Note: Descriptions are shown in the official language in which they were submitted.
21873p~
BLEACH COMPOSITIONS COMPRISING PROTEASE ENZYME
TECHNICAL FIELD
The present invention relates to cleaning and bleaching compositions which
employ protease enzymes to boost performance especially on dingy stains and
soil.
Bleaching, fabric laundering, automatic dishwashing and sanitizing
compositions with
improved bleach activity are provided.
BACKGROUND OF THE INVENTION
It has been found that certain levels of bleach activators and peroxygen
bleaching compounds can be used with certain levels of protease enzymes in
bleaching compositions to obtain surprisingly effective dingy soil clean-up.
The
combined effect of the bleach activators, peroxygen bleaching compound and the
proteases, which hydrolyzes protein based stains, is greater in this bleaching
composition than expected, especially in light of the fact that bleach is
known to
oxidize enzymes. Without meaning to be limited by theory, it is believed that
at these
levels, there is a synergy between the bleach activator/peroxygen bleaching
compound and the protease so that the combined cleaning effect of the two is
greater
than the additive effect of each one separately.
Accordingly, it is an object of the present invention to provide improved
cleaning and bleaching compositions using bleaching compounds and protease
enzymes. It is another object herein to provide a means for removing dingy
soils and
stains from fabrics using the bleaching systems and protease enzymes of this
invention. These and other objects are secured herein, as will be seen from
the
following disclosures.
BACKGROUND ART
The use of amido-derived bleach activators in laundry detergents is described
in U.S. Patent 4,634,551. Lactam activators are described in Canadian
Application
Serial Nos. 2,161,266 and 2,161,214, EP 699,230 and EP 705,326.
Protease enzymes are described in EP 451,244; U.S. Patent No. 5,185,250; U.S.
Patent No. 5,204,015; and Canadian Application Serial No. 2,173,106.
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_, , 21873Q5
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SLTIyQyiARY OF THE INVENTION
The present invention encompasses bleach compositions which provide dingy
clean-up comprising protease enzymes, a bleach compound capable of yielding
hydrogen peroxide in an aqueous liquor, and one or more bleach activators,
such that
S the combined performance of the bleach activator/bleaching compound and the
protease enzyme as measured by the Hunter Whiteness Value is more than
additive;
and wherein further such compositions do not comprise nonanoyloxyben-
zenesulfonate (HOBS) as the sole bleach activator.
Modified protease bacterial serine protease enzymes obtained from Bacillus
subtili , Bacillus lentus or Bacillus licheniformis are preferred. Said
enzymes
comprise at least about 0.001%, preferably from about 0.001% to about 5%, of
the
detergent compositions.
In a particularly preferred embodiment the protease enzyme is selected from
the '
group consisting of a protease enzyme having N76D/S 103A/V 104I subtilisin
variant
derived from Bacillus lentus subtilisin, a protease enzyme having K27R/V
104I/N 1235/
T274A subtilisin variant derived from Bacillus lentus subtilisin and mixtures
thereof.
Preferred bleaching agents are ~~ers selected from the group consisting of
H202, perborate, percarbonate, persulfate and mixtures thereof. Particularly
preferred bleaching agents comprise percarbonate or perborate bleach, or
mixtures
thereof. Preferred bleach activators are selected from acyl lactam-type
activators,
amido-derived activators, alkanoyloxybenzenesulfonates, and mixtures thereof.
Particularly preferred activators which are employed in the present invention
include benzoyl caprolactam, nonanoyl caprolactam, benzoyl valerolactam,
nonanoyl valerolactain, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5-trimethyl-
hexanoyl valerolactam, octanoyl caprolactam; octanoyl valerolactam, decanoyl
caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl
valerolactam, (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)-
oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, benzoyloxy-
benzenesulfonate, and mixtures thereof. Examples of highly preferred
substituted
benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl valerolactam,
ethylbenzoyl caprolactam, ethylbenzoyl valerolactam, propylbenzoyl
caprolactam,
propylbenzoyl valerolactam, isopropylbenzoyl caprolactam, isopropylbenzoyl
valerolactam, butylbenzoyl caprolactam, butylbenzoyl valerolactam, tert-
butylbenzoyl caprolactam, tert-butylbenzoyl valerolactam, pentylbenzoyl
3 5 caprolactam, pentylbenzoyl valerolactam, hexylbenzoyl caprolactam,
hexylbenzoyl
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21873p5
2a
valerolactam, ethoxybenzoyl caprolactam, ethoxybenzoyl valerolactam,
propvxybenzoyl caprolactam, propoxy-benzoyl valerolactam, isopropoxybenzoyl
caprolactam, isopropoxybenzoyl valero-lactam, butoxybenzoyl caprolactam,
butoxybenzoyl valerolactam, tert-butoxy-benzoyl caprolactam, tert-
butoxybenzoyl
valerolactam, pentoxybenzoyl capro-lactam, pentoxybenzoyl valerolactam,
hexoxybenzoyl caprolactam, hexoxybenzoyl valerolactam, 2,4,6-trichlorobenzoyl
IS
25
35
21873p5
3
capr~lactam, 2,4,6-trichlorobenzoyl valerolactam, pentafluorobenzoyl
caprolactam,
pentafluorobenzoyl valerolactam, dichlorobenzoyl caprolactam, dimethoxybenzoyl
caprolactam, 4-chlorobenzoyl caprolactam, 2,4-dichlororbenzoyl caprolactam,
terephthaloyl dicaprolactam, pentafluorobenzoyl caprolactam,
pentafluorobenzoyl
valerolactam, dichlorobenzoyl valerolactam, dimethoxybenzoyl valerolactam, 4
chlorobenzoyl valerolactam, 2,4-dichlorobenzoyl valerolactam, terephthaloyl
divalerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam,
dinitro
benzoyl caprolactam, dinitrobenzoyl valerolactam, and mixtures thereof. The
compositions herein may also comprise NOES, but not as the sole bleach
activator
present in the bleaching composition.
Particularly preferred are bleach activators selected from the group
consisting of benzoyl caprolactam, benzoyl valerolactam, nonanoyl caprolactam,
nonanoyl valerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl
valerolactam,
octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl
valerolactam, undecanoyl caprolactam, undecanoyl valerolactam, 3,5,5-trimethyl-
hexanoyl caprolactam, 3,5,5-trimethylhexanoyl valerolactam, dinitrobenzoyl
capro-
lactam, dinitrobenzoyl valerolactam, terephthaloyl dicaprolactam,
terephthaloyl
divalerolactam, (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamido-
caproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, ben-
zoyloxybenzenesulfonate, and mixtures thereof.
Preferably, the molar ratio of hydrogen peroxide yielded by the peroxygen
bleaching compound to bleach activator is greater than about 1Ø Most
preferably,
the molar ratio of hydrogen peroxide to bleach activator is at least about
1.5.
The invention also encompasses detergent compositions, especially laundry
detergents, comprising otherwise conventional surfactants and other detersive
ingredients.
