Note: Descriptions are shown in the official language in which they were submitted.
Y~ ~O 95/03382 ~ 216 l 3 7 3 p~~S94106951
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.
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-
vinylimidazole homo-and copolymers. Examples of said polymers
are described in prior art documents such as DE 2 814 287-A
which relates to detergent compositions comprising 0.1 to 10
SUBSTITUTE SHEET (~lll.E 2~
~~ s~ ~~~ r
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 discloses electrolyte-free liquid
detergent compositions comprising zeolite A, nonionic
surfactants and dye transfer inhibiting polymers. The~ dye
transfer.i,nhibiting polymers are homo-and copolymers selected
from N-vinylpyrrolidone and/or N-vinylimidazole and/or N-
vinyloxazolidone.
It has now been found that the N-vinylimidazole N-
vinylpyrrolidone copolymers are very efficient in eliminating
transfer of solubilized or suspended dyes while enhancing the
detergency performance of specific detergent ingredients
formulated therewith.
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 relates to a detergent composition
comprising 0.01% to l0o by weight of N-vinylimidazole N-
vinylpyrrolidone copolymer having an average molecular weight
range from 5,000 to 1,000,000 and a molar ratio of N-
vinylimidazole to N-vinylpyrrolidone from 1:1 to 1:0.2,
i~.;.y
a
CA 02167373 1999-08-02
3
characterised in that said composition further comprises a non-
alkylbenzene sulfonate containing surfactant system.
Detailed description of the invention
The N-vinylimidazole N-vinylpyrrolidone copolymer
The present invention comprises as an essential detergent
ingredient a polymer selected from the N-vinylimidazole
N-vinylpyrrolidone copolymers.
Said N-vinylimidazole N-vinylpyrrolidone have found to enhance
the detergency performance of certain detergent ingredients
formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone polymers have an
average molecular weight range from 5000-1,000,000,
preferably from 20,000-200,000.
Highly preferred polymers for use in detergent compositions
according to the present invention comprise a polymer selected
from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said
polymer has an average molecular weight range f rom 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. In
addition, it has been found that an excellent overall detergency
performance of detergent compositions comprising N-vinylimidazole
N-vinylpyrrolidone 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,OOO; most preferably from 10,000
to 20,000.
The N-vinylimidazole N-vinylpyrrolidone copolymers characterized
by having said average molecular weight range provide excellent
dye transfer inhibiting properties while not adversely affecting
the cleaning performance of detergent compositions formulated
therewith.
2167373
WO 95/03382 PCT/US94I06951
4
The N-vinylimidazole N-vinylpyrrolidone copolymer of the
present invention has G molair 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
lineair 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 to by weight of the detergent
composition.
DETERGENT INGREDIENTS
The detergent compositions according to the present
invention comprise in addition to the N-vinylimidazole N-
vinylpyrrolidone copolymers certain specific detergent
ingredients.
It has been found that the combination of N-vinylimidazole N-
vinylpyrrolidone copolymers with said detergent ingredients
enhances the dye transfer inhibiting properties of the N-
vinylimidazole N-vinylpyrrolidone copolymers.
A first class of ingredients are surfactant systems wherein
the surfactant is a non-alkylbenzene sulfonate salt containing
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 non-alkylbenzene sulfonate salt containing
surfactant systems to be used according to the present
invention comprise as a surfactant one or more of the nonionic
and/or anionic surfactants described herein. These 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.
SUBSnTUiF SHEET (~ll~E 28y
"~O 95103382
PCT/ITS94/06951
Polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols are suitable for use as the
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
t.ype 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
SUBSTINf E SHEFT (~119.E 2~
2167373
WO 95/03382 PCTIUS94/06951
6
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 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- positions on the preceding saccharide
units.
The preferred alkylpolyglycosides have the formula
R20(CnH2n0)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 10, preferably from about
1.3 to about 3, most preferably from about 1.3 to about 2.7.
SUBSnTUTf SHEET (~lif.E 2~
~'y0 95103382
2 ~16 7 3 7 3 pC~j~~S94/06951
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 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
SUBSTTTUtf SHE~T (~111.E 2~
2167373
WO 95/03382 PCTIUS94106951
8
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
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-Clq 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,
I I
O R1
wherein R1 is H, or R1 is C1_q hydrocarbyl, 2-hydroxy ethyl,
2-hydroxy propyl or a mixture thereof, R2 is CS-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.
