Note: Descriptions are shown in the official language in which they were submitted.
M WO 95/03388 , ~ ~ PCT/US94/06950
-1-
DETERGENT COMPOSITIONS INHIBITING
DYE TRANSFER
Field of the Invention
The present invention relates to a composition and a process
for inhibiting dye transfer between fabrics during washing.
More in particular, the present invention relates to detergent
compositions comprising N-vinylimidazole N-vinylpyrrolidone
copolymers having low average molecular weight
Background of the Invention
One of the most persistent and troublesome problems arising
during modern fabric laundering operations is the tendency of
some colored fabrics to release dye into the laundering
solutions. The dye is then transferred onto other fabrics being
washed therewith.
One way of overcoming this problem would be to complex or
adsorb the fugitive dyes washed out of dyed fabrics before they
have the opportunity to become attached to other articles in
the wash.
Polymers have been used within detergent compositions to
inhibit dye transfer.
One type of such polymers are N-vinylimiidazole homo-and
copolymers. Examples of said polymers are described in DE 2 814
WO 95103388 2 i 6 7 3 71 PCTIUS94/06950
2
287-A relates to detergent compositions comprising 0.1 to 10
wt% water-soluble or water-dispersible N-vinyl imidazole homo-
or copolymer in combination with anionic and/or nonionic
surfactants and other detergent ingredients. EP 372 291 relates
to a process for washing discolouration-sensitive textiles. The
wash liquor contains anionic/nonionic surfactants and
watersoluble polymers e.g. (co)polymers N-vinylimidazole, N-
vinyloxazolidone or N-vinylpyrrolidone. EP 327 927 describes a
granular detergent additive comprising water-soluble polymeric
compounds based on N-vinylpyrrolidone and/or N-vinylimidazole
and/or N-vinyloxazolidone and cationic compounds. DE 4027832-A
assigned to Henkel discloses electrolyte-free liquid detergent
compositions comprising zeolite A, nonionic surfactants and dye
transfer inhibiting polymers. The dye transfer inhibiting
polymers are homo-and copolymers selected from N-
vinylpyrrolidone and/or N-vinylimidazole and/or N-
vinyloxazolidone.
These prior art documents describe N-vinyl imidazole
copolymers as dye transfer inhibiting polymers having a
molecular weight range from 10,000 to 1,000,000. The preferred
N-vinylimidazole copolymers that are described have a molecular
weight from 20,000 to 200,000.
Unfortunately, the overall detergency performance of detergent
compositions formulated with said N-vinylimidazole copolymers
are affected by the presence of said polymers. As a
consequence, the detergent formulator is faced with a difficult
task of providing detergent compositions which have an
excellent overall detergent performance.
It has now been found that a selected group of N-
vinylimidazole copolymers are very efficient in eliminating
transfer of solubilized or suspended dyes while not adversely
affecting the overall detergency performance of the detergent
composition formulated therewith.
3
This finding allows to formulate detergent compositions which
exhibit excellent cleaning and dye transfer inhibiting
properties.
According to another embodiment of this invention a process
is also provided for laundering operations involving colored
fabrics.
Summary of the Invention
The present invention is directed to a detergent composition
comprising: clay; a metallo catalyst; greater than 1% by
weight of the detergent composition of a surfactant system; and
from 0.01% to 10% by weight of the detergent composition of a
copolymer of N-vinylimidazole and N-vinylpyrrolidone, the
copolymer having a molar ratio of N-vinylimidazole to
N-vinylpyrrolidone of from 1:1 to 1:0.2 and an average
molecular weight of from 5,000 to 50,000.
Detailed Description of the Invention
The N-vinylimidazole N-vinylpyrrolidone copolymer
The present invention relates to detergent compositions
comprising a polymer selected from N-vinylimidazole
N-vinylpyrrolidone copolymers characterized in that said
polymer has an average molecular weight range from 5,000 to
50,000 more preferably from 8,000 to 30,000, most preferably
from 10,000 to 20,000.
It has been surprisingly found that an excellent overall
detergency performance of detergent compositions comprising
said copolymers can be obtained by selecting a specific average
molecular weight range from 5,000 to 50,000; more preferably
from 8,000 to 30,000; most preferably from 10,000 to 20,000.
The average molecular weight range was determined by light
scattering as described in Barth H. G. and Mays J. W. Chemical
Analysis Vol 113. "Modern Methods of Polymer Characterization."
The N-vinylimidazole N-vinylpyrrolidone copolymers
characterized by having said average molecular weight range
n.. b,
WO 95/03388 216 7 3 71 PCT/US94/06950
4
provide excellent dye transfer inhibiting properties while not
adversely affecting the cleaning performance of detergent
compositions formulated therewith.
In addition, it has been found that the detergency performance
of certain detergent ingredients has been enhanced by the
presence of said N-vinylimidazole N-vinylpyrrolidone copolymers
of the present invention.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the
present invention has a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to
0.3, most preferably from 0.6 to 0.4 .
The N-vinylimidazole N-vinylpyrrolidone copolymers can be
linear or branched. The level of the N-vinylimidazole N-
vinylpyrrolidone present in the detergent compositions is from
0.01 to 10%, more preferably from 0.05 to 5%, most preferably
from 0.1 to 1% by weight of the detergent composition.
DETERGENT INGREDIENTS
The compositions according to the present invention comprise
in addition to the N-vinylimidazole N-vinylpyrrolidone
copolymers a surfactant system wherein the surfactant can be
selected from nonionic and/or anionic and/or cationic and/or
ampholytic and/or zwitterionic and/or semi-polar surfactants.
Preferred surfactant systems to be used according to the
present invention comprise as a surfactant one or more of the
nonionic surfactants described herein. These nonionic
surfactants have found to be very useful in that the dye
transfer inhibiting performance of the N-vinylimidazole N-
vinylpyrrolidone copolymers has been increased in the presence
of said surfactants.
NONIONICS
Polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols are suitable for use as the
WO 95/03388 3 ~ ~ PCT/US94/06950
nonionic surfactant of the surfactant systems of the present
invention, with the polyethylene oxide condensates being
preferred. These compounds include the condensation products of
alkyl phenols having an alkyl group containing from about 6 to
about 14 carbon atoms, preferably from about 8 to about 14
carbon atoms, in either a straight-chain or branched-chain
configuration with the alkylene oxide. In a preferred
embodiment, the ethylene oxide is present in an amount equal to
from about 2 to about 25 moles, more preferably from about 3 to
about 15 moles, of ethylene oxide per mole of alkyl phenol.
Commercially available nonionic surfactants of this type
include IgepalTM CO-630, marketed by the GAF Corporation: and
TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm
& Haas Company. These surfactants are commonly referred to as
alkylphenol alkoxylates (e. g., alkyl phenol ethoxylates).
