete by the virtual disappe~ ce of the isethionate peaks at ~53.5 ppm and ~57.4
ppm, and the emergence of product peaks at ~51.4 ppm (-~H2SO3Na) and ~67.5 ppm
(~H2cH2so3Na)~ 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
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71
mol% of potassium phosphate, monobasic as buffer and heating on a Kugelrohr
appa~ s (Aldrich) at 200~C for ~ 3 hrs. at ~1 mm Hg to afford 77g of yellow waxysolid. 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 9
Synthesis of Sodium 2-~2-(2-HYdroxvethoxv)ethoxy~ethanesulfonate Monomer
To a 1 L, three neck, round bottom flask equipped with a magnetic stirring bar,
modified Claisen head, condenser (set for ~lictill~tion)~ thermometer, and temperature
controller (Therm-O-WatchTM, I2R) is added isethionic acid, sodiurn salt (Aldrich,
l 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 bisulfite. The
solution is stirred for one hour. A peroxide indicator strip shows a very weak positive
test. Sodium hydroxide pellets (MCB, 2.5g, 0.0625 mol) are added, followed by
diethylene glycol (Fisher, 303.3g, 2.86 mol). The solution is heated at l 90C~ under
argon overnight as water distills from the reaction mixture. A 13C-NMR(DMSO-d6)
shows that the reaction is complete by the disa~,a.~lce 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-toluen~ulfonic acid monohydrate in
diethylene glycol. (Alternatively, meth~neslllfonic acid may be used.) The 13C-NMR
spectrum ofthe product shows resonances at ~51ppm (-CH2SO3Na), ~60ppm (-
CH20H), and at ~69 ppm, ~72 ppm, and ~77 ppm for the rem~ining four methylenes.
Small resonances are also visible for the sodium p-toluenesulfonate which formed during
neutralization. The reaction affords 45 lg of a 3S.3% solution of sodium 2-[2-(2-
hydroxyethoxy)ethoxy]eth~neslllfonate 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 appaLal~ls (Aldrich) at 150C~ for ~ 3 hrs. at ~1 mm Hg
to give the desired "SE3" (as defined herein above) as an extremely viscous oil or glass.
EXAMPLE 10
Synthesis of Sodiurn 2-{2-r2-(2-Hydroxvethoxy)ethoxy]ethoxY~ethanesulfonate Monomer
To a 1 ~, three neck, round bottom flask equipped with a magnetic stirring bar,
modified Claisen head, condenser (set for ~lictill~tion)~ thermometer, and te~ e~ re
controller (Therm-O-WatchTM, I2R) is added isethionic acid, sodium salt (Aldrich,
205.0g, 1.38 mol) and distilled water (~200 ml). After dissolution, one drop of hydrogen
peroxide (Aldrich, 30% by wt. in water) is added to oxidize traces of bisulfite. The
solution is stirred for one hour. A peroxide indicator strip shows a very weak positive
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72
test. Sodiurn hydroxide pellets (MCB, 5.5g, 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 1 90C~
under argon overnight as water distills from the reaction mixture. A 1 3C-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 ~5 lppm (-
CH2SO3Na), ~60ppm (-CH2OH), and at ~67 ppm, ~69 ppm, and ~72 ppm for the
rem~ining methylenes. The solution is cooled to room t~ pe~ re and neutralized to
pH 7 with methanesulfonic acid (Aldrich). The reaction affords 650g of a 59.5%
solution of sodium 2-t2-[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
~dlllS (Aldrich) at 180C~ for~ 5.5 hrs. at ~1 mrn 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 moresoluble buffer is the salt of N-methylmorpholine with meth~n~sl~lfonic acid.
Alternatively, the pH can be controlled by frequent or continuous addition of acid such
dS meth~n~sulfonic acid to m~int~in 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
p~ep~dlions.
Other prepaldlions use a larger excess of triethylene glycol such as 5 to 10 moles
per mole of isethionate.
EXAMPLE 1 1
Synthesis of an Oli~omer of Sodiurn 2-~2-(2-Hvdroxyethoxy)ethoxy~ethanesulfonate,
Dimeth~vl Terephthalate~ Sodium 2-(2.3-Dihvdroxypropoxy)ethanesulfonate~ Glvcerin.
