Note: Descriptions are shown in the official language in which they were submitted.
CA 02270465 1999-04-29
WO 98/20092 PCT/U597119899
1
HAND WASH LAUNDRY DETERGENT COMPOSITIONS CONTAINING A
' COMBINATION OF SURFACTANTS AND SOIL RELEASE POLYMER
TECHNICAL FIELD
The subject invention involves laundry detergent compositions containing a
certain mixture of surfactants and soil release polymer.
BACKGROUND OF THE INVENTION
Throughout the world, many people clean fabrics by machine washing with
compositions containing soap and/or detergent. Products which provide improved
cleaning of fabrics are continually being sought.
It is an object of the subject invention to provide detergent laundry
compositions which provide superior cleaning performance in machine wash
laundry operations.
SUMMARY OF THE INVENTION
The subject invention involves laundry detergent compositions, preferably
in granular form, comprising:
a) from about 6% to about 18% surtactant comprising:
1) from about 5% to about 10% anionic surtactant selected from
alkylbenzene sulfonate surfactant, alkyl sulfate surfactant and
alkyl ethoxy ether sulfate surfactant having an average of from
about 0.5 to about 9 moles ethoxy per mole surfactant;
2) from about 0.2% to about 2% hydroxyalkyl quaternary
ammonium cationic surfactant having the structure:
R R'nR"mN+ Z-,
wherein R is long-chain alkyl) R' is short-chain alkyl) R" is
H(OCH2CHB)p-, B is H or CH3, n is 0 to 3) m is 0 to 3, n + m is
3, p is from about 0.5 to about 4, p times m is from about 0.5 to
about 4, and Z' is a water-soluble anion; and
3) from 0.4% to about 8% nonionic surfactant selected from alkyl
ethoxy alcohol surfactant having an average of from about 0.5
CA 02270465 1999-04-29
WO 98I20092 PCT/~JS97/19899
2
to about 25 moles ethoxy per mole surfactant, amine oxide
surfactant, and polyhydroxy fatty acid amide surfactant;
b) from about 0.05 to about 4% polymeric soil release agent comprising:
1 ) from about 10% to about 99.5% esters comprising, per mole of
said ester:
i) from about 1 to about 2 moles of sulfonated poly-
ethoxy/propoxy end-capping units of the formula
(M03S)(CH2)m(CH2CH20)(RO}n- wherein M is a salt-
forming ration such as sodium or tetraalkylammonium, m
is 0 or 1) R is ethylene, propylene or a mixture thereof, and
n is from 0 to 2; and mixtures thereof;
ii) from about 0.5 to about 66 moles of units selected from
the group consisting of:
a) oxyethyleneoxy units;
b) a mixture of oxyethyleneoxy and oxy-1,2-
propyleneoxy units having an oxyethyleneoxy to oxy-
1,2-propyleneoxy mole ratio ranging from 0.5:1 to
about 10:1; and
c) a mixture of a) or b) with poly(oxyethylene)oxy units
wherein said poly(oxyethylene)oxy units have a
degree of polymerization of from 2 to 4; provided that
when said poly(oxyethylene)oxy units have a degree
of polymerization of 2, the mote ratio of
poly(oxyethytene)oxy units to total group ii) units
ranges from 0:1 to about 0.33:1; and when said
poly{oxyethylene)oxy units have a degree of
polymerization of 3, the mole ratio of
poly(oxyethylene)oxy units to total group ii) units
ranges from 0:1 to about 0.22:1; and when said
poly(oxyethylene)oxy units have a degree of
polymerization of 4, the mole ratio of
poly(oxyethylene)oxy units to total group ii) units
ranges from 0:1 to about 0.14:1;
iii) from about 1.5 to about 40 moles of terephthaloyl units;
and
iv) from 0 to about 26 moles of 5-sulfoisophthaloyl units of the
formula -(O)C(C6H3)(S03M)C(O)- wherein M is a salt
CA 02270465 1999-04-29
WO 98/20092 PCT/US97/19899
3
forming cation such as an alkali metal or
tetraalkylammonium ion;
2) from about 0.5% to about 20% crystallization-reducing stabilizer
selected from sulfonate-type hydrotrope, alkylbenzene
sulfonate, paraffin sulfonate, and mixtures thereof; and
~ c) from about 80% to about 94% other components.
DETAILED DESCRIPTION OF THE INVENTION
All percentages used herein are weight percent unless otherwise specified.
As used herein, the term "alkyl" means a hydrocarbyl moiety which is
straight {linear) or branched, saturated or unsaturated. Unless othervvise
specified, alkyl are preferably saturated ("alkanyl") or unsaturated with
double
bonds ("alkenyl'~, preferably with one or two double bonds. As used herein
"long
chain alkyl" means alkyl having about 8 or more carbon atoms, and "short-chain
alkyl" means alkyl having about 3 or fewer carbon atoms.
The term "tallow" is used herein in connection with materials having alkyl
mixtures derived from fatty acid mixtures from tallow which typically are
linear and
have an approximate carbon chain length distribution of 2% C14, 29% Clg, 23%
C 1 g, 2% palmitoleic, 41 % oleic, and 3% linoleic {the first three listed
being
saturated). Other mixtures with similar alkyl distribution, such as those from
palm
oil and those derived from various animal tallows and lard) are also included
within
the term tallow. The tallow, as used herein, can also be hardened (i.e,
hydrogenated) to convert part or al! of the unsaturated alkyl moieties to
saturated
alkyl moieties.
The term "coconut" is used herein in connection with materials having alkyl
mixtures derived from fatty acid mixtures from coconut oil which typically are
linear
and have an approximate carbon chain length distribution of about 8~!o Cg, 7~0
C10, 48% C12) 17% C14, 9% Clg, 2% Clg, 7% oleic, and 2% linoleic (the first
six
listed being saturated). Other mixtures with similar alkyl distribution, such
as palm
kernel oil and babassu oil) are included within the term coconut.
Compositions of the subject invention are preferably in solid, granular form,
although other forms of laundry detergents are also included.
' Surfactants
Compositions of the subject invention comprise from about 6% to about
18o surfactant) preferably from about 8% to about 15% surfactant, more
preferably from about 10% to about 14% surfactant, more preferably still from
about 11 % to about 13% surfactant.
CA 02270465 1999-04-29
WO 98I20092 PCT/US97/19899
4
As used herein, "alkylbenzene suifonate" surfactant means a salt of
alkylbenzene sulfonic acid with an alkyl portion which is linear or branched,
preferably having an average chain length of from about 9 to about 16 carbon
atoms, more preferably from about 11 to about 14 carbon atoms. The alkyl are
preferably saturated. Branched or mixed branched and linear alkylbenzene
sulfonate is known as ABS. Linear alkylbenzene sulfonate, known as LAS, is
more biodegradable than ABS, and is preferred for the subject invention
compositions. The acid forms of ABS and LAS are referred to herein as NABS
and HLAS, respectively. Alkylbenzene sulfonates and processes for making them
are disclosed in U.S. Patent Nos. 2,220,099 and 2,477,383, incorporated herein
by reference.
The salts of the alkylbenzene sulfonic acid are preferably the alkali metal
salts, such as sodium and potassium, especially sodium. Salts of alkylbenzene
sulfonic acid also include magnesium and ammonium. A particularly preferred
LAS surfactant has saturated linear alkyl with an average of 11.5 to 12.5
carbon
atoms, and is a sodium salt (C11.5-C12.5~S~Na).
As used herein, "alkyl sulfate surfactant" or "AS" includes the salts of alkyl
sulfuric acid, with a long-chain alkyl, linear or branched, preferably linear,
preferably having an average chain length from about 10 to about 16 carbon
atoms, more preferably from about 12 to about 15 carbon atoms. Especially
preferred is alkyl sulfate made by sulfating primary alcohol derived from
coconut or
tallow and mixtures thereof. Salts of alkyl sulfate include sodium, potassium,
lithium, ammonium, and alkylammonium salts. Preferred salts of alkyl sulfate
are
sodium and potassium salts, especially sodium.