The condensation products of primary and secondary aliphatic
alcohols with from about 1 to about 25 moles of ethylene oxide
are suitable for use as the nonionic surfactant of the nonionic
surfactant systems of the present invention. The alkyl chain of
the aliphatic alcohol can either be straight or branched,
primary or secondary, and generally contains from about 8 to
about 22 carbon atoms. Preferred are the condensation products
of alcohols having an alkyl group containing from about 8 to
about 20 carbon atoms, more preferably from about 10 to about
18 carbon atoms, with from about 2 to about 10 moles of
ethylene oxide per mole of alcohol. Examples of commercially
available nonionic surfactants of this type include TergitolTM
15-S-9 (the condensation product of C11-C15 linear alcohol with
9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the
condensation product of C12-C14 Primary alcohol with 6 moles
ethylene oxide with a narrow molecular weight distribution),
both marketed by Union Carbide Corporation; NeodolTM 45-9 (the
condensation product of C14-C15 linear alcohol with 9 moles of
ethylene oxide), NeodolTM 23-6.5 (the condensation product of
C12-C13 linear alcohol with 6.5 moles of ethylene oxide),
NeodolTM 45-7 (the condensation product of C14-C15 linear
alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the
WO 95/03388 216 7 3 71 ~T~S94/06950
6
condensation product of C14-C15 linear alcohol with 4 moles of
ethylene oxide) marketed by Shell Chemical Company, and KyroTM
EOB (the condensation product of C13-C15 alcohol with 9 moles
ethylene oxide), marketed by The Procter & Gamble Company.
Also useful as the nonionic surfactant of the surfactant
systems of the present invention are the alkylpolysaccharides
disclosed in U.S. Patent 4,565,647, Llenado, issued January 21,
1986, having a hydrophobic group containing from about 6 to
about 30 carbon atoms, preferably from about 10 to about 16
carbon atoms and a polysaccharide, e.g. a polyglycoside,
hydrophilic group containing from about 1.3 to about 10,
preferably from about 1.3 to about 3, most preferably from
about 1.3 to about 2.7 saccharide units. Any reducing
saccharide containing 5 or 6 carbon atoms can be used, e.g.,
glucose, galactose and galactosyl moieties can be substituted
for the glucosyl moieties (optionally the hydrophobic group is
attached at the 2-, 3-, 4-, etc. positions thus giving a
glucose or galactose as opposed to a glucoside or galactoside).
The intersaccharide bonds can be, e.g., between the one
position of the additional saccharide units and the 2-, 3-, 4-,
and/or 6- positioa~s on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula
R20(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl,
alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures
thereof in which the alkyl groups contain from about 10 to
about 18, preferably from about 12 to about 14, carbon atoms; n
is 2 or 3, preferably 2: t is from 0 to about 10, preferably 0;
and x is from about 1.3 to about l0, preferably from about 1.3
to about 3, most preferably from about 1.3 to about 2.7. The
glycosyl is preferably derived from glucose. To prepare these
compounds, the alcohol or alkylpolyethoxy alcohol is formed
first and then reacted with glucose, or a source of glucose, to
form the glucoside (attachment at the 1-position). The
WO 95/03388 216 7 3 71 pCT~S94/06950
7
additional glycosyl units can then be attached between their 1-
position and the preceding glycosyl units 2-, 3-, 4- and/or 6-
position, preferably predominately the 2-position.
Other suitable nonionic surfactants are the condensation
products of ethylene oxide with a hydrophobic base formed by
the condensation of propylene oxide with propylene glycol are
also suitable for use as the additional nonionic surfactant of
the nonionic surfactant systems of the present invention. The
hydrophobic portion of these compounds will preferably have a
molecular weight of from about 1500 to about 1800 and will
exhibit water insolubility. The addition of polyoxyethylene
moieties to this hydrophobic portion tends to increase the
water solubility of the molecule as a whole, and the liquid
character of the product is retained up to the point where the
polyoxyethylene content is about 50% of the total weight of the
condensation product, which corresponds to condensation with up
to about 40 moles of ethylene oxide. Examples of compounds of
this type include certain of the commercially-available
PluronicTM surfactants, marketed by BASF.
Also suitable for use as the nonionic surfactant of the
nonionic surfactant system of the present invention, are the
condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and
ethylenediamine. The hydrophobic moiety of these products
consists of the reaction product of ethylenediamine and excess
propylene oxide, and generally has a molecular weight of from
about 2500 to about 3000. This hydrophobic moiety is condensed
with ethylene oxide to the extent that the condensation product
contains from about 40% to about 80% by weight of
polyoxyethylene and has a molecular weight of from about 5,000
to about 11,000. Examples of this type of nonionic surfactant
include certain of the commercially available TetronicTM
compounds, marketed by BASF.
Preferred for use as the nonionic surfactant of the
surfactant systems of the present invention are polyethylene
WO 95/03388 2 1 6 7 3 7 1 ~T~S94I06950
8
oxide condensates of alkyl phenols, condensation products of
primary and secondary aliphatic alcohols with from about 1 to
about 25 moles of ethylene oxide, alkylpolysaccharides, and
mixtures thereof. Most preferred are Cg-C14 alkyl phenol
ethoxylates having from 3 to 15 ethoxy groups and Cg-Clg
alcohol ethoxylates (preferably C10 avg.) having from 2 to 10
ethoxy groups, and mixtures thereof.
Highly preferred nonionic surfactants are polyhydoxy fatty
acid amide surfactants of the formula:
R2 - C - N - Z,
O R1
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl or a mixture thereof, R2 is C5-31 hYdrocarbyl,
and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl
chain with at least 3 hydroxyls directly connected to the
chain, or an alkoxylated derivative thereof. Preferably, R1 is
methyl, R2 is a straight C11-15 alkyl or alkenyl chain such as
coconut alkyl or mixtures thereof, and Z is derived from a
reducing sugar such as glucose, fructose, maltose, lactose, in
a reductive amination reaction.
When included in such laundry detergent compositions, the
nonionic surfactant systems of the present invention act to
improve the greasy/oily stain removal properties of such
laundry detergent compositions across a broad range of laundry
conditions.
ANIONIC 80RFACTANTB
Highly preferred anionic surfactants include alkyl
alkoxylated sulfate surfactants hereof are water soluble salts
2167371
WO 95/03388 PCT/US94106950
9
or acids of the formula RO(A)mS03M wherein R is an
unsubstituted Clp-C24 alkyl or hydroxyalkyl group having a C10-
C24 alkyl component, preferably a C12-C20 alkyl or
hydroxyalkyl, more preferably C12-Clg 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 H or a cation which can be, for
example, a metal cation (e. g., sodium, potassium, lithium,
calcium, magnesium, etc.), ammonium or substituted-ammonium
cation. Alkyl ethoxylated sulfates as well as alkyl
propoxylated sulfates are contemplated herein. Specific
examples of substituted ammonium cations include methyl-,
dimethyl, trimethyl-ammonium cations and quaternary ammonium
cations such as tetramethyl-ammonium and dimethyl piperdinium
cations and those derived from alkylamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the like.
