Note: Descriptions are shown in the official language in which they were submitted.
-~'O 94I28105 216 2 3 6 2 pCT/(JS94/05371
BLEACHING COMPOUNDS COMPRISING N-ACYL CAPROLACTAM AND
ALKANOYLOXYBENZENF SULFONATE BLEACH ACTIVATORS
s
FIELD OF THE INVENTION
The present invention relates to laundry detergents and automatic dishwashing
compositions with activated bleaching systems which are effective under mixed
soil
to conditions, especially mixtures of hydrophobic and hydrophilic soils and
stains.
BACKGROUND OF THE INVENTION
15 It has long been known that peroxygen bleaches are effective for stain
and/or soil
removal from fabrics) but that such bleaches are temperature dependent. At a
laundry
liquor temperature of 60~C, peroxygen bleaches are only partially effective.
As the
laundry liquor temperature is lowered below 60~C, peroxygen bleaches become
relatively
ineffective. As a consequence, there has been a substantial amount of
industrial research
2o to develop bleaching systems which contain an activator that renders
peroxygen bleaches
effective at laundry liquor temperatures below 60~C.
Numerous substances have been disclosed in the art as effective bleach
activators.
One widely-used bleach activator is tetraacetyl ethylene diamine (TAED). TAED
provides effective hydrophilic cleaning especially on beverage stains, but has
limited
25 performance on dingy stains and body soils. Another type of activator, such
as
nonanoyloxy-benzenesulfonate (HOBS) and other activators which generally
comprise
long chain alkyl moieties, is hydrophobic in nature and provides excellent
performance on
dingy stains.
It would seem that a combination of bleach activators, such as TAED and NOBS,
3o would provide an effective detergent composition which would perform well
on both
hydrophilic and hydrophobic soils and stains. However, many of the hydrophilic
activators devetoped thus far, including TAED, have been found to have limited
efficacy,
especially at laundry liquor temperatures below 60~C. Another consideration in
the
development of consumer products effective on both types of soils is the
additional costs
35 associated with the inclusion of two or more bleach activators.
Accordingly, it is of
substantial interest to the manufacturers of bleaching systems to find a less
expensive type
of hydrophilic bleaching activator.
CA 02162362 1999-04-20
-2-
By the present invention, it has now been discovered that the class of bleach
activators derived from hydrophilic N-acyl caprolactams performs very well
when
combined with the cleaning performance of hydrophobic
alkanoyloxybenzenesulfonate
and has the added benefit of being relatively inexpensive to manufacture.
Accordingly,
the present invention solves the long-standing need for an inexpensive
bleaching system
which performs efficiently and effectively at low temperatures and under mixed
soil load
conditions especially mixtures of hydrophobic and hydrophilic soils.
BACKGROUND ART
U.S. Patent 4,545,784, Sanderson, issued October 8, 1985, discloses the
adsorption of activators onto sodium perborate monohydrate.
U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, discloses
alkanoyloxybenzenesulfonate activators, including the preferred
nonanoyloxybenzenesulfonate activator used herein.
SUMMARY OF THE INVENTION
The present invention relates to bleaching systems and methods which employ
them for cleaning fabrics under mixed soil load conditions. Said bleaching
system
comprises:
i) a peroxygen bleaching compound;
ii) a hydrophilic N-acyl caprolactam bleach activator wherein the acyl moiety
of said N-acyl caprolactam is of the formula R1 --C(O)-- wherein R1 is H
or an alkyl or aryl group containing from about 1 to about 6 carbon atoms;
and
iii) an alkanoyloxybenzenesulfonate bleach activator, wherein said alkanoyl
moiety contains from about 8 to about 12 carbon atoms; such that the
molar ratio of N-acyl caprolactam:alkanoyloxybenzenefulfonate:
peroxygen bleaching compound is approximately 1:2.2:7.7.
The preferred alkanoyl moieties of said alkanoyloxybenezene- sulfonate bleach
activators contain from about 8 to about 12 carbon atoms, preferably from
about 8 to
about 11 carbons. Highly preferred moieties are members selected from the
group
CA 02162362 1999-04-20
-2a-
consisting of octanoyl, nonanoyl, decanoyl, dodecanoyl, 3,5,5-trimethylhexa-
noyl, 2-
ethylhexanoyl, and mixtures thereof.
The acyl moieties of said N-acyl caprolactam bleach activators have the
formula
R'-CO-wherein Rl is H or an alkyl, aryl, alkaryl, or alkoxyaryl group
containing from
about 1 to about 6 carbon atoms. In preferred embodiments, Rl is a member
selected
from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, and
phenyl
substituents.
The peroxygen bleaching compound can be any peroxide source, and is preferably
a member selected from the group consisting of sodium perborate monohydrate,
sodium
perborate tetrahydrate, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, sodium
percarbonate, sodium peroxide and mixtures thereof. Highly preferred peroxygen
bleaching compounds are selected from the group consisting of sodium perborate
'"O 94I28105 PCT/US94/05371
3
monohydrate, sodium perborate tetrahydrate) sodium percarbonate and mixtures
thereof
The most highly preferred peroxygen bleaching compound is sodium percar-
bonate.
The invention also encompasses detergent compositions in granular, paste,
liquid,
or bar form which comprise the aforesaid bleaching system together with
detersive
ingedients which are present in the composition at the levels indicated
hereinafter.
The bleaching method herein is preferably conducted with agitation of the
fabrics
with an aqueous liquor containing the aforesaid compositions at levels from
about 50 ppm
to about 27,500 ppm, and is especially adapted for conditions in which the
fabrics are
soiled with both hydrophobic and hydrophilic soils. The method can be carried
out at any
1o desired washing temperature, even at temperatures below about 60~C) and is
readily
conducted at temperatures in the range of from about 5~C to about 45~C. The
method
can be conducted conveniently using a composition which is in bar fornt, but
can also be
conducted using ganules, flakes, powders, pastes, and the like.
