Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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DETERGENT CC~.L ;)~ )NS COMPRISING HYDROXYACID COMPOUNDS
Fi~ld of the invention
The present invention relates to detergent compositions producing reduced
encrustation. More particularly, it relates to detergent compositions
comprising a hydroxyacid compound, wherein said hydroxyacid
compound is present in a specific amount.
Backpround of the invention
In fabric w~shin~ processes carried out in an ~lk~line environment,
formation of insoluble material occurs, which deposits and/or forms on
the heater parts of the washing machine (so-called heater encrustation).
The encrustation may be produced by various components which include:
high hardness water, carbonate builders and percarbonate bleaches.
High hardness water generally occurs in European countries, where an
amount of at least 267 ppm equivalent of calcium carbonate and
m~gn~sillm carbonate can be found in water (e.g. at least 15~ Hardness).
Sodium carbonate is used in laundry detergent formulations, particularly
in applications where a high pH is required so as to obtain effective
cle~nin performance. A problem encountered with the use of high levels
of carbonate is that calcium and m~Pnesillm ions present in the washing
water readily form precipitates with the carbonates; and which then
deposit on the heater elements of the washing machine.
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Although high levels as such of carbonates are detrimental to the heater
element, low levels may as well be detrimental to the heater element after
repeated washes.
Not to be bound by theory, it is believed that the heater encrustation
problem is linked to the solvation/temperature parameter. The more the
temperature increases, the less calcium carbonate and/or magnesium
carbonate are solvated, thus producing the formation of a precipitate on
the heater.
The detergent form~ tor thus faces the challenge of form~ in~ an
environmentally friendly product which minimi~es the occurrence of any
unwelcome encrustation and which is also inexpensive.
The prior art contains numerous examples of anti-encrustation agents for
fabrics and for m~chine surfaces.
EP-A-0,291,859 discloses phosphorus cont~ining compounds as effective
inhibitor compounds of encrustation. More particularly disclosed is
hydroxy-ethane 1,1 diphosphonate (HEDP).
EP-A-0,463,802 discloses certain class of dicarboxylic acids in amount
less than 30% by weight of the delel~ent composition as crystal growth
inhibitor for preventing the fabric encrustation problem.
The Applicant has found that the problem of heater encrustation is
particularly troublesome with detergent composition comprising
carbonate-producing compounds together with calcium binding capacity
compounds, wherein the weight ratio of the sum of said carbonate-
producing compounds to the sum of said calcium binding capacity
compounds is of at least 0.3:1.
Calcium binding capacity compounds are compounds which prevent the
salt formation of CaC03 by chelation of the calcium ion, i.e. compounds
which have a higher binding capacity for the calcium ion than the
carbonate. More particularly, for the purpose of the invention a calcium
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binding capacity compound is a compound having a coefficient of calcium
binding capacity of at least 0.6.
For the purpose of the invention, t~e coefficient of calcium binding
capacity is determined by the following steps considering that one part of
calcium binding capacity compound for 100 parts (= lOOg) of detergent
composition and 15 litres of wash are used.
1 d~ H = 0,000 18 moles of Ca~ + or equivalent of Ca+ + per litre
(e.g. Ca+ + and Mg+ +)
MW = Molecular Weight of the considered compound.
1. Determination of the number x of moles of calcium binding
capacity compound per part.
MW
2. Determination of the number y of moles of calcium binding
capacity compound per part and per equivalent.
=y
number of equivalent
necess~ry to bind
1 equivalent of Ca++
3. Determination of the number z of moles of calcium binding
capacity compound per part, per equivalent and per litre.
Y =z
4. Determination of the coe~ficient C of calcium binding capacity
compound in d~H per part.
