Note: Descriptions are shown in the official language in which they were submitted.
1336891
CM264M
DETERGENT COMPOSITIONS
CONTAINING CELLUIASE GRANULATES
Technical field
The present invention is related to granular detergent
compositions which are useful for cleaning and softening of
fabrics, and for giving other fabric-care benefits such as
AppPArance improvements and rejuvenation.
The compositions herein contain a fabric-soft~n;ng clay
material, and a cellulase enzyme, which is in the form of
granulates containing calcium carbonate.
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1336894
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Back~round of the Invention
It has been the objective of many detergent
manufacturers to formulate laundry detergent compositions
which provide the good cleaning performance expected of
them, and which also exhibit fabric-care properties,
inclusive of softness.
Representative of such detergent compositions are
the ones which have been disclosed in British Patent
1,514,275 (published June 14, 1978), British Patent
1,400,898 (published July 23, 1975), or EPA 0 026 528
(published April 8, 1981).
Cellulase enzymes have already been used in deter-
gent compositions for their cleaning abilities, as
disclosed in British Patent Application GB-A 2,095,275
(published September 29, 1985), GB-2,094,826 (published
September 22, 1982), or Japanese Patent 57108-199
(published July 6, 1982).
Cellulases have also been found to give softness
benefits to fabrics, as in U.S. 4,425,307.
EP-A 0 120 528 (published October 3, 1984) teaches
alkaline softening detergent compositions comprising a
synergistic mixture of a water-insoluble C10-C26 tertiary
amine and cellulase.
EP-A O 177 165 (published April 9, 1986) discloses
alkaline softening detergent compositions containing a
mixture of smectite clay and cellulase.
EP-A O 220 016 (published April 19, 1987) discloses
the fabric color-clarification effect derivable from the
use of cellulasç in a detergent context.
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1336894
When such detergent and/or softening compositions are
in granular forms, the cellulase enzymes are usually
incorporated in the composition in the form of granulates,
also identified as marumes, or prills, which are supplied
by the enzyme manufacturer.
U.S. 4,435,307, which relates to a hardness reducing
agent for detergent compositions, discloses the use of
cellulase granulates, and mentlons certain ingredients
which need to be incorporated to the granulates during
their making, for e.g. non-dusting and color purposes.
It has been discovered, however, that certain of these
ingredients are detrimental to the softness/fabric care
properties of the composition, when cellulase granulates
containing these ingredients are incorporated into a
detergent composition.
When looking for a replacement to these undesirable
ingredients, it has now been discovered that water-
insoluble salts of calcium, surprisingly substantially
enhance the softness/fabric care performance of the
detergent compositions containing the enzyme granulates.
It is therefore the object of the present invention to
provide detergent compositions which possess excellent
softness/fabric care properties, due to the use of
cellulase granulates containing a water-insoluble salt of
calcium.
Summary of the Invention
The present invention relates to granular detergent
compositions containing a fabric-softening clay material,
and cellulase granulates containing from 1% to 50%, by
weight, preferably 5% to 15% of the granulates, of calcium
carbonate.
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Calcium carbonate is preferably coated onto the
cellulase granulates.
m e invention also relates to the above-described
cellulase granulates per-sé.
Detailed DescriPtion of the Invention
The compositions herein are capable of cleaning and
softening the treated fabrics, as well as giving benefits
in te s of fabric appearance improvements and
re~uvenation .
miS is achieved by the presence, in the granular
compositions herein, of surface active agents, of
fabric-softening clay materials, and of cellulase
granulates containing calcium carbonate.
In the following, these compulsory, as well as optional
ingredients are described in detail :
m e Cellulase
The cellulase usable in the present invention may be
any bacterial or fungal cellulase having a pH optimum of
between 5 and 9.S.
Suitable cellulases are disclosed in U.S. 4,435,307,
GB-A-2.095.275 (published September 29, 1982), U.S.
3,844,890, and EP-A 0 220 016 (published April 29, 1987).
:
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Examples of such cellulases are cellulases produced by
a strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly by the Humicola strain DSM 1800,
and cellulases produced by a fungus of Bacillus N or a
cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas
of a marine mollusc (Dolabella Auricula Solander).
Activity determination for the cellulase herein is
based on the hydrolysis of carboxymethyl cellulose.
Generated low molecular reducing carbohydrates are
colorimetrically determined by the ferrocyanide reaction
as described by W.S. Hoffman "J. Biol. Chem." 120,51
(1973). Key conditions of incubation are pH = 7.0,
temperature of 40 C and incubation time of 20 minutes.