The aqueous laundry liquor typically comprises at least about 300 ppm of
~5 conventional detergent ingedients) as well as at least about 25 ppm of the
bleaching
compound and at least about 25 ppm of the mixture of bleach activators.
Preferably, the
liquor comprises from about 900 ppm to about 20,000 ppm of conventional
detergent
ingredients, from about 100 ppm to about 25,000 ppm of the bleaching compound
and
from about 100 ppm to about 2,500 ppm of the bleach activators. The
conventional
2o detergent ingedients and bleaching system will typically be combined into a
detergent
composition such as a granular laundry detergent or laundry detergent bar.
The conventional detergent ingredients employed in said method and in the
compositions herein comprise from about 1% to about 99.8%, preferably from
about 5%
to about 80%, of a detersive surfactant. Optionally, the detergent ingredients
comprise
25 from about 5% to about 80% of a detergent builder. Other optional detersive
adjuncts
can also be included in such compositions at conventional usage levels.
All percentages) ratios, and proportions herein are by weight, unless
otherwise
specified. All documents cited are incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
3o The bleaching system employed in the present invention provides effective
and
efficient surface bleaching of fabrics which thereby removes stains and/or
soils from the
fabrics. The bleaching system is particularly efficient at cleaning a mixture
of soil loads,
especially mixtures of hydrophobic and hydrophilic soils. Hydrophobic soils
are generally
associated with lipid and protein-based soils and stains, such as body soils,
blood, etc.) but
35 are also effective on so-called "dingy soils". Dingy soils are those that
build up on textiles
after numerous cycles of usage and washing, and result in a gay or yellow tint
on white
fabrics. Hydrophilic soils include food and beverage stains.
PCT/US94l05371
Wo 94b><0$ 21 b 2 3 6 2
4
The bleaching mechanism and, in particular, the surface bleaching mechanism
are
not completely understood. However, it is generally believed that the N-acyl
bleach
activator undergoes nucleophilic attack by a perhydroxide anion, which is
generated from
the hydrogen peroxide evolved by the peroxygen bleaching compound, to form a
peroxycarboxylic acid. This reaction is commonly referred to as perhydrolysis.
It is also
believed, that the N-acyl and alkanoyloxybenzenesulfonate bleach activators
within this
invention can render peroxygen bleaches more efficient even at laundry liquor
.
temperatures wherein bleach activators are not necessary to activate the
bleach, i.e.,
above about 60~C. Therefore, with bleach systems of the invention, less
peroxygen
bleach is required to achieve the same level of surface bleaching performance
as is
obtained with the peroxygen bleach alone.
The components of the bleaching system herein comprise the bleach activator
and
the peroxide source, as described hereinafter.
Bleach Activators
1s The bleach activators of type b) employed in the present invention are
hydrophilic
N-acyl caprolactams of the formula:
O
II
0 C -C hit-C H2
R'-C-NBC -CH ~CH2
H2 z
wherein R 1 is H or an alkyl, aryl) alkaryl, or alkoxyaryl group containing
from about 1 to
2o about 6 carbon atoms. Caprolactam activators wherein the R 1 moiety
contains from
about 1 to about 6 carbon atoms provide hydrophilic bleaching which affords
beverage
and food stain removal.
Benzoyl caprolactam, i. e.) wherein R 1 is a phenyl substituent, has now been
found
to be unique among the bleach activator compounds, inasmuch as it appears to
exhibit
25 both hydrophobic and hydrophilic bleaching activity. This
hydrophobiclhydrophilic
bleaching capability makes benzoyl caprolactam the activator of choice for the
formulator
who is seeking broad spectrum bleaching activity, and wishes to use a single
caprolactam
activator for hydrophilic cleaning and for additional hydrophobic performance
in
combination with the alkanoyloxybenzenesulfonate activator.
3o Highly preferred hydrophilic N-acyl caprolactams are selected from the
group
consisting of formyl caprolactam, acetyl caprolactam, propanoyl caprolactam,
butanoyl
caprolactam) pentanoyl caprolactam, hexanoyl caprolactam, and benzoyl
caprolactam.
Methods of making N-aryl caprolactams are well known in the art. Example I,
included below, illustrates a preferred laboratory synthesis. Contrary to the
teachings of
3 s U. S . Pat. 4, 545, 784, cited above, the bleach activator is preferably
not absorbed onto the
2162362
-a'O 94/28105 PCT/US94/05371
peroxygen bleaching compound. To do so in the presence of other organic
detersive
ingredients could cause safety problems.
The bleach activators of type c) employed in the present invention are
alkanoy(oxybenzenesulfonates of the formula:
0
a
R~-C-O O S03M
s
wherein R1-C(O)- contains from about 8 to about 12, preferably from about 8 to
about
11, carbon atoms and M is a suitable cation, such as an alkali metal,
ammonium, or
substituted ammonium canon, with sodium and potassium being most preferred
Highly preferred hydrophobic alkanoyloxybenzenesulfonates are selected from
the
goup consisting of nonanoyloxybenzenesulfonate) 3,5,5-
trimethylhexanoyloxybenzene-
sulfonate, 2-ethylhexanoyloxybenzenesulfonate, octanoyloxybenzenesulfonate)
decanoyl-
oxybenzenesulfonate) dodecanoyloxybenzenesulfonate, and mixtures thereof.
The bleaching system comprises at least about 0.1 %, preferably from about 0.1
% to
about 30%, more preferably from about 1 % to about 30%, most preferably from
about
3% to about 25%, by weight, of type b) and type c) bleach activators.
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,
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
2o components of the bleaching systems herein.
The Peroxygen Bleachin Compound
The peroxygen bleaching compounds useful herein are those capable of yielding
hydrogen peroxide in an aqueous liquor. These compounds are well known in the
art and
include hydrogen peroxide and the alkali metal peroxides, organic peroxide
bleaching
compounds such as urea peroxide) and inorganic persalt bleaching compounds,
such as
the alkali metal perborates, percarbonates) perphosphates, and the like.