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0,0001 8
Described hereinafter are examples of some coefficient of binding
capacity compounds.
a. Coefficient of binding capacity of trisodium citrate
(MW= 258g.mol-1)
1- x = 258 = 0,003876 mol
2- 1 equivalent of citrate is necessary to bind 1 equivalent of
Ca++
x = y = 0,003876 mol
0,003876
3- Z = 15 = 0,0002~83 mol
0.0002583
4- C citrate= = 1.44
0.0001 8
b. Coefficient of binding capacity of sodium soap
(MW c 278g.mol~l)
1- x = 278 = 0,003597 mol
2- 2 equivalents of sodium soap are necessary to bind 1
equivalent of Ca+ +.
0,003597
Y = 2 = 0,00179785 mol
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0,001 79785
3 z = =0,0001199 mol
0 0001 199
4 C soap = = 066
0, 0001 8
Preferred calcium binding capacity compounds are selected from Zeolite
A, Zeolite P (B), Zeolite MAP, Zeolite X, delta-Na2Si2Os (NaSKS-6),
citrate, soap and mixtures thereof.
According to the described method for determinin~ coefficient of binding
capacity compounds, the following coefficient of binding capacity for
zeolite A and SKS-6 were found.
Builder Component Coef~lcient of calcium
binding c~p3c~ity
compound
d~H/ part
Zeolite A 1.07
Layered Silicate (SKS-6) 0.89
Preferably, for the purpose of the invention, calcium binding capacity
compounds have builder capacity.
By calcium binding capacity, it is meant the calcium binding capacity of
the considered detergent composition which is the sum of all the calcium
binding capacities builder compounds present in said detergent
composition.
The calcium binding capacity delivered by each builder present in the
detergent composition is calculated by multiplying the level of builder
used in the composition with the coefficient of calcium builder capacity of
said builder.
The source of carbonate may be selected from carbonates, bicarbonates,
sesquicarbonates, percarbonates and mixtures thereof.
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The Applicants have now surprisingly found that the provision of a
minimllm amount of hydroxyacid compounds or any salts thereof in the
detergent composition ameliorates a tendency towards encrustation.
It is therefore an object of the present invention to provide compositions
for use in laundry and machine dishwashing methods, wherein said
compositions show less propensity to cause encrustation.
It is another object of the present invention to provide compositions which
produce reduced encrustation whilst having a weight ratio of carbonate
producing compounds to said calcium binding capacity compounds of at
least 0.3:1 and more particularly of at least 0.5:1.
It is another object of the invention to provide a method for reducing
heater encrustation.
S~ ry of the invention
The present invention relates to a detergent composition comprising one
or more surf~ct~nts and one or more hydroxyacid compounds selected
from monocarboxylic acid, alicyclic polycarboxylic acid, heterocyclic
polycarboxylic acid and aromatic polycarboxylic acid compounds and
salts thereof, substih~terl with at least one hydroxyl group, wherein said
hydroxyacid compound is present in amount less than 5~.
Also provided herein is a method for reducing heater encrustation, which
comprises cont~ctin~ the heater with an effective amount of an aqueous
solution of a detergellt composition comprising said hydroxyacid.
Technical field of the invention
The present invention contemplates detergent compositions producing
effective encrustation reduction when used in laundry or dish washing
machines. The encrustation may occur on any machine surface but arises
principally on heaters and is produced by the combination of a source of
ions, principally provided by the high degree of water hardness, and a
source of carbonate selected from percarbonates, carbonates,
bicarbonates, sesquicarbonates and mixtures thereof.
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The source of ions generally arises from a high degree of water hardness
but is not limite~ thereto. Hence, components of the detergent
composition such as calcium and/or m~gnesium ions per se or as salts per
se may also serve as a source of ions for the purpose of the invention.
A visual observation is made for determining the presence of calcium
and/or m~nesillm carbonate. The material subject to the encrustation
(e.g. heater) is immersed in an acidified water solution (2N sulfuric acid).
The observation of an effervescence on top of the material indicates the
presence of calcium and/or m~gneSi~m carbonate encrustation.
The essential component for the purpose of the invention is a crystal
growth inhibitor of the hydroxyacid type.