As used herein, "alkyl ethoxy ether sulfate surfactant" or "AES" has the
following structure: R"'O(C2H40)xS03M. R"' is long-chain alkyl preferably
having
an average of from about 10 to about 16, more preferably from about 12 to
about
15, carbon atoms. R"' is preferably saturated. R"' is preferably linear. The
"degree of ethoxylation" (number of moles of ethoxy per mole of surfactant) is
represented by x, and is, on average, from about 0.5 to about 9, preferably
from
about 1 to about 7, more preferably from about 2 to about 5, especially about
3. M
is a water-soluble cation, for example) an alkali metal cation (e.g., sodium,
potassium, lithium), an alkaline earth metal cation (e.g., calcium,
magnesium),
ammonium or substituted-ammonium cation. M is preferably sodium or potassium)
especially sodium.
The compositions of the subject invention comprise from about 5% to
about 10% anionic surfactant selected from alkylbenzene sulfonate surfactant,
CA 02270465 1999-04-29
WO 98/20092 PCT/US9'1/19899
alkyl sulfate surfactant, and alkyl ethoxy ether surfactant; the subject
compositions
preferably comprise from about 6% to about 9%, more preferably from about 6.5~
to about 8.5%, -more preferably still from about 7% to about 8~Jo such anionic
surfactant. The anionic surfactant preferably comprises at least about 50%,
more
preferably at least about 80%, more preferably still about 100%, alkylbenzene
sulfonate surtactant.
As used herein, "hydroxyalkyl quaternary ammonium cationic surfactant" or
"HAQA" means a surfactant having the following structure: R R'nR"mN+ Z-. R is
a long-chain alkyl, linear or branched, preferably having an average of from
about
9 to about 16, more preferably from about 12 to about 14, carbon atoms. R is
preferably saturated. R is preferably linear. R' is a short-chain alkyl having
from 1
to about 3 carbon atoms; R' is preferably methyl or ethyl, especially methyl.
R" is
H(OCH2CH8)p-; wherein B is H or CH3, preferably H; and p is on average from
about 0.5 to about 4, preferably from about 0.8 to about 2, more preferably
about
1. n is 0 to 3, preferably 1 or 2, more preferably 2. m is 0 to 3, preferably
1 or 2,
more preferably 1. n + m is 3. p times m is from about 0.5 to about 4,
preferably
from about 0.8 to about 2, preferably about 1. Z- is a water soluble anion)
such as
halide, sulfate, methylsulfate, ethylsulfate, phosphate, hydroxide, fatty acid
{laurate) myristate, palmitate) oleate) or stearate), or nitrate anion.
Preferably Z' is
chloride, bromide or iodide) especially chloride.
The subject compositions comprises from about 0.2% to about 2% of
HAQA cationic surfactant, preferably from about 0.3% to about 1.2%) more
preferably less than about 1 %) even more preferably from about 0.4% to about
0.8%, more preferably still from about 0.5% to about 0.7%.
As used herein, "alkyl ethoxy alcohol nonionic surfactant" or "AE" means
an ethoxylated fatty alcohol surfactant. Such surfactant preferably has a long-
chain alkyl, preferably having an average of from about 9 to about 18, more
preferably from about 12 to about 15 carbon atoms. The alkyl is preferably
saturated. The alkyl is preferably linear. For the AE surfactant, the "degree
of
ethoxylation" (number of moles of ethoxy per mole of surfactant) is, on
average)
from about 0.5 to about 25, preferably from about 5 to about 12) more
preferably
from about 6 to about 10, especially about 7-9.
As used herein) "amine oxide surfactant" has the structure:
O
R1 tOR2)xN~R3)2
CA 02270465 1999-04-29
WO 98I20092 PCT/US97/19899
6
wherein R1 is long-chain alkyl, preferably having an average of from about 10
to
about 18, more preferably from about 12 to about 18, carbon atoms; R2 is an
alkylene or hydroxyafkylene containing from about 2 to about 3 carbon atoms; x
is
from 0 to about 3, preferably 0 or 1, more preferably 0; and each R3 is alkyl
or
hydroxyalkyl, preferably alkyl, having from about 1 to about 3) preferably 1,
carbon
atoms. Preferred amine oxide surfactants are alkyl dimethyl amine oxides.
As used herein, "polyhydroxy fatty acid amide surfactant" has the formula:
O R5
R4-C -N -V
wherein R4 is long-chain alkyl) preferably having an average of from about 10
to
about 18) more preferably from about 12 to about 16, carbon atoms; R5 is about
C1-C6 alkyl, hydroxyalkyl, or alkyloxyalkyl, preferably methyl; and V is a
polyhydroxyhydrocarbyl moiety preferably derived from a reducing sugar.
Suitable
reducing sugars include glucose, fructose, maltose, lactose, galactose,
mannose)
and xylose. As raw materials for making such surfactant, high dextrose com
syrup, high fructose com syrup, and high maltose com syrup can be utilized as
well as the individual sugars listed above. These com syrups may yield a mix
of
sugar components for V. R4-CO-N< can be, for example, cocamide, stearamide,
oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
Synthesis methods for producing polyhydroxy fatty acid amides are found in
U.S.
Patent 5,194,639 issued March 16, 1993 to Connor, Scheibel and Severson
incorporated herein by reference.
The subject compositions comprise from about 0.4% to about 8% nonionic
surfactant selected from alkyl ethoxy alcohol surfactant, amine oxide
surfactant,
and polyhydroxy fatty acid amide surfactant; the subject compositions
preferably
comprise from about 2% to about 7%, more, preferably from about 3% to about
6%, more preferably still from about 3.5% to about 5%, such nonionic
surfactant.
Such nonionic surfactant preferably comprises at feast about 50~~, more
preferably at least about 80%, more preferably still about 100%, alkyl ethoxy
ether
surfactant. Preferably the weight ratio of the nonionic surfactant to HAQA
cationic
surfactant is greater than about 2, more preferably greater than about 4, and
even
more preferably greater than about 5, and most preferably greater than about
6.
The subject compositions preferably include only) or substantially only, the
surfactants disclosed hereinabove, such that the surfactant system of the
subject
compositions preferably consists essentially of, or consists of) anionic
surfactant
selected from the group consisting of alkylbenzene sulfonate, alkyl sulfate
and
CA 02270465 1999-04-29
WO 98I20092 PCT/US97/19899
7
AES surfactant (more preferably alkylbenezene sulfonate surfactant); HAQA
surfactant; and nonionic surfactant selected from the group consisting of AE
surfactant) amine oxide surfactant, and polyhydroxy fatty acid amide
surfactant
(more preferably AE surfactant).
Polymeric Soil Release Aaent
Polymeric soil release agent, hereinafter "SRA" is included in the subject
detergent compositions which comprise from about 0.05% to about 4%) preferably
from about 0.06% to about 1.5%, more preferably from about 0.08% to about
0.7%, also preferably from about 0.16~lo to about 0.4%, also preferably from
about
0.07% to about 0.14%, SRA.
SRA typically has 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 of fabric
with
SRA to be more easily cleaned in later washing of the fabric.
SRA useful in the subject invention compositions is disclosed in U.S.
Patent No. 5,415,807 issued to Gosselink, Pan) Kellett and Hall on May 16,
1995,
incorporated herein by reference. SRA encompasses composition mixtures
comprising oiigomeric, substantially linear, sulfonated poly-ethoxy/propoxy
end-
capped esters and crystallization-reducing stabilizers.
The esters employed comprise oxyethyleneoxy units and terephthaloyl
units. Preferred esters additionally comprise units of oxy-1,2-propyleneoxy,
sulfoisophthalate and, optionally, poly(oxyethylene)oxy units with degree of
polymerization from 2 to 4. The SRA useful herein is a mixture of such esters
with
reaction by-products) crystallization-reducing stabilizers, and the like,
wherein the
SRA contains from about 10% to about 99.5% of said linear end-capped esters)
preferably from about 25% to about 97% more preferably from about 50% to
about 94~l0, of such esters. The esters are of relatively low molecular weight
(i.e.,
generally below the range of fiber-forming polyesters) typically ranging from
about
500 to about 8,000. Excellent SRA compositions are those wherein at least
about
50% by weight of said ester has a molecular weight ranging from about 500 to
about 5,000, and the SRA comprises at least about 3% of said crystallization-
reducing stabilizer.
Taken in its broadest aspect) the SRA encompasses an oligomeric ester
"backbone" which is end-capped on one, or preferably both) ends of the
backbone
by the essential end-capping units.