Highly preferred anionic surfactants include alkyl
alkoxylated sulfate surfactants hereof are water soluble salts
or acids of the formula RO(A)mS03M wherein R is an
SUBSPTUTE SHfE'f (l~llf.E 28j
unsubstituted C10-C24 alkyl or hydroxyalkyl group having a
,C10-C24 alkyl component, pr-ferably a C12-C20 alkyl or
hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A
is an e.thoxy 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-C18E(1.0)M), C12-Clg alkyl polyethoxylate.(2.25)
sulfate (C12-C18E(2.25)M), C12-C18 alkyl polyethoxylate (3.0)
sulfate (C12-C18E(3.0)M), and C12-Clg alkyl polyethoxylate
(4.0) sulfate (C12-C18E(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 .
0
II
R3 - CH - C - OR4 - . . .
S03M
2167373
WO 95103382 PCT/US94/06951
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-C22 primary of secondary alkanesulfonates, Cg-C24
olefinsulfonates, sulfonated polycarboxylic acids prepared by
sulfonation of the pyrolyzed product of alkaline earth metal
citrates, e.g., as described in British patent specification
SUBSTf PTf E SHE~T (~t~.E 2~
11
No. 1,082,179, C8-C2q alkylpolyglycolethersulfates (containing
up to 10 moles of ethylene oxide); alkyJ 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-C18 monoesters) and diesters of
sulfosuccinates (especially saturated and unsaturated C6-C12
diesters), acyl 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(CH2CH20)k-CH2C00-M+ wherein R is a~CB-
C22 alkyl,
k is an integer from 0 to 10, and M is a soluble salt-fonaing
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 Herch)~.
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$ to
about -40$, preferably from about~3$ to about 20$ by weight of
such anionic surfactants.
The alkyl alkoxylated sulfate surfactants have found to
provide superior dye transfer inhibition versus the alkyl
benzene sulfonates surfactants in that said alkyl alkoxylated
sulfate surfactants improve the dye transfer inhibiting
performance of the N-vinyl imidazole N-vinylpyrrolidone
copolymers.
2167373
WO 95103382 PCT/US94106951 -
12
The laundry detergent compositions of the present invention
may also contain cationic, ampholytic, zwitterionic, and semi-
polar surfactants, as well as the nonionic and/or anionic
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) yl2R5N+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-Cq alkyl, C1-Cq
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
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)
SUBSnTUiE SHEET (~111.E 2~
'"":0 95/03382 l ~ ~ ~ PCT/US94/06951
13
wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is
independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -
(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 Oo to about 25~,
preferably from about 3o to about 15o 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
SUBSnTU'f~ SHE~T (~lll.E 2t~
WO 95/03382 216 7 3 7 3 pCT~S94/06951 -'
14
of secondary or tertiary amines, or aliphatic derivatives of
heterocyclic secondary and tertiary amines in which the
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 Oo to about 15g,
preferably from about to 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 ammoniuni, quaternary
phosphonium or tertiary sulfonium compounds. See U.S. Patent
No. 3,929,678 to Laughlin ef 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 to 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
SUBSnTUT~ SH~T ~~l.E 2~
A
CA 02167373 1999-08-02
of alkyl groups and hydroxyalkyl groups containing from about 1
to about 3 carbon atoms; and water-soluble sulfoxides
containing one alkyl 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
O
R3 ( ORs ) ,~I1 ( RS ) a
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, e.g., through
an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C,o-Cle
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%,
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 1% by weight, preferably from
about 3% to about 65%, more preferably from about 10% to about
25% by weight of total surfactants.
16 ;~ ~~
A second class of detergent ingredients that has found to
provide enhanced dye transfer inhibiting benefits are enzymes
selected from peroxidases, cellulases or 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 w 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-2.0?5.028 : 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 50KDa,~: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 No. 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.
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 immunoligical cross-reaction with the antibody of the
17
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 Lipolase (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 Canadian Patent Application No. 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.
Other 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,
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
v
1a
mg to about 3 mg, of active enzyme per gram of the
composition.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of H.subtilis and
B.licheniforms. 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.
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, Rapidase, Maxamyl (International Bio-Synthetics,
Inc.) and Termamyl, (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, cal-cium formate and calcium
propionate. Calcium ions can ~-be used in combination:v.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
19 ~ ~ ~~ ~ ~ ~ .