One CMCase unit is defined as the amount of enzyme
which forms per minute an amount of reducing carbohydrate
equivalent to 10 mole of glucose, in the above-
described conditions.
A useful range of cellulase activity in the present
context is from 5 to 1360, preferably from 60 to 140
CMCase activity units/gram of detergent composition.
The Cellulase Granulates
Cellulase enzymes for use in granular detergent
compositions are typically supplied in the form of
granulates, e.g. marumes or prills.
Such granulates contain a majority of crude cellulase
enzyme, together with additional ingredients, such as
polyethylene glycol, at typical levels of from 5 % to 7 %,
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and cellulose at typical levels of about 10%. the
polyethylene glycol for use herein can have a molecular
weight in the range from S00 to 8000.
The amount of cellulase in the granules is determined
by the total cellulase activity of the cn~rosition, which
has to be in the limits set up hereinabove.
It has been discovered that certain materials which
have been used by enzyme manufacturers as
dustness-preventing and whitening agents, which are
Titanium dioxide and Magnesium silicate, interact
negatively with the softness performance of the
compositions herein.
The compositions of the invention should, therefore,
preferably by free of Titanium dioxide and Magnesium
silicate.
It has now been found that calcium carbonate possesses
the dustness-preventing function when added to the
cellulase granulates, and also giveSunexpected
softness/fabric care benefits as shown hereinafter.
The calcium carbonate should be present in the
cellulase granulates, at levels of from 1% to 10%,
preferably 5% to 15% by weight, of the granulates.
Calcium carbonates of a particle size range from 1 to
10 microns have been found to be particularly suitable for
the purpose of the present invention.
1336894
The calcium carbonate used herein may be used as is
or in coated form, typically coated with stearic acid.
In a preferred execution of the present invention,
calcium carbonate, either as is or already coated with
e.g. stearic acid, is coated onto the cellulase
granulates.
Cellulase granulates can be prepared in a number of
different ways, for example by means of a "Marumerizer"
as described in British Pat. Nos. 1,362,365 and 1,361,387
or by means of a granulating machine, as described in
Aufbereitungs-Technik No. 3/1970, pp. 147-153 and No.
5/1970, pp. 262-278, or can be prilled granulates as
described in Belgian Patent Specification No. 760.135.
In all cases, the granulates must have low dusting
properties.
The calcium carbonate herein is either mixed with
the other ingredients during the making of the
granulates, or mixed with cellulase before granulation,
or, preferably, coated onto the granulates which have
been prepared as described hereinabove, by conventional
coating methods.
The cellulase granulates according to the present
invention are present at levels of from 1~ to 50~ by
weight of the detergent composition herein, preferably
1.5% to 10~ by weight.
The surface-active agent
The surface active agent useful herein may be
selected from anionic, nonionic, zwitterionic surfactants
and is present at levels of from 1~ to 50~ by weight of
the composition, preferably from 10~ to 30~.
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3~89 1
Sultable anionic surfactants are water-soluble salts
of alkyl benzene sulphonates, alkyl sulphates, alkyl
polyethoxy ether sulphates, paraffin sulphonates, alpha-
olefin sulphonates, alpha-sulphocarboxylates and their
esters, alkyl glyce n 1 ether sulphonates, fatty acid
monoglyceride sulphates and sulphonates, alkyl phenol
polyethoxy either sulphates, 2-acyloxt-alkane-1-
sulphonates, and beta-alkyloxy alkane sulphonates.
Especially preferred alkyl benzene sulphonates have 9
to 15 carbon atoms in a linear or branched alkyl chain,
especially from 11 to 13 carbon atoms. Suitable alkyl
sulphates have from 10 to 22 carbon atoms in the alkyl
chain, more especially from 12 to 18 carbon atoms.
Suitable alkyl polyethoxy ether sulphates have from 10 to
18 carbon atoms in the alkyl chain and have an average of
from 1 to 12 - CH2CH20- groups per molecule,
especially from 10 to 16 carbon atoms in the alkyl chain
and an average of from 1 to 6 -CH2CH20-groups per
molecule.