CA 02270465 1999-04-29
WO 98I20092 PCT/US97/19899
8
The essential end-capping units are anionic hydrophifes derived from
sulfonated poly-ethoxy/propoxy groups and connected to the esters by an ester
linkage.
Certain noncharged) hydrophobic aryldicarbonyl units are essential in the
backbone unit of the oligoesters. Preferably, these are exclusively
terephthaloyl
units. Other noncharged, hydrophobic dicarbonyl units, such as isophthaloyl,
adipoyl or the like, can also be present if desired, provided that the soil
release
properties of the esters (especially polyester substantivity) are not
significantly
diminished.
It is also possible optionally to incorporate additional hydrophilic units
into
the backbone units of said esters. For example, anionic hydrophilic units
capable
of forming two ester bonds may be used. Suitable anionic hydrophilic units of
this
specific type are well illustrated by sulfonated dicarbonyl units, such as
sulfoisophthaloyl, i.e., -(O)C(C6Hg)(S03M)C(O)- wherein M is a salt-forming
cation
such as an alkali metal or tetraalkylammonium ion.
Generally, if it is desired to modify the units of the esters) use of
additional
hydrophilic units is preferable to use of additional noncharged, hydrophobic
units.
Preferred esters of the SRA comprise, per mole of said ester.
i) from about 1 to about 2 moles of sulfonated poly-ethoxylpropoxy end-
capping units of the formula (M03S)(CH2)m(CH2CH20)(RO)n- wherein
M is a salt-forming cation such as sodium or tetraalkylammonium, m is
0 or 1, R is ethylene) propylene or a mixture thereof, and n is from 0 to
2; and mixtures thereof;
ii) from about 0.5 to about 66 moles of units selected from the group
consisting of:
a) oxyethyleneoxy units;
b) a mixture of oxyethyleneoxy and oxy-1,2-propyleneoxy units
wherein said oxyethyleneoxy units are present in an
oxyethyleneoxy to oxy-1,2-propyleneoxy mole ratio ranging from
0.5:1 to about 10:1; and
c) a mixture of a) or b) with poly(oxyethylene)oxy units wherein said
poly(oxyethylene)oxy units have a degree of polymerization of
from 2 to 4; provided that when said poly(oxyethylene)oxy units
have a degree of polymerization of 2, the mole ratio of
poly(oxyethylene)oxy units to total group ii) units ranges from 0:1
to about 0.33:1; and when said poly(oxyethylene)oxy units have a
degree of polymerization of 3, the mole ratio of
CA 02270465 1999-04-29
WO 98/20092 PCT/US97/19899
9
poly(oxyethylene)oxy units to total group ii) units ranges from 0:1
to about 0.22:7; and when said poly(oxyethylene)oxy units have a
degree of polymerization of 4, the mole ratio of
poly(oxyethylene)oxy units to total group ii) units ranges from 0:1
to about 0.14:1;
iii) from about 1.5 to about 40 moles of terephthaioyl units; and
iv) from 0 to about 26 moles of 5-sulfoisophthaloyl units of the formula
-(O)C(CgHg)(S03M)C(O)- wherein M is a salt forming cation such as
an alkali metal or tetraalkylammonium ion.
The preferred end-capping units of the esters are of the formula
(M03S)(CH2)m(CH2CH20)(RO)n- wherein M is a salt-forming ration such as
sodium or tetraalkylammonium, m is 0 or 1) R is ethylene, propylene, or a
mixture
thereof, and n is from 0 to 2; and mixtures thereof. The end-capping units are
more preferably sodium 2-(2-hydroxyethoxy)ethanesulfonate. Prefen-ed end-
capped esters are essentially in the doubly end-capped form, comprising about
2
moles of said end-capping units per mole of said ester.
The ester "backbone" of the soil release agent, by definition, comprises all
the units other than the end-capping units; all the units incorporated into
the esters
being interconnected by means of ester bonds. Preferably) in embodiments
wherein the ester backbones comprise only terephthaloyl units and
oxyethyleneoxy units, the terephthaloyl units iii) ranges from about 1 to
about 10
moles per ester. In preferred embodiments incorporating oxy-1,2-propyleneoxy
units, the ester backbone comprises terephthaloyi units, oxyethyleneoxy, and
oxy-
1,2-propyleneoxy units; the mole ratio of the latter two types of unit ranging
from
0.5:1 to about 10:1.
In still other highly preferred embodiments, hydrophilic units such as 5-
sulfoisophthaloyl are present in the backbone and generally comprise from
about
0.05 to about 26 moles per mole of said ester.
The poly{oxyethylene)oxy units) which aid in the rate of dissolution of the
ester) typically constitute from 0 to about 25 mole percent of total
oxyalkyleneoxy
units per ester depending upon the degree of polymerization of the
poly(oxyethylene)oxy units and the length of the ester backbone.
The subject SRA is well illustrated by one comprising at least about 25%
ester having the empirical formula:
(CAP)x(EG/PG)y('17z
wherein (CAP) represents the sodium salt form of said end-capping units i);
(EGIPG) represents said oxyethyleneoxy, oxy-1,2-propyleneoxy, and
CA 02270465 1999-04-29
WO 98/20092 PCT/US97/19899
poly(oxyethylene)oxy units ii); (T) represents said terephthaloyl units iii);
x is from
about 1 to 2; y is from about 0.5 to about 7; z is from about 1.5 to about 7;
wherein
x) y, and z represent the average number of moles of the corresponding units
per
mole of said ester. More preferably in esters of this type, the
oxyethyleneoxy:oxy-
1,2-propyleneoxy mole ratio ranges from about 1:1 to about 10:1; x is about 2,
y is
from about 1 to about 6, and z is from about 2 to about 6.
The backbone of the esters herein are preferably modified by incorporation
of hydrophiles such as 5-sulfoisophthalate. A preferred SRA comprises at least
about 25% ester having the empirical formula:
(CAP)x(EG/PG)y(T)z(SIP)q
wherein (CAP)) {EG/PG)) and (T) are as defined above and (S!P) represents the
sodium salt form of said 5-sulfoisophthaloyl units iv); x is from about 1 to
2; y is
from about 0.5 to about 66; z is from about 1.5 to about 40; q is from about
0.05 to
about 26; the oxyethyleneoxy:oxy-1,2-propyleneoxy mole ratio ranges from about
0.5:1 to about 10:1; wherein x, y, z and q represent the average number of
moles
of the corresponding units per mole of said ester. More preferably in esters
of this
type, EG:PG is from about 1:1 to about 5:1, x is about 2, y is from about 3 to
about
18, z is from about 3 to about 15, and q is from about 0.5 to about 4; more
preferably still x is about 2, y is about 5, z is about 5, and q is about 1.
The SRA also comprises certain crystallization-reducing stabilizers selected
from the group consisting of:
1 ) sulfonate-type hydrotrope selected from the group consisting of:
a) (R1)nAr-S03M;
b) (R2)Ar(SOgM)-O-(R2)Ar(SOgM); and
c) mixtures thereof;
wherein Ar is an aromatic hydrocarbon group, preferably phenyl, each
R1 is hydrogen or a C1-C4 alkyl group, each R2 is a C1-C18 alkyl
group, n is from 0 to 3, and M is an alkali metal or tetraalkylammonium
ion;
2) alkali metal and tetraalkylammonium salts of linear and branched
alkylbenzenesulfonate wherein the alkyl group is from about C5 to
about C16, preferably from about C1p to about C14;
3) alkyl chain sulfonate including paraffin sulfonate and other thermally-
stable alkyl sulfonate variations, such as olefin sulfonate and beta-
alkoxysulfonate, with about 4 to about 20 carbon atoms, provided the
alkyl sulfonate is substantially free of substituents capable of entering
CA 02270465 1999-04-29
WO 98/20092 PCT/U597/19899
11
into esterificationltransesterification reactions under the conditions used
for forming the soil release agent; and
4) mixtures thereof.
The stabilizers can be integrated into the soil release agent to reduce the
substantial difficulties attributable to undesirable crystallization of the
oligomer
during preparation and/or after introduction into the wash liquor. Oligomers
with
high ratios of oxyethleneoxy to oxy-7 ,2-propyleneoxy units (EG/PG) in the
backbone structure are especially susceptible to crystallization.
The SRA preferably comprises, in addition to the ester, from about 0.5% to
about 20% of crystallization-reducing stabilizer selected from sulfonate-type
hydrotrope, alkylbenzenesulfonate, paraffin sulfonate) and mixtures thereof.