Mixtures of two
or more such bleaching compounds can also be used, if desired.
Preferred peroxygen bleaching compounds include sodium perborate, commercially
available in the form of mono-, tri-, and tetra-hydrate, sodium pyrophosphate
3o peroxyhydrate, urea peroxy- hydrate) sodium peroxide, and sodium
percarbonate.
Particularly preferred are sodium perborate tetrahydrate, sodium perborate
monohydrate
and sodium percarbonate. Sodium percarbonate is especially preferred because
it is very
stable during storage and yet still dissolves very quickly in the bleaching
liquor. It is
believed that such rapid dissolution results in the formation of higher levels
of
percarboxylic acid and, thus, enhanced surface bleaching performance.
WO 94I28105 216 2 3 6 2 PCT/US94/05371
6
Highly preferred percarbonate can be in uncoated or coated' form. The average
particle size of uncoated percarbonate ranges from about 400 to about 1200
microns,
most preferably from about 400 to about 600 microns. If coated percarbonate is
used, the
preferred coating materials include mixtures of carbonate and sulphate,
silicate,
borosilicate, or fatty carboxylic acids.
The bleaching system comprises at least about 0.1 %, preferably from about 1 %
to
about 75%, more preferably from about 3% to about 40%, most preferably from
about ,
3% to about 25%, by weight, of a peroxygen bleaching compound capable of
yielding
hydrogen peroxide in an aqueous solution.
1 o The weight ratio of bleach activator to peroxygen bleaching compound in
the
bleaching system typically ranges from about 2:1 to 1:5. In preferred
embodiments, the
ratio ranges from about 1:1 to about 1:3.
The bleach activator/bleaching compound systems herein are useful per se as
bleaches. However, such bleaching systems are especially useful in
compositions which
can comprise various detersive adjuncts such as surfactants, builders,
enzymes, and the
like as disclosed hereinafter.
Detersive Surfactant
The amount of detersive surfactant included in the fully-formulated detergent
compositions afforded by the present invention can vary from about 1% to about
99.8%)
zo by weight of the detergent ingredients, depending upon the particular
surfactants used and
the effects desired. Preferably, the detersive surfactants comprise from about
5% to about
80%, by weight of the detergent ingredients.
The detersive surfactant can be nonionic) anionic, ampholytic, zwitterionic,
or
cationic. Mixtures of these surfactants can also be used. Preferred detergent
15 compositions comprise anionic detersive surfactants or mixtures of anionic
surfactants
with other surfactants, especially nonionic surfactants.
Noniimiting examples of surfactants useful herein include the conventional
C 11 ~ I 8 ~'1 a sulfonates and primary, secondary, and random alkyl sulfates,
the
C 10~ 18 ~'1 ~koxy sulfates, the C 10-C 18 alkyl polyglycosides and their
corresponding
3o sulfated polyglycosides, C 12-C 18 alpha-sulfonated fatty acid esters, C 12-
C 18 alkyl and
alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C
12-C 18
betaines and sulfobetaines ("sultaines")) C 10-C 1 g amine oxides, and the
like. Other
conventional useful surfactants are listed in standard texts.
One particular class of adjuncri nonionic surfactants especially useful herein
3s comprises the polyhydroxy fatty acid amides ofthe formula:
O R1
(I) R2-C-N-Z
216262
--"~J 94/28105 . PCT/US94105371
7
wherein: R 1 is H, C 1-C8 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl) or a
mixture
thereoly preferably C~-C4 alkyl, more preferably C 1 or C2 alkyl, most
preferably C 1 alkyl
(i.e., methyl); and R is a CS-C32 hydrocarbyl moiety, preferably straight
chain C7-C 19
alkyl or alkenyl) more preferably straight chain C9-C 17 alkyl or alkenyl,
most preferably
, 5 straight chain C 11-C 19 alkyl or alkenyl, or mixture thereof; and Z is a
polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least
2 (in the
case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing
sugars)
directly connected to the chain, or an alkoxylated derivative (preferably
ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing sugar in a
reductive
1o amination reaction; more preferably Z is a glycityl moiety. Suitable
reducing sugars
include glucose, fructose, maltose) lactose, galactose, mannose, and xytose,
as well as
glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn
syrup) and
high maltose corn syrup can be utilized as well as the individual sugars
listed above.
These corn syrups may yield a mix of sugar components for Z. It should be
understood
t5 that it is by no means intended to exclude other suitable raw materials. Z
preferably will
be selected from the group consisting of -CH2-(CHOH)n-CH20H,
-CH(CH20H~(CHOH)n-1-CH20H, -CH2-(CHOH)2(CHOR') (CHOH)-CH20H, where
n is an integer from 1 to 5, inclusive) and R' is H or a cyclic mono- or poly-
saccharide)
and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is
4,
2o particularly -CH2-(CHOH)4-CH20H.
In Formula (I)) RI can be, for example, N-methyl, N-ethyl, N-propyl, N-
isopropyl,
N-butyl, N-isobutyl) N-2-hydroxy ethyl, or N-2-hydroxy propyl. For highest
sudsing, R 1
is preferably methyl or hydroxyalkyl. If lower sudsing is desired, R1 is
preferably C2-C8
alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl and
2-ethyl hexyl.
25 R2-CO-N< can be, for example, cocamide, stearamide, oleamide, iauramide)
myristamide, capricamide, palmitamide, tallowamide, etc.
Detergent Builders
Optional detergent ingredients employed in the present invention contain
inorganic
and/or organic detergent builders to assist in mineral hardness control. If
used, these
3o builders comprise from about 5% to about 80% by weight of the detergent
compositions.
Inorganic detergent builders include) but are not limited to, the alkali
metal,
ammonium and alkanolammonium salts of polyphosphates (exemplified by the
tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates))
phosphonates,
phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates,
35 and aluminosilicates. However, non-phosphate builders are required in some
locales.