For the purpose of the invention, hydroxyacid compounds will be present
in amount of less than 5%, ~rerel~bly from 0.01% to 4% and most
preferably from 0.2% to 3 % by weight of the detergent composition.
The hydroxyacid compound is selected from monocarboxylic acid,
alicyclic polycarboxylic acid, heterocyclic polycarboxylic acid and
aromatic polycarboxylic acid compounds and salts thereof, substit~lte~
with at least one hydlroxyl group and salts thereof. When utilised in salt
form, alkali metals, such as sodium, potassium and lithium, or
alkanol~mmonium salts are preferred.
More specifically, these are selected from acyclic, alicyclic, heterocyclic
and aromatic carboxylic acids having the general formulae
(a)
y
I
Rl X C R2
Z m
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(b)
x C
I
Z n
or
(c)
Y
wherein Rl represents H,Cl 30 alkyl or alkenyl optionally substit~lte~l by
hydroxy, carboxy, sulfo or phosphono groups or attached to a
polyethylenoxy moiety cont~inin~ up to 20 ethyleneoxy groups; R2
represents H,C14 alkyl, alkenyl or hydroxy alkyl, or alkaryl, sulfo, or
phosphono groups;
X represents a single bond; O; S; SO; SO2; NRl; or C=O;
Y represents H; carboxy; hydroxy; carboxymethyloxy; or
Cl 30 alkyl or aLkenyl optionally substi~lte~l by hydroxy or carboxy
groups;
Z represents H; or carboxy; hydroxy; carboxymethyloxy;
m is an integer from 1 to 10;
n is an integer from 3 to 6;
p, q are integers from 0 to 6, p + q being from 1 to 6; and wherein, X,
Y, and Z each have the same or different representations when repeated
in a given molecular formula, and wherein at least one Y or Z in a
molecule contains a carboxyl group, and wherein the molecule contains at
least one hydroxyl group in the position alpha of at least one of the
carboxyl group, and wherein in formula a) the molecule does not contain
more than one carboxyl group.
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Preferred hydroxyacid compounds are compounds selected from glycolic
acid, lactic acid, mandelic acid, hydroxypropionic acid and salicylic aci
- and salts thereof. A most preferred hydroxyacid compound is glycolic
acid or salt thereof.
~ For the purpose of the invention, mixtures of any of the hydroxyacid
compounds described herein before may also be used.
The detergent composition of the invention also contains one or more
surf~ct~ntc.
Non limiting examples of surfactants useful herein, typically at levels
from 1 % to 55%, by weight, include the conventional C1 1-C1g alkyl
benzene sulfonates ("LAS") and primary, branched-chain and random
C1o-C20 alkyl slllf~tes ("AS"), the C1o-C1g secondary (2,3) alkyl
slllf~tec of the formula CH3(CH2)X(CHOSO3-M+) CH3 and CH3
(CH2)y(CHOS03~M+) CH2CH3 where x and (y ~ 1) are integers of at
least 7, preferably a~ least 9, and M is a water-solubilizing cation,
especially sodium, lln~ rated sulfates such as oleyl sulfate, the C1o-C1g
alkyl alkoxy sulfates (''AEXS''; especially EO 1-7 ethoxy sulfates),
Clo-C18 aL~yl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C10 18 glycerol ethers, the C1o-C1g alkyl
polyglycosides and their corresponding slllf~te-l polyglycosides, and
C12-C1 8 alpha-sulfonated fatty acid esters. If desired, the conventional
nonionic and amphoteric surfactants such as the C12-C1g alkyl
ethoxylates ("AE"), including the so-called narrow peaked alkyl
ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates
and mixed ethoxy/propoxy), C12-C1g betaines and sulfobetaines
("slllt~inPs"), C10-cl8 amine oxides, and the like, can also be included in
the overall compositions. The C1o-C1g N-alkyl polyhydroxy fatty acid
amides can also be used. Typical examples include the C12-C1g N-
methylgl~ mitles. See WO 9,206,154. Other sugar-derived surfactants
include the N-aL~coxy polyhydroxy fatty acid amides, such as C1o-C1g N
(3-methoxypropyl) pll~c~mi~e. The N-propyl through N-hexyl C12-C1g
~hlc~mides can be used for low s~ ing. Clo-C20 conventional soaps
may also be used. If high sudsing is desired, the branched-chain C1o-
C16 soaps may be used.