Preferred SRA comprises from about 3% to about 18%, more preferably from
about 6% to about 15%, more preferably still from about 9% to about 13% of
said
stabilizers.
A preferred SRA having an oligomer with empirical formula
(CAP)2(EGIPG)5(T)5(SIP)1 with 12% linear sodium dodecylbenzenesulfonate as
a stabilizer, designated SRA-1 herein, is made as described in Example V of
U.S.
5,415,807, columns 19-20. Therein an ester composition is made from sodium 2-
(2-hydroxyethoxy)-ethanesulfonate, dimethyl terephthalate, dimethyl 5-
sulfoisophthalate sodium salt, ethylene glycol and propylene glycol, with the
integration of 12% of linear sodium dodecylbenzenesulfonate as a stabilizer.
The
ratio of ethylene glycol to propylene glycol incorporated in the oligomer is
2.1:1.
To a 250 ml, three neck, round bottom flask equipped with a magentic
stirring bar) modified Claisen head, condenser (set for distillation),
thermometer,
and temperature controller (THERM-O-WATCH~ , 12R) is added sodium 2-(2-
hydroxyethoxy)ethanesulfonate (18.4 g) 0.096 mol)(prepared as in Example 1 of
U.S. Patent 5,415,807)) dimethyl terephthalate (Aldrlch, 46.5 g, 0.240 mol),
dimethyl 5-sulfoisophthalate sodium salt (Aldrich, 14.2 g, 0.048 mol),
ethylene
glycol (Baker) 89.2 g) 1.44 moi), propylene glycol (Baker, 109.4 g, 1.44 mol))
hydrated monobutyl-tin oxide (M8T Chemicals) 0.47 g, 2% of total reaction
weight), sodium acetate (MCB, 0.89 g, 2 mol % of dimethyl 5-sulfoisophthalate,
sodium salt), SIPONATE LDS-10~ (Alcolac) linear sodium
dodecylbenzenesulfonate) 10.0 g, vacuum dried, 12% of final oligomer weight),
and silicone oil (DOW 710~ , 0.08 g, 0.1 % of final oligomer weight). This
mixture
' is heated to 180~C and maintained at that temperature overnight under argon
as
methanol and water distill from the reaction vessel. The material is
transferred to
a 1000 ml, single neck, round bottom flask and heated gradually over about 20
CA 02270465 1999-04-29
WO 98/20092 PCT/US97/19899
12
minutes to 240~C in a Kugelrohr apparatus (Aldrich) at about 0.5 mm Hg and
maintained there for 5 hours. The reaction flask is then allowed to air cool
quite
rapidly to near room temperature under vacuum (approximately 30 minutes). The
reaction affords 56 g of the desired oligomer as an opaque, green solid.
Other Components
The compositions of the subject invention comprise from about 81 % to
about 94%, preferably from about 84% to about 92%, more preferably from about
86% to about 90%, other components commonly used in laundry detergent
products. A typical listing of the classes and species of other surfactants,
builders
and other ingredients that may be included in the subject compositions appears
in
U.S. Patent No. 3,664,96i, issued to Norris on May 23, 1972, incorporated
herein
by reference, and EP 550,652, published on April 16, 1992. The following are
representative of such materials, but are not intended to be limiting.
Deter4ent Builders
The compositions of the subject invention optionally but preferably
comprise detergent builders which 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.
Inorganic detergent builders include, but are not limited to, the alkali
metal,
ammonium and alkanolammonium salts of polyphosphates (exemplified by the
tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, silicates) carbonates (including bicarbonates and
sesquicarbonates), and aluminosilicates. Non-phosphate builders are required
in
some locales.
In situations where phosphorus-based builders can be used, the various
alkali metal phosphates such as the well-known sodium tripolyphosphates
(STPP),
sodium pyrophosphate (TSPP) and sodium orthophosphate can be used; STPP
and TSPP are preferred, especially STPP. Phosphonate builders such as ethane-
1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example,
U.S. Patents 3,159, 581; 3,213, 030, 3,422,021; 3,400,148 and 3,422,137) can
also
be used.
Examples of silicate builders are the alkali metal silicates) particularly
those
having a Si02: Na20 ratio in the range of about 1.6:1 to about 3.2:1,
preferably
about 1.6:1; and layered silicates, such as the layered sodium silicates
described
in U.S. Patent 4,664,839, issued May 12) 1987 to Rieck. Other silicates may
also
CA 02270465 1999-04-29
WO 98/20092 PCT/(1597/19899
13
be useful) such as, for example, magnesium silicate, which can serve as a
crispening agent in granular formulations, as a stabilizing agent for oxygen
bleaches) and as a component of suds control systems.
Examples of carbonate builders are the alkali metal carbonates and
bicarbonates. Preferred is sodium carbonate.
Aluminosilicate builders are useful in the subject compositions.
Aluminosilicate builders are of great importance in many currently marketed
granular detergent compositions. Aluminosilicate builders include those having
the empirical formula: Mz(zA102)y~vH20 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 v is
an integer
from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669) Knummel et al., issued October 12, 1976. Preferred synthetic
crystalline aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In
an
especially preferred embodiment, the crystalline aluminosilicate ion exchange
material has the formula: Nal2((A102)12(Si02)~2)~vH20 wherein v is from about
20 to about 30, especially about 27. This material is known as Zeolite A.
Dehydrated zeolites (v = about 0 - 10) may also be used. Preferably) the
aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the subject compositions 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. Preferred polycarboxylate builders
include citrates, succinates) and oxydisuccinates. Polycarboxylate builders
can
generally be added to the compositions in acid form, but can also be added in
the
fom~ of neutralized salts) such as sodium.
The compositions of the subject invention comprise from 0% to about 80%
builders, preferably from about 10% to about 70%, more preferably from about
20% to about 60%, more preferably still from about 30% to about 50%. The
subject compositions preferably comprise from about 5% to about 40%, more
preferably from about 10% to about 30~l0, more preferably still from about 15%
to
about 25%, STPP. The subject compositions preferably comprise from about 290
to about 30% sodium carbonate, more preferably from about 5% to about 25%,
CA 02270465 1999-04-29
WO 98/20092 PCT/US97/19899
14
more preferably still from about 10% to about 20%. The subject compositions
preferably comprise from 0% to about 15% silicates, more preferably from about
3% to about 10%, more preferably still from about 5% to about 8%.
Chelatina Aaent
The subject detergent compositions may also optionally contain one or
more iron and/or manganese chelating agent. Such chelating agent can be
selected from the group consisting of amino carboxylates) amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
Without intending to be bound by theory, it is believed that the benefit of
these
materials is due in part to their exceptional ability to remove iron and
manganese
ions from washing solutions by formation of soluble chelates. This agent is
also
useful in stabilizing bleaching components of the subject compositions.
Amino carboxylates useful as optional chelating agents include
ethylenediamine tetraacetates, N-hydroxyethylethylenediamine triacetates,
nitrilo-
triacetates, ethylenediamine tetraproprionates, triethylenetetraamine
hexaacetates, diethylenetriamine pentaacetates, and ethanoldiglycines; alkali
metal, ammonium) and substituted ammonium salts thereof; and mixtures thereof.
Amino phosphonates are also suitable for use as chelating agents in the
subject compositions, when at least low levels of total phosphorus are
permitted in
detergent compositions. Preferably, these amino phosphonates do not contain
alkanyl or alkenyl groups with more than about 6 carbon atoms. Preferred amino
phosphonates are diethylenetriamine penta(methylene phosphoric acid),
ethylenediamine tetra(methylene phosphoric acid), and mixtures and salts and
complexes thereof. Particularly preferred are sodium) zinc, magnesium) and
aluminum salts and complexes thereof, and mixtures thereof. Preferably such
salts or complexes have a molar ratio of metal ion to chelant molecule of at
least
about 1:1, preferably at least about 2:1.
Such chelating agent can be included in the subject compositions at a level
of from 0% to about 5~0, preferably from about 0.1 % to about 2~0, more
preferably
from about 0.2% to about 1 %, more preferably still from about 0.3% to about
0.5%.
Magnesium sulfate can optionally be included in the subject compositions
as a stabilizer for the above chelating agents. It is included at a level of
from 0%
to about 4%, preferably from about 0.5% to about 2%.