Examples of silicate builders are the alkali metal silicates, particularly
those having a
Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the
layered
sodium silicates described in U.S. Patent 4,664,839, issued May 12) 1987 to H.
P. Rieck,
PCT/US94/05371
WO 94I28105
8
available from Hoechst under the trademark "SKS"; SKS-6 is an especially
preferred
layered silicate builder.
Carbonate builders, especially a finely ground calcium carbonate with surface
area
greater than 10 m2/g, are preferred builders that can be used in granular
compositions.
The density of such alkali metal carbonate built detergents can be in the
range of 450-8S0
g/1 with the moisture content preferably below 4%. Examples of carbonate
builders are
the alkaline earth and alkali metal carbonates as disclosed in German Patent
Application
No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are especially useful in the present invention.
Preferred
aluminosilicates are zeolite builders which have the formula:
Nazl(A102)z (Si02)y]'xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0
to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing
aluminosilicate ion exchange materials is disclosed in U. S. Patent 3,985,669,
Krummel, et
al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate
ion exchange
materials useful herein are available under the designations Zeolite A,
Zeolite P (B), and
2o Zeolite X. Preferably, the aluminosilicate has a particle size of about 0.1-
10 microns in
diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds, such as
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.
Other useful detergent builders include the ether hydroxypolycarboxylates)
copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3) 5-
trihydroxy
3o 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,S-tricar-
boxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders) e.g., citric acid and soluble salts thereof (particularly
sodium salt),
are preferred polycarboxylate builders that can also be used in granular
compositions,
especially in combination with zeolite and/or layered silicate builders.
---~J 94/28105 216 2 3 6 2 pCT/US94105371
9
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.
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.
Qptional Detersive Adiuncts
As a preferred embodiment, the conventional detergent ingredients employed
herein
can be selected from typical detergent composition components such as
detersive
surfactants and detergent builders. Optionally) the detergent ingredients can
include one
or more other detersive adjuncts 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. Usual detersive adjuncts of detergent compositions
include the
ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et al. Adjuncts
which can
also be included in detergent compositions employed in the present invention,
in their
conventional art-established levels for use (generally from 0% to about 20% of
the
2o detergent ingredients) preferably from about 0.5% to about 10%), include
enzymes,
especially proteases, lipases and cellulases, color speckles, suds boosters,
suds
suppressors, antitarrtish and/or anticorrosion agents) soil-suspending agents,
soil release
agents, dyes, fillers, optical brighteners) germicides, alkalinity sources,
hydrotropes)
antioxidants, enzyme stabilizing agents) perfumes, solvents, solubilizing
agents, clay soil
removal/anti-redeposition agents) polymeric dispersing agents, processing
aids, fabric
softening components static control agents) etc.
Bleach systems optionally, but preferably, will also comprise a chelant which
not
only enhances bleach stability by scavenging heavy metal ions which tend to
decompose
bleaches) but also assists in the removal of polyphenolic stains such as tea
stains) and the
like. Various chelants) including the aminophosphonates) available as DEQUEST
from
Monsanto) the nittilotriacetates) the hydroxyethyl-ethylenediamine
triacetates, and the
like) are known for such use. Preferred biodegradable, non-phosphorus chelants
include
ethylenediamine disuccinate ("EDDS"; see U.S. Patent 4,704,233) Hartman and
Perkins),
ethylenediamine-N,N-diglutamate (EDDG) and 2-hydroxypropylenediamine-N,N-
disuccinate (I~DDS) compounds. Such chelants can be used in their alkali or
alkaline
earth metal salts, typically at levels from about 0.1 % to about 10% of the
present
compositions.
PCT/US94/05371
W0 94/28105 ~ ~ 6 ~ 3 6 2
Optionally, the detergent compositions employed herein can comprise, in
addition
to the bleaching system of the present invention) one or more other
conventional
bleaching agents, activators, or stabilizers which are not rendered
ineffective from
interaction with the nucleophilic and body soils. In general) the formulator
will ensure
s that the bleach compounds used are compatible with the detergent
formulation. .
Conventional tests, such as tests of bleach activity on storage in the
presence of the
separate or fully-formulated ingredients, can be used for this purpose. .
Specific examples of optional bleach activators for incorporation in this
invention
include) hydrophobic N-acyl caprolactam bleach activators wherein the aryl
moiety
t o contains from 6 to 12 carbon atoms) the benzoxazin-type bleaching
activators disclosed in
U.S. Patent 4,966,723, Hodge et al, issued Oct. 30, l990, and the bleach
agents and
activators disclosed in U.S. Patent 4,634,551, Burns et al, issued Jan. 6,
1987. Such
bleaching compounds and agents can be optionally included in detergent
compositions in
their conventional art-established levels of use, generally from 0% to about
15%, by
is weight of detergent composition.
Bleaching activators of the invention are especially useful in conventional
laundry
detergent compositions such as those typically found in granular detergents or
laundry
bars. U.S. Patent 3,178,370) Okenfuss, issued April 13, 1965, describes
laundry
detergent bars and processes for making them. Philippine Patent 13,778,
Anderson)
2o issued Sept. 23, 1980, describes synthetic detergent laundry bars. Methods
for making
laundry detergent bars by various extrusion methods are well known in the art.
The following examples are given to further illustrate the present invention,
but are
not intended to be limiting thereof.
EXAMPLE I
25 Synthesis of Benzoyl Caprolactam - To a two.liter three necked round
bottomed
flask equipped with a condenser) overhead stirrer and 250m1 addition funnel is
charged
68.2g (0.6 moles) caprolactam) 70g (0.7 moles) triethylamine and 1 liter of
dioxane; the
resulting solution is heated to reflux ( 120~C). A solution of 84.4g (0.6
moles) benzoyl
chloride dissolved in 200m1 of dioxane is then added over 30 minutes) and the
mixture is
3o refluxed for a further 6 hours. The reaction mixture is then cooled)
filtered) and the
solvent removed by rotary evaporation to yield 121.7g of the product as an oil
which
crystallizes on 'standing. This crude product is then redissolved in toluene
and
precipitated with hexane, yielding 103g (79% theoretical yield) of a white
solid which
which is shown by NMR to be over 95% pure, with the remaining material being
benzoic
35 acid.