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Other suitable surfactants suitable for the purpose of the invention are the
anionic alkali metal sarcosinates of formula:
R-CON(Rl)CH2COOM
wherein R is a Cg-C17 linear or br~nche~l aLkyl or alkenyl group, Rl is a
Cl-C4 alkyl group and M is an alkali metal ion. Preferred examples are
the lauroyl, cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in
the form of their sodium salts.
Mixtures of anionic and nonionic surfactants are especially useful. Other
conventional useful surf~ct~nts are listed in st~ncl~rd texts.
The detergent compositions of the invention may also contain additional
detergent components. The precise nature of these additional components
and levels of incorporation thereof will depend on the physical form of the
composition, and the nature of the cleaning operation for which it is to be
used.
The compositions of the invention may, for example, be form~ te~l as
hand and m~chin~ laundry detergent compositions, including laundry
additive compositions and compositions suitable for use in the
pretre~tmçnt of st~ine-l fabrics and machine dishwashing compositions.
When incorporated in compositions suitable for use in a machine washing
method, eg: machine laundry and machine dishwashing methods, the
compositions of the invention ~refelably contain one or more additional
adjunct ingre-liçnts.
Adjunct Inpredients
The compositions herein can optionally include one or
more other detergent adjunct materials or other materials for ~si~ting or
enh~ncing cleaning performance, treatment of the substrate to be cleaned,
or to modify the ~esthetics of the de~ergel~t composition (e.g., colorants,
dyes, etc.).
Non-limiting examples of such adjunct materials include carbonate
producing compounds and calcium binding capacity compounds.
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Preferred species among the carbonate producing compounds are selected
from percarbonates, calcium carbonates, bicarbonates, sesquicarbonates
and mixtures thereof.
Preferred species among the calcium binding capacity compounds are
builders compounds each having a coefficient of calcium binding capacity
of at least 0.6.
In an embo(1im~nt of the invention, there is provided compositions which
ameliorate a tendency towards encrustation whilst having a weight ratio of
carbonate producing compounds to said calcium binding capacity
compounds of at least 0.3:1 and preferably of at least 0.5:1.
The following are illustrative examples of such adjunct materials,
particularly calcium carbonate producing compounds and calcium binding
capacity compounds.
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 l~lln-lering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depeIlr3inE upon the end use of
the composition and its desired physical form. Granular formulations
typically comprise from 10% to 80%, more typically from 15% to 50%
by weight, of the delervent builder. Lower or higher levels of builder,
however, are not meant to be excluded.
Inorganic or phosphate-cont~ining detergent builders include, but
are not limited to, the alkali metal, ammonium and alkanol~mmonium
salts of polyphosphates (exemplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates).
Non-phosphate builders may also be used. These can include, but are not
restricted to phytic acid, silicates, alkali metal carbonates (including
bicarbonates and sesquicarbonates), sulphates, aluminosilic~te~,
monomeric polycarboxylates5 homo or copolymeric polycarboxylic acids
or their salts in which the polycarboxylic acid comprises at least two
carboxylic radicals separated from each other by not more than two
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carbon atoms, organic phosphonates and aminoalkylene poly (alkylene
phosphonates).
The compositions herein also function in the presence of the so-called
"weak" builders (as compared with phosphates) such as citrate, or in the
so-called "underbuilt" situation that may occur with zeolite or layered
silicate builders.
