TECHNICAL FIELD
[0001] The present invention relates to cleaning and bleaching compositions which employ
oleoyl sarcosinate surfactants to boost performance. Bleaching, fabric laundering,
automatic dishwashing and sanitizing compositions with improved oxygen bleach activity
are provided.
BACKGROUND OF THE INVENTION
[0002] It is common practice for formulators of cleaning compositions to include bleaching
agents such as sodium perborate or sodium percarbonate in such compositions for their
bleach effect. Such bleaches are widely recognized for their ability to remove various
stains and soils from fabrics. In like manner, formulators of automatic dishwashing
compositions have found that various bleaching agents can assist in the removal of
tea stains, proteinaceous soils, from dishware. Various fabric bleach and/or pre-soaking
compositions also comprise percarbonate or perborate bleaches.
[0003] Unfortunately, many bleaching agents do not function optimally under all usage conditions.
As a general proposition, perborate and percarbonate bleaches are more effective in
hot water than in cold. Yet, many consumers now conduct fabric laundering and other
cleaning operations under moderate-to-cold water temperatures (below about 60°C).
To improve the performance of perborate and percarbonate bleaches, manufacturers have
turned to the so-called "bleach activators". Such activators typically comprise organic
molecules which interact with perborate or percarbonate to release "per-acid" bleaching
species. The combination of bleach-plus-activator functions well over a wide range
of water temperatures and usage conditions. It is also known that various transition
metal cations, such as manganese, have the potential to function as bleach activators,
presumably by virtue of their catalytic interaction with peroxide or per-acid bleaching
species.
[0004] Unfortunately, many peracids, bleach activators and transition metal catalysts can
cause fabric damage. Without being limited by theory, it is believed that fabric damage
from bleaching compounds is due to the precipitation of the activators and catalysts
onto fabrics which causes fabric damage upon radical formations with hydrogen peroxide.
Likewise, the bleaching species may precipitate onto the fabrics and cause isolated
spotting and fabric damage. Fabric damage can be particularly dramatic at lower temperatures
because many of the peracids, activators and catalysts solubilize more slowly at colder
temperatures and, therefore, readily precipitate upon the fabric surfaces.
[0005] It has now been discovered that bleach compositions comprising oleoyl sarcosinate
surfactant can be used to provide effective, improved bleaching. Further, these compositions
seem to deter fabric damages caused by the peracids, catalysts and bleach activators.
Without being limited by theory, it is believed that the oleoyl sarcosinate is particularly
effective at solubilizing the bleaching compounds and dispersing it throughout the
wash liquor, especially at cooler temperatures (less than 60°C). Thus, the precipitation
of bleaching compounds in the wash liquor is reduced.
[0006] Accordingly, it is an object of the present invention to provide improved cleaning
and bleaching compositions using bleaching compounds and oleoyl sarcosinate surfactants.
It is another object herein to provide a means for removing soils and stains from
fabrics and dishware using the bleaching systems and oleoyl sarcosinate of this invention.
The compositions also provide excellent color care for dyed fabrics and excellent
skin mildness for handwash operations. These and other objects are secured herein,
as will be seen from the following disclosures.
BACKGROUND ART
[0007] Oleoyl sarcosinate is described in the following patents and publications: U.S. 2,542,385,
U.S. 3,402,990; U.S. 3,639,568; U.S. 4,772,424; U.S. 5,186,835; European Patent Publication
505,129; British Patent Publication 1,211,545; Japanese Patent Publication 39/232194;
Japanese Patent Publication 62/295997; Japanese Patent Publication 02/180811, and
Chemical Abstracts Service abstracts No.s 61:3244q, 70:58865x, and 83:181020p. Japanese
application JP 55-102697A describes oleoyl sarcosinate in compositions containing
percarbonate bleach.
[0008] The use of manganese with various complex ligands to enhance bleaching is reported
in the following United States Patents: 4,430,243, 4,728,455; 5,246,621, 5,244,594;
5,284,944; 5,194,416, 5,246,612, 5,256,779, 5,280,117, 5,274,147; 5,153,161; 5,227,084;
5,114,606; 5,114,611. See also: EP 549,271 A1, EP 544,490 A1; EP 549,272 A1; and EP
544,440 A2.
[0009] The use of amido-derived bleach activators in laundry detergents is described in
U.S. Patent 4,686,063 and U.S. Patent 4,634,551. Another class of bleach activators
comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723,
issued October 30, 1990. Coated bleach percuscors are disclosed in WO 92/13798.
SUMMARY OF THE INVENTION
[0010] The present invention encompasses bleach compositions comprising oleoyl sarcosinate
surfactant and a specific bleaching agent, namely a bleaching composition comprising
bleaching compound capable of yielding hydrogen peroxide in an aqueous liquor and
from 0.1% to 55% by weight of oleoyl sarcosinate surfactant and comprising one or
more bleach activators, wherein said bleach activators are members selected from the
group consisting of:
a) alkanoyloxybenzenesulfonate bleach activators;
b) tetraacetylethylenediamine;
c) an amido-derived bleach activator of the general formula
or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms,
R5 is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms and
L is a leaving group;
d) a benzoxazin-type bleach activator of the formula
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR6, wherein R6 is H or an alkyl group and carbonyl functions;
e) N-acyl lactam bleach activators of the formula:
wherein n is from 0 to 8, preferably from 0 to 2, and R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons,
or a substituted phenyl group containing from 6 to 18 carbon atoms, and
f) mixtures of a), b) and c).
[0011] The present invention encompasses bleach compositions comprising oleoyl sarcosinate
surfactant, a bleaching agent, especially a bleach which is a member selected from
the group consisting of H
2O
2, perborate, percarbonate persulfate and peracid bleaches, and one or more selected
bleach activators. Preferred bleaching agents comprise percarbonate or perborate bleach,
or mixtures thereof. Preferred bleach activators are selected from acyl lactam-type
activators, amido-derived activators, benzoaxin-type activators, tetraacetylethylene-diamine
(TAED), alkanoyloxybenzenesulfonates, including nonanoyloxybenzene-sulfonate (NOBS),
and benzoyloxybenzenesulfonate (BOBS), and mixtures thereof. Peracids may also be
included in the present compositions. Suitable peracids include amido peracids, cationic
peracids, nonylamide of peroxyadipic acid (NAPAA), and mixtures thereof.
[0012] Additionally, the present invention further encompasses bleach compositions comprising
oleoyl sarcosinate surfactant, a bleaching agent, one or more selected bleach activators,
and a catalytically-effective amount of one or more bleach catalysts, especially metal
bleach catalysts.