Ethvlene Glycol~ and Propylene Glvcol )
To a 2SOml, three neck, round bottom flask equipped with a m~gn~tic stirring
bar, modified Claisen head, condenser (set for ~istill~tion), thermometer, and
temperature controller (Therm-O-Watch(~), I2R) is added sodium 2-[2-(2-
hydroxyethoxy)ethoxy]eth~n~slllfonate (7.0g, 0.030 mol), dimethyl terephth~l~te (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, 14.0g, 0.225 mol), propylene
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73
glycol (Fisher, 17.5g, 0.230 mol), and titanium (IV) propoxide (0.Olg, 0.02% oftotal
reaction weight). This mixture is heated to 180~C and m~int~ined at that te~ elalule
overnight under argon as methanol and water distill from the reaction vessel. The
material is transferred to a 500ml, single neck, round bottom flask and heated gradually
over about 20 minutes to 240~C in a Kugelrohr a~paldllls (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 -C(O)OCH2CH20(0)C- at ~63.2 ppm (diester) and a resonance for -
C(O)OCH2CH20H 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 ~51.6 ppm
representing the sulfoethoxy groups (-CH2SO3Na) are also present. A 1H-
NMR(DMSO-d6) shows a resonance at ~7.9 ppm represetlting terephth~l~te aromatic
hydrogens. Analysis by hydrolysis-gas chromatography shows that the mole ratio of
incorporated ethylene glycol to incoll.oraled 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 repl. scllt 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 12
Synthesis of an Oligomer of Sodium 2-r2-(2-HYdroxvethoxy)ethoxy]ethanesulfonate~Dimethvl T~ te. Sodium 2-(2~3-DihydroxYpropoxY)eth~n~slllfonate~ Ethylene
G1YCO1. and Propylene GIYCO1)
To a 250ml, three neck, round bottom flask equipped with a magnetic stirring
bar, modified Claisen head, con-ien~er (set for ~ till~tion)~ thermometer, and
te~ )el~ re controller (Thenn-O-Watch(~), I2R) is added sodium 2-[2-(2-
hydroxyethoxy)ethoxy]eth~nçsulfonate (7.0g, 0.030 mol), dimethyl terephth~ te (14.4g,
0.074 mol), sodium 2-(2,3-dihydroxypropoxy)eth~neculfonate (6.6g, 0.030 mol),
ethylene glycol (Baker, 14.0g, 0.225 mol), propylene glycol (Fisher, 18.3g, 0.240 mol),
and titanium (IV) propoxide (0.01g, 0.02% of total reaction weight). This mixture is
heated to 180~C and m~in~ ed at that tell.l.cldlw~ overnight under argon as methanol
distills from the reaction vessel. The material is transferred to a 500ml, single neck,
round bottom flask and heated gradually over about 20 minutes to 240~C in a Kugelrohr
app~dllls (Aldrich) at about 0.1 mm Hg and m~int~in~d there for 110 minutes. Thereaction flask is then allowed to air cool quite rapidly to near room temperature under
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WO 97142286 PCT/US97/06918
74
vacuum (~30 min.) The reaction affords 24.4g of the desired oligomer as a brown glass.