EXAMPLE II
Synthesis of Nonanoyloxybenzenesulfonate - A 500 m1 3-neck flask is fitted
with a ,
reflux condenser and mechanical stirrer. The flask is purged with nitrogen and
charged
'O 94/28105 216 2 3 6 2 pCT~S94/05371
with 0.25 moles on nonanoyl chloride in 200 ml of dry toluene. Anhydrous p-
phenol-
sulfonate, monosodium salt (0.20 moles) is added as a powder, and the
resulting mixture
refluxed under nitrogen for 16 hours. The mixture is cooled to room
temperature and
diluted with 200 ml diethyl ether. The precipitated solid is collected by
filtration and
washed with 100 ml of diethyl ether. The solid is triturated with 200 ml of
boiling
methanol. After cooling, the solid is collected by filtration, washed with 100
m1 of
methanol, and dried under vacuum. NMR and cationic titration analyses shows
the
resulting nonanoyloxybenzenesulfonate) sodium salt (0.15 moles) to be over 98%
pure.
EXAMPLE III
to A ganular detergent composition is prepared comprising the following
ingredients.
Component Wei ht
C 12 linear alkyl benzene sulfonate 22
Phosphate (as sodium tripolyphosphate) 20
Sodium carbonate 10
Sodium silicate 3
Sodium percarbonate* 20
Ethylenediamine disuccinate chelant (EDDS) 0.4
Sodium sulfate .5
Benzoyl caprolactam 5
2o Nonanoyloxybenzenesulfonate 5
Minors, filler** and water Balance to 100%
*Average particle size of 400 to 1200 microns.
**Can be selected from convenient materials such as CaC03, talc, clay,
silicates, and the
like.
Aqueous crutcher mixes of heat and alkali stable ~ components of the detergent
compositions are prepared and spray-dried. The other ingedients are admixed so
that the
detergent composition contains the ingredients tabulated at the levels shown.
The detergent granules with bleaching system are added together with a 6 lb.
(2.7
kg) load of fabrics to a Sears KENMORE washing machine. Actual weights of
detergent
3o and ester compositions are taken to provide a 1000 ppm concentration of the
detergent
composition in the I7 gallon (65 I) water-fill machine. The water used has 7
gains/gallon
hardness and a pH of 7 to 7.5 prior to (about 9 to about 10.5 after) addition
of the
detergent composition.
The fabrics are laundered at 35~C (95~F) for a foil cycle ( 12 min. ) and
rinsed at
2loC (70~F).
At the end of the last rinse cycle, the test swatches are dried in a dryer.
Tristimulus
meter readings (L,a,b) are then determined for each test swatch. Whiteness
performance
WO 94I28105 216 2 3 6 2 PCTlUS94/05371
12
in terms of Hunter Whiteness Values (W) is then calculated according to the
following
equation:
W = (7L2 - 40Lb)/700
The higher the value for W) the better the whiteness performance. In the above
test, fabrics exposed to the bleaching system display significantly improved
whiteness after
laundering compared with fabrics which have not been exposed to the bleaching
system of
the invention.
to EXAMPLE IV
A ganular detergent composition is prepared
comprising the following ingredients.
Component Wei hg't
Anionic alkyl sulfate 7
Nonionic surfactant 5
IS Zeolite (0.1-10 micron) IO
Trisodium citrate 2
SKS-6 silicate builder 10
Acrylate maleate polymer 4
Bertioyi caprolactam 10
2o Nonanoyloxybenzenesulfonate 10
Sodium percarbonate 25
Sodium carbonate ~ 5
Ethylenediamine disuccinate chelant (EDDS) - 0.4
Suds suppressor 2
25 Enzymes* 1.5
Soil release agent 0.2
Minors, filler** and water Balance to 100%
* 1:1:1 mixture of protease, lipase) and
cellulase.
**Can be selected from convenient materials, talc, clay, silicates,
such as CaC03 and the
30 like.
Aqueous crutcher mixes of heat and alkali stable components of the detergent
compositions are prepared and spray-dried. The other ingedients are admixed so
that the
detergent composition contains the ingredients tabulated at the levels shown.
The detergent ganul~s with bleaching system are added together with a 2.7 kg
(6
3s lb.) load of fabrics to an automatic washing machine. Actual weights of
detergent and
ester compositions are taken to provide a 5000 ppm concentration of the
detergent
composition in the 17 liter (4.5 gallon) water-fill machine. The water used
has 7 grains/
2i62362
"'O 94/28105 ~ 3 PCT/US94/05371
gallon hardness and a pH of 7 to 7.5 prior to (about 9 to about 10.5' after)
addition of the
detergent composition.
The fabrics are laundered at 40~C ( 104~F) for a full cycle (40 min. ) and
rinsed at
21 oC (70~F).
At the end of the last rinse cycle, the test swatches are dried in a dryer.
Tristimulus
meter readings (L,a,b) are then determined for each test swatch. Whiteness
performance
in terms of Hunter Whiteness Values (W) is then calculated according to the
following
equation:
W = (7L2 - 40Lb)/700
The higher the value for W, the better the whiteness performance. In the above
test, fabrics exposed to the bleaching system display significantly improved
whiteness after
laundering compared with fabrics which have not been exposed to the bleaching
system of
the invention.
EXAMPLE V
A laundry bar suitable for hand-washing
soiled fabrics is prepared comprising
the
following ingredients.