Examples of silicate builders are the so called 'amorphous' alkali
metal silicates, particularly those having a SiO2:Na2O ratio in the range
1.6:1 to 3.2:1 and cryst~lline layered silicates, such as the layered sodium
silicates described in U.S. Patent 4,664,839. NaSKS-6 is the trademark
for a cryst~lline layered silicate marketed by Hoechst (commonly
abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6
silicate builder does not contain ~ minium. NaSKS-6 has the delta-
Na2Si2Os 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 siliç~tes, such as those having the general formula
NaMSixO2x+ 1-yH2O wherein M is sodium or hydrogen, x is a number
from 1.9 to 4, prere~ably 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 g~mm~ forms.
As noted above, the delta-Na2Si2Os (NaSKS-6 form) is most preferred
for use herein. Other silicates may also be useful such as for example
m~gnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilising agent for oxygen bleaches, and as a
component of suds control systems.
Examples of carbonate builders are the ~lk~line earth and alkali
metal carbonates as disclosed in German Patent Application No.
2,321,001 published on November 15, 1973. Such carbonate builders act
as builders to remove divalent metal ions such as calcium and additionally
provides ~lk~linity and aids in soil removal.
~ luminosilicate 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:
-
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Naz[(Alo2)z(sio2)y]~X1~20
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 0.5, and x is an integer from 15 to 264.
Useful ~ minosilicate ion exch~n~e materials are commercially
available. These aluminosilic~te~ can be cryst~lline or amorphous in
structure and can be naturally-occurring ~ minosilicates or synthetically
derived. A method for producing alumino.cilic~te ion exchange materials
is disclosed in U.S. Patent 3,985,669. Preferred synthe~ic cryst~lline
~lllminosilicate ion exchange materials useful herein are available under
the tlesi~n~tions Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In
an especially preferred embo-lime~t, the cryst~lline ~lllminosilicate ion
exchange material has the formula:
Na12[(Al~2) 12(sio2) 12] ~ xH2O
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 ~lll~inosilicate has a particle size of 0.1 10 microns in
~i~meter.
Organic dete~ lt 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, ~ref~rably 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
neutralised salt. When lltili7e~l in salt form, alkali metals, such as
sodium, pot~si-lm, ~nd lithium, or alkanol~mmonium salts are preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of polycarboxylate
builders encomr~ses the ether polycarboxylates, including
oxydisuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent
3,635,830. See also "TMS/TDS" builders of U.S. Patent 4,663,071.
Suitable ether polycarboxylates also include cyclic compounds,
particularly alicyclic compounds, such as those described in U.S. Patents
3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful deter~ellcy builders include the ether
hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene
or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-
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14
trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali
metal, ammonium and substituted ammonium salts of polyacetic acids
such as ethylene~i~mine tetraacetic acid and nitrilotriacetic acid, as well
as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic
acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders of particular
importance for heavy duty liquid detergent formulations due to their
availability from renewable resources and their biodegradability. Citrates
can also be used in granular compositions, especially in combination with
zeolite and/or layered silicate builders. Oxydisuccinates are also
especially useful in such compositions and combinations.
Also suitable in the compositions cont~inin~ the present invention
are the 3,3-dicarboxy~-oxa-1,6-hexanedioates and the related compounds
disclosed in U.S. Patent 4,566,984. Useful succinic acid builders include
the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A
particularly plerer~ed compound of this type is dodecenylsuccinic acid.
Specific examples of succinate builders include: laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-
pe~t~ cenylsuccinate, and the like. Laurylsuccinates are the preferred
builders of this group, and are described in EP 0,200,263.
Other suitable polycarboxylates are disclosed in U.S. Patent
4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322.
Fatty acids, e.g., C12-C1g monocarboxylic acids, can also be
incorporated into the compositions alone, or in combination with the
aforesaid builders, especially citrate and/or the succinate builders, to
provide additional builder activity. Such use of fatty acids will generally
result in a ~limimltion of s~l~lsing, which should be taken into account by
the form~ tor.
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.
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Patents 3,159,5819 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can
also be used.