A 1 3C-NMR(DMSO-d6) shows a resonance for -C(O)OCH2CH20(0)C- at ~63.2 ppm
(diester) and a resonance for -C(O)OCH2CH20H at ~59.4 ppm (monoester). The ratioof the diester peak to monoester peak is measured to be 8. Resonances at ~51.5 ppm
and ~51.6 ppm representing the sulfoethoxy groups (-CH2S03Na) are also present. A
lH-NMR(DMSO-d6) shows a resonance at ~7.9 ppm lep1esellling terephth~l~te
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 13
SYnthesis of an Oligomer of Sodium 2-~2-~2-Hydroxyethoxy)ethoxy]ethanesulfonate~Dimethyl Terephth~l~te. Sodium 2-(2~3-Dihydroxypropoxy)ethanesulfonate, Glvcerin~
Ethvlene GIYCOL and Propylene GIYCOI )
To a 250ml, three neck, round bottom flask equipped with a magnetic stirring
bar, modified Claisen head, con-lPn~r (set for ~ t~ tion)~ thermometer, and
temperature controller (Therm-O-Watch(~), I2R) is added sodium 2-[2-(2-
hydroxyethoxy)ethoxy]eth~nesl-lfonate (7.0g, 0.030 mol), dimethyl terephth~l~te (9.6g,
0.049 mol), sodium 2-(2,3-dihydroxypropoxy)eth~neslllfonate (2.2g, 0.010 mol),
glycerin (Baker, 1.8g, 0.020 mol), ethylene glycol (Baker, 6.1g, 0.100 mol), propylene
glycol (Fisher, 7.5g, 0.100 mol), and titanium (IV) propoxide (O.Olg, 0.02% of total
reaction weight). This mixture is heated to 1 80~C and m~int~ined at that temperature
overnight under argon as methanol distills from the reaction vessel. The material is
L~ ,ed to a 250ml, single neck, round bottom flask and heated gradually over about
20 min~ltes to 240~C in a Kugelrohr ap~dL~ls (Aldrich) at about 3 mm Hg and
m~int~ine~l there for 1.5 hours. The reaction flask is then allowed to air cool quite
rapidly to near room t~ alLlre under vacuum (~30 min.) The reaction affords 18.1g
of the desired oligomer as a brown glass. A 1 3C-NMR(DMSO-d6) shows a resonance
for -C(O)OCH2CH20(0)C- at~63.2 ppm (diester). A resonance for -
C(O)OCH2CH20H 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 le~lesç.,~ g the
sulfoethoxy groups (-CH2S03Na) are also present. A lH-NMR(DMSO-d6) shows a
resonance at ~7.9 ppm ~ s~ .ling terephth~l~te 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
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WO 97/42286 PCT/US97/06918
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 14
Synthesis of an Oligomer of Sodium 2-~2-(2-Hydroxyethox~l)ethoxyleth~nesnlfonate,
Dimethyl TerephthAIate Sodium 2-(2,3-DihvdroxYpropoxy)ethanesulfonate~ Glvcerol. Ethylene GIYCOI~ and PropYlene Glycol)
To a 250ml, three neck, round bottom flask equipped with a m~gllPtic stirring
bar, modified Claisen head, condenser (set for ~licti11~tion)~ thermometer, and
telllpeldl lre controller (Therm-O-Watch(g), I2R) is added sodium 2-~2-(2-
hydroxyethoxy)ethoxy]ethanesulfonate (2.7g, 0.011 mol, as in Example 2), dimethyl
terephth~l~te (12.0g, 0.062 mol, Aldrich), sodium 2-(2,3-
dihydroxypropoxy)eth~n~snlfonate (5.0g, 0.022 mol, as in Example 1), glycerol (Baker,
0.50g, 0.0055 mol), ethylene glycol (Baker, 6.8g, 0.110 mol), propylene glycol (Baker,
8.5g, 0.112 mol), and titanium (IV) propoxide (0.Olg, 0.02% of total reaction weight).
This mixture is heated to 180~C and ..,Ai,.~ ed at that t~,npel~ e overnight under
argon as methanol and water distill from the reaction vessel. The material is transferred
to a 500ml, single neck, round bottom flask and heated gradually over about 20 mimltes
to 240~C in a Kugelrohr al~paldlus (Aldrich) at about 0.5 mm Hg and m~int~inPrl there
for 150 min~tes The reaction flask is then allowed to air cool quite rapidly to near room
tel.lp~.dlule under vacuum (~30 min.) The reaction affords 16.7g of the desired
oligomer as a brown glass. A 13C-NMR(DMSO-d6) shows a resollance for -
C(O)OCH2CH20(0)C- at ~63.2 ppm (diester) and a resonance for -C(O)OCH2CH20H
at ~59.4 ppm (monoester). The ratio of the peak height for the diester resonance to that
of the monoester resonal1ce is measured to be 6.1. Resonances at ~51.5 ppm and ~51.6
ppm repres~ntin~ the sulfoethoxy groups (-CH2SO3Na) are also present. A lH-
NMR(DMSO-d6) shows a resonance at ~7.9 ppm reprçsçnting 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
240~C in a Kugelrohr al)p~dllls at about 0.5 mm Hg and m~int~ined there for 80
minLIteS. A 13C-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
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76
peak. The solubility of this material is tested as above and it is also found to be readily
soluble under these conditions.