Polymeric Disaersina Aaent
The subject compositions preferably comprise polymeric dispersing agent.
Suitable polymeric dispersing agent includes polymeric polycarboxylates and
CA 02270465 1999-04-29
WO 98I20092 PCT/US9?/19899
polyethylene glycois, 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 agent enhances overall detergent builder pertormance, when used in
combination with other builders (including lower molecular weight
polycarboxylate)
by crystal growth inhibition, particulate soil release peptization, and anti-
redeposition.
Polymeric polycarboxylate material can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include ~ acrylic acid) malefic acid (or malefic anhydride),
fumaric
acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemaionic acid. The presence in the polymeric polycarboxylate of
monomeric segments, containing no carboxylate radicals such as vinylmethyl
ether, styrene, ethylene, etc. is suitable provided that such segments do not
constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylate can be derived from acrylic
acid. Such acrylic acid-based polymer which is useful is the water soluble
salts of
polymerized acrylic acid. The average molecular weight of such polymer in the
acid form preferably ranges from about 2,000 to about 10,000, more preferably
from about 4,000 to about 7,000 and most preferably from about 4,000 to about
5,000. Water-soluble salts of such acrylic acid polymer can include, for
example)
the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of
this type are known materials. Use of polyacrylate of this type in detergent
compositions has been disclosed, for example) in Diehl, U.S. Patent 3,308,067,
issued March 7, 1967.
Acrylic/maleic-based copolymer may also be used as a preferred
component of the dispersing agent. Such material includes the water soluble
salts
~f copolymer of acrylic acid and malefic acid (or malefic anhydride). The
average
molecular weight of such copolymer in the acid form preferably ranges from
about
2,000 to about 100,000) more preferably from about 4,000 to about 80,000, most
preferably from about 7,000 to about 65,000. The ratio of acrylate to maleate
segments in such copolymer will generally range from about 30:1 to about 1:1,
more preferably from about 10:1 to about 2:1. Water-soluble salts of such
acrylic
acid/maleic acid copolymer can include, for example, the alkali metal,
ammonium
and substituted ammonium salts. Soluble acrylatelrnaleate copolymer of this
type
is known material which is described in European Patent Application 066 915)
published December 15, 1982, as well as in EP 193 360, published September 3,
CA 02270465 1999-04-29
WO 98/20092 PCT/LTS97/19899
16
1986, which also describes such polymer comprising hydroxypropylacrylate.
Still
other useful dispersing agents include the maleic/acryliclvinyl alcohol
terpolymers.
Such material is also disclosed 'in EP 193 360) including) for example, the
45I45/10 terpolymer of acryliGmaleic/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 range for this
purpose
ranges from about 500 to about 100,000, preferably from about 1,000 to about
50,000) more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used,
especially in conjunction with zeolite builders. Dispersing agents such as
polyaspartate preferably have an average molecular weight of about 10,000.
Another type of preferred dispersing agent includes carboxymethylcellulose
(CMC) material. Such material is well-known in the art.
The above polymeric dispersing agent, if included, is typically at a level
from 0% to about 7%, preferably from about 0.5% to about 3%, more preferably
from about 1 % to about 2.5%. Polyacrylate and acrylidmaleic copolymer
dispersing agent is preferably included in the subject compositions at a level
of
from about 0.5% to about 3%) more .preferably from about 1% to about 2%. A
CMC-type dispersing agent is preferably included in the subject compositions
at a
level of from about 0.1 % to about 1 %) more preferably from about 0.2% to
about
0.5%.
Another optional ingredient in the subject compositions is a soil dispersing
agent which is a water soluble or dispersible alkoxylated polyalkyleneamine
material. Such material can be included in the subject compositions at a level
from 0% to about 1 %, preferably from about 0.1 % to about 0.8%, more
preferably
from about 0.3% to about 0.50.
The alkoxylated polyalkyleneamine material has a polyalkyleneamine
backbone of amine units having the general formula:
(H2N-R1-)q+1 (-NH-R1-)r ('N-R1-)q {-NH2)
wherein:
(i) each (H2N-R1-) unit is bonded to {-NH-R1-) or (>N-R1-);
(ii) each (-NH-R1-) unit is bonded to any two units, provided that each is
bonded to no more than one of (H2N-R1-) and (-NH2);
(iii) each (>N-R1-) unit is bonded to any three units) provided that each is
bonded to no more than two of (H2N-R1-) and (-NH2);
(vii) the (-NH2) is bonded to (-NH-R1-) or (>N-R1-);
CA 02270465 1999-04-29
WO 98/Z0092 PCT/US97/19899
17
provided that each bond described in (i), (ii), (iii) and (iv) is between N of
one unit
and R1 of another unit.
In the above general formula, q is on average from 0 to about 250,
preferably from about 1 to about 100, more preferably from about 3 to about
40,
more preferably still from about 5 to about 25, still more preferably from
about 7 to
about 15.
In the above general formula, r is on average from about 3 to about 700,
preferably from about 4 to about 200) more preferably from about 6 to about
80,
more preferably still from about 8 to about 50, still more preferably from
about 15
to about 30.
In the above general formula, the ratio q:r is preferably from 0 to about 1:4,
more preferably from about 1:1.5 to about 1:2.5, more preferably still about
1:2.
In the above general formula, R1 is linear alkanylene having from 2 to
about 12 carbon atoms, preferably from 2 to about 4 carbon atoms. For
preferred
poiyalkyleneamine backbones, less than about 50% of the R1 moieties have more
than 3 carbon atoms, more preferably less than about 25% R1 moieties have
more than 3 carbon atoms, more preferably still less than about 10% R1
moieties
have more than 3 carbon atoms. More preferred R1 is selected from ethylene,
1,2-propylene, 1, 3-propylene, and mixtures thereof. For most preferred
backbones, substantially all R1 units are the same. Most preferred R1 is
ethylene.
The polyalkyleneamine backbone described above has a molecular weight
of at least about 180 daltons, preferably has a molecular weight of from about
800
to about 5000 daltons) more preferably has a molecular weight of from about
1000
to about 2500 daltons.
On the above polyalkyleneamine backbone, from about 50% to about
100~!o of the hydrogens bonded to the nitrogens are substituted; preferably
from
about 90% to about 100% of the hydrogens bonded to the nitrogens are
substituted; more preferably substantially all of the hydrogens bonded to the
nitrogens are substituted.
Substituents for the hydrogens bonded to the nitrogens are
poly(aikyleneoxy) units having the formula
_(R30)pR2.
In the above formula, R3 is alkanylene having from 2 to about 6 carbon
atoms, preferably from 2 to about 4 carbon atoms. R3 is preferably selected
from
ethylene, 1,2-propylene) and mixtures thereof. More preferably R3 is ethylene.
In the above formula, R2 is selected from hydrogen, alkanyl having from 1
to about 4 carbon atoms, and mixtures thereof. Preferably R2 is hydrogen.
CA 02270465 1999-04-29
WO 98l20092 PCT/US97/19899
18
In the above formula, p is on average from about 1 to about 50, preferably
from about 3 to about 10. In general, p preferably increases with increasing
molecular weight of the polyalkyleneamine backbone.
Those skilled in the art of alkoxylation of polyalkyleneamines recognize that
the "degree of ethoxylation" is defined as the average number of alkoxylations
per
nitrogen atom substituent site and may be expressed as a fractional number. A
polyalkyleneamine may have a degree of ethoxylation equal to 1 or greater and
still have less than 100% of the polyalkyleneamine backbone nitrogen
substituent
sites substituted.
The relative proportion of primary) secondary, and tertiary amine units in
the polyalkyleneamine backbone will vary, depending on the manner of
preparation of the backbone.
Preferred "polyalkyleneamine backbones" herein include both
polyalkyleneamine (PAA) and polyalkyleneimine (PAI); preferred backbones are
polyethyleneamine (PEA) and polyethyleneimine (PEI).
PEA is obtained by a reaction involving ammonia and ethylene dichloride,
followed by fractional distillation. Common PEA's include triethylenetetramine
(TETA), tetraethylenepentamine (TEPA), and tetrabutylenepentamine. Above
pentamine, i.e., hexamine) heptamine, octamine and possibly nonamine) the
cogenerically derived mixture does not readily separate by distillation and
can
include other materials such as cyclic amines and piperazines. There can also
be
present cyclic amines with side chains in which nitrogen atoms appear. See
U.S.