Exemplary surfactants are C12-Clg alkyl polyethoxylate (1.0)
sulfate (C12-ClgE(1.0)M), C12-Clg alkyl polyethoxylate (2.25)
sulfate (C12-ClgE(2.25)M), C12-Clg alkyl polyethoxylate (3.0)
sulfate (C12-ClgE(3.0)M), and C12-Clg alkyl polyethoxylate
(4.0) sulfate (C12-ClgE(4.0)M), wherein M is conveniently
selected from sodium and potassium.
Suitable anionic surfactants to be used are alkyl ester
sulfonate surfactants including linear esters of Cg-C20
carboxylic acids (i.e., fatty acids) which are sulfonated with
gaseous S03 according to "The Journal of the American Oil
Chemists Society", 52 (1975), pp. 323-329. Suitable starting
materials would include natural fatty substances as derived
from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially
for laundry applications, comprise alkyl ester sulfonate
surfactants of the structural formula .
O
R3 - CH - C - OR4
S03M
WO 95/03388 PCT/US94/06950
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an
alkyl, or combination thereof, and M is a cation which forms a
water soluble salt with the alkyl ester sulfonate. Suitable
salt-forming cations include metals such as sodium, potassium,
and lithium, and substituted or unsubstituted ammonium cations,
such as monoethanolamine, diethanolamine, and triethanolamine.
Preferably, R3 is C10-C16 alkyl, and R4 is methyl, ethyl or
isopropyl. Especially preferred are the methyl ester sulfonates
wherein R3 is C10-C16 alkyl.
Other suitable anionic surfactants include the alkyl sulfate
surfactants hereof are water soluble salts or acids of the
formula ROS03M wherein R preferably is a C10-C24 hydrocarbyl,
preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl
component, more preferably a C12-Clg alkyl or hydroxyalkyl, and
M is H or a cation, e.g., an alkali metal cation (e. g. sodium,
potassium, lithium), or ammonium or substituted ammonium (e. g.
methyl-, dimethyl-, and trimethyl ammonium cations and
quaternary ammonium cations such as tetramethyl-ammonium and
dimethyl piperdinium cations and quaternary ammonium cations
derived from alkylamines such as ethylamine, diethylamine,
triethylamine, and mixtures thereof, and the like). Typically,
alkyl chains of C12-C16 are preferred for lower wash
temperatures (e. g. below about 50°C) and C16-18 alkyl chains
are preferred for higher wash temperatures (e. g. above about
50°C).
Other anionic surfactants useful for detersive purposes can
also be included in the laundry detergent compositions of the
present invention. These can include salts (including, for
example, sodium, potassium, ammonium, and substituted ammonium
salts such as mono-, di- and triethanolamine salts) of soap,
Cg-C20 linear alkylbenzenesulfonates, C8-C22 primary of
secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the pyrolyzed
product of alkaline earth metal citrates, e.g., as described in
''~
11
British patent specification No. 1,082,179, Ce-C24 alkylpoly-
glycolethersulfates (containing up to 10 moles of ethylene
oxide); alkyl glycerol sulfonates, fatty acyl glycerol
sulfonates, fatty oleyl glycerol sulfates, alkyl phenol
ethylene oxide ether sulfates, paraffin sulfonates, alkyl
phosphates, isethionates such as the acyl isethionates, N-acyl
taurates, alkyl succinamates and sulfosuccinates, monoesters
of sulfosuccinates (especially saturated and unsaturated C12-Cla
monoesters) and diesters of sulfosuccinates (especially
saturated and unsaturated C6-C12 diesters), aryl sarcosinates,
sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being
described below), branched primary alkyl sulfates, and alkyl
polyethoxy carboxylates such as those of the formula
RO (CHZCHzO) k-CHZCOO-M+ wherein R is a C$-C22 alkyl, k is an
integer from 0 to 10, and M is a soluble salt-forming cation.
Resin acids and hydrogenated resin acids are also suitable,
such as rosin, hydrogenated rosin, and resin acids and
hydrogenated resin acids present in or derived from tall oil.
Further examples are described in "Surface Active Agents and
Detergents" (Vol. I and II by Schwartz, Perry and Berch). A
variety of such surfactants are also generally disclosed in
U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin,
et al. at Column 23, line 58 through Column 29, line 23.
When included therein, the laundry detergent compositions of
the present invention typically comprise from about 1 o to about
400, preferably from about 3% to about 20o by weight of such
anionic surfactants.
The alkyl alkoxylated sulfate surfactants are preferred over
the alkyl sulfates and alkyl benzene sulfonates in that these
alkyl alkoxylated sulfate surfactants synergistically improve
the dye transfer inhibiting performance of the N-vinyl
imidazole N-vinylpyrrolidone copolymers.
WO 95/03388 216 7 3 71 pCT~S94/06950 ..
12
The laundry detergent compositions of the present invention
may also contain cationic, ampholytic, zwitterionic, and semi-
polar surfactants, as well as nonionic surfactants other than
those already described herein. Preferred cationic surfactant
systems include nonionic and ampholytic surfactants.
Cationic detersive surfactants suitable for use in the
laundry detergent compositions of the present invention are
those having one long-chain hydrocarbyl group. Examples of such
cationic surfactants include the ammonium surfactants such as
alkyldimethylammonium halogenides, and those surfactants having
the formula .
[R2(OR3)y][R4(OR3)y]2R5N+X-
wherein R2 is an alkyl or alkyl benzyl group having from about
8 to about 18 carbon atoms in the alkyl chain, each R3 is
selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-,
-CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures thereof: each R4 is
selected from the group consisting of C1-C4 alkyl, C1-C4
hydroxyalkyl, benzyl ring structures formed by joining the two
R4 groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose
or hexose polymer having a molecular weight less than about
1000, and hydrogen when y is not 0: R5 is the same as R4 or is
an alkyl chain wherein the total number of carbon atoms of R2
plus R5 is not more than about 18: each y is from 0 to about 10
and the sum of the y values is from 0 to about 15: and X is any
compatible anion.
Highly preferred cationic surfactants are the water-soluble
quaternary ammonium compounds useful in the present composition
having the formula .
R1R2R3R4N+X (i)
wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is
independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -
WO 95/03388 2 1 6 7 3 7 1 ~T~S94/06950
13
(C2H40) xH where x has a value from 2 to 5, and X is an anion.
Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for R1 is C12-C15 Particularly
where the alkyl group is a mixture of chain lengths derived
from coconut or palm kernel fat or is derived synthetically by
olefin build up or OXO alcohols synthesis. Preferred groups for
R2R3 and R4 are methyl and hydroxyethyl groups and the anion X
may be selected from halide, methosulphate, acetate and
phosphate ions.