The following describe high density liquid detergent compositions according to
the present invention:
TABLE I
weight %
In~redient 15 16 17 18
Polyhydroxy Coco-Fatty Acid Amide 3.65 3.50 -- --
C12-C13 Alcohol Ethoxylate Eg 3.65 0.80 -- --
SodiumC12-C1s AlcoholSulfate 6.03 2.50 -- --
Sodium C 12-c 15 Alcohol Ethoxylate 9.29 15.10 -- --
E2.s Sulfate
Sodium C 14-C 15 Alcohol Ethoxylate -- -- 18.00 18.00
E2 25 Sulfate
Alkyl N-Methyl Glucose Amide -- -- 4.50 4.50
Clo Amidopropyl Amine -- 1.30 -- --
Citric Acid 2.44 3.00 3.00 3.00
Fatty Acid (C12-C14) 4.23 2.00 2.00 2.00
NEODOL 23 91 -- -- 2.00 2.00
Ethanol 3.00 2.81 3.40 3.40
Monoethanolamine 1.50 0.75 1.00 1.00
Propanediol 8.00 7.50 7.50 7.00
Boric Acid 3.50 3.50 3.50 3.50
Tetraethylenepent~min~ 1.18 -- --
Sodiurn Toluene Sulfonate 2.50 2.25 2.50 2.50
NaOH 2.08 2.43 2.62 2.62
Minors2 1.60 1.30 0.27 0.27
Cotton Soil Release Polymer3 0.50 0.50 -- --
Cotton Soil Release Polymer4 -- -- 2.00 1.00
Non-cotton Soil Release PolymerS 0.33 0.22 -- --
Non-cotton Soil Release Polymer6 -- -- 1.00 --
Non-cotton Soil Release Polymer7 -- -- -- 1.00
Water8 balance balance balance balance
1. Eg Ethoxylated Alcohols as sold by the Shell Oil Co.
, ~ . . .. . . . . . ...
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WO 97142286 PCT/US97/06918
77
2. Minors - includes optical brightener and enzymes (protease~ lipase, cellulase, and
amylase).
3. Cotton soil release polymer according to Example 7.
4. Cotton soil release polymer according to Example l.
5. Non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et
al., issued November 6, 1990.
6. Non-cotton soil release polymer according to Example 11.
7. Non-cotton soil release polymer according to U.S. Patent 4,702,857, Gosselink,
issued October 27, 1987.
8. Balance to 100% can, for example, include minors like optical bri~ht~ner,
perfume, suds ~ullplessel, soil di~p~l~allt, protease, lipase, cellulase, chel~tin~ agents,
dye transfer inhibiting agents, additional water, and fillers, including CaC03, talc,
silicates, etc.
TABLE II
wei~ht %
In~redient 19 20 21 22
Polyhydroxy Coco-FattyAcid Amide 2.50 2.50 -- --
C12-Cl3 Alcohol Ethoxylate Eg -- -- 3.65 0.80
Sodium C 12-c 15 Alcohol Sulfate -- -- 6.03 2.50
Sodium C 12-c 15 Alcohol Ethoxylate 20.15 20.15 -- --
El.g Sulfate
Sodium C 14-C 15 Alcohol Ethoxylate -- -- 18.00 18.00
E2.2s Sulfate
Alkyl N-Methyl Glucose Arnide -- -- 4.50 4.50
Clo Amidopropyl Arnine 0.50 0.50 -- --
CitricAcid 2.44 3.00 3.00 3.00
Fatty Acid (C12-C14) 2.00 2.00
NEODOL23 91 0.63 0.63 -- --
Ethanol 3.00 2.81 3.40 3.40
Monoethanolamine 1.50 0.75 1.00 1.00
Propanediol ~.00 7.50 7.50 7.00
Boric Acid 3.50 3.50 3.50 3.50
Ethoxylate tetraethylenep~ .. ine2 0.50 -- -- 0.50
Tetraethylenep~nt~mint? -- 1.18 -- --
Sodium Toluene Sulfonate 2.50 2.25 2.50 2.50
I
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78
NaOH 2.08 2.43 2.62 2.62
Minors3 1.60 1.30 0.27 0.27
Cotton Soil Release Polymer4 0.50 0.50
Cotton Soil ReleasePolymerS -- -- 2.00 1.00
Non-cotton Soil Release Polymer6 0.33 -- -- 0.55
Non-cotton Soil Release Polymer7 -- 0.50 1.00 --
Non-cotton Soil Release Polymer8 -- -- -- 1.00
Water9 balance balance balance balance
1. Eg Ethoxylated Alcohols as sold by the Shell Oil Co.
2. Ethoxylated tetraethylenepe~ line (PEI 189 Els-EIg) according to U. S. 4,597,898
Vander Meer issued July 1, 1986.