Component Weight
C 12 linear all:~rl benzene sulfonate30
Phosphate (as sodium tripolyphosphate)7
2o Sodium carbonate 15
Sodium pyrophosphate 7
Coconut monoethanolamide 2
Zeolite A (0.1-10 microns) 5
Carboxymethylcellulose 0.2
Polyacrylate (m.w. 1400) 0.2
Benzoyl caprolactam 6.5
Nonanoyloxybenzenesulfonate 6.5
Sodium percarbonate 15
Brightener, perfume 0.2
3o Protease 0.3
CaS04 1
MgS04 1
Water and Filler' Balance to l00%
"Can be selected from convenient materials
such as CaC03, talc, clay, silicates,
and the
like.
The detergent laundry bars are processed
in conventional soap or detergent
bar
making equipment as commonly used Testing is conducted
in the art. following the
methods used in Example IV. In the
test, fabrics exposed to the bleaching
system display
PCTlUS94/05371
W094/28105 2162362
significantly improved whiteness after laundering compared with fabrics which
have not
been exposed to the bleaching system of the invention.
EXAMPLE VI
A laundry bar is prepared by a procedure identical to that of Example V, with
the
two exceptions that 20% of a 1:1:1 mixture of pentanoyl caprolactam, hexanoyl
caprolactam, and benzoyl caprolactam is substituted for the benzoyl
caprolactam bleach
activator, and the level of sodium percarbonate is increased to 20%. The
laundering
method of Example IV is repeated. In the test) all fabrics display
significantly improved
whiteness after laundering compared with fabrics which have not been exposed
to the
~o bleaching system of the invention.
EXAMPLE VII
A laundry bar is prepared by a procedure identical to that of Example V, with
the
single exception that 15% of a 1:1 mixture of acetyl caprolactam and benzoyl
caprolactam
is substituted for the benzoyl caprolactam bleach activator. The laundering
method of
Example IV is repeated. In the test, all fabrics display significantly
improved whiteness
after laundering compared with fabrics which have not been exposed to the
bleaching
system of the invention.
EXAMPLE VIII
A laundry bar is prepared by a procedure identical to that of Example V, with
the
2o single exception that an equivalent amount of
3,5,5-trimethylhexanoyloxybenzenesulfonate is substituted for the
nonanoyloxybenzene
sulfonate bleach activator. The laundering method of Example IV is repeated.
In the test,
all fabrics display significantly improved whiteness after laundering compared
with fabrics
which have not been exposed to the bleaching system of the invention.
EXAMPLE IX
A laundry bar is prepared by a procedure identical to that of Example V, with
the
exceptions that 6% of a 1:1 mixture of benzoyi caprofactam and a benzoxazin-
type bleach
activator, as disclosed in U.S. Pat. 4,966,723) is substituted for the benzoyl
caprolactam
bleach activator and an equivalent amount of 2-
ethylhexanoyloxybenzenesulfonate is
3o substituted for the nonanoyloxybenzene sulfonate bleach activator. The
laundering
method of Example IV is repeated. In the test, all fabrics display
significantly improved
whiteness after laundering compared with fabrics which have not been exposed
to the
bleaching system of the invention.
EXAMPLE X
A bleaching system is prepared comprising the following ingredients.
Component Weight
Benzoyl caprolactam 1 S
Nonanoyloxybenzenesulfonate 15
--'O 94I28105 ~ ~ ~ ~ PCT/US94/05371
Sodium percarbonate 45
Chelant (ethylenediamine disuccinate, EDDS) 10
Filler* and water Balance to 100%
*Can be selected from convenient materials such as CaC03, talc, clay,
silicates) and the
5 like.
Testing is conducted following the methods used in Example V with the single
exception that the an equivalent amount of the above bleaching system is
substituted for
the detergent composition used in Example V. In the test, fabrics exposed to
the
bleaching system display significantly improved whiteness aRer laundering
compared with
1o fabrics which have not been exposed to the bleaching system of the
invention.
While the compositions and processes of the present invention are especially
useful
in conventional fabric laundering operations) it is to be understood that they
are also
useful in cleaning system which involves low water:fabric ratios. One such
system is
disclosed in U.S. Patent 4,489,455, Spendel, issued Dec. 25, 1984, which
involves a
~ s washing machine apparatus which contacts fabrics with wash water
containing detersive
ingredients using a low water: fabric ratio rather than the conventional
method of
immersing fabrics in an aqueous bath. The compositions herein provide
excellent
bleaching performance in such mechanical systems. Typically, the ratio of
water fabric
ranges from about 0.5:1 to about 6: I (liters of water:kg of fabric).
Zo EXAMPLE XI
Using the machine and operating conditions disclosed in U.S. Patent 4,489,455,
cited above, 25 grams of a composition according to Example V herein are used
to
launder fabrics with concurrent bleaching. If desired, sudsing of the
composition can be
minimized by incorporating therein from 0.2% to 2% by weight of a fatty acid,
secondary
is alcohol) or silicone suds controlling ingredient. In the test, fabrics
exposed to the
bleaching system display significantly improved whiteness after laundering
compared with
fabrics which have not been exposed to the bleaching system of the invention.
Contrary to the teachings of U.S. Pat. 4,545,784, cited above, the bleach
activator
is preferably not absorbed onto the peroxygen bleaching compound. To do so in
the
3o presence of other organic detersive ingredients could cause safety
problems. It has now
been discovered that the caprolactam bleach activators of this invention can
be dry-mixed
with peroxygen bleaching compounds, especially perborate, and thereby avoid
potential
safety problems.
EXAMPLE XII
3s A laundry bar suitable for hand-washing soiled fabrics is prepared
comprising the
following ingredients.