All percentages, ratios and proportions herein are by weight, unless otherwise
specised.
DETAILED DESCRIPTION OF THE INV',ENTION
Without limitation by theory, it is believed that dingy soils and stains are
the
result of combinations of fatty soils and particulate soils. Fatty soils
comprise lipids,
proteins, and pigments that are deposited on fabrics from contact with human
or
animal skin. The majority of lipids are secreted from the sebecous gland as
sebum.
Proteins and pigments from skin fragments are liberated by the breakdown of
skin
cells. Particulate soils comprise mostly airborne soil and floor/ground dust.
It is
believed that sebum is the major soil present on laundry, and its removal is
important
because unremoved fat acts as a matrix to hold particulate soils. Further it
is
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_ 21873p5
4
believed that compounds present in the sebum oxidize to contribute to
yellowing of
fabrics. Particulate soils include topsoil and products produced during the
incomplete combustion of petroleum products.
The performance on dingy clean-up can be measured in terms of the Hunter
Whiteness Values (W), which is calculated according to the following equation:
W=(7L2-40Lb)/700
wherein L,a,b are determined from a tristimulus meter reading and represent a
three
axis opponent color scale system based on the theory that color is perceived
by
black-white (L), red-green (a), and yellow-blue (b) sensations. The higher the
value
for W, the better the whiteness performance and dingy clean-up. See R. S.
Hunter
and R. W. Harold, The Measurement of Ap earance, Second Ed., John Wiley &
Sons, New York, 1987 and ATM Standards on Color and A~nearance
Measurement, Third Ed., ASTM, Philadelphia, PA, 1991.
Compositions of the present invention comprise protease enzyme and bleach
activator/bleach compounds at levels such that the Hunter Whiteness Value for
the
composition is more than additive, i.e., the W for the composition is greater
than
the sum of the W s for compositions without protease plus the W's for
compositions without the bleach activator/bleach compound as determined by a
statistically significant number of tests.
Protease enzymes Protease enzymes are usually present in such commercial
preparations at levels sufficient to provide at least about 0.005 Anson units
(ALI) of
activity per gram of composition. Therefore, said enzymes comprise at least
about
0.001%, preferably from about 0.001% to about 5%, of the detergent
compositions.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B.subtilis, B.lentus and B.licheniforms. Another
suitable
protease is a modified bacterial serine protease enzyme obtained from Bacillus
sub ilis or Bacillus licheniformis, having maximum activity throughout the pH
range of 8-12, developed and sold by Novo Industries A/S under the
trade mark ESPERASE. The preparation of this enzyme and analogous enzymes is
described in British Patent Specification No. 1,243,784 of Novo. Proteolytic
enzymes suitable for removing protein-based stains that are commercially
available
include those sold under the trademarks ALCALASE and SAVINASE by Novo
Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc.
(The Netherlands). Other proteases include Protease A (see European Patent
Application 130,756, published January 9, 1985) and Protease B (see European
Patent Application 251,446 published January 7, 1988, and European
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21873p5
Patent Application 130,756, Bott et al, published January 9, 1985). Most
preferred
is what is called herein "Protease C", which is a variant of an alkaline
serine
protease from Bacillus, particularly Bacillus lentus, in which arginine
replaced
lysine at position 27, tyrosine replaced valise at position 104, serine
replaced
5 asparagine at position 123, and ala,nine replaced threonine at position 274.
Protease C is described in EP 451,244; U.S. Patent No. 5,185,250; and U.S.
Patent No. 5,204,015. Also preferred are protease which are described in
Canadian Application Serial No. 2,173,106 entitled Bleaching Compositions
Comprising
Protease Enzymes. Genetically modified variants, particularly of Protease C,
are also
included herein.
Bleaching Compounds- Bleaching compositions herein contain bleaching
mixtures containing a bleaching agent and one or more bleach activators, in an
amount sufficient to provide bleaching of the stain or stains of interest.
Bleaching
agents will typically be at levels of from about 1% to about 80%, more
typically from
about 5% to about 20%, of the detergent composition, especially for fabric
laundering. Bleach and pre-soak compositions may comprise from 5% to 99% of
the
bleaching agent. 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
mixture comprising the bleactung agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for
detergent compositions in textile cleaning, hard surface cleaning, or other
cleaning
purposes that are now known or become known. These include oxygen bleaches as
well as other bleaching agents. Perborate bleaches, e.g., sodium perborate
(e.g.,
mono- or tetra-hydrate) can be used herein.
Peroxygen bleaching agents are preferably used in the compositions. Suitable
peroxygen bleaching compounds include sodium carbonate peroxyhydrate and
equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g.OXONETM,
manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about 1,000
micrometers,
not more than about 10% by weight of said particles being smaller than about
200
micrometers and not more than about 10% by weight of said particles being
larger
than about 1,250 micrometers. Optionally, the percarbonate can be coated with
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2187305
6
silicate, borate or water-soluble surfactants. Percarbonate is available from
various
commercial sources such as FMC, Solvay and Tokai Denka.
The compositions of the present invention may also comprise mixtures of
bleaching activators.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably combined with bleach activators, which lead to the in situ
production in
aqueous solution (i.e., during the washing process) of the peroxy acid
corresponding
to the bleach activator.
Alkanoyloxybenzenesulfonates - Suitable alkanoyloxybenzenesulfonate bleach
activators which can be employed in the present invention are of the formula:
O
n
Rt-C-0 O S03M
wherein R1-C(O)- contains from about 8 to about 12 carbon atoms (provided that
when R1 is nonanoyl the compositions herein comprise at least one other bleach
activator) and ~M is a suitable ration, such as an alkali metal, ammonium, or
substituted ammonium ration, with sodium and potassium being most preferred.
I~ghly preferred hydrophobic alkanoyloxybenzenesulfonates are selected from
the group consisting of 3,5,5-trimethylhexanoyloxybenzenesulfonate, 2-ethyl-
hexanoyloxybenzenesulfonate, octanoyloxybenzenesulfonate, decanoyloxybenzene-
sulfonate, dodecanoyloxybenzenesulfonate, and mixtures thereof.
Amido Derived Bleach Activators - The amido derived bleach activators
which can be employed in the present invention are amide substituted compounds
of the general formulas:
O O O 0
R~--C-N-RZ-C-L, R~-N-C-R2-C-L
~I I
R5 Rs
or mixtures thereof, wherein R~ is an alkyl, aryl or alkaryl group containing
from about 1 to about 14 carbon atoms, RZ is an alkylene, arylene or
alkarylene group containing from about 1 to about 14 carbon atoms, RS is H or
an alkyl,
aryl or alkaryl group containing from about 1 to about 10 carbon atoms and L
can be
2107305
6a
essentially any suitable leaving group. A leaving group is any group that is
displaced from the bleaching activator as a consequence of the nucleophilic
attack
on the bleach activator by the perhydroxide anion. This, the perhydrolysis
reaction,
results in the formation of the peroxycarboxylic acid. Generally, for a group
to be
a suitable leaving group it must exert an electron attracting effect. It
should also
fonm a stable entity so that the rate of the back reaction is negligible. This
facilitates the nucleophilic attack by the perhydroxide anion.