[0013] Preferred activators which are optionally employed in the present invention include
benzoyl caprolactam, nonanoyl caprolactam, benzoyl valerolactam, nonanoyl valerolactam,
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, nonanoyloxy-benzenesulfonate, benzoyloxybenzenesulfonate,
tetraacetylethyl-enediamine, 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 caprolactam, pentylbenzoyl valerolactam, hexylbenzoyl caprolactam, hexylbenzoyl
valerolactam, ethoxybenzoyl caprolactam, ethoxybenzoyl valerolactam, propoxybenzoyl
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
caprolactam, 2,4,6-trichlorobenzoyl valerolactam, pentafluorobenzoyl caprolactam,
pentafluorobenzoyl valerolactam, dichlorobenzoyl caprolactam, dimethoxybenzoyl caprolactam,
3-chlorobenzoyl caprolactam, 2,4-dichlororbenzoyl caprolactam, pentafluorobenzoyl
caprolactam, pentafluorobenzoyl valerolactam, dichlorobenzoyl valerolactam, dimethoxybenzoyl
valerolactam, 3-chlorobenzoyl valerolactam, 2,4-dichlorobenzoyl valerolactam, terephthaloyl
divalerolactam, 4-nitrobenzoyl capro-lactam, 4-nitrobenzoyl valerolactam, dinitrobenzoyl
caprolactam, dinitrobenzoyl valerolactam, and mixtures thereof.
[0014] 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, undecenoyl caprolactam,
undecenoyl valerolactam, 3,5,5-trimethyl-hexanoyl caprolactam, 3,5,5-trimethylhexanoyl
valerolactam, dinitrobenzoyl capro-lactam, dinitrobenzoyl valerolactam, (6-octanamidocaproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate,
nonanoyloxybenzenesulfonate, benzoyloxybenzenesulfonate, tetraacetylethylenediamine,
and mixtures thereof.
[0015] Preferably, the molar ratio of hydrogen peroxide yielded by the peroxygen bleaching
compound to bleach activator is greater than 1.0. Most preferably, the molar ratio
of hydrogen peroxide to bleach activator is at least 1.5.
[0016] Preferred compositions herein are those wherein the bleach catalyst is a metal-based
catalyst.
[0017] The invention also encompasses detergent compositions, especially laundry detergents,
comprising otherwise conventional surfactants and other detersive ingredients.
[0018] The invention also encompasses detergent or bleach compositions comprising oleoyl
sarcosinate surfactant, a bleaching agent, and a catalytically effective amount of
a water-soluble manganese salt.
[0019] The invention also encompasses a method for improving the bleaching performance of
oxygen or per-acid bleach compositions, comprising adding thereto oleoyl sarcosinate
surfactant in the presence of selected ligands and a catalytically effective amount
of manganese cations. This provides a method for removing stains from fabrics, comprising
contacting said fabrics with an aqueous medium comprising said compositions.
[0020] All percentages, ratios and proportions herein are by weight, unless otherwise specified.
DETAILED DESCRIPTION OF THE INVENTION
1. Oleoyl Sarcosinate
[0021] The present invention compositions comprise oleoyl sarcosinate, in its acid and/or
salt form selected as desired for the compositions and uses herein, having the following
formula:
wherein M is hydrogen or a cationic moiety. Preferred M are hydrogen and alkali metal
salts, especially sodium and potassium. Oleoyl sarcosinate is commercially available,
for example as Hamposyl O supplied by W. R. Grace & Co. Bleaching compositions according
to the present invention comprise from 0.1% to 55%, preferably from 1% to 20%, and
most preferably from 3% to 15%, of oleoyl sarcosinate by weight of the composition.
[0022] In addition to the commercially-available oleoyl sarcosinate, oleoyl sarcosinate
useful herein can also preferably be prepared from the ester (preferably the methyl
ester) of oleic acid and a sarcosine salt (preferably the sodium salt) under anhydrous
reaction conditions in the presence of a base catalyst with a basicity equal to or
greater than alkoxide catalyst (preferably sodium methoxide) For example, the reaction
may be illustrated by the scheme :
[0023] This salt may optionally be neutralized to form the oleoyl sarcosinate in its acid
form.
[0024] The preferred method for preparing oleoyl sarcosinate is conducted at a temperature
from 80°C to 200°C, especially from 120°C to 200°C. It is preferred to conduct the
reaction without solvent although alcohol solvents which have a boiling point of at
least 100°C and are stable to the reaction conditions (ie. glycerol is not acceptable)
can be used. The reaction may proceed in 85% yield with a molar ratio of methyl ester
reactant to sarcosine salt reactant to basic catalyst of 1:1:0.05-0.2.
[0025] Methyl ester mixtures derived from high oleic content natural oils (preferably having
at least 60%, more preferably at least 75%, and most preferably at least 90% oleic
content) are especially preferred as starting materials. Examples include high-oleic
sunflower and rapeseed/canola oil. In addition, a high-oleic methyl ester fraction
derived from either palm kernel oil or tallow is acceptable. It is to be understood
that such oils typically will contain some levels of impurities, including some fatty
acid impurities that may be converted to sarcosinate compounds by this synthesis method.
For example, commodity canola/rapeseed oil may comprise a majority of oleic acid,
and a mixture of fatty acid impurities such as palmitic, stearic, linoleic, linolenic
and/or eicosenoic acid, some or all of which are converted to the sarcosinate by this
reaction method. If desired for formulation purposes, some or all of such impurity
materials may be excluded from the starting oil before preparing the oleoyl sarcosinate
to be used in the present compositions.
[0026] Finally, sarcosine remaining in the reaction mixture can be converted to an amide
by addition of maleic or acetic anhydride to the mixture, thereby minimizing the sarcosine
content and any potential for formation of undesired nitrogen-containing impurities.
[0027] The synthesis of oleoyl sarcosinate may be carried out as follows to prepare the
sodium oleoyl sarcosinate.
[0028] Synthesis of Oleoyl Amide of Sarcosine Sodium Salt - A 2 L, 3-neck, round bottom flask is fitted with thermometer, Dean-Stark trap with
condenser, mechanical stirring, and a gas inlet adapter through which nitrogen is
passed over the reaction mixture. The reaction vessel is charged with sarcosine (43.3
g, 0 476 mol), sodium methoxide 25% in methanol (97.7 g, 0 452 mol), and methanol
(400 mL). The reaction is refluxed 15 min to neutralize the sarcosine and then methyl
ester derived from Cargill regular high-oleyl sunflower oil (148.25 g, 0.5 mol) is
added. After the methanol is removed with the Dean-Stark trap, reaction mixture is
heated to 170°C for 1 hr to drive off any water. The reaction is initiated by the
addition of sodium methoxide 25% in methanol (15.4 g, 0.0714 mol). Reaction is kept
at 170°C for 2.5 hr during which methanol is collected in the Dean-Stark trap. The
reaction is allowed to cool slightly and then methanol (200 g) is added. Maleic anhydride
(9.43 g, 0.095 mol) is added to the methanol solution and the reaction is stirred
at 60°C for 0.5 hr. Then most of the methanol is removed by rotary evaporation and
acetone (2 L) is added to precipitate the product. The product is collected by suction
filtration and allowed to air dry to give an off-white solid. Analysis of the reaction
mixture by GC indicates the majority of the product is oleoyl sarcosinate, with minor
amounts of the following impurities: sarcosine, oleic acid, and the sarcosinates derived
from palmitic acid, stearic acid, and linoleic acid.