Examples of suitable quaternary ammonium compounds of
formulae (i) for use herein are .
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide:
choline esters (compounds of formula (i) wherein R1 is -CH2-
O-C-C12-14 alkyl and R2R3R4 are methyl).
O di-alkyl imidazolines [compounds of formula (i)].
Other cationic surfactants useful herein are also described
in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
When included therein, the laundry detergent compositions of
the present invention typically comprise from 0% to about 25%,
preferably from about 3% to about 15% by weight of such
cationic surfactants.
Ampholytic surfactants are also suitable for use in the
laundry detergent compositions of the present invention. These
surfactants can be broadly described as aliphatic derivatives
of secondary or tertiary amines, or aliphatic derivatives of
heterocyclic secondary and tertiary amines in which the
WO 95/03388 ~ i ~ ~ ~ ~ ~ PCT/US94106950
14
aliphatic radical can be straight- or branched-chain. One of
the aliphatic substituents contains at least about 8 carbon
atoms, typically from about 8 to about 18 carbon atoms, and at
least one contains an anionic water-solubilizing group, e.g.
carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to
Laughlin et al., issued December 30, 1975 at column 19, lines
18-35, for examples of ampholytic surfactants.
When included therein, the laundry detergent compositions of
the present invention typically comprise from 0% to about 15%,
preferably from about 1% to about 10% by weight of such
ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in laundry
detergent compositions. These surfactants can be broadly
described as derivatives of secondary and tertiary amines,
derivatives of heterocyclic secondary and tertiary amines, or
derivatives of quaternary ammonium, quaternary phosphonium or
tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to
Laughlin et al., issued December 30, 1975 at column 19, line 38
through column 22, line 48, for examples of zwitterionic
surfactants.
When included therein, the laundry detergent compositions of
the present invention typically comprise from 0% to about 15%,
preferably from about 1% to about 10% by weight of such
zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category of
nonionic surfactants which include water-soluble amine oxides
containing one alkyl moiety of from about 10 to about 18 carbon
atoms and 2 moieties selected from the group consisting of
alkyl groups and hydroxyalkyl groups containing from about 1 to
about 3 carbon atoms: water-soluble phosphine oxides containing
one alkyl moiety of from about 10 to about 18 carbon atoms and
2 moieties selected from the group consisting of alkyl groups
and hydroxyalkyl groups containing from about 1 to about 3
carbon atoms; and water-soluble sulfoxides containing one alkyl
15
moiety of from about 10 to about 18 carbon atoms and a moiety
selected from the group consisting of alkyl and hydroxyalkyl
moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic. detergent surfactants include the amine
oxide surfactants having the formula
R3 ( OR4 ) XN C OR5 ) 2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or
mixtures thereof containing from about 8 to about 22 carbon
atoms; R4 is an alkylene or hydroxyalkylene group containing
from about 2 to about 3 carbon atoms or mixtures thereof; x is
from 0 to about 3; and each RS is an alkyl or hydroxyalkyl
group containing from about 1 to about 3 carbon atoms or a
polyethylene oxide group containing from about 1 to about 3
ethylene oxide groups. The RS groups can be attached to each
other, a . g . , through an oxygen or nitrogen atom, to form a ring
structure.
These amine oxide surfactants in particular include Clo-Cls
alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy
ethyl amine oxides.
When included therein, the laundry detergent compositions of
the present invention typically comprise from 0% to about 15 0 ,
preferably from about 1% to about 10% by weight of such
semi-polar nonionic surfactants.
The present invention further provides laundry detergent
compositions comprising at least to by weight, preferably from
about 3% to about 650, more preferably from about loo to about
25% by weight of total surfactants.
Preferred detergent ingredients that can be included are
detersive enzymes which can be included in the detergent
formulations for a wide variety of purposes including removal
of protein-based, carbohydrate-based, or triglyceride-based
stains, for example, and prevention of refugee dye transfer.
The enzymes to be incorporated include proteases, amylases,
r
16
lipases, cellulases, and peroxidases, as well as mixtures
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.
Enzymes are normally incorporated at levels sufficient to
provide up to about 5 mg by weight, more typically about 0.05
mg to about 3 mg, of active enzyme per gram of the composition.
Highly preferred enzymes to be incorporated in the detergent
compositions according to the present invention are cellulases
or peroxidases and mixtures thereof.
The cellulases usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH
optimum of between 5 and 9.5. Suitable cellulases are disclosed
in U.S. Patent 4,435,307, Barbesgoard et al, which discloses
fungal cellulase produced from Humicola insolens. Suitable
cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275
and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a
strain of Humicola insolens (Humicola grisea var. thermoidea),
particularly the Humicola strain DSM 1800, and cellulases
produced by a fungus of Bacillus N or a cellulase 212-producing
fungus belonging to the genus Aeromonas, and cellulase
extracted from the hepatopancreas of a marine mollusc
(Dolabella Auricula Solander).
Other suitable cellulases are cellulases originated from
Humicola Insulens having a molecular weight of about 50 KDa,
an isoelectric point of 5 . 5 and containing 415 amino acids .
Especially suitable cellulase are the cellulase having color
care benefits. Examples of such cellulases are cellulase
described in United States Patent 5, 520, 838 issued May 28, 1996
Carezyme (Novo). It has been found that the N-vinyl imidazole
N-vinylpyrrolidone copolymers synergistically improve the
performance in of the cellulases in terms of colour appearance.
17
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in British
Patent 1,372,034. Suitable lipases include those which show a
positive immunological cross-reaction with the antibody of the
lipase, produced by the microorganism Pseudomonas fluorescent
IAM 1057. This lipase is available from Amano Pharmaceutical
Co. Ltd. , Nagoya, Japan, under the trade mark Lipase P "Amano, "
hereinafter referred to as "Amano-P".
Especially suitable Lipase are lipase such as M1 Lipase
( Ibis ) and LipolaseTM (Novo) .
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 of pigments removed from substrates
during wash operations to other substrates in the wash
solution. Peroxidase enzymes are known in the art, and include,
for example, horseradish peroxidase, ligninase, and
haloperoxidase such as chloro- and bromo-peroxidase.
Peroxidase-containing detergent compositions are disclosed, for
example, in PCT International Application WO 89/099813 and in
CA 2,122,987 filed October 28, 1992.
It has been found that the N-vinyl imidazole
N-vinylpyrrolidone copolymers synergistically improve the dye
transfer inhibiting performance of the peroxidase.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B.subtilis and B.licheni-
forms. Proteolytic enzymes suitable for removing protein-based
stains that are commercially available include those sold under
the trademarks Alcalase, Savinase and Esperase by Novo
Industries A/S (Denmark) and Maxatase by International
Bio-Synthetics, Inc. (The Netherlands) and FN-base by Genencor,
Optimase and Opticlean by MKC.