The L group must be sufficiently reactive for the reaction to occur within the
optimum time frame (e.g., a wash cycle). However, if L is too reactive, this
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WO 95/29225 ~ PCT/(TS95103725
activator will be difficult to stabilize for use in a bleaching composition.
These
characteristics are generally paralleled by the pKa of the conjugate acid of
the
leaving group, although exceptions to this convention are known. Ordinarily,
leaving groups that exhibit such behavior are those in which their conjugate
acid
has a pKa in the range of from about 4 to about 13, preferably from about 6 to
about 11 and most preferably from about 8 to about 11.
Preferred bleach activators are those of the above general formula wherein
R1, R2 and RS are as defined for the peroxyacid and L is selected from the
group
consisting of
Y R3 R3Y
-0 , -0 ~ Y , and -O
0 1 O a
-N-C-R -N N -N-C-CH-R
I ~ ~ I I ,
R3 ~ R3 Y
I
Y
R3 Y
-O-C H=C -C H=C H2 -O-C H=C -C H=C H2
p Y O
0 C H2-C\ ~ ~NR4
_0-C-R~ -fV~ /NR4 -N~.C/
O ~ O
R3 O Y
I II I
-O-C=C HR4 , and -N-S-C H-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from
about 1 to about 14 carbon atoms, R3 is an alkyl chain containing from 1 to
about
8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
+ She preferred solubi3zing groups are -S03 M+, -CO~ M+, -S04 M+,
-N (R )4X and O<--N(R )3 and most preferably -S03-M and -C02-M+
wherein R3 is an alkyl chain containing from about 1 to about 4 carbon atoms,
M is
a cation which provides solubility to the bleach activator and X is an anion
which
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WO 95/29225
PCT/US95/03725
8
provides solubility to the bleach activator. Preferably, M is an alkali metal,
ammonium or substituted ammonium cation, with sodium and potassium being
most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
It
should be noted that bleach activators with a leaving group that does not
contain a
S solubilizing groups should be well dispersed in the bleaching solution in
order to
assist in their dissolution.
Preferred bleach activators are those of the above general formula wherein L
is selected from the group consisting of.
Y R3 RsY
-0 ~ , -O ~ Y , and -0
wherein R3 is as defined above and Y is -S03-M+ or -C02-M+ wherein M is as
defined above.
Preferred examples of bleach activators of the above formulae include (6-
octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfo-
nate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
Another important class of bleach activators provide organic peracids as
described herein by ring-opening as a consequence of the nucleophilic attack
on the
carbonyl carbon of the cyclic ring by the perhydroxide anion. For instance,
this
ring-opening reaction in lactam activators involves attack at the lactam ring
carbonyl by hydrogen peroxide or its anion. Since attack of an acyl lactam by
hydrogen peroxide or its anion occurs preferably at the exocyclic carbonyl,
obtaining a significant fraction of ring-opening may require a catalyst.
When the activators are used, optimum surface bleaching performance is
obtained with washing solutions wherein the pH of such solution is between
about
8.5 and 10.5 and preferably between 9.5 and 10.5 in order to facilitate the
perhydrolysis reaction. Such pH can be obtained with substances commonly
known as buffering agents, which are optional components of the bleaching
systems herein.
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
0 0
O C -C H2-C H2 O C -C H2-C H2
R6-C-N~ ~CH2 R6-C-N~ I
3 0 C H2-C H2 C H2-C H2
wherein R6 is H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from
1 to
about 12 carbon atoms, or a substituted phenyl group containing from about 6
to
r
21873 05
9
about 18 carbons. See Canadian Application Serial No. 2,161,214 and EP
705,326,
which disclose substituted benzoyl lactams. See also U.S. Patent 4,545,784,
issued to
Sanderson, October 8, 1985 which discloses acyl caprolactams, including
benzoyl
caprolactam, adsorbed into sodium perborate.
Various nonlimiting examples of activators which may also comprise the
bleach compositions disclosed herein include those in U.S. Patent 4,915,854,
issued
April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. See also U.S.
4,634,551 for
other typical bleaches and activators useful herein.
Ad~,unct Ingredients
. The compositions herein can optionally include one or more other detergent
adjunct materials or other materials for assisting or enhancing cleaning
performance,
treatment of the substrate to be cleaned, or to modify the aesthetics of the
detergent
composition (e.g., perfumes, colorants, dyes, etc.). The following are
illustrative
examples of such adjunct materials.
Detersive Surfactants - Nonlimiting examples of surfactants useful in
detergent compositions herein typically at levels from about 1% to about 55%,
by
weight, include the conventional C 11-C 1 g alkyl benzene sulfonates ("LAS")
and
primary, branched-chain and random C 10-C2p alkyl sulfates ("AS "), the C 10-C
18
secondary (2,3) alkyl sulfates of the formula CH3(CH2~(CHOS03-M+) CH3 and
CH3 (CH2h,(CHOS03-M+) CH2CH3 where x and (y + 1) are integers of at least
about 7, preferably at least about 9, and M is a water-solubilizing canon,
especially
sodium, unsaturated sulfates such as oleyl sulfate, the C l0-C 1 g alkyl
alkoxy sulfates
("AEXS"; especially EO I-7 ethoxy sulfates), C 10-C 1 g alkyl alkoxy
carboxylates
(especially the EO 1-5 ethoxycarboxylates), the C 10-I 8 BIYcerol ethers, the
C l 0-C 1 g
alkyl polyglycosides and their corresponding sulfated polyglycosides, and C 12-
C 18
alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and
amphoteric surfactants such as the C I2-C 1 g alkyl ethoxylates ("AE")
including the
so-called narrow peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates
(especially ethoxylates and mixed ethoxy/propoxy), C 12-C 1 g betaines and
sulfobetaines ("sultaines"), C 1 p-C 1 g amine oxides, and the like, can also
be included
in the overall compositions. The C l 0-C 1 g N-alkyl polyhydroxy fatty acid
amides can
also be used. Typical examples include the C 12-C 1 g N-methylglucamides. See
WO
9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy
fatty
acid amides, such as C l0-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl
through N-hexyl C 12-C 1 g glucamides can be used for low sudsing. C 1 p-C20
conventional soaps may also be used. If high sudsing is desired, the branched-
chain
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PCT/I1S95/03725
WO 95129225
C 10-C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are
especially useful. Other conventional useful surfactants are listed in
standard texts.