[0029] Bleaching Compounds and Bleaching Agents - In addition to oleoyl sarcosinate surfactant, bleaching compositions herein also
contain bleaching agents or 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 1% to
80%, more typically from 5% to 20%, of the detergent composition, especially for fabric
laundering. Bleach and pre-soak compositions may comprise from 5% to 99% of the bleaching
agent. If present, the amount of bleach activators will typically be from 0.1% to
60%, more typically from 0.5% to 40% of the bleaching mixture comprising the bleaching
agent-plus-bleach activator.
[0030] The bleaching agents used herein can be any of the bleaching agents useful for detergent
compositions in textile 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.
[0031] 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., OXONE, manufactured commercially by DuPont) can also be used.
[0032] A preferred percarbonate bleach comprises dry particles having an average particle
size in the range from 500 micrometers to 1,000 micrometers, not more than 10% by
weight of said particles being smaller than 200 micrometers and not more than 10%
by weight of said particles being larger than 1,250 micrometers. Optionally, the percarbonate
can be coated with silicate, borate or water-soluble surfactants. Percarbonate is
available from various commercial sources such as FMC, Solvay and Tokai Denka.
[0033] The compositions of the present invention may also comprise mixtures of bleaching
activators.
[0034] Peroxygen bleaching agents, the perborates, the percarbonates, 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.
[0035] Alkanoyloxybenzenesulfonates - Suitable alkanoyloxybenzenesulfonate bleach activators which can be employed in
the present invention are of the formula
wherein R
1-C(O)- contains from 8 to 12, preferably from 8 to 11, carbon atoms and M is a suitable
cation, such as an alkali metal, ammonium, or substituted ammonium cation, with sodium
and potassium being most preferred.
[0036] Highly preferred hydrophobic alkanoyloxybenzenesulfonates are selected from the group
consisting of nonanoyloxybenzenesulfonate, 3,5,5-trimethylhexanoyloxybenzenesulfonate,
2-ethylhexanoyloxybenzenesulfonate, octanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate,
dodecanoyloxybenzenesulfonate, and mixtures thereof.
[0037] 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
or mixtures thereof, wherein R
1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R
2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms,
R
5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms, and
L is 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
form a stable entity so that the rate of the back reaction is negligible. This facilitates
the nucleophilic attack by the perhydroxide anion.
[0038] 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 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 4
to 13, preferably from 6 to 11 and most preferably from 8 to 11.
[0039] Preferred bleach activators are those of the above general formula wherein R
1, R
2 and R
5 are as defined for the peroxyacid and L is selected from the group consisting of:
and mixtures thereof, wherein R
1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R
3 is an alkyl chain containing from 1 to 8 carbon atoms, R
4 is H or R
3, and Y is H or a solubilizing group.
[0040] The preferred solubilizing groups are -SO
3-M
+, -CO
2-M
+, -SO
4-M
+, -N
+(R
3)
4X
- and O<--N(R
3)
3 and most preferably -SO
3-M
+ and -CO
2-M
+ wherein R
3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides
solubility to the bleach activator and X is an anion which 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 solubilizing groups should be well dispersed in the
bleaching solution in order to assist in their dissolution.
[0041] Preferred bleach activators are those of the above general formula wherein L is selected
from the group consisting of:
wherein R
3 is as defined above and Y is -SO
3-M
+ or -CO
2-M
+ wherein M is as defined above.
[0042] Preferred examples of bleach activators of the above formulae include (6-octanamidocaproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate,
and mixtures thereof.
[0043] 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. Another example of ring-opening bleach activators
can be found in activators, such as those disclosed in U.S. Patent 4,966,723, Hodge
et al, issued Oct. 30, 1990.
[0044] Such activator compounds disclosed by Hodge include the activators of the benzoxazin-type,
having the formula:
including the substituted benzoxazins of the type
wherein R
1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R
2, R
3, R
4, and R
5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR
6 (wherein R
6 is H or an alkyl group) and carbonyl functions.
[0045] A preferred activator of the benzoxazin-type is:
[0046] 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.
[0047] Still another class of preferred bleach activators includes the acyl lactam activators,
especially acyl caprolactams and acyl valerolactams of the formulae
wherein R
6 is H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon
atoms, or a substituted phenyl group containing from 6 to 18 carbons. See copending
U.S. applications 08/064,562 and 08/082,270, 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.
[0048] 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.
[0049] Bleaching Agents - Another optional, yet preferable, category of bleaching agent that can be used without
restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable
examples of this class of agents include magnesium monoperoxyphthalate hexahydrate
(INTEROX), the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric
acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent
4,483,781, Hartman, issued November 20, 1984; U.S. Pat. App 740,446, Burns et al,
filed June 3, 1985, European Pat. App. 0,133,354, Banks et al, published February
20, 1985; and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly
preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described
in U.S. Patent 4,634,551, and 4,686,063, both Burns et al., issued January 6, 1987,
and August 11, 1987, respectively.
[0050] Suitable amidoperoxyacids are of the formula:
wherein R
1, R
2, and R
5 are as defined for the amido-derived type bleach activators described above.
[0051] Preferred organic peroxyacids are selected from the group consisting of 4-nonylamino-4-oxoperoxybutyric
acid, 6-(nonyl-amino)-6-oxoperoxycaproic acid, decylsulphonylperpropionic acid, and
heptyl, octyl-n nonyl-, decyl-sulphonylperbutyric acid, and mixtures thereof.
[0052] Example 1 of U.S. Pat. 4,686,063 contains one description of the synthesis fo NAPSA,
from col. 8, line 40 to col. 9, line 5, and NAPAA, from col. 9 line 15 to col. 9,
line 65.
[0053] The superior bleaching/cleaning action of the present compositions is achieved with
safety to natural rubber machine parts and other natural rubber articles, including
fabrics containing natural rubber and natural rubber elastic materials. The bleaching
mechanism and, in particular, the surface bleaching mechanism are not completely understood.
However, it is generally believed that the bleach activator undergoes nucleophilic
attack by a perhydroxide anion, which is generated from the hydrogen peroxide evolved
by the peroxygen bleach, to form a peroxycarboxylic acid. This reaction is commonly
referred to as perhydrolysis.
[0054] The amido-derived and lactam bleach activators herein can also be used in combination
with rubber-safe, enzyme-safe, hydrophilic activators such as TAED, typically at weight
ratios of amido-derived or caprolactam activators; TAED in the range of 1:5 to 5:1,
preferably 1:1.
Bleach Catalyst
[0055] The bleach catalyst material used herein can comprise the free acid form, the salts,
and the like. It is to be appreciated that the bleach catalyst does not function as
a bleach by itself. Rather, it is used as a catalyst to enhance the performance of
conventional bleaches and, in particular, oxygen bleaches such as perborate, percarbonate,
persulfate, especially in the presence of bleach activators.
[0056] One type of bleach catalyst is a catalyst system comprising a heavy metal cation
of defined bleach catalytic activity, such as copper, iron or manganese cations, an
auxiliary metal cation having little or no bleach catalytic activity, such as zinc
or aluminum cations, and a sequestrant having defined stability constants for the
catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such
catalysts are disclosed in U.S. Pat. 4,430,243.