18
Of interest in the category of proteolytic enzymes,
especially for liquid detergent compositions, are enzymes
referred to herein as Protease A and Protease B. Protease A is
described in European Patent Application 130,756. Protease B
is described in EP 251 446 published January 7, 1988.
Amylases include, for example, -amylases obtained from a
special strain of B.licheniforms, described in more detail in
British Patent Specification No. 1,296,839 (Novo). Amylolytic
proteins include, for example, RapidaseT"', Maxamyl'~"'
(International Bio-Synthetics, Inc.) and Termamyl'r''', (Novo
Industries).
In liquid formulations, an enzyme stabilization system is
preferably utilized. Enzyme stabilization techniques for
aqueous detergent compositions are well known in the art. For
example, one technique for enzyme stabilization in aqueous
solutions involves the use of free calcium ions from sources
such as calcium acetate, calcium formate and calcium
propionate. Calcium ions can be used in combination with short
chain carboxylic acid salts, preferably formates. See, for
example, U.S. Patent 4,318,818. It has also been proposed to
use polyols like glycerol and sorbitol. Alkoxy-alcohols,
dialkylglycoethers, mixtures of polyvalent alcohols with
polyfunctional aliphatic amines (e. g., such as diethanolamine,
triethanolamine, di-isopropanolamime, etc.), and boric acid or
alkali metal borate. Enzyme stabilization techniques are
additionally disclosed and exemplified in U.S. Patent
4,261,868, U.S. Patent 3,600,319, and European Patent
Application Publication No. 0 199 405. Non-boric acid and
borate stabilizers are preferred. Enzyme stabilization systems
are also described, for example, in U.S. Patent Nos. 4,261,868,
3,600,319 and 3,519,570. Other suitable detergent ingredients
that can be added are enzyme oxidation scavengers which are
described in EP 553 607 published August 4, 1993. Examples of
such enzyme oxidation scavengers are ethoxylated tetraethylene
polyamines.
19
Especially preferred detergent ingredients are combinations
with technologies which also provide a type of color care
benefit. Examples of these technologies are
polyvinylpyrrolidone polymers such as described in EP 0 508 034
and polyamine-N-oxide containing polymers such as described in
CA 2,140,289 filed June 30, 1993 and EP 579 295 published
January 19, 1994. Other examples are cellulase and/or
peroxidases and/or metallo catalysts for color maintenance
rejuvenation. Such metallo catalysts are described in EP 596
184 published November 6, 1992.
In addition, it has been found that the N-imidazole
N-vinylpyrrolidone copolymers according to the present
invention eliminate or reduce the deposition of the
metallo-catalyst onto the fabrics resulting in improved
whiteness benefit.
Preferred detergent ingredients that can be included in the
detergent compositions of the present invention include
bleaching agents.
These bleaching agent components can include one or more
oxygen bleaching agents and, depending upon the bleaching agent
chosen, one or more bleach activators. When present bleaching
compounds will typically be present at levels of from about 1%
to about 10%, of the detergent composition. In general,
bleaching compounds are optional components in non-liquid
formulations, e.g. granular detergents. If present, the amount
of bleach activators will typically be from about 0.1% to about
60%, more typically from about 0.5% to about 40% of the
bleaching composition.
The bleaching agent component for use herein can be any of
the bleaching agents useful for detergent compositions
including oxygen bleaches as well as others known in the art.
In a method aspect, this invention further provides a method
for cleaning fabrics, fibers, textiles, at temperatures below
20
about 50°C, especially below about 40°C, with a detergent
composition containing N-vinylimidazole N-vinylpyrrolidone
copolymers in combination with bleaching agents.
The bleaching agent suitable for the present invention can
be an activated or non-activated bleaching agent.
One category of oxygen 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 meta-chloro perbenzoic acid,4-nonylamino-4-oxoperoxybutyric
acid and diperoxydodecanedioic acid. Such bleaching agents are
disclosed in U.S. Patent 4,483,781, U.S. Patent 4,634,551,
European Patent Application 0,133,354 and U.S. Patent
4,412,934. Highly preferred bleaching agents also include
6-nonylamino-6-oxoperoxycaproic acid as described in U.S.
Patent 4,634,551.
Another category of bleaching agents that can be used
encompasses the halogen bleaching agents. Examples of
hypohalite bleaching agents, for example, include trichloro
isocyanuric acid and the sodium and potassium
dichloroisocyanurates and N-chloro and N-bromo alkane
sulphonamides. Such materials are normally added at 0.5-10% by
weight of the finished product, preferably 1-5o by weight.
Preferably, the bleaches suitable for the present invention
include peroxygen bleaches. Examples of suitable water-soluble
solid peroxygen bleaches include hydrogen peroxide releasing
agents such as hydrogen peroxide, perborates, e.g. perborate
monohydrate, perborate tetrahydrate, persulfates,
percarbonates, peroxydisulfates, perphosphates and
peroxyhydrates. Preferred bleaches are percarbonates and
perborates.
The hydrogen peroxide releasing agents can be used in
combination with bleach activators such as tetraacetyl-
21 .~
ethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS,
described in U.S. Patent 4,412,934), 3,5,-trimethylhexano-
loxybenzenesulfonate (ISONOBS, described in EP 120,591) or
pentaacetylglucose (PAG), which are perhydrolyzed to form a
peracid as the active bleaching species, leading to improved
bleaching effect. Also suitable activators are acylated citrate
esters such as disclosed in CA 2,124,787 filed December 4,
1992.
The hydrogen peroxide may also be present by adding an
enzymatic system (i.e. an enzyme and a substrate therefore)
which is capable of generating hydrogen peroxide at the
beginning or during the washing and/or rinsing process. Such
enzymatic systems are disclosed in EP 537 381 published April
4, 1993.
Other peroxygen bleaches suitable for the present invention
include organic peroxyacids such as percarboxylic acids.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of
non-oxygen bleaching agent of particular interest includes
photoactivated bleaching agents such as the sulfonated zinc
and/or aluminum phthalocyanines. These materials can be
deposited upon the substrate during the washing process. Upon
irradiation with light, in the presence of oxygen, such as by
hanging clothes out to dry in the daylight, the sulfonated zinc
phthalocyanine is activated and, consequently, the substrate
is bleached. Preferred zinc phthalocyanine and a photoactivated
bleaching process are described in U.S. Patent 4,033,718.
Typically, detergent compositions will contain about 0.025% to
about 1.25%, by weight, of sulfonated zinc phthalocyanine.
Preferably, the compositions according to the present
invention comprise a clay. It has been found that the
N-vinylimidazole N-vinylpyrrolidone copolymers according to the
present invention are very compatible with the clays in that
the dye transfer inhibiting properties of the polymers are not
WO 95/03388 2 1 6 7 3 7 1 ~T~S94/06950
22
adversely affected by the presence of clays formulated
therewith. In addition, it has been found that the softening
performance of clays formulated with the N-vinylimidazole N-
vinylpyrrolidone copolymers has been maintained. Especially
suitable are clays such as fabric softening clays which are
described in EP 0 522 206.