Suitable paraffin sulphonates are essentially linear
and contain from 8 to 24 carbon atoms, more especially
from 14 to 18 carton atoms. Suitable alpha-olefin
sulphonates have from 10 to 24 carbon atoms, more
especially from 14 to 16 carbon atoms; alpha-olefin
sulphonates can be made by reaction with sulphur trioxide,
followed by neutralization under conditions such that any
sultones present are hydrolyzed to the corresponding
hydroxy alkane sulphonates. Suitable alpha-sulphocarboxy-
lates contain from 6 to 20 carbon atoms; included herein
are not only the salts of alpha-sulphonated fatty acids
but also their esters made from alcohols containing 1 to
14 carbon atoms.
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Suitable alkyl glyceryl ether sulphates are ethers of
alcohols having from 10 to 18 carbon atoms, more especially
those derived from coconut oil and tallow. Suitable alkyl
phenol polyethoxy ether sulphates have from 8 to 12 carbon
atoms in the alkyl chain and an average of from 1 to 6
-CH2CH20-groups per molecule. Suitable 2-acyloxyalkane
-l-sulphonates contain from 2 to 9 carbon atoms in the
acyl group and from 9 to 23 carbon atoms in the alkane
moiety. Suitable beta-alkyloxy alkane sulphonates contain
from 1 to 3 carbon atoms in the alkyl group and from 8 to
20 carbon atoms in the alkane moiety.
The alkyl chains of the foregoing anionic surfactants
can be derived from natural sources such as coconut oil to
tallow, or can be made synthetically as for example by
using the Ziegler or Oxo processes. Water-solubility can
be achieved by using alkali metal, ammonium, or alkanol-
ammonium cations; sodium is preferred. Mixtures of anionic
surfactants are contemplated by this invention; a satisfac-
tory mixture contains alkyl benzene sulphonate having 11-13
carbon atoms in the alkyl group and alkyl sulphate having
12 to 18 carbon atoms in the alkyl group.
Suitable nonionic surfactants to be incorporated in
the compositions herein, are water-soluble ethoxylated
materials of HLB 11.5-17.0 and include (but are not
limited to) C10-C20 primary and secondary alcohol
ethoxylates and C6-C10 alkylphenol ethoxylates.
C14-C18 llnear primary alcohols condensed with from
seven to thirty moles of ethylene oxide per mole of
alcohol are preferred, examples being C14-C15 (E0)7,
C16-C18 (E0)25 and especially C16-C18 (E0)11.
Cationic co-surfactants which can be used herein,
include water-soluble quaternary ammonium compounds of the
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form R4R5R6R7N+X-, wherein R4 is alkyl having from 10 to 20,
preferably from 12-18 carbon atoms, and Rs/ R6 and R7 are
each Cl to C7 alkyl preferably methyl; X~ is an anion,
e.g. chloride. Examples of such trimethyl ammonium
compounds include Cl2-Cl4 alkyl trimethyl ammonium chloride
and cocoalkyl trimethyl ammonium methosulfate.
The compositions of the invention are essentially
free of water-insoluble long-chain alkyl amine softening
agents, and derivatives thereof, since it has been
discovered that they interact negatively with cellulase,
in the pH conditions of the present invention.
Derivatives of the amine softening agents include the
corresponding amine compounds. Such amine softening
agents are disclosed in e.g. EP.A 0.026.528 and EP.l
0.120.528. and include in particular amines of the
formula RlR2R3N where Rl and R2 are C6 to C20 alkyl chains,
and R3 is Cl to C10 alkyl chain or hydrogen.
The compositions herein are formulated at a pH in
the range of from 6.5 to 9.5, measured as a 1~ solution
of the composition in distilled water. At this pH range,
the cellulases for use herein have their optimum
performance.
The fabric-softeninq clay material
The compositions herein must contain a clay
softening agent.
Such clay softening agents are well-known in the
detergency patent literature and are in broad commercial
use, both in Europe and in the United States. Included
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among such clay softeners are various heat-treated
kaolins and various multi-layer smectites. Preferred
clay softeners are smectite softener clays that are
described in German patent document 23 34 899 and in U.K.
patent 1,400,898, which can be referred to for details.
The most preferred clay fabric softening materials
include those materials of bentonitic origin, bentonites
being primarily montmorillonite type clays together with
various impurities, the level and nature of which depends
on the source of the clay material. Softener clays are
used in the preferred compositions at levels of at least
1%, generally 1-20~, preferably 2-10~.
Optional inqredients
The compositions herein may contain, in addition to
the essential ingredients, certain optional ingredients.