Patent 2,792,372) Dickinson, issued May 14, 1957, incorporated herein by
reference, which describes the preparation of PEA.
PEI includes the preferred polyalkyleneamine backbones useful herein.
PEI can be prepared, for example, by polymerizing ethyleneimine in the
presence
of a catalyst such as carbon dioxide, sodium bisulfate, sulfuric acid,
hydrogen
peroxide) hydrochloric acid, acetic acid, etc. Specific methods for preparing
PEI's
are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5,
1939;
U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent
2,20f:,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, 1951
(all
herein incorporated by reference). In addition to the linear and branched
PEI's,
the compounds useful herein also include the cyclic amines that are typically
farmed as artifacts of synthesis. The presence of these materials may be
increased or decreased depending on the conditions chosen by the formulator.
CA 02270465 1999-04-29
WO 98I20092 PCT/US97/19899
19
The following is a non-limiting example of the synthesis of a preferred soil
dispersing agent.
Preparation of PEI 1800 E7:
"PEI 1800 E7" has a polyethyleneimine backbone having an average
molecular weight of about 1800, a ratio of q: r of about 1:2, and an average
degree
of ethoxylation of about 7.
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 introduction of ethylene oxide as
a
liquid. A -20 Ib. net weight cylinder of ethylene oxide is set up to deliver
ethylene
oxide as a liquid by pumping to the autoclave with the cylinder placed on a
scale
so that the weight change of the cylinder can be monitored.
A 750 g portion of PEl (Nippon Shokubai, EPOMIN SP-018~ having a
listed average molecular weight of 1800 and a ratio of q:r of about 1:2))
equating
to about 0.417 moles of polymer and 17.4 moles of nitrogen substitution sites,
is
added to the autoclave. The autoclave is then sealed and purged of air (by
applying vacuum to minus 28" Hg followed by pressurization with nitrogen to
250
psia, then venting to atmospheric pressure). The autoclave contents are heated
to
130~C while applying vacuum. After about one hour, the autoclave is charged
with
nitrogen to about 250 psia while cooling the autoclave to about 105 ~C.
Ethylene
oxide is then added to the autoclave incrementally over time while closely
monitoring the autoclave pressure) temperature, and ethylene oxide flow rate.
The ethylene oxide pump is turned off and cooling is applied to limit any
temperature increase resulting from any reaction exotherm. The temperature is
maintained between 100 and 110~C while the total pressure is allowed to
gradually
increase during the course of the reaction to a maximum of about 350 psia.
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 substitution site), the
temperature is increased to 110~C and the autoclave is allowed to stir for an
additional hour. At this point, vacuum is applied to remove any residual
unreacted
ethylene oxide. (If a degree of ethoxylation of 1 was desired, the process
would
now proceed directly to the deodorization step below.)
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
substituent sites). The methoxide solution is sucked into the autoclave under
vacuum and then the autoclave temperature controller setpoint is increased to
CA 02270465 1999-04-29
WO 98I20092 PCT/US97/19899
'130~C. A device is used to monitor the power consumed by the agitator. The
agitator power is monitored along with the temperature and pressure. Agitator
power and temperature values gradually increase as methanol is removed from
the autoclave and the viscosity of the mixture increases and stabilizes in
about 1
hour indicating that most of the methanol has been removed. The mixture is
further heated and agitated under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105~C while it is being
charged with nitrogen to 250 psia and then vented to atmospheric pressure. The
autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added
to
the autoclave incrementally as before while closely monitoring the autoclave
pressure) temperature, and ethylene oxide flow rate while maintaining the
temperature between 100 and 110~C and limiting any temperature increases due
to reaction exotherm. After the addition of 4500 g of ethylene oxide
(resulting in a
total of 7 moles of ethylene oxide per mole of PEI nitrogen substituent site)
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
sparging with inert gas (argon or nitrogen) through a gas dispersion frit and
through the reaction mixture for about 1'/ hour while agitating and heating
the
mixture to about 100-130~C.
Enzymes
Enzymes can be included in the subject compositions for a wide variety of
fabric laundering purposes, including removal of protein-based, carbohydrate-
based, or triglyceride-based stains, for example, and for the prevention of
refugee
dye transfer) and for fabric restoration. The enzymes which may be
incorporated
include proteases, amylases, lipases, cellulases, and peroxidases, as well as
mixtures of two or more thereof. Other types of enzymes may also be included.
They may be of any suitable origin, such as vegetable, animal) bacterial,
fungal
and yeast origin. However, their choice is governed by several factors such as
pH-activity and/or stability optima, thermostability, stability in the
presence of
active detergents, builders and so on. In this respect bacterial or fungal
enzymes
are preferred, such as bacterial amylases and proteases) and fungal
cellulases.
CA 02270465 1999-04-29
WO 98I20092 PCT/LTS97/19899
21
The subject compositions typically comprise from 0% to about 5%,
preferably from about 0.1 ~I~ to about 2%, more preferably about 0.5% to about
1.5%, of commercial enzyme preparations.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniforms. Another suitable
protease is
obtained from a strain of Bacillus) having maximum activity throughout the pH
range of 8-12) developed and sold by Novo Industries A/S under the registered
trade name ESPERASE~. The preparation of this enzyme and analogous
enzymes is described in British Patent Specification No. 1,243,784 of Novo.
Proteolytic enzymes suitable for removing protein-based stains that are
commercially available include those sold under the tradenames ALCALASE~ and
SAVINASE~ by Novo Industries A/S (Denmark) and MAXATASE~ by International
Bio-Synthetics, Inc. (The Netherlands).
Protease enzymes in commercial preparations are included in the subject
compositions at levels sufficient to provide from about 0.004 to about 2 Anson
units (AU) of activity per gram of the compositions, preferably from about
0.006 to
about 0.1 AU, also from about 0.005 to about 0.02 AU.
Amylases include, for example, a-amylases described in British Patent
Specification No. 1,296,839 (Novo), RAPIDASE~, International Bio-Synthetics,
Inc. and TERMAMYL~, Novo Industries. Amylase is preferably included in the
subject compositions such that the activity of the amylase is from about 0.02
KNU
to about 5 KNU per gram of the composition, more preferably from about 0.1 KNU
to about 2 KNU, more preferably still from about 0.3 KNU to about 1 KNU. (KNU
is a unit of activity used commercially by Novo Ind.)
The cellulases usable in the subject compositions include both bacterial
and fungal cellulase. Preferably, they will have a pH optimum of between 5 and
9.5. Cellulases disclosed in PCT Patent Application No. WO 91I17243, such as
CAREZYME~ (Novo), are especially useful cellulases.
Cellufase is preferably included in the subject compositions such that the
activity of the cellulase is from about 0.1 CEVU to about 20 CEVU per gram of
the
composition) more preferably from about 1 CEVU to about 10 CEVU) more
preferably still from about 2 CEVU to about 5 CEVU. (The activity of a
cellulase
material (CEVU) is determined from the viscosity decrease of a standard CMC
solution as follows. A substrate solution is prepared which contains 35g/1 CMC
(Hercules 7 LFD) in 0.1 M tris buffer at pH 9Ø The cellulase sample to be
analyzed is dissolved in the same buffer. 10m1 substrate solution and 0.5m1
enzyme solution are mixed and transferred to a viscosimeter (e.g., Haake VT
181,
CA 02270465 1999-04-29
WO 98/20092 PCT/US97/19899
22
NV sensor, 181 rpm), thermostated at 40~C. Viscosity readings are taken as
soon
as possibly after mixing and again 30 minutes later. The activity of a
cellulase
solution that reduces the viscosity of the substrate solution to one half
under these
conditions is defined as 1 CEVU/liter.)
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such a Pseudomonas stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. The LIPOLASE~ enzyme
derived from Humicola lanuginosa and commercially available from Novo (see
also
EP 341 947) is a prefer-ed lipase.
Lipase is preferably included in the subject compositions such that the
activity of the lipase is from about 0.001 KLU to about 1 KLU per gram of the
composition, more preferably from about 0.01 KLU to about 0.5 KLU, more
preferably still from about 0.02 KLU to about 0.1 KLU. (KLU is a unit of
activity
used commercially by Novo Ind.)
Peroxidase enzymes are used in combination with oxygen sources, e.g.)