The compositions according to the present invention may
further comprise a builder system. Any conventional builder
system is suitable for use herein including aluminosilicate
materials, silicates, polycarboxylates and fatty acids,
materials such as ethylenediamine tetraacetate, metal ion
sequestrants such as aminopolyphosphonates, particularly
ethylenediamine tetramethylene phosphoric acid and diethylene
triamine pentamethylenephosphonic acid. Though less preferred
for obvious environmental reasons, phosphate builders can also
be used herein.
Suitable builders can be an inorganic ion exchange
material, commonly an inorganic hydrated aluminosilicate
material, more particularly a hydrated synthetic zeolite such
as hydrated zeolite A, X, B or HS.
Another suitable inorganic builder material is layered
silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered
silicate consisting of sodium silicate (Na2Si205).
Suitable polycarboxylates containing one carboxy group
include lactic acid, glycolic acid and ether derivatives
thereof as disclosed in Belgian Patent Nos. 831,368, 821,369
and 821,370. Polycarboxylates containing two carboxy groups
include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, malefic acid, diglycollic acid,
tartaric acid, tartronic acid and fumaric acid, as well as the
ether carboxylates described in German Offenlegenschrift
2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the
sulfinyl carboxylates described in Belgian Patent No. 840,623.
Polycarboxylates containing three carboxy groups include, in
23
particular, water-soluble citrates, aconitrates and citra-
conates as well as succinate derivatives such as the carboxy-
methyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in Canadian Patent No. 973,771,
and the oxypolycarboxylate materials such as 2-oxa-1,1,3-pro-
pane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxy-
disuccinates disclosed in British Patent No. 1,261,829,
1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxy-
lates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing sulfo substituents include the sulfosuccinate
derivatives disclosed in British Patent Nos. 1,398,421 and
1,398,422 and in U.S. Patent 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No. 1,082,179,
while polycarboxylates containing phosphone substituents are
disclosed in British Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclo-
pentane-cis,cis,cis-tetracarboxylates, cyclopentadienide
pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis,cis,cis-tetra-
carboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates,
2,2,5,5-tetrahydrofuran-tetracarboxylates,1,2,3,4,5,6-hexane-
hexacarboxylates and carboxymethyl derivatives of polyhydric
alcohols such as sorbitol, mannitol and xylitol. Aromatic
polycarboxylates include mellitic acid, pyromellitic acid and
the phthalic acid derivatives disclosed in British Patent No.
1,425,343.
Of the above, the preferred polycarboxylates are hydroxy-
carboxylates containing up to three carboxy groups per
molecule, more particularly citrates.
Preferred builder systems for use in the present compositions
include a mixture of a water-insoluble aluminosilicate builder
such as zeolite A or of a layered silicate (sks/6), and a
water-soluble carboxylate chelating agent such as citric acid.
WO 95/03388 216 7 3 71 pCT~S94/06950
24
A suitable chelant for inclusion in the detergent
compositions in accordance with the invention is
ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali
metal, alkaline earth metal, ammonium, or substituted ammonium
salts thereof, or mixtures thereof. Preferred EDDS compounds
are the free acid form and the sodium or magnesium salt
thereof. Examples of such preferred sodium salts of EDDS
include Na2EDDS and Na4EDDS. Examples of such preferred
magnesium salts of EDDS include MgEDDS and Mg2EDDS. The
magnesium salts are the most preferred for inclusion in
compositions in accordance with the invention.
Especially for the liquid execution herein, suitable fatty
acid builders for use herein are saturated or unsaturated C10-
18 fatty acids, as well as the corresponding soaps. Preferred
saturated species have from 12 to 16 carbon atoms in the alkyl
chain. The preferred unsaturated fatty acid is oleic acid.
Preferred builder systems for use in granular compositions
include a mixture of a water-insoluble aluminosilicate builder
such as zeolite A, and a watersoluble carboxylate chelating
agent such as citric acid.
Other builder materials that can form part of the builder
system for use in granular compositions include inorganic
materials such as alkali metal carbonates, bicarbonates,
silicates, and organic materials such as the organic
phosphonates, amino polyalkylene phosphonates and amino
polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-
polymeric acids or their salts, in which the polycarboxylic
acid comprises at least two carboxyl radicals separated from
each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000 and
their copolymers with malefic anhydride, such copolymers having
a molecular weight of from 20,000 to 70,000, especially about
40,000.
25 ~ ,
Detergency builder salts are normally included in amounts of
from 10% to 80% by weight of the composition preferably from
20o to 70% and most usually from 30% to 60% by weight.
Another optional ingredient is a suds suppressor, exemplified
by silicones, and silica-silicone mixtures. Silicones can be
generally represented by alkylated polysiloxane materials while
silica is normally used;in finely divided forms exemplified by
silica aerogels and xerogels and hydrophobic silicas of various
types. These materials can be incorporated as particulates in
which the suds suppressor is advantageously releasably
incorporated in a water-soluble or water-dispersible,
substantially non-surface-active detergent impermeable carrier.
Alternatively the suds suppressor can be dissolved or dispersed
in a liquid carrier and applied by spraying on to one or more
of the other components.
A preferred silicone suds controlling agent is disclosed in
Bartollota et al. U.S. Patent 3,933,672. Other particularly
useful suds suppressors are the self-emulsifying silicone suds
suppressors, described in German Patent Application DTOS 2 646
126 published April 28, 1977. An example of such a compound is
DC-544, commercially available from Dow Corning, which is a
siloxane-glycol copolymer. Especially preferred suds
controlling agent are the suds suppressor system comprising a
mixture of silicone oils and 2-alkyl-alcanols. Suitable
2-alkyl-alcanols are 2-butyl-octanol which are commercially
available under the trade name Isofol 12~. Such suds
suppressor system are described in CA 2,146,636 filed October
15, 1993.
Especially preferred silicone suds controlling agents are
described in Copending European Patent Appln. No. 92201649.8
Said compositions can comprise a silicone/silica mixture in
combination with fumed nonporous silica such as Aerosil~.
WO 95/03388 216 l 3 l 1 PCT/US94/06950
26
The suds suppressors described above are normally employed at
levels of from 0.001% to 2% by weight of the composition,
preferably from 0.01% to 1% by weight.
Other components used in detergent compositions may be
employed, such as soil-suspending agents soil-release agents,
optical brighteners, abrasives, bactericides, tarnish
inhibitors, coloring agents, and/or encapsulated or non-
encapsulated perfumes.