Builders - Detergent builders can optionally be included in the compositions
herein to assist in controlling mineral hardness. Inorganic as well as organic
builders
5 can be used. Builders are typically used in fabric laundering compositions
to assist in
the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically comprise at least about 1% builder. Liquid formulations typically
comprise
10 from about 5% to about 50%, more typically about 5% to about 30%, by
weight, of
detergent builder. Granular formulations typically comprise from about 10% to
about 80%, more typically from about 15% to about 50% by weight, of the
detergent
builder. Lower or higher levels of builder, however, are not meant to be
excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric
meta
phosphates), phosphonates, phytic acid, silicates, carbonates (including
bicarbonates
and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate
builders are required in some locales. Importantly, the compositions herein
function
surprisingly well even in the presence of the so-called "weak" builders (as
compared
with phosphates) such as citrate, or in the so-called "underbuilt" situation
that may
occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates,
such as
the layered sodium silicates described in U.S. Patent 4,664,839, issued May
12, 1987
to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate
marketed
by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders,
the
Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-
Na2Si05 morphology form of layered silicate. It can be prepared by methods
such
as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a
highly preferred layered silicate for use herein, but other such layered
silicates, such
as those having the general formula NaMSix02x+1 ~yH20 wherein M is sodium or
hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0
to 20,
preferably 0 can be used herein. Various other layered silicates from Hoechst
include
NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted
above, the delta-Na2Si05 (NaSKS-6 form) is most preferred for use herein.
Other
silicates may also be useful such as for example magnesium silicate, which can
serve
WO 95/29225 218 7 3 0 5
PCT/US95/03725
as a crispening agent in granular formulations, as a stabilizing agent for
oxygen
bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published
on
November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are of great importance in most currently marketed heavy duty
granular
detergent compositions, and can also be a significant builder ingredient in
liquid
detergent formulations. Aluminosilicate builders include those having the
empirical
formula:
Mz(zA102)y]~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from
1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic
crystalline
aluminosilicate ion exchange materials useful herein are available under the
designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an
especially
preferred embodiment, the crystalline aluminosilicate ion exchange material
has the
formula:
Na 12~(~02) 12(Si02) 12] W20
wherein x is from about 20 to about 30, especially about 27. This material is
known
as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably,
the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds. As
used herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate
groups, preferably at least 3 carboxylates. Polycarboxylate builder can
generally be
added to the composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such as sodium,
potassium,
and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One important category of polycarboxylate builders
encompasses
the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg,
U.S.
Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent
3,635,830,
2187305
12
issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071,
issued to Bush et al, on May S, 1987. Suitable ether polycarboxylates also
include
cyclic compounds, particularly alicyclic compounds, such as those described in
U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other usefi~l detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid, the
various alkali metal, ammonium and substituted ammonium salts of polyacetic
acids
such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as
polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid,
polymaleic
acid, benzene .1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and
soluble
salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium
salt), are polycarboxylate builders of particular importance for heavy duty
liquid
detergent formulations due to their availability from renewable resources and
their
biodegradability. Citrates can also be used in granular compositions,
especially in
combination with zeolite and/or layered silicate builders. Oxydisuccinates are
also
especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in
U.S.
Patent 4,566,984, Bush, issued January 28, 1986. Usefirl succinic acid
builders
include the CS-C20 alkyl and alkenyl succinic acids and salts thereof. A
particularly
preferred compound of this type is dodecenylsuccinic acid. Specific examples
of
succinate builders include: laurylsuccinate, myristylsuccinate,
palmitylsuccinate, 2
dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
Laurylsuccinates are the preferred builders of this group, and are described
in
European Patent Application 200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl,
issued
March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C I 2-C 1 g monocarboxylic acids, can also be incorporated
into the compositions alone, or in combination with the aforesaid builders,
especially
citrate and/or the succinate builders, to provide additional builder activity.
Such use
of fatty acids will generally result in a diminution of sudsing, which should
be taken
into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in
the formulation of bars used for hand-laundering operations, the various
alkali metal
B
2187305
13
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate
and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-
hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S.
Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be
used.
n~g,~ - Optional enzymes can be included in the formulations herein for a
wide variety of fabric laundering purposes, including removal of protein-
based,
carbohydrate-based, or triglyceride-based stains, for example, and for the
prevention
of refugee dye transfer, and for fabric restoration. The enzymes to be
incorporated
include 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. However, their
choice is
governed by several factors such as pH-activity and/or stability optima;
thermostability, stability versus active detergents, builders and so on. In
this respect
bacterial or fungal enzymes are preferred, such as bacterial amylases and
fungal
cellulases.
Enzymes are normally incorporated at levels sufficient to provide up to about
5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme
per
gram of the composition. Stated otherwise, the compositions herein will
typically
comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a
commercial enzyme preparation.
Amylases include, for example, a-amylases described in British Patent
Specification No. 1,296,839 (Novo), RAPIDASE-'~"', International Bio-
Synthetics, Inc.
and TERMAMYL~, Novo Industries.
The cellulase usable in the present invention include both bacterial or fungal
cellulase. Preferably, they will have a pH optimum of between S and 9.5.
Suitable
cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued
March 6,
1984, which discloses fungal cellulase produced from Humicola insolens and
Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the
genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine
mollusk (Dolabella Auricula Solander). suitable cellulases are also disclosed
in GB-
A-2.075.028; GB-A-2.095.275 and DE-OS-2'.247.832. CAREZYME~"' (Novo) is
especially useful.
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. See also lipases in Japanese
Patent
Application 53,20487, laid open to public inspection on February 24, 1978.
This
B
21873p5
14
lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under
the
trade mark Lipase P "Amano," hereinafter referred to as "Amano-P." Other
commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.
Chromobacter viscosum var. lipolyticum NR.R.LB 3673, commercially available
from
Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from
U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. The LIPOLASE'~"'' enzyme derived from Humicola
lanuginosa
and commercially available from Novo (see also EPO 341,947) is a preferred
lipase
for use herein.
Peroxidase enzymes are used in combination with oxygen sources, e.g.,
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching," i.e. to prevent transfer of dyes or pigments removed
from
substrates during wash operations to other substrates in the wash solution.
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, published October 19, 1989, by O.
Kirk,
assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation into
synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139,
issued
January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S.
P=.~.~nt
4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219,
Hughes,
issued March 26, 1985, both. Enzyme materials useful for liquid detergent
formulations, and their incorporation into such formulations, are disclosed in
U.S.
Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in
detergents
can be stabilized by various techniques. Enzyme stabilization techniques are
disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to
Gedge, et al, and European Patent Application Publication No. 0 199 405,
published October 29, 1986, Venegas. Enzyme stabilization systems are also
described,
for example, in U.S. Patent 3,519,570.
Enzyme Stabilizers - The enzymes employed herein are stabilized by the
presence of water-soluble sources of calcium and/or magnesium ions in the
finished
compositions which provide such ions to the enzymes. (Calcium ions are
generally
somewhat more effective than magnesium ions and are preferred herein if only
one
type of cation is being used.) Additional stability can be provided by the
presence of
various other art-disclosed stabilizers, especially borate species: see
Severson, U.S.