For instance, it is preferred that through-the-wash
detergent compositions contain a detergent builder and/or
metal ion sequestrant. Compounds classifiable and well-
known in the art as detergent builders include the
nitrilotriacetates, polycarboxylates, citrates, water-
soluble phosphates such as tri-polyphosphate and sodium
ortho- and pyro-phosphates, and mixtures thereof. Metal
ion sequestrants include all of the above, plus materials
like ethylenediaminetetraacetate, the amino-polyphospho-
nates and a wide variety of other poly-functional organic
acids and salts too numerous to mention in detail here.
See U.S. Patent 3.579.454 for typical examples of the use
of such materials in various cleaning compositions.
Preferred polyfunctional organic acids species for use
herein are citric acid, ethylene diamine tetramethylene-
phosphonic acid, and diethylene triaminepentamethylene-
phosphonic acid.
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1336891
A further class of detergency builder materials useful
in the present invention are insoluble sodium alumino-
silicates. The 1-10 micron size zeollte (e.g., zeolite A)
builders disclosed in German patent 24.22.655 are especial-
ly preferred for use in low-phosphate or non-phosphate
compositions. In general, the builder/sequestrant will
comprise from 0.5 X to 45 % of the composition.
The compositions herein can also contain fatty acids,
saturated or unsaturated, and the corresponding soaps.
iuitably fatty acids, saturated or unsaturated, have from
10 to 18 carbon atoms in the alkyl chain. Preferred are
unsaturated species having from 14 to 18 carbon atoms in
the alkyl chain, most preferably oleic acid. The
corresponding soaps can also be used. The optional fatty
acid/soaps are used in levels up to 20 X.
The compositions herein can also contain compounds of
the general formula R-CH(COOH)CH2(COOH) i.e. derivatives
of succinic acid, wherein R is C10-C20 alkyl or
alkenyl, preferably C12-C16, or wherein R may be
substituted with hydroxyl, sulfo, sulfoxy or sulfone
substituents.
The succinate builders are preferably used in the form
of their water-soluble salts, including the sodium, potas-
sium, ammonium and alkanolammonium salts.
Specific examples of succinate builders include :
lauryl succinate, myristyl succinate, palmityl succinate,
2-dodecenyl succinate (preferred), 2-pentadecenyl succi-
nate, and the like.
Also useful as builders in the present context are the
compounds described in U.S. patent 4.663.071, l.e. mixtures
~ /3 ~ 1336894
of tartrate monosuccinic acid and tartrate l,su~ ic ~c;~
in a weight ration of monosuccinic to disuccinic of from
97:3 to 20:80, preferably 95:5 to 40:60.
Another optional ingredient is a bleaching agent.
Preferred are peroxygen bleaching agents such as sodium
perborate, commercially available in the form of mono- and
tetra-hydrates, sodium carbonate peroxyhydrate, sodium
pyrophosphate peroxyhydrate and urea peroxyhydrate.
Bleach activators may be used in combination with the
above peroxygen bleaching agents. Classes of bleach
activators include esters, imides, imidazoles, oximes, and
carbonates. In those classes, preferred materials include
methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sul-
fonates such as sodium 4-octanoyloxybenzene sulfonate;
sodium-4-octanoyloxybenzene sulfonate, and sodium-4-
decanoyloxybenzenesulfonate : biophenol diacetate; tetra
acetyl ethylene diamine; tetra acetyl hexamethylene
diamine; tetra acetyl methylene diamine.
Other highly preferred peroxygen bleach activators
which are disclosed in U.S. Patents 4,483,778 and
4,539,130, are alpho-substituted alkyl or alkenyl esters,
such as sodium-4(2-chlorooctanoyloxy)benzene sulfonate,
sodium 4-(3, 5, 5-trimethyl hexanoyloxy)benzene sulfonate.
Suitable peroxyacids are also peroxygen bleach activators
such as described in published European Patent Application
0 166 571, i.e., compounds of the general type RXAOOH and
RXAL, wherein R is a hydroxcarbyl group, X is a hetero-
atom, A is a carbonyl bridging group and L is a leaving
group, especially oxybenzenesulfonate.
Enzymes other than cellulases, such as proteolytic,
amylolytic, or lipolytic enzymes can be used in addition to
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the cellulase herein.
Soil-release/soil-suspending agents can be present
in the composition herein at levels typically from 0.1
to 10~ by weight. In particular: alkoxylated poly-
amines suitable as clay-soil removal/anti-redeposition
agents can be used. These components, as well as their
preparation, are disclosed in EP-A 0 112 593.