[0057] Other types of bleach catalysts include the manganese-based complexes disclosed in
U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts
include Mn
IV2(u-O)
3(1,4,7-trimethyl-1,4,7-triazacyclononane)
2-(PF
6)
2, Mn
III2(u-O)
1(u-OAc)
2(1,4,7-trimethyl-1,4,7-triazacyclononane)
2 (ClO
4)
2, Mn
IV4(u-O)
6(1,4,7-triazacyclononane)
4(ClO
4)
4, Mn
IIIMn
IV4(u-O)
1(u-OAc)
2. (1,4,7-trimethyl-1,4,7-triazacyclononane)
2(ClO
4)
3, and mixtures thereof. Others are described in European Pat. App. Pub. No. 549,272.
Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane,
2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane,
and mixtures thereof.
[0058] The bleach catalysts useful in machine dishwashing compositions and concentrated
powder detergent compositions may also be selected as appropriate for the present
invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S.
Pat. 5,227,084.
[0059] See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such
as Mn
IV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH
3)
3(PF
6).
[0060] Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a
water-soluble complex of manganese (II), (III), and/or (IV) with a ligand which is
a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol,
adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
[0061] U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition
metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands
are of the formula:
wherein R
1, R
2, R
3, and R
4 can each be selected from H, substituted alkyl and aryl groups such that each R
1-N=C-R
2 and R
3-C=N-R
4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging
group selected from O, S. CR
5R
6, NR
7 and C=O, wherein R
5, R
6, and R
7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups.
Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole,
and triazole rings. Optionally, said rings may be substituted with substituents such
as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine.
Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine
complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl
2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate,
Co(2,2-bispyridylamine)
2- O
2ClO
4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridyl-amine) iron(II)
perchlorate, and mixtures thereof.
[0062] Other examples include Mn gluconate, Mn(CF
3SO
3)
2, Co(NH
3)
5Cl, and the binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands,
including N
4Mn
III(u-O)
2Mn
IVN
4)
+and [Bipy
2Mn
III(u-O)
2Mn
IVbipy
2]-(ClO
4)
3.
[0063] The bleach catalysts of the present invention may also be prepared by combining a
water-soluble ligand with a water-soluble manganese salt in aqueous media and concentrating
the resulting mixture by evaporation. Any convenient water-soluble salt of manganese
can be used herein. Manganese (II), (III), (IV) and/or (V) is readily available on
a commercial scale. In some instances, sufficient manganese may be present in the
wash liquor, but, in general, it is preferred to add Mn cations in the compositions
to ensure its presence in catalytically-effective amounts. Thus, the sodium salt of
the ligand and a member selected from the group consisting of MnSO
4, Mn(ClO
4)
2 or MnCl
2 (least preferred) are dissolved in water at molar ratios of ligand:Mn salt in the
range of 1:4 to 4:1 at neutral or slightly alkaline pH. The water may first be de-oxygenated
by boiling and cooled by sparging with nitrogen. The resulting solution is evaporated
(under N
2, if desired) and the resulting solids are used in the bleaching and detergent compositions
herein without further purification.
[0064] In an alternate mode, the water-soluble manganese source, such as MnSO
4, is added to the bleach/cleaning composition or to the aqueous bleaching/cleaning
bath which comprises the ligand. Some type of complex is apparently formed
in situ, and improved bleach performance is secured. In such an
in situ process, it is convenient to use a considerable molar excess of the ligand over the
manganese, and mole ratios of ligand:Mn typically are 3:1 to 15:1. The additional
ligand also serves to scavenge vagrant metal ions such as iron and copper, thereby
protecting the bleach from decomposition. One possible such system is described in
European Pat. App. Pub. No. 549,271.
[0065] While the structures of the bleach-catalyzing manganese·complexes of the present
invention have not been elucidated, it may be speculated that they comprise chelates
or other hydrated coordination complexes which result from the interaction of the
carboxyl and nitrogen atoms of the ligand with the manganese cation. Likewise, the
oxidation state of the manganese cation during the catalytic process is not known
with certainty, and may be the (+II), (+III), (+IV) or (+V) valence state. Due to
the ligands' possible six points of attachment to the manganese cation, it may be
reasonably speculated that multi-nuclear species and/or "cage" structures may exist
in the aqueous bleaching media. Whatever the form of the active Mn·ligand species
which actually exists, it functions in an apparently catalytic manner to provide improved
bleaching performances on stubborn stains such as tea, ketchup, coffee, blood, and
the like.
[0066] Other bleach catalysts are described, for example, in European Pat. App. Pub. Nos.
408,131 (cobalt complex catalysts), 384,503, and 306,089 (metallo-porphyrin catalysts),
U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European
Pat. App Pub No. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845
(aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373
(manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing
salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations),
and U.S. 4,728,455 (manganese gluconate catalysts).
[0067] If employed in the compositions and processes herein, the bleach catalyst is used
in a catalytically effective amount. By "catalytically effective amount" is meant
an amount which is sufficient, under whatever comparative test conditions are employed,
to enhance bleaching and removal of the stain or stains of interest from the target
substrate. Thus, in a fabric laundering operation, the target substrate will typically
be a fabric stained with, for example, various food stains. For automatic dishwashing,
the target substrate may be, for example, a porcelain cup or plate with tea stain
or a polyethylene plate stained with tomato soup. The test conditions will vary, depending
on the type of washing appliance used and the habits of the user. Thus, front-loading
laundry washing machines of the type employed in Europe generally use less water and
higher detergent concentrations than do top-loading U.S.-style machines. Some machines
have considerably longer wash cycles than others. Some users elect to use very hot
water; others use warm or even cold water in fabric laundering operations. Of course,
the catalytic performance of the bleach catalyst will be affected by such considerations,
and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions
can be appropriately adjusted. As a practical matter, and not by way of limitation,
the compositions and processes herein can be adjusted to provide on the order of at
least one part per ten million of the active bleach catalyst species in the aqueous
washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably
from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
To illustrate this point further, on the order of 3 micromolar manganese catalyst
is effective at 40°C, pH 10 under European conditions using perborate and a bleach
activator (e.g., benzoyl caprolactam). An increase in concentration of 3-5 fold may
be required under U.S. conditions to achieve the same results. Conversely, use of
a bleach activator and the manganese catalyst with perborate may allow the formulator
to achieve equivalent bleaching at lower perborate usage levels than products without
the manganese catalyst.
Adjunct Ingredients
[0068] 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 and dyes). The following are illustrative examples of such
adjunct materials.
[0069] Detersive Surfactants - Nonlimiting examples of optional, detersive surfactants useful in detergent compositions
herein typically at levels from 1% to 55%, by weight, include the conventional C
11-C
18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C
10-C
20 alkyl sulfates ("AS"), the C
10-C
18 secondary (2,3) alkyl sulfates of the formula CH
3(CH
2)
x(CHOSO
3-M
+) CH
3 and CH
3 (CH
2)
y(CHOSO
3-M
+) CH
2CH
3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a
water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate,
the C
10-C
18 alkyl alkoxy sulfates ("AE
xS", especially x up to 7 EO ethoxy sulfates), C
10-C
18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C
10-18 glycerol ethers, the C
10-C
18 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
12-C
18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates
and C
6-C
12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C
12-C
18 betaines and sulfobetaines ("sultaines"), C
10-C
18 amine oxides, and the like, can also be included in the overall compositions. The
C
10-C
18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include
the C
12-C
18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the
N-alkoxy polyhydroxy fatty acid amides, such as C
10-C
18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C
12-C
18 glucamides can be used for low sudsing. C
10-C
20 conventional soaps may also be used. If high sudsing is desired, the branched-chain
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.