4,537,706. Typical detergents, especially liquids, will comprise from about 1
to
WO 95129225 PCT/US95/03725
about 30, preferably from about 2 to about 20, more preferably from about 5 to
about 15, and most preferably from about 8 to about 12, millimoles of calcium
ion
per liter of finished composition. This can vary somewhat, depending on the
amount
of enzyme present and its response to the calcium or magnesium ions. The level
of
5 calcium or magnesium ions should be selected so that there is always some
minimum
level available for the enzyme, after allowing for complexation with builders,
fatty
acids, etc., in the composition. Any water-soluble calcium or magnesium salt
can be
used as the source of calcium or magnesium ions, including, but not limited
to,
calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium
10 hydroxide, calcium formate, and calcium acetate, and the corresponding
magnesium
salts. A small amount of calcium ion, generally from about 0.05 to about 0.4
millimoles per liter, is often also present in the composition due to calcium
in the
enzyme slurry and formula water. In solid detergent compositions the
formulation
may include a sufficient quantity of a water-soluble calcium ion source to
provide
15 such amounts in the laundry liquor. In the alternative, natural water
hardness may
since.
It is to be understood that the foregoing levels of calcium and/or magnesium
ions are sufficient to provide enzyme stability. More calcium and/or magnesium
ions
can be added to the compositions to provide an additional measure of grease
removal
performance. Accordingly, as a general proposition the compositions herein
will
typically comprise from about 0.05% to about 2% by weight of a water-soluble
source of calcium or magnesium ions, or both. The amount can vary, of course,
with
the amount and type of enzyme employed in the composition.
The compositions herein may also optionally, but preferably, contain various
additional stabilizers, especially borate-type stabilizers. Typically, such
stabilizers
will be used at levels in the compositions from about 0.25% to about 10%,
preferably
from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by
weight of boric acid or other borate compound capable of forming boric acid in
the
composition (calculated on the basis of boric acid). Boric acid is preferred,
although
other compounds such as boric oxide, borax and other alkali metal borates
(e.g.,
sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
Substituted boric acids (e.g., phenylboronic acid, butane boronic acid, and p-
bromo
phenylboronic acid) can also be used in place of boric acid.
Polymeric Soil Release Agent - Any polymeric soil release agent known to
those skilled in the art can optionally be employed in the compositions and
processes
of this invention. Polymeric soil release agents are characterized by having
both
hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such
as
1
WO 95/29225 PCT/US95/03725
16
polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic
fibers
and remain adhered thereto through completion of washing and rinsing cycles
and,
thus, serve as an anchor for the hydrophilic segments. This can enable stains
occurring subsequent to treatment with the soil release agent to be more
easily
cleaned in later washing procedures.
The polymeric soil release agents useful herein especially include those soil
release agents having: (a) one or more nonionic hydrophile components
consisting
essentially of (i) polyoxyethylene segments with a degree of polymerization of
at least
2, or (ii) oxypropylene or polyoxypropylene segments with a degree of
polymerization of from 2 to 10, wherein said hydrophile segment does not
encompass
any oxypropylene unit unless it is bonded to adjacent moieties at each end by
ether
linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and
from 1 to
about 30 oxypropylene units wherein said mixture contains a sufficient amount
of
oxyethylene units such that the hydrophile component has hydrophilicity great
enough to increase the hydrophilicity of conventional polyester synthetic
fiber
surfaces upon deposit of the soil release agent on such surface, said
hydrophile
segments preferably comprising at least about 25% oxyethylene units and more
preferably, especially for such components having about 20 to 30 oxypropylene
units,
at least about 50% oxyethylene units; or (b) one or more hydrophobe components
comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said
hydrophobe
components also comprise oxyethylene terephthalate, the ratio of oxyethylene
terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii)
C4-C6
alkylene or oxy C4-C6 alkylene segments, or mixtures therein, (iii) poly
(vinyl ester)
segments, preferably polyvinyl acetate), having a degree of polymerization of
at least
2, or (iv) C1-C4 alkyl ether or Cg hydroxyalkyl ether substituents, or
mixtures
therein, wherein said substituents are present in the form of C1-C4 alkyl
ether or C4
hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such
cellulose
derivatives are amphiphilic, whereby they have a sufficient level of C1-C4
alkyl ether
and/or Cg hydroxyalkyl ether units to deposit upon conventional polyester
synthetic
fiber surfaces and retain a sufficient level of hydroxyls, once adhered to
such
conventional synthetic fiber surface, to increase fiber surface
hydrophilicity, or a
combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of
polymerization of from about 200, although higher levels can be used,
preferably
from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4-C6
alkylene hydrophobe segments include, but are not limited to, end-caps of
polymeric
soil release agents such as M03S(CH2)nOCH2CH20-, where M is sodium and n is
. ? 21873p5
17
an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26,
1988
to Gosselink.
Polymeric soil release agents useful in the present invention also include
cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric
blocks
of ethylene terephthalate or propylene terephthalate with polyethylene oxide
or
polypropylene oxide terephthalate, and the like. Such agents are commercially
available and include hydroxyethers of cellulose such as METHOCEL (Dow).
Cellulosic soil release agents for use herein also include those selected from
the
group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent
4,000,093, issued December 28, 1976 to Nicol, et al.
Soil release agents characterized by polyvinyl ester) hydrophobe segments
include graft copolymers of polyvinyl ester), e.g., C 1-C6 vinyl esters,
preferably
polyvinyl acetate) grafted onto polyalkylene oxide backbones, such as
polyethylene
oxide backbones. See European Patent Application 0 219 048, published April
22,
1987 by Kud, et al. Commercially available soil release agents of this kind
include
the SOKALAN"'~ type of material, e.g., SOKALAN HP-22, available from BASF
(West
Germany).
One type of preferred soil release agent is a copolymer having random blocks
of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The
molecular
weight of this polymeric soil release agent is in the range of from about
25,000 to
about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S.
Patent 3,893,929 to Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat
units
of ethylene terephthalate units contains 10-I S% by weight of ethylene
terephthalate
units together with 90-80% by weight of polyoxyethylene terephthalate units,
derived
from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples
of
this polymer include the commercially available material ZELCON~ 5126 (from
Dupont) and MILEASE~ T (from ICI). See also U.S. Patent 4,702,857, issued
October
27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated product of a
substantially linear ester oligomer comprised of an oligomeric ester backbone
of
terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently
attached to the backbone. These soil release agents are described fully in
U.S. Patent
4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other
suitable polymeric soil release agents include the terephthalate polyesters of
U.S.
Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-
capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to
2187305
is
Gosselink, and the block polyester oligomeric compounds of U.S. Patent
4,702,857,
issued October 27, 1987 to Gosselink.
Preferred polymeric soil release agents also include the soil release agents
of
U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which
discloses
anionic, especially sulfoarolyl, end-capped terephthalate esters.
If utilized, soil release agents will generally comprise from about 0.01% to
about 10.0%, by weight, of the detergent compositions herein, typically from
about
0.1% to about 5%, preferably from about 0.2% to about 3.0%.