It is to be understood that the term "polyamines" as
used herein represents generically the alkoxylated poly-
amines, both in their amine form and in their
quaternarized form. Such materials can conveniently be
represented as molecules of the empirical structures with
repeating units:
N R ~ Amine form
¦ n
(Alkoxy)y
and
Rl
r I R ~ x~ Quaternized form
(Alkoxy)y
wherein R is a hydrocarbyl group, usually of 2-6 carbon
atoms; R1 may be a Cl-C20 hydrocarbon; the alkoxy groups
are ethoxy, propoxy, and the like, and y is 2-30, most
preferably 10-20; n is an integer of at least 2,
preferably 2-20, most preferably 3-5; and X~ is an anionic
such as halide or methylsulfate, resulting from the
quaternization reaction.
~";,
- 15 - 133689~
The most highly preferred polyamines for use herein
are the so-called ethoxylated polyethylene imines, i.e.,
the polymerized reaction product of ethylene oxide with
ethyline-imine, having the general formula:
(EtO) ~ I-cH2-cH2 ] N - (EtO)y
(EtO)y (EtO)y
wherein n is an integer of 3 to 5 and y is an integer of
10 to 20.
Soil suspending agents can also be selected from
polyethylene glycols, of molecular weight 400 to 1000,
polyacrylates, or copolymers of acrylic acid and maleic
anhydride/acid.
The detergent compositions herein are preferably
free of carboxymethylcellulose.
Moreover, the compositions herein can contain, in
addition to ingredients already mentioned, various other
optional ingredients typically used in commercial
products to provide aesthetic or additional product
performance benefits. Typical ingredients include pH
regulants, perfumes, dyes, optical brighteners,
hydrotropes and gel-control agents, freeze-thaw
stabilizers, bactericides, preservatives, suds control
agents, bleach stabilizing agents.
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EXPERIMENTAL PART 1 3 3 6 8 9 1
A granular detergent composition was prepared,
according to the following table:
In~redients X by wei~ht
Sodium Linear C12 alkyl benzene sulfonate 11.0
Sodium Tallow alkyl sulfate 5.0
Tallow alcohol ethoxylate (E011)0.3
Sodium tripolyphosphate 24.0
Bentonite clay 8.5
Soil suspending agent* 2.0
Proteolytic enzyme 0.9
Sodium sulfate, water, minorsup to balance
copolymer of acrylic and maleic acid, MW 60.000(sodium salt).
From the basic composition hereinabove, two composi-
tions were prepared :
Composition A, to be used as reference, where cellulase
granulates (1.79 X by weight of total composition)
containing crude cellulase enzymes and cellulose, were
dry-mixed with the rest of the composition.
Composition B, a composition according to the present
invention, where cellulase granulates (1.79 % by weight of
total composition) containlng crude cellulase enzyme,
cellulose, and a coating of polyethylene glycol (5 %
weight level of granulates, MW 1500) and of calcium
carbonate (10 % weight level of granulates).
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In both compositions A and B, the cellulase was of
the type described in U.S. 4,435,307 and its amounts were
such as to give an activity of 68 CMCase activity units/g
of composition.
Compositions A and B were compared for softness and
fabric-care performance.
The design of the test was such as to compare
softness of textile pieces laundered 4, 8 and 12 times
(multi-cycle) each time with invention and reference
composition.
The testing conditions were as follows:
-Product usage: 92 grams = 0.75 ~ conc.
-Wash temperature: 40C.
-18 grains/gallon (0.31 g/1) water hardness (3:1
Ca/Mg ratio).
The washed and line dried swatches were compared by
a panel of two expert judges, working independently, by a
paired comparison technique using a 9-point Scheffe
scale. Differences were recorded in panel score units
(psu), positive being performancewise better. (*)
indicate significant results, with least significant
difference (LSD) calculated at 95~ confidence.
The testing results were as follows:
.
a) Softnessnumber of cycles comp.B vs. comp.A
(bath towels)4 +0.38 psu
8 +1.00* psu
12 +0.75* psu
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b) Fabric appearance (improved color and anti-pilling
performance)
(average on main cottom items)
number of cycles comp.B vs. comp. A
4 + 0.69* psu
8 ~ 0.75* psu
12 ~ 0.75* psu
The effect of polyethyleneglycol coating alone was
measured as well, and results indicated negative
performance effect, thus showing that the positive effect
on both softness and fabric appearance are due to the
presence of the calcium carbonate.