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. Patents 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.
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 .O 508
034 and polyamine-N-oxide containing polymers such as
described in Canadian Patent Application No. 2, 140, 289 filed June
30, 1998. 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
20
typically be from about O.lo 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
about 50°C, especially below about 40°C, with a detergent
composition cc:~=aining N-vinylimidazole N-vinylpyrrolidone
copolymers in cc:nbination 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, 9-nonylamino-4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such
bleaching agents are disclosed in U.S. Patent 4,483;'781,
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. Examp~le's 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 1-5$ by weight.
Prefe,rably, the bleaches suitable for the present invention
include peroxygen bleaches. Examples of-suitable water-soluble
solid peroxygen,bleaches include hydrogen peroxide releasing
21
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
tetraacetylethylenediamine (TAED), nonanoyloxybenzene-
sulfonate (NOHS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate (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 Canadian Patent
Application No. 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 2inc
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
2167373
WO 95/03382 PCT/US94I06951 -
22
photoactivated bleaching process are described in U.S. Patent
4,033,718. Typically, detergent compositions will contain
about 0.025o to about 1.250, 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
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 phosphonic 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).
SUBSnTUTE SH~T (~11~.E 28~
2167373
"''~O 95/03382 PCT/US94/06951
23
Suitable polycarboxylates containing one carboxy group
include lactic acid, glycolic acid and ether derivat;-~es
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, maleic 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 particular, water-soluble citrates,
aconitrates and citraconates as well as succinate derivatives
such as the carboxymethyloxysuccinates described in British
Patent No. 1,379,241, lactoxysuccinates described in
Netherlands Application 7205873, and the oxypolycarboxylate
materials such as 2-oxa-1,1,3-propane tricarboxylates
described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Patent No. 1,261,829,
1,1,2,2-ethane ~ tetracarboxylates, 1,1,3,3-propane
tetracarboxylates 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 No. 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
cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide
pentacarboxylates, 2,3,4,5-tetrahydro-furan - cis, cis, cis-
tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates,
2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-
hexane -hexacarboxylates and and carboxymethyl derivatives of
polyhydric alcohols such as sorbitol, mannitol and xylitol.
Aromatic poly-carboxylates include mellitic acid, pyromellitic
SUBSTintf~ SHE~T (~ti~.E 2~
WO 95103382 2 1 6 7 3 7 3 pCT~S94/06951
24
acid and the phtalic acid derivatives disclosed in British
Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are
hydroxycarboxylates 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.
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,
SUBSTITUtE SHEET (~llf.E Z~
2167373
" 'O 95/03382 PCT/US94/06951
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 GH-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000 and
their copolymers with maleic anhydride, such copolymers having
a molecular weight of from 20,000 to 70,000, especially about
40, 000.
Detergency builder salts are normally included in amounts of
from l0o to 80o by weight of the composition preferably from
20~ 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
SUBSTITUf~ SHEET (~tfl.E 2~
26
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 R.
Such suds suppressor system are described in Canadian Patent
Application No. 2,146,636 filed October 15, 1993.
Especially preferred silicone suds controlling agents are
described in EP 573,699 published June 6, 1992.
Said compositions can comprise a silicone/silica mixture in
combination with fumed nonporous silica such as Aerosil~.
The suds suppressors described above are normally employed
at levels of from 0.001'k 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 won-
encapsulated perfumes.
Antiredeposition and soil suspension agents suitable_herein
include cellulose derivatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcell_ulose, and homo-.or
co-polymeric polycarboxylic acids, or their salts. Polymers of
this _type include the polyacrylates and maleic-.anhydride-
acrylic acid copolymers previously mentioned.as builders, as
well as copolymers of maleic. anhydride with ethylene,
methylvinyl ether. or methacryli;c acid, the .:maleic 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.
Pre,ferred ,optical brighteners are~ anionic in character,
examples of, which are disodium 4,41-bis-(2-diethanolamino-4-
~~O 95/03382
216 7 3 7 3 p~/ZJS94/06951
27
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.
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 0.25o to 2.5o 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) 0.4] T (PO
H)0.25((PEG)43CH3)0.75
where PEG is - (OC2H4 ) 0-, PO is (OC3H60) and T is (pcOC6H4C0) .