[0070] Builders - Detergent builders can optionally be included in the compositions herein to assist
in controlling mineral hardness. Inorganic as well as organic builders can be used.
Builders are typically used in fabric laundering compositions to assist in the removal
of particulate soils.
[0071] 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 1% builder. Liquid formulations typically comprise from 5% to 50%, more typically
5% to 30%, by weight, of detergent builder Granular formulations typically comprise
from 10% to 80% more typically from 15% to 50% by weight, of the detergent builder.
Lower or higher levels of builder, however, are not meant to be excluded.
[0072] 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 metaphosphates), phosphonates,
phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates. However, non-phosphate builders an 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.
[0073] Examples of silicate builders are the alkali metal silicates, particularly those
having a SiO
2:Na
2O ratio in the range 1.0:1 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-Na
2SiO
5 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 NaMSi
xO
2x+1·yH
2O 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-Na
2SiO
5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful
such as for example magnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds
control systems.
[0074] 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.
[0075] 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:
M
z/n[(AlO
2)
z(SiO
2)
y]·xH
2O
wherein z and y are integers usually of at least 6, the molar ratio of z to y is in
the range from 1.0 to 0. and x is an integer from 0 to 264, and M is a Group IA or
IIA element, e.g., Na, K, Mg, Ca with valence n.
[0076] 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[(AlO
2)
12(SiO
2)
12]·xH
2O
wherein x is from 20 to 30, especially 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 0.1-10 microns in diameter.
[0077] 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.
[0078] 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, issued January 18,
1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al,
on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly
alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
[0079] Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers
of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2,
4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal,
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.
[0080] 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.
[0081] Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates
and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January
28, 1986. Useful succinic acid builders include the C
5-C
20 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 0,200,263, published
November 5, 1986.
[0082] 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.
[0083] Fatty acids, e.g., C
12-C
18 monocarboxylic acids such as oleic acid and/or its salts, 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.
[0084] 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
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.
[0085] Enzymes - 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 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. However, their choice is governed by several factors such
as pH-activity and/or stability optima, thermostability, stability versus active detergents
and builders. In this respect bacterial or fungal enzymes are preferred, such as bacterial
amylases and proteases, and fungal cellulases.
[0086] Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg
by weight, more typically 0.001 mg to 3 mg, of active enzyme per gram of the composition.
Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%,
preferably 0.01%-2% by weight of a commercial enzyme preparation. Protease enzymes
are usually present in such commercial preparations at levels sufficient to provide
from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
[0087] Suitable examples of proteases are the subtilisins which are obtained from particular
strains of B. subtilis and B. licheniforms. Another suitable protease is obtained
from a strain of Bacillus, having maximum activity throughout the pH range of 8-12,
developed and sold by Novo Industries A/S under the registered trade name ESPERASE.
The preparation of this enzyme and analogous enzymes is described in British Patent
Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based
stains that are commercially available include those sold under the tradenames ALCALASE
and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics,
Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application
130,756, published January 9, 1985) and Protease B (see European Patent Application
251,446, and European Patent Application 130,756, Bott et al, published January 9,
1985). Other proteases include Protease A (see European Patent Application 130,756,
published January 9, 1985) and Protease B (see European Patent Application 251,446,
and European Patent Application 130,756, Bott et al, published January 9, 1985). Other
proteases include Protease A (see European Patent Application 130,756, published January
9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed
April 28, 1987, and European 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 valine at position
104, serine replaced asparagine at position 123, and alanine 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 copending
application U.S. Serial No. 08/136,797, entitled Protease-containing Cleaning Compositions
and copending Application U.S. Serial No. 08/136,626, entitled Bleaching Compositions
Comprising Protease Enzymes, which are incorporated herein by reference. Genetically
modified variants, particularly of Protease C, are also included herein.
[0088] Amylases include, for example, α-amylases described in British Patent Specification
No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo
Industries.
[0089] The cellulase usable in the present invention include both bacterial or fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases
are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, 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.
[0090] 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 lipase is available from
Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name 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 NRRLB
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.
[0091] 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. It may be desired to use, in
combination with these peroxidases, materials viewed as being peroxidase accelerators
such as phenolsulfonate and/or phenothiazine.
[0092] A wide range of enzyme materials and means for their incorporation into synthetic
detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January
5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457,
Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March
26, 1985, 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, Application No. 86200586.5, published October 29, 1986,
Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent
3,519,570.
[0093] Enzyme Stabilizers - The enzymes employed herein are stabilized by the pressure 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 1 to 30, preferably from 2 to 20, more preferably from
5 to 15, and most preferably from 8 to 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 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, 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 hydroxide, calcium formate, and calcium acetate,
and the corresponding magnesium salts. A small amount of calcium ion, generally from
0.05 to 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 such amounts in the laundry liquor. In the alternative, natural water hardness
may suffice.
[0094] 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 0 05% to 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.
[0095] 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 0.25% to 10%, preferably from 0.5% to 5%,
more preferably from 0.75% to 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.
It is to be recognized that such materials may also be used in formulations as the
sole stabilizer as well as being used in combination with added calcium and/or magnesium
ions.
[0096] Finally, it may be desired to add chlorine scavengers, especially to protease-containing
compositions, to protect the enzymes from chlorine typically, present in municipal
water supplies. Such materials are described, for example, in U.S. Patent 4,810,413
to Pancheri et al.
[0097] 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 characterised by having both hydrophilic segments, to hydrophilize the
surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments,
to deposit upon hydrophobic fibers and remain adhered thereto through completion of
washing and rinsing cycles 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.
[0098] 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 polymenzation 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 25%
oxyethylene units and more preferably, especially for such components having 20 to
30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobe
components comprising (i) C
3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise
oxyethylene terephthalate, the ratio of oxyethylene terephtahlate: C
3 oxyalkylene terephthalate units is 2:1 or lower, (ii) C
4-C
6 alkylene or oxy C
4-C
6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably
polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are
present in the form of C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose
derivatives are amphiphilic, whereby they have a sufficient level of C
1-C
4 alkyl ether and/or C
4 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).
[0099] Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization
of from 200, although higher levels can be used, preferably from 3 to 150, more preferably
from 6 to 100. Suitable oxy C
4-C
6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric
soil release agents such as MO
3S(CH
2)
nOCH
2CH
2O-, where M is sodium and n is an integer form 4-6, as disclosed in U.S. Patent 4,721,580,
issued January 26, 1988 to Gosselink.
[0100] 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 C
1-C
4 alkyl and C
4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol,
et al.
[0101] Soil release agents characterized by poly(vinyl ester) hydrophobe segments include
graft copolymers of poly(vinyl ester), e.g., C
1-C
6 vinyl esters, preferably poly(vinyl 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).