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching", i.e. to prevent transfer of dyes or pigments removed
from
substrates during wash operations to other substrates in the wash solution.
A wide range of enzyme materials and means for their incorporation into
synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139,
issued January 5) 1971 to McCarty et al. Enzymes are further disclosed in U.S.
Patent 4,101,457, Place et al., issued July 18, 1978, and in U.S. Patent
4,507,219, Hughes, issued March 26, 1985. '
Enzymes for use in detergents can be stabilized by various techniques.
Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent
3,600,319) issued August 17, 1971 to Gedge et al.) and European Patent
Application No. 199 405, published October 29, 1986, Venegas. Enzyme
stabilization systems are also described, for example, in U.S. 3,519,570.
Bleachin4 Compounds - Bleaching A4ents and Bleach Activators
The subject detergent compositions may optionally contain bleaching agent
or a bleaching composition containing a bleaching agent and one or more bleach
activator. Bleaching agent typically is at a level from 0% to about 25%,
preferably
from about 5% to about 20%, of the subject compositions. The amount of bleach
activator typically is from 0% to about 10%, preferably from about 0.5% to
about
5% of the subject compositions.
The bleaching agent can be any of the bleaching agents useful for
detergent compositions in textile cleaning, hard surface cleaning, or other
cleaning
CA 02270465 1999-04-29
WO 98/20092 PCT/U597/19899
23
purposes that are now known or become known. These include oxygen bleaches
as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate
(e.g., mono- or tetra-hydrate) can be used. A preferred level of perborate
bleach
in the subject composition is from about 5% to about 20%) more preferably from
about 10% to about 16%.
Another category of bleaching agent that can be used encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of
this
class of agents include magnesium monoperoxyphthalate hexahydrate) the
magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric
acid, diperoxydodecanedioic acid, and 6-nonylamino-6-oxoperoxycaproic acid.
Other peroxygen bleaching agents can 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~,
manufactured commercially by DuPont) can also be used.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agent, (perborate, percarbonate, etc.), is preferably
combined with a bleach activator, which leads to the in situ production in
aqueous
solution (i.e.) during the washing process) of the peroxy acid corresponding
to the
bleach activator. Various non limiting 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 (NOES) and tetraacetyl ethylenediamine
(TAED) activators are typical, and mixtures thereof can also be used. A
preferred
level of NOBS or TAED bleach activator in the subject compositions is from
about
0.5% to about 5%, more preferably from about 0.8% to about 3%) more preferably
still from about 1.2% to about 2.5~!0.
Fabric Softenin4 Clav
A preferred fabric softening clay is a smectite-type clay. The smectite-type
clays can be described as expandable, three-layer clays; i.e., alumino-
silicates
and magnesium silicates) having an ion exchange capacity of at least about 50
meq/100 g of clay. Preferably the clay particles are of a size that they
cannot be
perceived tactilely, so as not to have a gritty feel on the treated fabric of
the
clothes. The fabric softening clay, if any is desired, can be included in the
subject
invention compositions at levels of from about 0.1 % to about 20%, preferably
from
about 0.2% to about 15%, more preferably from about 0.3~to to about 10%.
While any of the smectite-type clays are useful in the subject invention
compositions) certain clays are preferred. For example, Gelwhite GP is an
CA 02270465 1999-04-29
WO 98I20092 PCTIUS97/19899
24
extremely white form of smectite-type clay and is therefore preferred when
formulating white detergent compositions. Volclay BC, which is a smectite-type
clay mineral containing at least 3% iron (expressed as Fe2O3) in the crystal
lattice, and which has a very high ion exchange capacity, is one of the most
efficient and effective clays for use in the instant compositions from the
standpoint
of product performance. On the other hand, certain smectite-type clays are
sufficiently contaminated by other silicate minerals that their ion exchange
capacities fall below the requisite range; such clays are not preferred in the
subject compositions.
Clav Flocculating Aqent
It has been found that the use of a clay flocculating agent in a composition
containing softening clay provides improved softening clay deposition onto the
clothes which results in better clothes softening pertormance, compared to
that of
compositions comprising softening clay alone. The polymeric clay flocculating
agent is selected to provide improved deposition of the fabric softening clay.
Typically such materials have a high molecular weight, greater than about
100,000. Examples of such materials can include long chain polymers and
copolymers derived from monomers such as ethylene oxide, acrylamide, acrylic
acid) dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, and
ethylene imine. Gums, like guar gums, are suitable as well. The preferred clay
flocculating agent is a polyethylene oxide) polymer. The amount of clay
flocculating agent included in the subject compositions, if any) is about 0.2%-
2%,
preferably about 0.5%-1 %.
Dye Transfer Inhibiting in4redient
Another optional component in the subject compositions is a dye transfer
inhibiting (DTI) ingredient to prevent diminishing of color fidelity and
intensity in
fabrics. A prefer-ed polymeric DTI material is capable of binding fugitive
dyes to
prevent them from depositing on the fabrics. Non-limiting examples of
polymeric
DTI materials include polyvinylpyrridine N-oxide, polyvinylpyrrolidone (PVP),
PVP-
polyvinylimidazole copotymer, and mixtures thereof. Copolymers of N-
vinylpyrrolidone and N-vinytimidazole polymers (refer-ed to as "PVPI") are
also
preferred. The amount of DTI included in the subject compositions, if any, is
about 0.05%-5%, preferably about 0.2%-2%.
Photobleach
A preferred optional component of the subject invention composition is a
photobleach material) particularly phthalocyanine photobleaches which are
described in U.S. Patent 4,033,718 issued July 5, 1977, incorporated herein by
CA 02270465 1999-04-29
WO 98/20092 PCT/US97119899
reference. Preferred photobleach is a metal phthalocyanine compound, the metal
preferably having a valance of +2 or +3; zinc and aluminum are preferred
metals.
Such photobieach is available, for example, under the tradename TINOLUS. Zinc
phthalocyanine sulfonate is available commercially under the tradename
QUANTUM~ from Ciba Geigy. The photobleach component, if included, is
typically in the subject compositions at a level from 0% to about 0.02%,
preferably
from about 0.001 % to about 0.01 %.
Filler
Sodium sulfate and calcium carbonate are well known and often used as
filler components of the subject compositions. Filler also includes minerals,
such
as talc and hydrated magnesium silicate-containing minerals, where the
silicate is
mixed with other minerals, e.g., ofd mother rocks such as dolomite. Sodium
sulfate is a prefer-ed filler material. Filler material is typically at a
level from 0% to
about 60%) preferably from about 15% to about 40%) more preferably from about
20% to about 35%.
Optical Briahtener
Any optical brightener or other brightening or whitening agent known in the
art can be incorporated into the subject detergent compositions. Commercial
optical brighteners which may be useful can be classified into subgroups,
which
include, but are not necessarily limited to, derivatives of stilbene,
pyrazoline)
coumarin, carboxylic acid, methinecyanine, dibenzothiphene-5,5-dioxide, azole,
S-
and 6-membered ring heterocycles, and other miscellaneous agents. Examples of
such brighteners are disclosed in "The Product and Application of Fluorescent
Brightening Agents", M. Zahradnik, Published by John Wiley ~ Sons, New York
(1982). Anionic brighteners are preferred.
Specific examples of optical brighteners which are useful in the subject
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
brighteners from Verona. Other brighteners disclosed in this reference
include:
TINOPAL UNPA~) TINOPAL CBS~ and TINOPAL SBAA~, TINOPAL AMS-GX~,
available from Ciba-Geigy; ARTIC WHITE CC~ and ARTIC WHITE CWD~,
available from Hilton-Davis) located in Italy; the 2-(4-stryl-phenyl)-2H-
napthol[1,2-
d)triazales; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'-
bis(stryl)bisphenyls; and the
aminocoumarins. Specific examples of these brighteners include 4-methyl-7-
diethylamino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenyl-
phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-d]oxazole;
and
CA 02270465 1999-04-29
WO 98/20092 PCT/US97/19899
26
2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. See also U.S. Patent 3,646,015,
issued February 29, 1972 to Hamilton.
Preferred brighteners also include 4,4'-bis((4-anilino-6-bis(2-hydoxyethyl)-
amino-1,3,5-trizin-2-yl)amino)stilbene-2,2'-disulfonic acid disodium salt, 4-
4'-bis(2-
sulfostyryl}biphenyl and 4,4'-bis((4-anilino-6-morpholino-1,3,5-triazin-2-yl)-
amino)stilbene-2,2'-disulfonic acid disodium salt.