Still another preferred soil release agent is an oligomer with repeat units of
terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-
propylene units. The repeat units form the backbone of the oligomer and are
preferably terminated with modified isethionate end-caps. A particularly
preferred
soil release agent of this type comprises about one sulfoisophthaloyl unit, 5
terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio
of from
about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-
ethanesulfonate. Said soil release agent also comprises from about 0.5% to
about
20%, by weight of the oligomer, of a crystalline-reducing stabilizer,
preferably
selected from the group consisting of xylene sulfonate, cumene sulfonate,
toluene
sulfonate, and mixtures thereof.
Chelatin~AQents - The detergent compositions herein may also optionally
contain one or more iron and/or manganese chelating agents. Such chelating
agents
can be selected from the group consisting of amino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents and
mixtures
therein, all as hereinafter defined. Without intending to be bound by theory,
it is
believed that the benefit of these materials is due in part to their
exceptional ability to
remove iron and manganese ions from washing solutions by formation of soluble
chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-
triacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,
ammonium, and
substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at lease low levels of total phosphorus are
permitted in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates) as DEQUESTr"'. Preferred, these amino phosphonates do
not
contain alkyl or alkenyl groups with more than about 6 carbon atoms.
B
PCT/US95/03725
WO 95/29225 ~ g 7 3 ~ 5
19
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et
al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such
as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent
4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1% to
about 10% by weight of the detergent compositions herein. More preferably, if
utilized, the chelating agents will comprise from about 0.1% to about 3.0% by
weight
of such compositions.
C_ lav Soil RemovaUAnti-redeposition Aeents - The compositions of the
present invention can also optionally contain water-soluble ethoxylated amines
having clay soil removal and antiredeposition properties. Granular detergent
compositions which contain these compounds typically contain from about 0.01%
to
about 10.0% by weight of the water-soluble ethoxylates amines; liquid
detergent
compositions typically contain about 0.01% to about 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred
clay
soil removal-antiredeposition agents are the cationic compounds disclosed in
European Patent Application 111,965, Oh and Gosselink, published June 27,
1984.
Other clay soil removaUantiredeposition agents which can be used include the
ethoxylated amine polymers disclosed in European Patent Application 111,984,
Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in
European
Patent Application 112,592, Gosselink, published July 4, 1984; and the amine
oxides
disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other
clay
soil removal and/or anti redeposition agents known in the art can also be
utilized in
the compositions herein. Another type of preferred antiredeposition agent
includes
the carboxy methyl cellulose (CMC) materials. These materials are well known
in
the art.
Polvmenc Di~ersing Agents - Polymeric dispersing agents can
advantageously be utilized at levels from about 0.1% to about 7%, by weight,
in the
compositions herein, especially in the presence of zeolite and/or layered
silicate
builders. Suitable polymeric dispersing agents include polymeric
polycarboxylates
and polyethylene glycols, although others known in the art can also be used.
It is
believed, though it is not intended to be limited by theory, that polymeric
dispersing
1
WO 95/29225 r
PCT/US95/03725
agents enhance overall detergent builder performance, when used in combination
with other builders (including lower molecular weight polycarboxylates) by
crystal
growth inhibition, particulate soil release peptization, and anti-
redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
5 copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic
acid. The presence in the polymeric polycarboxylates herein or monomeric
segments,
10 containing no carboxylate radicals such as vinylmethyl ether, styrene,
ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by
weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the water-
soluble
15 salts of polymerized acrylic acid. The average molecular weight of such
polymers in
the acid form preferably ranges from about 2,000 to 10,000, more preferably
from
about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-
soluble
salts of such acrylic acid polymers can include, for example, the alkali
metal,
ammonium and substituted ammonium salts. Soluble polymers of this type are
20 known materials. Use of polyacrylates of this type in detergent
compositions has
been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7,
1967.
Acrylic/maleic-based copolymers may also be used as a preferred component
of the dispersing/anti-redeposition agent. Such materials include the water-
soluble
salts of copolymers of acrylic acid and malefic acid. The average molecular
weight of
such copolymers in the acid form preferably ranges from about 2,000 to
100,000,
more preferably from about 5,000 to 75,000, most preferably from about 7,000
to
65,000. The ratio of acrylate to maleate segments in such copolymers will
generally
range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
Water-
soluble salts of such acrylic acid/maleic acid copolymers can include, for
example, the
alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate
copolymers of this type are known materials which are described in European
Patent
Application No. 66915, published December I5, 1982, as well as in EP 193,360,
published September 3, 1986, which also describes such polymers comprising
hydroxypropylacrylate. Still other useful dispersing agents include the
maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in
EP
193,360, including, for example, the 45/45/10 terpolymer of
acrylic/maleic/vinyl
alcohol.
21~73,~5
21
Another polymeric material which can be included is polyethylene glycol
(PEG). PEG can exhibit dispersing agent performance as well as act as a clay
soil
removal-antiredeposition agent. Typical molecular weight ranges for these
purposes
range from about 500 to about 100,000, preferably from about 1,000 to about
50,000, more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used,
especially in conjunction with zeolite builders. Dispersing agents such as
polyaspartate preferably have a molecular weight (avg.) of about 10,000.
Brightener - Any optical brighteners or other brightening or whitening agents
known in the art can be incorporated at levels typically from about 0.05% to
about
1.2%, by weight, into the detergent compositions herein. Commercial optical
brighteners which may be useful in the present invention can be classified
into
subgroups, which include, but are not necessarily limited to, derivatives of
stilbene, ,
pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-
dioxide,
azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents.
Examples of such brighteners are disclosed in "The Production and Application
of
Fluorescent Brightening Agents", M. Zahradnik, Published by- John Wiley &
Sons,
New York ( 1982).
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on
December 13, 1988. These brighteners include the PHORWHITETM series of
brighteners from Verona. Other brighteners disclosed in this reference
include:
Tinopal UNPA, Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic
White~'~"'' CC and Artic White CWD, available from Hilton-Davis, located in
Italy; the 2
(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-
stil- benes;
4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these
brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-
2-
yi)ethylene; 1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-
stryl-
napth-[ 1,2-d]oxazole; and 2-(stilbene-4-yl~2H-naphtho- [ 1,2-d]triazole. See
also
U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic
brighteners
are preferred herein.
Suds Suppressors - Compounds for reducing or suppressing the formation of
suds can be incorporated into the compositions of the present invention. Suds
suppression can be of particular importance in the so-called "high
concentration
cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-
loading
European-style washing machines.
WO 95/29225 PCT/US95103725
22
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well known to those skilled in the art. See, for example, Kirk
Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-
447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of
particular
interest encompasses monocarboxylic fatty acid and soluble salts therein. See
U.S.
Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids and salts thereof used as suds suppressor typically
have
hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable salts include the alkali metal salts such as sodium,
potassium, and
lithium salts, and ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight hydrocarbons
such
as paraf~m, fatty acid esters (e.g., fatty acid triglycerides), fatty acid
esters of
monovalent alcohols, aliphatic C 1 g-C40 ketones (e.g., stearone), etc. Other
suds
inhibitors include N-alkylated amino triazines such as tri- to hexa-
alkylmelamines or
di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric
chloride with
two or three moles of a primary or secondary amine containing 1 to 24 carbon
atoms,
propylene oxide, and monostearyl phosphates such as monostearyl alcohol
phosphate
ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and
phosphate
esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in
liquid
form. The liquid hydrocarbons will be liquid at room temperature and
atmospheric
pressure, and will have a pour point in the range of about -40°C and
about 50°C, and
a minimum boiling point not less than about 110°C (atmospheric
pressure). It is also
known to utilize waxy hydrocarbons, preferably having a melting point below
about
100°C. The hydrocarbons constitute a preferred category of suds
suppressor for
detergent compositions. Hydrocarbon suds suppressors are described, for
example,
in U.S. Patent 4,265,779, issued May S, 1981 to Gandolfo et al. The
hydrocarbons,
thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or
unsaturated
hydrocarbons having from about 12 to about 70 carbon atoms. The term
"paraffin,"
as used in this suds suppressor discussion, is intended to include mixtures of
true
paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises
silicone suds suppressors. This category includes the use of
polyorganosiloxane oils,
such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane
oils or
resins, and combinations of polyorganosiloxane with silica particles wherein
the
polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds
suppressors are well known in the art and are, for example, disclosed in U.S.
Patent
2~a7~o5
23
4,265,779, issued May 5, 1981 to Gandolfo et a) and European Patent
Application
No. 354,016, published February 7, 1990, by Starch, M.S.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which
relates to compositions and processes for defoaming aqueous solutions by
incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in
German
Patent Application DOS 2,124,526. Silicone defoamers and suds controlling
agents
in granular detergent compositions are disclosed in U.S. Patent 3,933,672,
Bartolotta
et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a suds controlling agent consisting essentially of
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about 1,500 cs. at 25°C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane
resin composed of (CH3)3Si01~2 units of Si02 units in a ratio of from
(CH3)3 Si01~2 units and to Si02 units of from about 0.6:1 to about
1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous phase is made up of certain polyethylene glycols or polyethylene-
polypropylene glycol copolymers or mixtures thereof (preferred), or
polypropylene
glycol. The primary silicone suds suppressor is branched/crosslinked and
preferably
not linear.
To illustrate this point further, typical liquid laundry detergent
compositions
with controlled suds will optionally comprise from about 0.001 to about 1,
preferably
from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5,
weight
of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of
a
primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a
resinous
siloxane or a silicone resin-producing silicone compound, (c) a finely divided
filler
material, and (d) a catalyst to promote the reaction of mixture components
(a), (b)
and (c), to form silanolates; (2) at least one nonionic silicone surfactant;
and (3)
polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having
a
solubility in water at room temperature of more than about 2 weight %; and
without
polypropylene glycol. Similar amounts can be used in granular compositions,
gels,
etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and
4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued
February
21873p5
24
22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column l,
line
46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol
and a copolymer of polyethylene glycoUpolypropylene glycol, all having an
average
molecular weight of less than about 1,000, preferably between about 100 and
800.
The polyethylene glycol and polyethylene/polypropylene copolymers herein have
a
solubility in water at room temperature of more than about 2 weight %,
preferably
more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an average
molecular weight of less than about 1,000, more preferably between about 100
and
800, most preferably between 200 and 400, and a copolymer of polyethylene
glycoUpolypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight
ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of
polyethylene glycol:copolymer of~polyethylene-polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain
polypropylene glycol, particularly of 4,000 molecular weight. They also
preferably
do not contain block copolymers of ethylene oxide and propylene oxide, like
PLURONICTM LI01.
Other suds suppressors useful herein comprise the secondary alcohols (e.g.,
2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as
the silicones
disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols
include the C6-C 16 alkyl alcohols having a C 1-C 16 chain. A preferred
alcohol is 2-
butyl octanol, which is available from Condea under the trademark ISOFOL 12.
Mixtures of secondary alcohols are available under the trademark ISALCHEM 123
from Enichem. Mrxed suds suppressors typically comprise mixtures of alcohol +
silicone at a weight ratio of 1:5 to 5: I .
For any detergent compositions to be used in automatic laundry washing
machines, suds should not form to the extent that they overflow the washing
machine. Suds suppressors, when utilized, are preferably present in a "suds
suppressing amount. By "suds suppressing amount" is meant that the formulator
of
the composition can select an amount of this suds controlling agent that will
sufficiently control the suds to result in a low-sudsing laundry detergent for
use in
automatic laundry washing machines.
The compositions herein will generally comprise from 0% to about 5% of
suds suppressor. When utilized as suds suppressors, monocarboxylic fatty
acids, and
salts therein, will be present typically in amounts up to about 5%, by weight,
of the
detergent composition. Preferably, from about 0.5% to about 3% of fatty
PCT/US95103725
WO 95/29225
monocarboxylate suds suppressor is utilized. Silicone suds suppressors are
typically
utilized in amounts up to about 2.0%, by weight, of the detergent composition,
although higher amounts may be used. This upper limit is practical in nature,
due
primarily to concern with keeping costs minimized and effectiveness of lower
S amounts for effectively controlling sudsing. Preferably from about 0.01 % to
about
1% of silicone suds suppressor is used, more preferably from about 0.25% to
about
0.5%. As used herein, these weight percentage values include any silica that
may be
utilized in combination with polyorganosiloxane, as well as any adjunct
materials that
may be utilized. Monostearyl phosphate suds suppressors are generally utilized
in
10 amounts ranging from about 0.1% to about 2%, by weight, of the composition.
Hydrocarbon suds suppressors are typically utilized in amounts ranging from
about
0.01% to about 5.0%, although higher levels can be used. The alcohol suds
suppressors are typically used at 0.2%-3% by weight of the finished
compositions.
Fabric Softeners - Various through-the-wash fabric softeners, especially the
15 impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl,
issued
December 13, 1977, as well as other softener clays known in the art, can
optionally
be used typically at levels of from about 0.5% to about 10% by weight in the
present
compositions to provide fabric softener benefits concurrently with fabric
cleaning.
Clay softeners can be used in combination with amine and cationic softeners as
20 disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March l,
1983 and U.S.
Patent 4,291,071, Hams et al, issued September 22, 1981.
Other Ingredients - A wide variety of other ingredients useful in detergent
compositions can be included in the compositions herein, including other
active
ingredients, carriers, hydrotropes, processing aids, dyes or pigments,
solvents for
25 liquid formulations, solid fillers for bar compositions, etc. If high
sudsing is desired,
suds boosters such as the C 1 p-C 16 alkanolamides can be incorporated into
the
compositions, typically at 1 %-10% levels. The C 10-C 14 monoethanol and
diethanol
amides illustrate a typical class of such suds boosters. Use of such suds
boosters
with high sudsing adjunct surfactants such as the amine oxides, betaines and
sultaines
noted above is also advantageous. If desired, soluble magnesium salts such as
MgCl2, MgS04, and the like, can be added at levels of, typically, 0.1%-2%, to
provide additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions
optionally can be further stabilized by absorbing said ingredients onto a
porous
hydrophobic substrate, then coating said substrate with a hydrophobic coating.