[0102] 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.
[0103] Another preferred polymeric soil release agent is a polyester with repeat units of
ethylene terephthalate units contains 10-15% 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.
[0104] 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 endcapped oligomeric esters of U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric
compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
[0105] 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.
[0106] 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 1.7 to 1.8, and two end-cap units
of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises
from 0.5% to 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.
[0107] If utilized, soil release agents will generally comprise from 0.01% to 10.0%, by
weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably
from 0.2% to 3.0%.
[0108] Chelating Agents - 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.
[0109] Amino carboxylates useful as optional chelating agents include ethylenediaminietetracetates,
N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates, diethylene-triaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
[0110] 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 DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more
than about 6 carbon atoms.
[0111] 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.
[0112] 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.
[0113] If utilized, these chelating agents will generally comprise from 0.1% to 10% by weight
of the detergent compositions herein. More preferably, if utilized, the chelating
agents will comprise from 0.1% to 3.0% by weight of such compositions.
[0114] Clay Soil Removal/Anti-redeposition Agents - 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 0.01%,
to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions
typically contain 0.01% to 5%.
[0115] 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, removal/antiredeposition
agents which can be used include the ethoxylated amine polymers disclosed in European
Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers
disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984;
and the amine oxides disclosed in U.S. 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.
[0116] Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be utilized at levels from 0.1%
to 7%, by weight, in the compositions herein. Suitable polymeric dispersing agents
include polymeric polycarboxylates and polyethylene glycols, although others known
in the art can also be used.
[0117] Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric
acids that can be polymerized to form suitable polymeric polycarboxylates include
acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic
acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the
polymeric polycarboxylates herein or monomeric segments, containing no carboxylate
radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that
such segments do not constitute more than 40% by weight.
[0118] Particularly, suitable polymeric polycarboxylates can be derived from acrylic acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble salts
of polymerized acrylic acid. The average molecular weight of such polymers in the
acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000
and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid
polymers can include, for example, the alkali metal, ammonium and substituted ammonium
salts. Soluble polymers of this type are known materials. Use of polyacrylates of
this type in detergent compositions has been disclosed, for example, in Diehl, U.S.
Patent 3,308,067, issued March 7, 1967.
[0119] Acrylic/maleic-based copolymers may also be used as a preferred component of the
dispersing/anti-redeposition agent. Such materials include the water-soluble salts
of copolymers of acrylic acid and maleic acid. The average molecular weight of such
copolymers in the acid form preferably ranges from 2,000 to 100,000. A preferred copolymer
has an average molecular weight of 2,000 to 15,000, more preferably 6,000 to 13,000,
and most preferably 7,000 to 12,000. Other preferred copolymers have an average molecular
weight from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate
to maleate segments in such copolymers will generally range from 30:1 to 1:2, more
preferably from 10:1 to 1:1, and most preferably 2.5:1 to 1:1. 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 15, 1982, as well as in EP 193, 360, published September 3, 1986,
which also describes such polymers comprising hydroxypropylacrylate. Still other useful
dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials
are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer
of acrylic/maleic/vinyl alcohol.
[0120] Particularly preferred dispersant polymers are low molecular weight modified polyacrylate
copolymers. Such copolymers contain as monomer units: a) from 90% to 10%, preferably
from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably
from 20% to 80% by weight of a substituted acrylic monomer or its salt and have the
general formula -[(C(R
2)C(R
1)(C(O)OR
3)]- wherein the incomplete valencies inside the square braces are hydrogen and at
least one of the substituents R
1, R
2 or R
3, preferably R
1 or R
2, is a 1 to 4 carbon alkyl or hydroxyalkyl group, R
1 or R
2 can be a hydrogen and R
3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer
wherein R
1 is methyl, R
2 is hydrogen and R
3 is sodium.
[0121] The low molecular weight polyacrylate dispersant polymer preferably has a molecular
weight of less than 15,000, preferably from 500 to 10,000 most preferably from 1,000
to 5,000. The most preferred polyacrylate copolymer for use herein has a molecular
weight of 3500 and is the fully neutralized form of the polymer comprising 70% by
weight acrylic acid and 30% by weight methacrylic acid.
[0122] Other suitable modified polyacrylate copolymers include the low molecular weight
copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,766,
and 5,084,535.
[0123] Agglomerated forms of the present invention may employ aqueous solutions of polymer
dispersants as liquid binders for making the agglomerate (particularly when the composition
consists of a mixture of sodium citrate and sodium carbonate). Especially preferred
are polyacrylates with an average molecular weight of from 1,000 to 10,000, and acrylate/maleate
or acrylate/fumarate copolymers with an average molecular weight of from 2,000 to
80,000 and a ratio of acrylate to maleate or fumarate segments of from 30:1 to 1:2.
Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate
monomers are disclosed in European Patent Application No. 66,915, published December
15, 1982.
[0124] Other dispersant polymers useful herein include the polyethylene glycols and polypropylene
glycols having a molecular weight of from 950 to 30,000 which can be obtained from
the Dow Chemical Company of Midland, Michigan. Such compounds for example, having
a melting point within the range of from 30° to 100°C can be obtained at molecular
weights of 1450, 3400, 4500, 6000, 7400, 9500, and 20,000. Such compounds are formed
by the polymerization of ethylene glycol or propylene glycol with the requisite number
of moles of ethylene or propylene oxide to provide the desired molecular weight and
melting point of the respective polyethylene glycol and polypropylene glycol. The
polyethylene, polypropylene and mixed glycols are referred to using the formula HO(CH
2CH
2O)
m(CH
2CH(CH
3)O)
n(CH(CH
3)CH
2O
oH wherein m, n, and o are integers satisfying the molecular weight and temperature
requirements given above.
[0125] Yet other dispersant polymers useful herein include the cellulose sulfate esters
such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate,
methylcellulose sulfate, and hydroxypropylcellulose sulfate. Sodium cellulose sulfate
is the most preferred polymer of this group.
[0126] Other suitable dispersant polymers are the carboxylated polysaccharides, particularly
starches, celluloses and alginates, described in U.S. Pat. No 3,723,322, Diehl, issued
Mar. 27, 1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No
3,929,107, Thompson, issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch
esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Pat
No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylated starches described in
U.S. Pat. No. 3,629,121, Eldib, issued Dec. 21, 1971; and the dextrin starches described
in U.S. Pat. No. 4,141,841, McDanald, issued Feb. 27, 1979; all incorporated herein
by reference. Preferred cellulose - derived dispersant polymers are the carboxymethyl
celluloses.
[0127] Yet another group of acceptable dispersants are the organic dispersant polymers,
such as polyaspartate.
[0128] 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 500 to 100,000,
preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.
[0129] Polyaspartate and polyglutamate dispersing agents may also be used, especially in
conjunction with zeolite builders. In compositions containing detergent builders,
it is believed, though it is not intended to be limited by theory, that polymeric
dispersing agents enhance overall detergent builder performance, especially zeolite
and/or silicate builders, when used in combination with other builders (including
lower molecular weight polycarboxylates) by crystal growth inhibition, particulate
soil release peptization, and anti-redeposition. Dispersing agents such as polyaspartate
preferably have a molecular weight (avg.) of 10,000.