Such optical brightener, or mixtures thereof, is typically at a level in the
compositions from 0% to about 1 %, preferably about 0.01 %-0.3%.
Suds Su~pressor
Compounds for reducing or suppressing the formation of suds can be
incorporated into the compositions of the subject invention. A wide variety of
materials may be used as suds suppressors. See, for example) Kirk Othmer
Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447
(John Wiley & Sons, Inc., 1979).
A preferred category of suds suppressor comprises silicone suds
suppressors. This category includes 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; U.S. Patent 3,933,672,
Bartolotta et al; U.S. Patent 4,652,392, Baginski et al) issued March 24,
1987; and
European Patent Application No. 89307851.9, published February 7, 1990. An
exemplary silicone based suds suppressor, designated SS-1 herein, is
polydimethylsiloxane with trimethylsilyl end blocking units available from Dow
Coming.
The subject compositions comprise from 0% to about 1 %, preferably from
about 0.05% to about 0.1 % suds suppressor.
Auxiliary Surfactant
The compositions of the subject invention can contain optional surfactants
commonly used in detergent products. Typical listings of the classes and
species
of such surfactants, e.g., anionic, nonionic) zwitterionic, and amphoteric
surfactants appear in U.S. 3,664,961) U.S. 3,929,678, U.S. 4,844,821, and EP
550,652. Such auxiliary surfactants may include C1p-C18 alkyl alkoxy
carboxylates (especially the ethoxyl_5 carboxylates) C10-C1g glycerol ethers,
C10-C1 g alkyl polyglycosides and their corresponding sulfated polyglycosides,
and C12-C1g a-sulfonated fatty acid esters. Such auxiliary surfactants may
CA 02270465 1999-04-29
WO 98/20092 PCT/US97/19899
27
include one or more of Cg-C12 alkyl phenol alkoxylates (especially ethoxylates
and mixed ethoxyfates/propoxylates), and C 12-C 1 g betaines and sulfobetaines
(sultaines). Conventional C1p-C20 fatty acid soaps are also possible auxiliary
surfactants. Such auxiliary surfactant is preferably not present, but can be
included at a level from 0% to a total of about 5%, also about 0.5-2%.
Water
The granular compositions of the subject invention typically comprise from
about 2% to about 15% water, preferably from about 4% to about 12% water,
more preferably from about 5% to about 10% water.
Miscellaneous
Dyes, pigments, germicides, perfumes, glycerine, sodium hydroxide,
alkylbenzene, fatty alcohol, and other minors, some of which ace impurities
carried
in from surfactant-making processes, can also be incorporated in the subject
compositions. If included, such other material is typically at a level from 0%
to
about 3%.
Examples
The following exemplify compositions of the subject invention, but are not
intended to be limitations of the scope of the subject invention. The examples
are
granular detergents which may be made by well-known processes, such as spray
drying of a paste or slurry, and agglomerating or dry blending in mixers.
The following list of components are utilized in the examples.
LAS: linear C11-C13 alkylbenzene sulfonate) sodium salt.
HDQA: linear C12-C14 dimethyl hydroxyethyf quaternary ammonium chloride.
AE: linear C14-C15 ethoxy (7) alcohol.
STPP: sodium tripolyphosphate.
Silicate: sodium silicate having a Si02:Na20 ratio of 1.6.
Carbonate: sodium carbonate.
DTPA: diethylenetriamine pentaacetate, sodium salt)
DTPMP: diethylenetriamine penta(methylene phosphonic acid).
A/M copolymer: copolymer of acrylic and malefic acids, designated SOKALAN
HP-22~ from BASF.
CMC: carboxymethyl cellulose having an average molecular weight of 63,000.
SRA-1: polymeric soil release agent described hereinabove.
Protease: protease enzyme product designated SAVINASE 13T~ from Novo
Industries.
Amylase: amylase enzyme product designated 120T from Novo Industries.
CA 02270465 1999-04-29
WO 98/20092 PCT/US97/19899
28
Cellulase: cellulase enzyme product designated CAREZYME 5T~ from Novo
Industries, having an activity of 5000 CEVUIg.
Lipase: lipase enzyme product designated LIPOLASE 100T~ from Novo
Industries.
Perborate: sodium perborate monohydrate or tetrahydrate.
TAED: ~tetraacetyl ethylenediamine.
ZPS: zinc phthalocyanine sulfonate) designated QUANTUM~, from Ciba Geigy.
MgS04: magnesium sulfate.
Brightener: stilbene disulfonate, designated BLANKOPHOR DML~, from Miles
Laboratories.
SS-1: polydimethylsiloxane with trimethyisilyl end blocking units designated
EAF-1, from Dow Coming.
Sulfate: sodium sulfate.
The numbers in the following tables are weight percents.
Examale
Com onents 1 2 3 4 5
LAS 6.9 8.0 6.9 5.99 9.73
HDQA 0.5 0.58 0.5 1.08 0.71
AE 4.5 5.4 4.5 4.28 6.39
SRA-1 0.10 Q.10 0.10 0.09 0.10
STPP 19.7 19.7 19.7 18.6 19.67
Silicate 6.0 6.0 6.0 7.2 6.0
Carbonate 17.5 17.5 17.5 20 17.5
DTPA 0.39 0.39 0.39 -- 0.39
DTPMP - -- -- 0.36 --
A/M co of mer 1.59 1.59 1.59 1.50 1.59
CMC 0.29 0.29 0.29 0.26 0.29
Protease 0.32 0.32 0.57 0.31 0.32
Am lace 0.18 0.18 0.38 0.17 0.18
Cellulase 0.16 0.16 0.16 0.07 0.16
Li ase 0.095 0.095 0.095 0.08 0.095
Perborate monoh 10.45 10.45 - -- 10.45
drate
Perborate tetrah -- -- 15.20 - --
drate
TAED 1.52 1.52 2.23 1.44 1.52
ZPS 0.0015 0.0015 0.0015 0.0015 0.0015
Bricthtener 0.114 0.114 0.114 0.11 0.114
CA 02270465 1999-04-29
WO 98/20092 PCTlUS97/19899
29
Perfume 0.23 0.40 0.22 0.23 0.22
M SO 1.45 1.45 1.45 0.54 1.45
SS-1 0.07 0.08 0.07 0.07 0.09
Moisture 9 9 9 7.2 9
Sulfate balancebalancebalancebalancebalance
Example
Com onents 6 7 8 9
LAS 7.5 7.5 7.5 7.5
HD~A 0.5 1.0 0.5 1.0
AE 0.5 0.5 4.0 4.0
SRA-1 0.2 0.2 0.2 0.2
STPP 13 13 13 13
Silicate 6.5 6.5 6.5 8.5
Carbonate 4.0 4.0 4.0 4.0
A/M co I mer 0.06 0.06 0.06 0.06
CMC 0.12 0.12 0.12 0.12
ZPS 0.0045 0.0045 0.0045 0.0045
Perfume 0.25 0.25 0.25 0.25
Moisture 5.3 5.3 5.3 5.3
Sulfate balancebalancebalancebalance
The subject invention includes processes for laundering fabrics using the
compositions described hereinabove. Preferred processes are machine washing
. operations using such compositions.
The subject processes include incorporating the subject compositions in
water, typically at concentrations of from about 3000 ppm to about 800Q ppm,
preferably from about 4000 ppm to about 7000 ppm, more preferably from about
5000 ppm to about 6000 ppm, in which fabrics are washed. The subject washing
. operations preferably are carried out at wash solution temperatures of from
about
10~C to about 90~C, more preferably from about 12~C to about 70~C, for a
period
of from about 10 min to about 60 min, more preferably from about 15 min to
about
40 min. The subject wash solutions are preferably within the pH range of from
about 9.5 to about 10.8, more preferably from about 10.0 to about 10.5.
While particular embodiments of the subject invention have been
described hereinabove, it will be obvious to those skilled in the art that
various
changes and modifications to the subject invention can be made without
departing
CA 02270465 1999-04-29
WO 98I20092 PCT/US97/19899
from the spirit and scope of the invention. It is intended to cover, in the
appended
claims, all such modifications that are within the scope of this invention.