Antiredeposition and soil suspension agents suitable herein
include cellulose derivatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcellulose, and homo- or
co-polymeric polycarboxylic acids or their salts. Polymers of
this type include the polyacrylates and malefic anhydride-
acrylic acid copolymers previously mentioned as builders, as
well as copolymers of malefic anhydride with ethylene,
methylvinyl ether or methacrylic acid, the malefic anhydride
constituting at least 20 mole percent of the copolymer. These
materials are normally used at levels of from 0.5% to 10% by
weight, more preferably from 0.75% to 8%, most preferably from
1% to 6% by weight of the composition.
Preferred optical brighteners are anionic in character,
examples of which are disodium 4,41-bis-(2-diethanolamino-4-
anilino -s- triazin-6-ylamino)stilbene-2:21 disulphonate,
disodium 4, - 41-bis-(2-morpholino-4-anilino-s-triazin-6-
ylaminostilbene-2:21 - disulphonate, disodium 4,41 - bis-(2,4-
dianilino-s-triazin-6-ylamino)stilbene-2:21 - disulphonate,
monosodium 41,411 -bis-(2,4-dianilino-s-triazin-6
ylamino)stilbene-2-sulphonate, disodium 4,41 -bis-(2-anilino-4-
(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-
2,21 - disulphonate, disodium 4,41 -bis-(4-phenyl-2,1,3-
triazol-2-yl)-stilbene-2,21 disulphonate, disodium 4,41bis(2-
anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-
ylamino)stilbene-2,21disulphonate and sodium 2(stilbyl-411-
(naphtho-11,21:4,5)-1,2,3 - triazole-211-sulphonate.
WO 95/03388 ~ 1 b 7 3 7 1 ~T~S94/06950
27
Other useful polymeric materials are the polyethylene
glycols, particularly those of molecular weight 1000-10000,
more particularly 2000 to 8000 and most preferably about 4000.
These are used at levels of from 0.20% to 5% more preferably
from 0.25% to 2.5% by weight. These polymers and the previously
mentioned homo- or co-polymeric polycarboxylate salts are
valuable for improving whiteness maintenance, fabric ash
deposition, and cleaning performance on clay, proteinaceous and
oxidizable soils in the presence of transition metal
impurities.
Soil release agents useful in compositions of the present
invention are conventionally copolymers or terpolymers of
terephthalic acid with ethylene glycol and/or propylene glycol
units in various arrangements. Examples of such polymers are
disclosed in the commonly assigned US Patent Nos. 4116885 and
4711730 and European Published Patent Application No. 0 272
033. A particular preferred polymer in accordance with EP-A-0
272 033 has the formula
(CH3(PEG)43)0.75(POH)0.25~T-PO)2.8(T-PEG)0.4JT(PO
H)0.25((PEG)43CH3)0.75
where PEG is -(OC2H4)O-,PO is (OC3H60) and T is (pcOC6H4C0).
Also very useful are modified polyesters as random copolymers
of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene
glycol and 1-2 propane diol, the end groups consisting
primarily of sulphobenzoate and secondarily of mono esters of
ethylene glycol and/or propane-diol. The target is to obtain a
polymer capped at both end by sulphobenzoate groups,
"primarily", in the present context most of said copolymers
herein will be end-capped by sulphobenzoate groups. However,
some copolymers will be less than fully capped, and therefore
their end groups may consist of monoester of ethylene glycol
and/or propane 1-2 diol, thereof consist "secondarily" of such
species.
WO 95/03388 21 b 7 3 7 l PCT/US94I06950
28
The selected polyesters herein contain about 46% by weight of
dimethyl terephtalic acid, about 16% by weight of propane -1.2
diol, about 10% by weight ethylene glycol about 13% by weight
of dimethyl sulfobenzoid acid and about 15% by weight of
sulfoisophtalic acid, and have a molecular weight of about
3.000. The polyesters and their method of preparation are
described in detail in EPA 311 342.
The detergent compositions according to the invention can be
in liquid, paste, gels or granular forms.
Especially preferred detergent compositions are detergent
compositions having a pH between 7-11, more preferably a pH
between 9=10.5.
Granular compositions according to the present invention can
also be in "compact form", i.e. they may have a relatively
higher density than conventional granular detergents, i.e. from
550 to 950 g/1; in such case, the granular detergent
compositions according to the present invention will contain a
lower amount of "inorganic filler salt", compared to
conventional granular detergents; typical filler salts are
alkaline earth metal salts of sulphates and chlorides,
typically sodium sulphate: "compact" detergents typically
comprise not more than 10% filler salt. The liquid compositions
according to the present invention can also be in "concentrated
form", in such case, the liquid detergent compositions
according to the present invention will contain a lower amount
of water, compared to conventional liquid detergents. Typically,
the water content of the concentrated liquid detergent is less
than 30%, more preferably less than 20%, most preferably less
than 10% by weight of the detergent compositions. Other
examples of liquid compositions are anhydrous compositions
containing substantially no water.
Both aqueous and non-aqueous liquid compositions can be
structured or non-structured.
The present invention also relates to a process for
inhibiting dye transfer from one fabric to another of
WO 95/03388 L ~ ~ ~ a PCT/US94/06950
29
solubilized and suspended dyes encountered during fabric
laundering operations involving colored fabrics.
T.he process comprises contacting fabrics with a laundering
solution as hereinbefore described.
The process of the invention is conveniently carried out in
the course of the washing process. The washing process is
preferably carried out at 5 °C to 75 °C, especially 20 to 60,
but the polymers are effective at up to 95 °C and higher
temperatures. The pH of the treatment solution is preferably
from 7 to 11, especially from 7.5 to 10.5.
The process and compositions of the invention can also be
used as detergent additive products.
Such additive products are intended to supplement or boost the
performance of conventional detergent compositions.
The detergent compositions according to the present invention
include compositions which are to be used for cleaning
substrates, such as fabrics, fibers, hard surfaces, skin etc.,
for example hard surface cleaning compositions (with or without
abrasives), laundry detergent compositions, automatic and non
automatic dishwashing compositions.
The following examples are meant to exemplify compositions of
the present invention, but are not necessarily meant to limit
or otherwise define the scope of the invention, said scope
being determined according to claims which follow.
I ' I I
2167371
WO 95/03388 PCTIUS94/06950
E%AMPLE I (A/B/C/D)
A liquid detergent composition according to the present
invention is prepared, having the following compositions .