[0130] Brightener - Any optical brighteners or other brightening or whitening agents known in the art
can be incorporated at levels typically from 0.05% to 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).
[0131] Specific examples of optical brighteners which are useful in the present compositions
are those identified in U.S Patent 4,790,856, issued to Wixon on December 13, 1988.
These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners
disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, 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-yl)ethylene;
1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-d]oxazole;
and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole. See also U.S. Patent 3,646,015,
issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.
[0132] 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.
[0133] 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.
[0134] The detergent compositions herein may also contain non-surfactant suds suppressors.
These include, for example: high molecular weight hydrocarbons such as paraffin, fatty
acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols
and aliphatic C
18-C
40 ketones (e.g., stearone). 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 -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure).
It is also known to utilize waxy hydrocarbons, preferably having a melting point below
100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent
compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent
4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include aliphatic,
alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having
from 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion,
is intended to include mixtures of true paraffins and cyclic hydrocarbons.
[0135] 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, discloded in U.S. Patent 4,265,779, issued May 5,
1981 to Gandolfo et al and European Patent Application 354,016, published February
7, 1990, by Starch, M.S.
[0136] 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.
[0137] Mixtures of silicone and silanated silica are described, for instance, in German
Patent Application DOS 2,214,526. 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.
[0138] 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 20×10-3 Pascal seconds to 1.5 Pascal seconds (20 cps to 1,500 cps at 25°C);
(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resin composed
of (CH3)3 SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to SiO2 units of from 0,6:1 to 1.2.1, and
(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid silica gel.
[0139] 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.
[0140] To illustrate this point further, typical liquid laundry detergent compositions with
controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to
0.7, most preferably from 0.05 to 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
22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line
46 through column 4, line 35.
[0141] The silicone suds suppressor herein preferably comprises polyethylene glycol and
a copolymer of polyethylene glyco/polypropylene glycol, all having an average molecular
weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol
and polyethylene/polypropylene copolymers herein have a solubility in water at room
temperature of more than 2 weight %, preferably more than 5 weight %. The prefered
solvent herein is polyethylene glycol having an average molecular weight of less than
1,000, more preferably between 100 and 800, most preferably between 200 and 400, and
a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
Preferred is a weight ratio of between 1:1 and 1:10, most preferably between 1:3 and
1:6, of polyethylene glycol copolymer of polyethylene-polypropylene glycol.
[0142] 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 PLURONIC L101.
[0143] 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 C
6-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. Mixed suds suppressor typically comprises mixtures of alcohol
+ silicone at a weight ratio of 1:5 to 5:1.
[0144] 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.
[0145] The compositions herein will generally comprise from 0% to 5% of suds suppressor.
When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein,
will be present typically in amounts up to 5%, by weight, of the detergent composition.
Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
Silicone suds suppressors are typically utilized in amounts up to 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 amounts for effectively controlling sudsing. Preferably from
0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 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 amounts
ranging from 0.1% to 2%, by weight, of the composition.
[0146] Hydrocarbon suds suppressors are typically utilized in amounts ranging from about
0.01% to 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.
[0147] Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays
of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as
other softener clays known in the art, can optionally be used typically at levels
of from 0.5% to 10% by weight in the present compositions to provide fabric softener
benefits concurrently with fabric cleaning. Clay softeners can be used in combination
with amine and cationic softeners as disclosed, for example in U.S. Patent 4,375,416,
Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September
22, 1981.
[0148] Dye 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 0.01% to 10% by weight of the composition,
preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.
[0149] More specifically, the poylamine N-oxide polymers preferred for use herein contain
units having the following structural formula: R-A
x-P; wherein P is a 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.
[0150] The N-O group can be represented by the following general structures:
wherein R
1, R
2, R
3, are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof;
x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part
of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides
has a pKa<10, preferably pKa<7, more preferred pKa<6.
[0151] 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".
[0152] 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 50,000 and
an amine to amine N-oxide ratio of 1:4.
[0153] 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 molecular weight range is
determined by light scattering as described in Barth, et al.,
Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which
are incorporated herein by reference.) 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.
[0154] The present invention compositions also may employ a polyvinyl-pyrrolidone ("PVP")
having an average molecular weight of from 5,000 to 400,000, preferably from 5,000
to 200,000, and more preferably from 5,000 to 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 500 to 100,000, preferably from 1,000 to 10,000. Preferably, the ratio
of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and
more preferably from 3:1 to 10:1.
[0155] The detergent compositions herein may also optionally contain from 0.005% to 5% by
weight of certain types of hydrophilic optical brighteners which also provide a dye
transfer inhibition action. If used, the compositions herein will preferably comprise
from 0.01% to 1% by weight of such optical brighteners.
[0156] The hydrophilic optical brighteners useful in the present invention are those having
the structural formula:
wherein R
1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R
2 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.
[0157] When in the above formula, R
1 is anilino, R
2 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 tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is
the preferred hydrophilic optical brightener useful in the detergent compositions
herein.
[0158] When in the above formula, R
1 is anilino, R
2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener
is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid disodium salt. This particular brightener species is commercially marketed under
the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
[0159] When in the above formula, R
1 is anilino, R
2 is morphilino and M is a cation 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 tradename Tinopal AMS-GX by Ciba Geigy Corporation.
[0160] The specific optical brightener species selected for use in the present invention
provide especially effective dye transfer inhibition performance benefits when used
in combination with the selected polymeric dye transfer inhibiting agents hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX,
Tinopal-PLC, 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 coefficient 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.
[0161] 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.
[0162] 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 liquid formulations, solid fillers
for bar compositions, etc. If high sudsing is desired, suds boosters such as the C
10-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 MgCl
2 and MgSO
4, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to
enhance grease removal performance.
[0163] 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 the substrate into the aqueous washing
liquor, where it performs its intended detersive function.
[0164] To illustrate this technique in more detail, a porous hydrophobic silica (trademark
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5%
of C
13-15 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 500-12,500 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.
[0165] 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.
[0166] Granular detergents can be prepared, for example, by spray-drying (final product
density 520 g/l) or agglomerating (final product density above 600 g/l) the Base Granule.
The remaining dry ingredients can then be admixed in granular or powder form with
the Base Granule, for example in a rotary mixing drum, and the liquid ingredients
(e.g., nonionic surfactant and perfume) can be sprayed on.
[0167] 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 6.5 and
11, preferably between 7.5 and 10.5. Liquid dishwashing product formulations preferably
have a pH between 6.8 and 9.0. 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.
[0168] The following examples illustrate compositions according to the invention, but are
not intended to be limiting thereof.
EXAMPLE I
[0169] A dry laundry bleach is as follows:
Ingredient |
% (Wt.) |
Sodium Percarbonate |
20 |
Benzoyl caprolactam |
10 |
Citrate |
10 |
Mn·catalyst* |
0.2 |
C12-18 alkyl ethoxy (0.6)sulfate |
12 |
Oleoyl Sarcosinate |
12 |
Water-soluble filler** |
Balance |
*MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, as described in U.S. Pat. Nos. 5,246,621 and 5,244,594. |
**Sodium carbonate, sodium silicate mixture (1:1). |
[0170] In the foregoing composition, the sodium percarbonate can be replaced by an equivalent
amount of perborate.