Preferred calcium binding capacity compounds among the builder species
described above are selected from Zeolite A, Zeolite P (B), Zeolite MAP,
Zeolite X, delta-Na2SiO2Os(NaSKS-6), citrate, soap and mixtures
thereof.
Additional crystal prowlL inhibitor
Although not nçce~s~ry for the purpose of the invention, additional crystal
g~owlll inhibitors may be used. Such components include the Cl-C4
diphosphonic acid, preferably the C2 diphosphonic acid such as ethylene
diphosphonic acid, a-hydroxy-2 phenyl, ethyl diphosphonic acid,
methylene diphosphonic acid, vinylidene l,l diphosphonic acid, 1,2
dihydroxyethane 1,1 diphosphonic acid an hydroxy-ethane 1,1
diphosphonic acidl and any salts thereof and mixtures thereof.
Rl~hir~ Compounds - Bleaching Apents and Bleach Activators
Deter~ent compositions of the present invention may also include an
inorganic perhydrate bleach, normally in the form of the sodium salt, as
the source of ~lk~line hydrogen peroxide in the wash liquor. This
perhydrate is normally incorporated at a level of from 0.01 % to 40% by
weight, more pr~ferably from 5 % to 35 % by weight and most preferably
from 8% to 30% by weight of the composition.
The perhydrate may be any of the alkali metal inorganic salts such as
perborate monohydrate or tetrahydrate, percarbonate, perphosphate and
persilicate salts, but is conventionally an alkali metal perborate or
percarbonate.
, Sodium percarbonate, which is the ~refe~ed perhydrate, is an addition
compound having a formula corresponding to 2Na2CO3.3H2O2, and is
available commercially as a crystalline solid. Most commercially
available material includes a low level of a heavy metal sequestrant such
as EDTA, l-hydroxyethylidene 1, l-diphosphonic acid (HEDP) or an
amino-phosphonate, that is incorporated during the m~nl1f~cturing
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16
process. The percarbonate can be incorporated into detergent
compositions without additional protection, but preferred executions of
such compositions utilise a coated form of the material. A variety of
coatings can be used including borosilicate borate, boric acid and citrate
or sodium silicate of SiO2:Na20 ratio from 1.6:1 to 3.4:1, preferably
2.8: 1, applied as an aqueous solution to give a level of from 2% to 10%,
(normally from 3% to 5%) of silicate solids by weight of the
percarbonate. However the most prefe,led coating is a mixture of sodium
carbonate and sulphate or sodium chloride.
The particle size range of the crystalline percarbonate is from 350
micrometers to 1500 micrometers with a mean of approximately 500-1000
micrometers.
Another category of bleaching agent that can be used in place of or in
combination with the mixture of an inorganic perhydrate and a bleach
activator encompasses the ~refolmed peracid bleaching agents and salts
thereof. Suitable examples of this class of agents include (6-octylamino)-
6-oxo-caproic acid, (~nonylamino)-6-oxo-caproic acid, (6-decylamino)-6-
oxo-caproic acid, m~gnesium monoperoxyph~h~l~te hexahydrate, the
m~nesillm salt of metachloro perbenzoic acid, ~nonyl~mino~-
oxoperol~y~u~y,ic acid and diperoxydodecanedioic acid. Such bleaching
agents are disclosed in U.S. Patent 4,483,781, U.S. Patent 4,634,551, EP
0,133,354, U.S. Patent 4,412,934 and EP 0,170,386.
Mixtures of ble~c-hin~: agents can also be used.
rrereLred peroxygen bleaching agents selected from alkali metal
perborates tetrahydrates and monohydrates and percarbonates are
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.
The amount of bleach activator will typically be from 0.01 % to 205'o,
more typically from 0.01 % tolO% and most preferably from 0.01 % to
8 % by weight of the detergent composition.