Component Wei~,ht
Linear alkyl benzene sulfonate 30
16 PCT~S94/05371
W0 94128105
Phosphate (as sodium tripolyphosphate) 7
Sodium carbonate 20
Sodium pyrophosphate 7
Coconut monoethanolamide 2
Zeolite A (0.1-10 microns) 5
Carboxymethylcellulose 0.2
Polyacrylate (m.w. 1400) 0.2
Benzoyl caprolactam 5
Nonanoyloxybenzenesulfonate 5
to Sodium perborate tetrahydrate 10
Brightener, perfume 0.2
Protease 0.3
CaS04 1
MgS04 1
Water 4
Filler* Balance to 100%
*Can be selected from convenient materials such as CaC03, talc, clay,
silicates, and the
like.
The detergent laundry bars are processed in conventional soap or detergent bar
Zo making equipment as commonly used in the art with the bleaching activator
dry-mixed
with the perborate bleaching compound and not ai~xed to the surface of the
perborate.
Testing is conducted following the methods used in Example IV. In the test,
fabrics
exposed to the bleaching system display significantly improved whiteness after
laundering
compared with fabrics which have not been exposed to the bleaching system of
the
invention.
EXAMPLE XIII
A laundry bar is prepared by a procedure identical to that of Example XII,
with the
single exception that an equivalent amount of 2-ethyloxybenzenesulfonate is
substituted
for the nonanoyloxy benzenesulfonate bleach activator. The laundering method
of
3o Example IV is repeated. In the test, all fabrics display significantly
improved whiteness
after laundering compared with fabrics which have not been exposed to the
bleaching
system of the invention.
EXAMPLE XIV
A laundry bar is prepared by a procedure identical to that of Example XII,
with the
exceptions that 6% of a 1:1 mixture of benzoyl caprolactam and hexanoyl
caprolactam is
substituted for the benzoyl caprolactam bleach activator and 6% of a 1:1
mixture of
dodecanoyloxyberuenesulfonate and decanoyloxybenzenesulfonate is substituted
for the
nonanoyloxybenzenesulfonate bleach activator. The laundering method of Example
IV is
"''0 94/28105 1 .~ 2 i 6 2 3 6 2 pCT~S94/05371
repeated. In the test, all fabrics display significantly improved whiteness
after laundering
compared with fabrics which have not been exposed to the bleaching system of
the
invention.
EXAMPLE XV
A laundry bar is prepared by a procedure identical to that of Example XII,
with the
single exception that 10% of a I :1 mixture of benzoyl caprolactam and a
benzoxazin-type
bleach activator, as disclosed in U.S. Pat. 4,966,723, is substituted for the
benzoyl
caprolactam bleach activator. The laundering method of Example IV is repeated.
In the
test, all fabrics display significantly improved whiteness after laundering
compared with
1o fabrics which have not been exposed to the bleaching system of the
invention.
EXAMPLE XVI
A laundry bar is prepared by a procedure identical to that of Example XII,
with the
single exception that 6% of a 1:1 mixture of benzoyl caprolactam and a bleach
activator,
as disclosed in U.S. Pat. 4,634,551, cited above, is substituted for the
benzoyl
caprolactam bleach activator. The laundering method of Example IV is repeated.
In the
test, all fabrics display significantly improved whiteness after laundering
compared with
fabrics which have not been exposed to the bleaching system of the invention.
EXAMPLE XVII
A granular detergent composition is prepared comprising the following
ingredients.
om orient Weight
Linear alkyl benzene sulfonate 20
Phosphate (as sodium tripolyphosphate) 20
Sodium carbonate 10
Sodium silicate 3
Sodium perborate tetrahydrate ~ _ 20
Ethylenediamine disuccinate chelant (EDDS) 0.4
Sodium sulfate 5.5
Hexanoyl caprolactam 5
Nonanoyloxybenzenesulfonate 5
3o Motors, filler** and water Balance to 100%
**Can be selected from convenient materials such as CaC03) talc, clay,
silicates, and the
like.
Aqueous crutcher mixes of heat and alkali stable components of the detergent
compositions are prepared and spray-dried. The other ingredients are dry-mixed
so that
the detergent composition contains the ingredients tabulated at the levels
shown.
Testing is conducted following the methods used in Example IV. In the test,
fabrics
exposed to the bleaching system display significantly improved whiteness after
laundering
WO 94/28105 ~ PCT/US94/05371
~18
compared with fabrics which have not been exposed to the bleaching system of
the
invention.
EXAMPLE XVIII
A granular detergent composition is prepared by a procedure identical to that
of
Example XVII, with the single exception that 15% of a 1:1 mixture of benzoyl
caprolactam and hexanoyl caprolactam is substituted for the hexanoyl
caprolactam bleach
activator. The laundering method of Example IV is repeated. In the test, all
fabrics
display significantly improved whiteness aRer laundering compared with fabrics
which
have not been exposed to the bleaching system of the invention.
to EXAMPLE XIX
A granular detergent composition is prepared by a procedure identical to that
of
Example XVIII, with the single exception that 6% of a 1:1 mixture of benzoyl
caprolactam and a benzoxazin-type bleach activator, as disclosed in U.S. Pat.
4,966,723,
is substituted for the hexanoyl caprolactam bleach activator. The laundering
method of
Example IV is repeated. In the test, all fabrics display significantly
improved whiteness
after laundering compared with fabrics which have not been exposed to the
bleaching
system of the invention.
EXAMPLE XX
A granular detergent composition is prepared by a procedure identical to that
of
2o Example XVIII) with the single exception that 6% of a 1:1:1 mixture of
octanoyloxybenxenesulfonate) decanoyloxybenzenesulfonate and a benzoxazin-type
bleach activator, as disclosed in U.S. Pat. 4,634,551) cited above, is
substituted for the
nonanoyloxybenezenesulfonate bleach activator. The laundering method of
Example IV is
repeated. In the test, all fabrics display significantly improved whiteness
after laundering
compared with fabrics which have not been exposed to the bleaching system of
the
invention.
A particularly preferred embodiment of this invention is a 1:2.2:7.7 molar
ratio of
N-acyl caprolactam to alkanoyloxybenzenesulfonate to peroxygen bleaching
compound.