3 Minors - includes optical brighlenPr and enzymes (protease, lipase, cellulase, and
amylase).
4. Cotton soil release polymer according to Example 7.
5. Cotton soil release polymer according to Example 4.
6. Non-cotton soil release polymer accordillg to U.S. Patent 4,968,451, Scheibel et al.,
issued November 6, 1990.
7. Non-cotton soil release polymer according to Example 11.
8. Non-cotton soil release polymer according to U.S. Patent 4,702,857, Gosselink,
issuedOctober27, 1987.
9. Balance to 100% can, for exarnple, include minors like optical bright~-ner, perfume,
suds suppresser, soil dispersant, protease, lipase, cellulase, chelating agents, dye
transfer inhibiting agents, additional water, and fillers, including CaCO3, talc,
silicates, etc.
TABLE III
Ingredients 23 24 2~ 26
Sodium C14-Cls Alcohol Ethoxylate 13.00 -- -- 8.43
E2 25 Sulfate
Sodiurn C 12-C 15 Alcohol Ethoxylate -- 18.00 13.00
E2 5 Sulfate
Sodiurn C12-C13 linear alkylbenzene 9.86 -- -- 8.43
sulfonate
Fatty Acid (C 12-C 14) 2.00 2.00 2.95
C12-C13 Alcohol Ethoxylate Eg -- -- -- 3.37
Clo Amidopropyl Amine -- -- 0.80 --
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NEODOL 23 91 2.22 2.00 1.60 --
Alkyl N-Methyl Glucose Amide -- 5.00 2.50 --
Citric Acid 7.10 3.00 3.00 3.37
Ethanol 1.92 3.52 3.41 1.47
Monoethanolarnine 0.71 1.09 1.00 1.05
Propanediol 4.86 8.00 6.51 6.00
Boric Acid 2.22 3.30 2.50 --
Ethoxylated Tetraethylenepent~n-ine 1.18 1.18 -- 1.48
Sodium Cumene Sulfonate 1.80 3.00 -- 3.00
Sodium Toluene Sulfonate -- -- 2.50 --
NaOH 6.60 2.82 2.90 2.10
Dodecyltrimethylammoniurn Chloride -- -- -- 0.51
Sodium Tartrate Mono and Di-succinate -- -- -- 3.37
Sodium Formate -- -- -- 0.32
Minors2 1.60 1.80 2.00 1.60
Cotton Soil Release Polymer3 0.50 2.00 -- --
Cotton Soil Release Polymer4 1.50 -- 2.00 3.00
Non-cotton Soil Release Polymer5 1.50 -- 2.00 --
Non-cotton Soil Release Polymer6 -- 1.15 -- 1.50
Water7 balance balance balance balance
1. Eg Ethoxylated Alcohols as sold by the Shell Oil Co.
2. Minors - includes optical brightener and enzymes (protease, lipase, cellulase, and
amylase).
3. Cotton soil release polymer according to Example 4.
4. Cotton soil release polymer according to Example 7.
5. Non-cotton soil release polymer according to Example 10.
6. Non-cotton soil release polymer according to Example 11.
7. Balance to 100% can, for example, include minors like optical bright~n~r,
perfume, suds suppresser, soil dispersant, protease, lipase, cellulase, chelating agents,
dye transfer inhibiting agents, additional water, and fillers, including CaCO3, talc,
silicates, etc.