These activators preferably comprise at least one acyl group forming the
peroxyacid precursor moiety bonded to a leaving group through an -O- or
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W O ~7~225
-N- linkage and may be selected from a wide range of classes. Various
nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854
and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS),
isononanoyloxybenzene sulfonate (ISONOBS) and tetraacetyl ethylene
mine (TAED) activators are typical, and mixtures thereof can also be
used.
Highly preferred amido-derived bleach activators are those of the
formulae:
RlN(R5)C(o)R2C(o)L or R1C(o)N(R5)R2C(o)L
wherein Rl is an alkyl group con~ininp from 6 to 12 carbon atoms, R2 is
an alkylene cont~ininF from 1 to 6 carbon atoms, R5 is H or alkyl, aryl,
or aL~caryl con~inin~ from 1 to 10 carbon atoms, and L is any suitable
leaving group. A leaving group is any group that is displaced from the
bleach activator as a consequence of the nucleophilic attack on the bleach
activator by the perhydrolysis anion. A ~refe~red leaving group is phenyl
sulfonate.
Preferred examples of bleach activators of the above formulae
include (6-oct~n~mido-caproyl)oxyben7~oneslllfonate~ (6-non~n~mido-
caproyl)oxyben7en~slllfonate, (6-~1ec~n~mi~o-caproyl)oxybenzene-
sulfonate, and mixtures thereof as described in U.S. Patent 4,634,551.
Another class of bleach activators comprises the benzoxazin-type
activators disclosed in U.S. Patent 4,966,723. A highly preferred
activator of the benzoxazin-type is:
~col
[~N~C~
Still another class of preferred bleach activators includes the acyl
lactam activators, especially acyl caprolactams and acyl valerolactams of
the formulae:
O O
O C--CH2--CH2 0 C--CH2--CH2
CH2--CH2 R--'C--N--CH--CH
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18
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group cont~ining
from 1 to 12 carbon atoms. Highly prefelled lactam activators include
benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl
caprol~ct~m, nonanoyl caprol~ct~m, ~lec~noyl caprol~t~m, undecenoyl
caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl
valerolactam, lm~leceJloyl valerol~ct~m, nonanoyl valerol~ct~m, 3,5,5
trimethylhexanoyl valerolactam and mixtures thereof. See also U.S.
Patent 4,545,784, which discloses acyl caprolactams, including benzoyl
caprolactam, adsorbed into sodium perborate.
Another class of preferred bleach activators include the cationic bleach
activators, derived from the valerolactam and acyl caprol~ct~m
compounds, of formula:
+
R~
X \ 11
CH~G; C--(CH2)X--CH2
CH2--CH2
wherein x is 0 or 1, substih~çnts R, R' and R" are each C1-C10 alkyl or
C2-C4 hydroxy alkyl groups, or [(CyH2y)O]n~RIll wherein y=2-4, n=1-
20 and R"' is a C1-C4 alkyl group or hydrogen and X is an anion.
Mixture of any of the bleach activators hereinbefore described may be
used.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can optionally be lltili7e~1 herein. One type of non-
oxygen bleaching agent of particular interest includes photoactivated
bleaching agents such as the sulfonated zinc and/or aluminium phthalo-
cyanines. See U.S. Patent 4,033,718. If used, detergent compositions
will typically contain from 0.025% to 1.25%, by weight, of such
bleaches, especially sulfonate zinc phthalocyanine.
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19
If desired, the bleaching compounds can be catalysed by means of a
m~ng~nese compound. Such compounds are well known in the art and
include, for example, the m~nganese-based catalysts disclosed in U.S.
Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat.
5,114,606; and EP 549,271Al, 549,272Al, 544,440A2, and 544,490Al;
Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-
trimethyl-l ,4,7-triazacyclononane)2(PF6)2, MnIII2(u-0)1(u-OAc)2(1,4,7-
trimethyl-l,4,7-triazacyclononane)2 (C104)2, MnIV4(u-0)6(1,4,7-
triazacyclononane)4(C104)4, MnIIIMnIV4(u-O)1(u-OAc)2 (1,4,7-
trimethyl-l ,4,7-triazacyclononane)2(C104)3, MnIV(l ,4,7-trimethyl-1,4,7-
triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-
based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and
U.S. Pat. 5,114,611. The use of m~ng~n~se with various complex
n~ls to enh~n~e bleaching is also reported in the following United
States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;
5,274,147; 5,153 9 161; 5,227,084.