This mixed caprolactam alkanoyloxybenzenesulfonate bleaching composition
delivers
3o stronger than expected performance on hydrophobic stains and hydrophilic
stains and on
dingy clean up.
EXAMPLE XXI
A laundry bar is prepared by a procedure identical to that of Example V, with
the
exceptions that the level of benzoyl caprolactam is 0.85%, the level of
nonanoyloxy-
3s benzenesutfonate bleach activator is 3% and sodium percarbonate is
substituted with 3%
perborate. The laundering method of Example IV is repeated. In the test, all
fabrics
display significantly improved whiteness after laundering compared with
fabrics which
have not been exposed to the bleaching system of the invention.
"'rJ 94I28105 ~ ~ 6 ~ 3 6 2 pCT/US94/05371
19
EXAMPLE XXII
A granular laundry detergent is prepared by a procedure identical to that of
Example III, with the exceptions that the level of benzoyl caprolactam is
0.85%, the level
of nonanoyloxybenzenesulfonate bleach activator is 3% and sodium percarbonate
is
substituted with 3% perborate. The laundering method of Example III is
repeated. In the
test, all fabrics display significantly improved whiteness after laundering
compared with
fabrics which have not been exposed to the bleaching system of the invention.
to EXAMPLE XXIII
A granular laundry detergent is prepared by a procedure identical to that of
Example IV, with the exceptions that the level of benzoyl caprolactam is
0.85%, the level
of nonanoyloxybenzenesulfonate bleach activator is 3% and sodium percarbonate
is
substituted with 3% perborate. The laundering method of Example IV is
repeated. In the
test, all fabrics display significantly improved whiteness after laundering
compared with
fabrics which have not been exposed to the bleaching system of the invention.
EXAMPLE XXIV
A laundry bar is prepared by a procedure identical to that of Example XI, with
the
exceptions that the level of benzoyl caprolactam is 0.85%, the level of
2o nonanoyloxybenzenesulfonate bleach activator is 3% and the level of sodium
perborate
tetrahydrate is 3%. The laundering method of Example XI is repeated. In the
test, all
fabrics display significantly improved whiteness after laundering compared
with fabrics
which have not been exposed to the bleaching system of the invention.
EXAMPLE XXV
i5 A granular laundry detergent is prepared by a procedure identical to that
of
Example XVII) with the exceptions that the level of
nonanoyloxybenzenesulfonate bleach
activator is 3%, the level of sodium perborate tetrahydrate is 3%) and the
hexanoyl
caprolactam is substituted with 0.85% benzoyl caprolactam. The laundering
method of
Example XVII is repeated. In the test, all fabrics display significantly
improved whiteness
3o after laundering compared with fabrics which have not been exposed to the
bleaching
system of the invention.
While the foregoing examples illustrate the use of the present technology in
cleaning/bleaching compositions designed for use in laundering, it will be
appreciated by
those skilled in the art that the bleaching systems herein can be employed
under any
35 circumstance where improved oxygen bleaching is desired. Thus, the
technology of this
invention may be used) for example, to remove stains and cleans dishes) to
bleach paper
pulp, to bleach hair, to cleanse and sanitize prosthetic devices such as
dentures) in
WO 94I28105 216 2 3 6 2 PCT/US94/05371
dentifrice compositions to clean teeth and kill oral bacteria, and in any
other
circumstances where bleaching is advantageous to the user.
EXAMPLE XXVI
A granular automatic dishwashing detergent composition wherein stain removal
and
5 cleaning benefits are achieved is prepared comprising the following
ingredients.
Component % by weight of active material
A B C
Citrate 15.00 15.00 20.00
Acusol 480N 1 6.00 6.00 6.90
Sodium carbonate 20.00 20.00 23.00
Component % by weig ht of
active
material
A B C_
Britesil H20) (Si02) 9.00 9.00 7.50
15Nonionic surfactant2 2.00 2.00 2.00
Savinase 12T 2.00 2.00 2.00
Termamyl 60T 1.00 1.00 I .00
Percarbonate (as Av0) 1.50 1.50 I .50
Nonanoyloxybenzenesulfonate 2.00 2.00 2.00
2oBenzoylcaprolactam 2.00 3.80 2.00
Diethylene triamine pentaacetic0.13 0.13 0.13
acid
1,1-hydroxyethanedishosphonic 0.50 0.50 0.50
acid
Sulfate) water, etc. Balance to
100%
pH 10.0 l0.0 l0.0
25I Dispersant from Rohm and Haas
2 Low cloud, high HLB nonionic
surfactant 7~l;VII
EXAMPLE
Tablet compositions of the present
invention are as follows:
Co~mt~onent % bar weisthtactive
of material
3oCitrate 20.90 20.90
Phosphate --- ---
Polyacrylate 2.70 2.70
Carbonate 14.00 l4.00
1,1-hydroxyethanedishosphonic 0.36 0.36
acid
35Silicate 2r(Si02) 12.20 12.20 ,
metaSilicate (Si02) --- ---
Paraffin 0.36 0.36
Benzotriazole 0.21 0.21
CA 02162362 1999-04-20
-21 -
Perborate tetrahydrate (as Av0) 0.64 0.64
Perborate monohydrate (as Av0) 0.22 0.22
Percarbonate (as Av0) -- --
Nonanoyloxybenzenesulfonate 2.00 2.00
Benzoylcaprolactam 3.20 5.10
Phenylbenzoate -- --
Diethylene triamine pentamethylene
phosphoric acid 0.09 0.09
Savinase 60T 1.10 1.10
Savinase 12T 1.58 1.58
Nonionic surfactant 1.l8 1.18
Termamyl 60T 1.10 1.10
Sulfate, water, etc. Balance
to 100%
pH 11 11
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 art. See,
for instance, Canadian Patent No. 2,115,425 laid open for public inspection on
March 4,
1993, and Canadian Patent Application Serial No. 2,133,445 laid open for
public
inspection on October 28, l993.