[0171] Additionally, in the foregoing composition, the bleach activator can be replaced
by an equivalent amount of the following activators: benzoyl valerolactam, nonanoyl
caprolactam, nonanoyl valerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam,
octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam,
undecenoyl caprolactam, undecenoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam,
3,5,5-trimethylhexanoyl valerolactam, dinitrobenzoyl caprolactam, dinitrobenzoyl valerolactam,
terephthaloyl dicaprolactam, terephthaloyl divalerolactam, (6-octan-amidocaproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate,
and mixtures thereof.
[0172] 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.
[0173] In use for fabric cleaning, the compositions are employed in conventional manner
and at conventional concentration. Thus, in a typical mode, the compositions are placed
in an aqueous liquor at levels which may range from 100 ppm to 10,000 ppm, depending
on soil load and the stained fabrics are agitated therewith.
EXAMPLE II
[0174] The following liquid detergent compositions are prepared (parts by weight).
Components |
Weight % |
Oleoyl Sarcosinate |
9 |
C12-18 alkyl ethoxy (0.6)sulfate |
12 |
C12-14 N-methyl glucamide |
6 |
C9-11 alkyl ethoxylate (eo = 8) |
3 |
C12-20 fatty acid |
4 |
Citric Acid |
0.5 |
Percarbonate |
5 |
Nonanoyl Caprolactam |
5 |
Protease |
0.5 |
Lipase |
0.2 |
Amylase |
0.1 |
Cellualase enzyme |
0.1 |
Brightener |
0.9 |
Soil release polymer z |
0.2 |
Water and miscellaneous to balance. |
[0175] The above compositions can further be modified by adding an equivalent amount of
a bleach catalysts identified in Example I.
[0176] The above compositions can be modified by replacing the nonanoyl capro-lactam with
an equivalent amount of the bleach activators identified in Example I.
EXAMPLE III
[0177] A bleaching system, useful as a bleach additive, is prepared comprising the following
ingredients.
Components |
Weight % |
Nonanoyl valerolactam |
15 |
Sodium percarbonate* |
25 |
Ethylenediamine disuccinate chelant |
10 |
Oleoyl Sarcosinate |
25 |
Minors, filler** and water |
Balance to 100% |
*Average particle size of 400 to 1200 microns. |
**Can be selected from convenient materials such as CaCO3, talc, clay, silicates, and the like. |
[0178] The above compositions can be modified by the addition of lipase enzymes.
[0179] The above compositions can also be modified by replacing the nonanoyl valerolactam
bleach activator with an equivalent amount of the bleach activators identified in
Example I and/or with the addition of 0.1% metal catalyst.
[0180] The above compositions can also be modified by replacing the percarbonate with an
equivalent amount of perborate.
EXAMPLE IV
[0181] A laundry bar with bleach is prepared by standard extrusion processes and comprises:
Oleoyl Sarcosinate (20%); sodium tripolyphosphate (20%); sodium silicate (7%), sodium
perborate monohydrate (10%); (6-decanamidocaproyl)oxybenzenesulfonate (10%), (1.0%);
MgSO
4 or talc filler; and water (5%).
[0182] The above compositions can be modified by the addition of lipase enzymes.
[0183] The above compositions can also be modified by replacing the (6-decanamidocaproyl)oxybenzenesulfonate
bleach activator with an equivalent amount of the bleach activators identified in
Example I and/or with the addition of 0.1% metal catalyst.
[0184] The above compositions can also be modified by replacing the perborate with an equivalent
amount of percarbonate.
EXAMPLE V
[0185] An automatic dishwashing composition is as follows.
Ingredient |
% (Wt.) |
Oleoyl Sarcosinate |
6 |
Trisodium Citrate |
15 |
Sodium Carbonate |
20 |
Silicate1 |
9 |
Nonionic Surfactant2 |
3 |
Sodium Polyacrylate (m.w 4000)3 |
5 |
Termamyl Enzyme (60T) |
1.1 |
Savinase Enzyme (12T) |
3.0 |
Sodium perborate monohydrate |
10 |
Benzoyl caprolactam |
2 |
Mn·catalyst4 |
0.03 |
Minors |
Balance |
1BRITESIL, PQ Corporation |
2Polyethyleneoxide/polypropyleneoxide low sudser |
3ACCUSOL, Rohm and Haas |
41:1 mole ratio of Mn cation and ligand to form MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, in situ |
[0186] In the above composition, the perborate can be replaced by an equivalent amount of
percarbonate.
[0187] In the above composition, the bleach catalyst can be replaced by an equivalent amount
of preformed bleach catalyst, as identified in Example I, or with metal cations and
ligands to form the bleach catalysts identified in Example I.
[0188] The above compositions can also be modified by replacing the benzoyl caprolactam
with an equivalent amount of the bleach activators identified in Example I.
[0189] In the above composition, the surfactant may be replaced by an equivalent amount
of any low-foaming, nonionic surfactant. Example include low-foaming or non-foaming
ethoxylated straight-chain alcohols such as Plurafac
TM RA series, supplied by Eurane Co., Lutensol
TM LF series, supplied by BASF Co., Triton
TM DF series, supplied by Rohm & Haas Co., and Synperonic
TM LF series, supplied by ICI Co.
[0190] Automatic dishwashing compositions may be in granular, tablet, bar, or rinse aid
form. Methods of making granules, tablets, bars, or rinse aids are known in the an
See, for instance, U.S Pat Serial Nos. 08/106,022, 08/147,222, 08/147,224, 08/147,219,
08/052,860, 07/867,941.
[0191] All of the foregoing granular compositions may be provided as spray-dried granules
or high density (above 600 g/l) granules or agglomerates. If desired, the Mn·catalyst
may be adsorbed onto and into water-soluble granules to keep the catalyst separate
from the balance of the compositions, thus providing additional stability on storage.
Such granules (which should not contain oxidizable components) can comprise, for example,
water-soluble silicates, carbonates and the like.
[0192] Although the foregoing compositions are typical of those useful herein, it is most
preferred that: (I) the compositions not contain STPP builder; (2) that the nonionic:anionic
surfactant ratio be greater than 1:1, preferably at least 1.5:1; and (3) that at least
1% perborate or other chlorine scavenger be present in the compositions to minimize
formation of MnO
2 in use.
[0193] While the foregoing examples illustrate the use of the present technology in cleaning/bleaching
compositions designed for use in laundering and dishcare, it will be appreciated by
those skilled in the art that the catalyzed bleaching systems herein can be employed
under any circumstance where improved oxygen bleaching is desired. Thus, the technology
of this invention may be used, for example, to bleach paper pulp, to bleach hair,
to cleanse and sanitize prosthetic devices such as dentures, in dentifrice compositions
to clean teeth and kill oral bacteria, and in any other circumstances where bleaching
is advantageous to the user.