TAB~E IV
Ingredients 27 28 29 30
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Sodium C 14-C 15 Alcohol Ethoxylate 13.00 8.43
E2 25 Sulfate
Sodiurn C12-CIs Alcohol Ethoxylate -- 18.00 13.00 --
E2 5 ~ulfate
Sodium C12-Cl3 linear alkylbenzene 9.86 -- -- 8.43
sulfonate
Fatty Acid (C12-C14) 2.00 2.00 2.95
C12-C13 Alcohol Ethoxylate Eg -- -- -- 3.37
C 10 Amidopropyl Arnine -- -- 0.80 --
NEODOL 23-91 2.22 2.00 1.60 --
Alkyl N-Methyl Glucose Amide -- 5.00 2.50 --
Citric Acid 7.10 3.00 3.00 3.37
Ethanol 1.92 3.52 3.41 1.47
Monoethanolamine 0.71 1.09 1.00 1.05
Propanediol 4.86 8.00 6.51 6.00
BoricAcid 2.22 3.30 2.50 --
Ethoxylated Tetraethylenep~ .o 1.18 1.18 -- 1.48
Sodiurn Cumene Sulfonate 1.80 3.00 -- 3.00
Sodium Toluene Sulfonate -- -- 2.50 --
NaOH 6.60 2.82 2.90 2.10
Dodecyltrimethylammonium Chloride -- -- -- 0.51
Sodium Tartrate Mono and Di-succinate -- -- -- 3.37
Sodium Formate -- -- -- 0.32
Minors2 1.60 1.80 2.00 1.60
Cotton Soil Release Polymer3 0.50 2.00 -- --
Cotton Soil Release Polymer4 1.50 -- 2.00 3.00
Non-cotton Soil Release PolymerS 1.50 -- 2.00 --
Non-cotton Soil Release Polymer6 -- 1.15 -- 1.50
Water7 balance balance balance balance
1. Eg Ethoxylated ~Icohols as sold by the Shell Oil Co.
2. Minors - includes optical bri~htenPr and enzymes (protease, lipase, cellulase, and
amylase).
3. Cotton soil release polymer according to Exarnple 7.
4. Cotton soil release polymer according to Example 1.
5. Non-cotton soil release polymer according to Example 10.
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6. Non-cotton soil release polymer according to Example 11.
7. Balance to 100% can, for example, include minors like optical brightener,
perfume, suds suppresser, soil dispersant, protease, lipase, cellulase, chelating agents,
dye transfer inhibiting agents, additional water, and fillers, including CaCO3, talc,
silicates, etc.
TABLE V
Ingredients 31 32 33 34 35
Polyhydroxy coco-fatty acid 3.50 3.50 3.15 3.50 3.00
amide
NEODOL 23-9 1 2.00 0.60 2.00 0.60 0.60
C2s Alkyl ethoxylate sulphate 19.00 19.40 19.00 17.40 14.00
C2s Alkyl sulfate -- -- -- 2.85 2.30
C 10 -Aminopropylamide -- -- -- 0.75 0.50
Citric acid 3.00 3.00 3.00 3.00 3.00
Tallow fatty acid 2.00 2.00 2.00 2.00 2.00
Ethanol 3.41 3.47 3.34 3.59 2.93
Propanediol 6.22 6.35 6.21 6.56 5.75
Monomethanol amine 1.00 0.50 0.50 0.50 0.50
Sodiumhydroxide 3.05 2.40 2.40 2.40 2.40
Sodium p-toluene sulfonate 2.50 2.25 2.25 2.25 2.25
Borax 2.50 2.50 2.50 2.50 2.50
Protease 2 0.88 0.88 0.88 0.88 0.88
Lipolase 3 0.04 0.12 0.12 0.12 0.12
Duramyl 4 0.10 0.10 0.10 0.10 0.40
CAREZYME 0.053 0.053 0.053 0.053 0.053
Optical Brightener 0.15 0.15 0.15 0.15 0.15
Cotton s~il release agent 5 1.18 1.18 1.18 1.18 1.75
Non-cotton soil release agent 6 0.22 0.15 0.15 0.15 0.15
Fumedsilica 0.119 0.119 0.119 0.119 0.119
Minors, aestetics, water balance balance balance balance balance
I . C 12-C13 alkyl E9 ethoxylate as sold by Shell Oil Co.
2. Bacillrls amyloliquefaciens subtilisin as described in WO 95/10615 published April
20, 1995 by Genencor Intern~tional.
3. Derived from Humicola lanuginosa and commercially available from Novo.
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82
4. Disclosed in WO 9510603 A and available from Novo.
5. PEI 1800 E7.
6. Terephth~ e co-polymer as disclosed in U.S. Patent 4,968,451, Scheibel et al.,
issued November 6, 1990.