% by weight of the total detergent composition
A H C D
Linear alkylbenzene sulfonate 10 - - -
Polyhydroxy fatty acid amide - 5 - 3
Alkyl alkoxylated sulfate - - 9 4
Alkyl sulphate 4 8 4 15
Fatty alcohol (C12-C15) ethoxylate 12 12 12 5
Fatty acid 10 10 10 10
Oleic acid 4 4 4 -
Citric acid 1 1 1 1
Diethylenetriaminepentamethylene 1.5 1.5 1.5 1.5
Phosphonic acid
NaOH 3.4 3.4 3.4 3.4
Propanediol 1.5 1.5 1.5 1.5
Ethanol 10 10 10 10
Ethoxylated tetraethylene pentamine0.7 0.7 0.7 0.7
Thermamyl R 300 KNU/g 0.1 0.1 0.1 0.1
Carezyme R 5000 CEW/g 0.02 0.02 0.02 0.02
Protease 40 mg/g 1.8 1.8 1.8 1.8
Lipolase R 100 KLU/g 0.1 0.1 0.1 0.1
Endoglucanase A 5000 CEW/g 0.5 0.5 0.5 0.5
Suds supressor (ISOFOLr) 2.5 2.5 2.5 2.5
H202 7.5 7.5 - -
N-vinylimidazole N-vinyl
pyrrolidone copolymer 0.1-1 0.1-1 0.1-1 0.1-1
Minors up to 100
WO 95/03388 ~ ~ ~ PCT/US94/06950
31
ERAMPhE II (A/H/C/D)
A liquid detergent composition according to the present
invention is prepared, having the following compositions .
% by weight of the total detergent composition
B_ C_ _D
Linear alkylbenzene sulfonate 10 - - -
Polyhydroxy fatty acid amide - 5 - 3
Alkyl alkoxylated sulfate - - g 4
Alkyl sulphate . 4 8 4 15
Fatty alcohol (C12-C15) ethoxylate 12 12 12 5
Fatty acid 10 10 10 10
Oleic acid 4 4 4 -
Citric acid 1 1 1 1
Diethylenetriaminepentamethylene 1.5 1.5 1.5 1.5
Phosphonic acid
NaOH 3.4 3.4 3.4 3.4
Propanediol 1.5 1.5 1.5 1.5
Ethanol 10 10 10 10
Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 0.7
Thermamyl R 300 KNU,/g - 0.1 0.1 0.1 0.1
Carezyme R 5000 CEW/g 0.02 0.02 0.02 0.02
Protease 40 mg/g 1.8 1.8 1.8 1.8
Lipolase R 100 KLU/g 0.1 0.1 0.1 0.1
Endoglucanase A 5000 CEW/g 0.5 0.5 0.5 0.5
Suds supressor (ISOFOLr) 2.5 2.5 2.5 2.5
H202 7.5 7.5 - -
N-vinylimidazole N-vinylpyrrolidone 0.1-1 0.1-1 0.1-1 0.1-1
copolymer
Metallo catalyst 0.1-1 0.1-1 0.1-1 0.1-1
Poly(4-vinylpyridine)-N-oxide 0.1-1 0.1-1 0.1-1 0.1-1
clay - - 4 4
peroxidase o.i 0.1 - -
Minors up to 100
i i i
2167371
WO 95/03388 PCTIUS94/06950
32
EXAMPLE III (A/B/C/D/E)
A compact granular detergent composition according to the
present invention is prepared, having the following
formulation:
% by weight of the total detergent composition
_A B _C _D E
Linear alkyl benzene sulphonat 11.40 - - - -
Polyhydroxy fatty acid amide - 10 - - - -
Alkyl alkoxylated sulfate - - 9 9 9
Tallow alkyl sulphate 1.80 1.80 1.80 1.80 1.80
C45 alkyl sulphate 3.00 3.00 3.00 3.00 3.00
C45alcohol 7 times ethoxylate 4.00 4.00 4.00 4.00 4.00
Tallow alcohol 11 times 1.80 1.80 1.80 1.80 1.80
ethoxylated
Dispersant 0.07 0.07 0.07 0.07 0.07
Silicone fluid 0.80 0.80 0.80 0.80 0.80
Trisodium citrate 14.00 14.00 14.00 14.00 14.00
Citric acid 3.00 3.00 3.00 3.00 3.00
Zeolite 32.50 32.50 32.50 32.50 32.50
Diethylenetriamine pentanethy- 0.6 0.6 0.6 0.6 0.6
lene phosphonic acid
Malefic acid acrylic acid .5.00 5.00 5.00 5.00 5.00
copolymer
Cellulase (active protein) 0.03 0.03 0.03 0.03 0.03
Alkalase/BAN 0.60 0.60 0.60 0.60 0.60
Lipolase 0.36 0.36 0.36 0.36 0.36
Sodium silicate 2.00 2.00 2.00 2.00 2.00
Sodium sulphate 3.50 3.50 3.50 3.50 3.50
Percarbonate - - - 20 -
Perborate 15 15 15 - -
TAED 5 - 5 5 -
N-vinylimidazole N-vinyl- 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1
pyrrolidone copolymer
Minors up to
100
WO 95/03388 ~ ~ ~ ~ PCT/US94/06950
33
EXAMPLE IV (A/H/C/D/E)
A compact granular detergent composition according the
to
present invention is prepared, having the following
formulation:
% by weight of the total detergent
composition
_A ~ C_ _D _E
Linear alkyl benzene sulphonat 11.40 - - - -
Polyhydroxy fatty acid amide - 10 - - -
Alkyl alkoxylated sulfate - - 9 9 9
Tallow alkyl sulphate 1.80 1.80 1.80 1.80 1.80
C45 alkyl sulphate 3.00 3.00 3.00 3.00 3.00
C45 alcohol 7 times ethoxylate 4.00 4.00 4.00 4.00 4.00
Tallow alcohol 11 times 1.80 1.80 1.80 1.80 1.80
ethoxylated
Dispersant 0.07 0.07 0.07 0.07 0.07
Silicone fluid 0.80 0.80 0.80 0.80 0.80
Trisodium citrate 14.00 14.00 14.00 14.00
14.00
Citric acid 3.00 3.00 3.00 3.00 3.00
Zeolite 32.50 32.50 32.50 32.50
32.50
Diethylenetriamine pentanethy- 0.6 0.6 0.6 0.6 0.6
lene phosphoric acid
Malefic acid acrylic acid 5.00 5.00 5.00 5.00 5.00
copolymer
Cellulase (active protein) 0.03 0.03 0.03 0.03 0.03
Savinase 0.60 0.60 0.60 0.60 0.60
Lipolase 0.36 0.36 0.36 0.36 0.36
Sodium silicate 2.00 2.00 2.00 2.00 2.00
Sodium sulphate 3.50 3.50 3.50 3.50 3.50
Percarbonate - - - 20 -
Perborate 15 15 15 - -
TAED 5 - 5 5 -
N-vinylimidazole N-vinyl- 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1
pyrrolidone copolymer
Metallo catalyst 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1
Poly(4-vinylpyridine)-N-oxide 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1
Clay - - - 4 4
peroxidase - 0.1 0.1 - -
Minors up to
100
WO 95/03388 216 7 3 71 PCTIUS94/06950
34
The above compositions (Example I,II (A/B/C/D) and II ,IV
(A/B/C/D/E)) were very good at displaying excellent cleaning
and detergency performance with outstanding color-care
performance on colored fabrics and mixed loads of colored and
white fabrics.