SUBSTiTUTf SHf E'f (~Rt~.E 2~
_..
28
Also very useful are modified polyesters as random
copolymers of dimethyl terephtalate; dimethyl
sulfoisophthalate, 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.
The selected polyesters herein contain about 96% 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 sulfoisophthalic 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
"°"'O 95/03382 PCT/US94/06951
29
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 300, 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
solubilized and suspended dyes encountered during fabric
laundering operations involving colored fabrics.
The 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.
SUBSTmJTF SHf ~T (~lfl.E 2~
216 7 3 7 3 PCT/US94I06951
WO 95103382
The following examples are meant to exemplify compositions
of ~he 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.
SUBST1TUTE SHEET (~111.E 2~
31
EXAMPLE 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 - ' S - 3
Alkyl alkoxylated sulfate - - g 4
Alkyl sulphate 4 8 4 15
Fatty alcohol (C12-C15) 12 12 ~ 12 5
ethoxylate
Fatty acid 10 10 10 10
,
Oleic acid 4 4 4 -
Citric acid _ 1 1 1 1
Diethylenetriaminepenta 1.5 1.5 1.5 1.5
methylene
Phosphonic acid
NaOH 3.4 3.9 3.4 3.4
Propanediol 1.5 1.5 1.5 , 1.5
Ethanol 10 10 10 10
Ethoxylated tetraethylene 0.7 0.7 0:7 0.7
pentamine
Thermamyl 300 KNU/g 0.1 0.1 0.1 0.1
Carezyme 5000 CEVtT/g . 0.02 0.02 0:02 0.02
Protease 40 mg/g 1.8 1.8 ~ 1.8 1.8
Lipolase~ 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
..
CA 02167373 1999-08-02
32
EXAMPLE II (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 _ _ g 4
Alkyl sulphate 4 8 4 15
Fatty alcohol (C12-Cls) 12 12 12 5
ethoxylate
Fatty acid 10 10 10 10
Oleic acid 4 4 4 -
Citric acid 1 1 1 1
Diethylenetriaminepenta 1.5 1.5 1.5 1.5
methylene
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 0.7 0.7 0.7 0.7
pentamine
Thermamyl~ 300 KNU/g 0.1 0.1 0.1 0.1
Carezyme~ 5000 CEVLJ/g 0.02 0.02 0.02 0.02
Protease 40 mg/g 1.8 1.8 1.8 1.8
Lipolase~ 100 KLU/g 0.1 0.1 0.1 0.1
Endoglucanase A 5000 CEVL1/g 0.5 0.5 0.5 0.5
Suds supressor (ISOFOLr) 2.5 2.5 2.5 2.5
Hz02 7.5 7.5 - _
N-vinylimidazole N-vinyl 0.1-1 0.1-1 0.1-10.1-1
pyrrolidone copolymer
Metallo catalyst 0.1-1 0.1-1 0.1-10.1-1
Poly (4-vinylpyridine)-N-oxide 0.1-1 0.1-1 0.1-10.1-1
Clay - - 4 4
peroxidase 0.1 0.1 -
Minors up 100
to
2167373
°"'O 95/03382 PCT/US94/06951
33
EXAMPLE III (A/s/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 H C D E
Linear alkyl benzene 11.40 - - - -
sulphonate
Polyhydroxy fatty acid - 10 - - -
amide
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 4.00 4.00 4.00 4.00 4.00
ethoxylate
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 penta 0.6 0.6 0.6 0.6 0.6
nethylene phosphonic acid
Maleic 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
SUBSnTUI~ SH'EET (~1LE 2~
WO 95/03382
21 b 7 3 7 3 PCT/US94/06951
34
EXAMPLE IV (A/s/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 H C D E
Linear alkyl benzene 11.40 - - - -
sulphonate
Polyhydroxy fatty acid - 10 - - -
amide
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 4.00 4.00 4.00 4.00 4.00
etoxylated
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 penta- 0.6 0.6 0.6 0.6 0.6
nethylene phosphonic aci d
Maleic 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 -
SUBSTtTUTE SH~T (~lfl.E 2~
~'"''O 95/03382 216 7 3 7 3 p~~s94/06951
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)- 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1
N-N-oxide
Clay - - - 4 4
peroxidase - 0.1 0.1 - -
Minors up to 100
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.
e~
SUBSnTiJT~ SHE~T (~lfl.E 2~