Preferably, the detersive ingredient is admixed with a surfactant before being
absorbed into the porous substrate. In use, the detersive ingredient is
released from
WO 95/29225 PCT/US95/03725
26
the substrate into the aqueous washing liquor, where it performs its intended
detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPERNAT D 10, DeGussa) is admixed with a proteolytic enzyme
solution containing 3%-S% of C13-15 ethoxylated alcohol (EO 7) nonionic
surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of
silica.
The resulting powder is dispersed with stirring in silicone oil (various
silicone oil
viscosities in the range of S00-12,500 can be used). The resulting silicone
oil
dispersion is emulsified or otherwise added to the final detergent matrix. By
this
means, ingredients such as the aforementioned enzymes, bleaches, bleach
activators,
bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and
hydrolyzable surfactants can be "protected" for use in detergents, including
liquid
laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as
carriers. Low molecular weight primary or secondary alcohols exemplified by
methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols
are
preferred for solubilizing surfactant, but polyols such as those containing
from 2 to
about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-
propanediol,
ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The
compositions
may contain from 5% to 90%, typically 10% to 50% of such carriers.
The detergent compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between
about 6.5 and about 11, preferably between about 7.5 and 10.5. Liquid
dishwashing
product formulations preferably have a pH between about 6.8 and about 9Ø
Laundry products are typically at pH 9-11. Techniques for controlling pH at
recommended usage levels include the use of buffers, alkalis, acids, etc., and
are well
known to those skilled in the art.
Dve Transfer Inhibiting_Agents - The compositions of the present
invention may also include one or more materials effective for inhibiting the
transfer
of dyes from one fabric to another during the cleaning process. Generally,
such dye
transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-
oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese
phthalocyanine, peroxidases, and mixtures thereof. If used, these agents
typically
comprise from about 0.01 % to about 10% by weight of the composition,
preferably
from about 0.01% to about 5%, and more preferably from about 0.05% to about
2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units having the following structural formula: R-Ax-P; wherein P is a
WO 95/29225 218 7 3 0 5 PCT/US95/03725
27
polymerizable unit to which an N-O group can be attached or the N-O group can
form part of the polymerizable unit or the N-O group can be attached to both
units; A
is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or
1; and
R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic
groups or
any combination thereof to which the nitrogen of the N-O group can be attached
or
the N-O group is part of these groups. Preferred polyamine N-oxides are those
wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole,
pyrrolidine,
piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
O O
W )x-N-~2~~ =N-~Uc
(R3)z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group
can be
attached or form part of any of the aforementioned groups. The amine oxide
unit of
the polyanvne N-oxides has a pKa < 10, preferably pKa <7, more preferred pKa
<6.
Any polymer backbone can be used as long as the amine oxide polymer
formed is water-soluble and has dye transfer inhibiting properties. Examples
of
suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters,
polyethers,
polyamide, polyimides, polyacrylates and mixtures thereof. These polymers
include
random or block copolymers where one monomer type is an amine N-oxide and the
other monomer type is an N-oxide. The amine N-oxide polymers typically have a
ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the
number of
amine oxide groups present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by an appropriate degree of N-oxidation. The
polyamine oxides can be obtained in almost any degree of polymerization.
Typically,
the average molecular weight is within the range of 500 to 1,000,000; more
preferred
1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of
materials
can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent compositions
herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight
of
about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to
as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI
has
an average molecular weight range from 5,000 to 1,000,000, more preferably
from
5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average
_. 21 873 05
28
molecular weight range is determined by light scattering as described in
Barth, et al.,
Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization".)
The
PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most
preferably
from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
The present invention compositions also may employ a polyvinyl-pyrrolidone
("PVP") having an average molecular weight of from about 5,000 to about
400,000,
preferably from about 5,000 to about 200,000, and more preferably from about
5,000
to about 50,000. PVP's are known to persons skilled in the detergent field;
see, for
example, EP-A-262,897 and EP-A-256,696. Compositions containing PVP can also
contain polyethylene glycol ("PEG") having an average molecular weight from
about
500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably,
the
ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about
2:1 to
about 50:1, and more preferably from about 3:1 to about 10:1.
The detergent compositions herein may also optionally contain from about
0.005% to 5% by weight of certain types of hydrophilic optical bcighteners
which
also provide a dye transfer inhibition action. If used, the compositions
herein will
preferably comprise from about 0.01% to 1% by weight of such optical
brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
Rt R2
N H H N
N O~--N , O C=C O N--~O N
~"-N H H
R2 S03M S~3M Rt
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl;
R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
potassium.
When in the above formula, R l is anilino, R2 is N-2-bis-hydroxyethyl and M
is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium
salt.
This particular brightener species is commercially marketed under the
trademark
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred
hydrophilic optical brightener useful in the detergent compositions herein.
w .. 2187305
29
When in the above formula, R 1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a canon such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-
(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
trademark Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a canon
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is
commercially marketed under the trademark '~inopal AMS-GX by Ciba Geigy
Corporation.
The specific optical brightener species selected for use in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used in
combination with the selected polymeric dye transfer inhibiting agents
hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO
and/or
IS PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,
Tinopal
SBM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer
inhibition in aqueous wash solutions than does either of these two detergent
composition components when used alone. Without being bound by theory, it is
believed that such brighteners work this way because they have high affinity
for
fabrics in the wash solution and therefore deposit relatively quick on these
fabrics.
The extent to which brighteners deposit on fabrics in the wash solution can be
defined
by a parameter called the "exhaustion coefficient". The exhaustion coefEcient
is in
general as the ratio of a) the brightener material deposited on fabric to b)
the initial
brightener concentration in the wash liquor. Brighteners with relatively high
exhaustion coefficients are the most suitable for inhibiting dye transfer in
the context
of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
types of compounds can optionally be used in the present compositions to
provide
conventional fabric "brightness" benefits, rather than a true dye transfer
inhibiting
effect. Such usage is conventional and well-known to detergent formulations.
The following examples illustrate compositions according to the invention,
but are not intended to be limiting thereof.
EXAMPLE I
A'bleach composition is as follows:
In e~ dient % t.
Sodium Percarbonate 20.0
(6-nonanamidocaproyl)oxybenzenesulfonate 10.0
' W O 95129225
2 I 8 7 3 0 5 pCT~S95/03725
Protease Enzyme* 1.0
Water-soluble filler** Balance
*Protease C
**Sodium carbonate, sodium silicate mixture (1:1).
5 The compositions of Example I can be used per se as a bleach, or can be
added to a pre-soak or surfactant-containing detergent composition to impart a
bleaching benefit thereto. Fabrics exposed to the compositions of Example I
exhibit
more performance benefits on dingy soils than the added single contributions
of
bleach and protease would predict.