Chel~tin~ A~ents - The detergent compositions herein may also
optionally contain one or more iron and/or m~n~nese chelating agents.
Such chelating agents can be selected from the group con~i~tin~ of amino
carboxylates, amino phosphonates, polyfunctionally-substitllte~ aromatic
chelating agents and mixtures therein, all as herein~fter 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
m~nE~nP!se ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethylene~ minPtetracetates, N-hydroxyethylethylene~ minetriacetates,
nitrilotriacetates, ethylene~ mine tel,~ro~lionates, triethylenetetra-
aminehex~et~tes, diethylenetri~minepent~cet~te~, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts therein and
mixtures therein.
Preferred biodegradable non-phosphorus chelants for use herein are
ethylçne~ mine disuccinate ("EDDS"), especially the [S,S] isomer as
described in U.S. Patent 4,704,233, ethylene~ mine-N,N'-digl~lt~m~te
(EDDG) and 2-hydroxypropylene-fli~mine-N~Nl-disuccinate (HPDDS)
compounds.
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Amino phosphonates are also suitable for use as chelating agents in
the compositions of the invention when at least low levels of total
phosphorus are permitted in detergent compositions, and include
ethylenP~ minetetrakis (methylenephosphonates) available under the
trademark DEQUEST 2041 from Monsanto and diethylene triamine
penta(methylenephosphonates) available under the trademark DEQUEST
2066 from Monsanto. Preferably, these amino phosphonates do not
contain aLt~yl or aLkenyl groups with more than 6 carbon atoms.
Polyfunctionally-substihlter~ aromatic chelating agents are also
useful in the compositions herein. See U.S. Patent 3,812,044. Preferred
compounds of this type in acid form are dihydroxydisulfobenzenes such
as 1,2-dihydroxy-3,5-disulfobenzene.
If lltili7~A, these chelating agents will generally comprise from
0.05% to 10% by weight of the detergellt compositions herein. More
preferably, if llt~ l, the chelating agents will comprise from 0.05 % to
2.0% by weight of such compositions.
Fn7~mes - 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 fugitive dye transfer, and for fabric
restoration. The enzymes to be incorporated include proteases, amylases,
lir~eee, cç~ eee~ and peroxitl~ees~ as well as mixtures thereof. Other
types of enzymes may also be included. They may be of any suitable
origin, such as vegetable, ~nim~l, bacterial, fungal and yeast origin.
However, their choice is gvvelLIed by several factors such as pH-activity
and/or stability optima, thermostability and stability versus active
dete~ents and builders. In this respect bacterial or fungal enzymes are
preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to provide
up to 5 mg by weight, more typically 0.01 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% by weight of a commercial
enzyme preparation.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B. licheniforms.
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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
GB 1,243,784 of Novo. Proteolytic enzymes suitable for removing
protein-based stains that are commercially available include those sold
under the tM~en~mes ALCALASE and SAVINASE by Novo ~n~ stries
A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc.
(The Netherlands). Other proteases include Protease A (see EP 130,756)
and Protease B (see EP257189). Preferred levels of proteases are from
0.01 % to 4.0% by weight of the detergent composition herein.
Amylases include, for example, a-amylases described in GB
1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and
TERMAMYL, Novo Tn~ltlstries. Flln~myl (Novo) is especially useful.
P~efeiled levels of amylases are from 0.01 % to 2.0% by weight of the
detergent composition herein.
The cell~ e~ 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,
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. ENDO A, CAREZYME both from Novo Tn~llstries A/S are
especially useful. Preferred levels of cellulases are from 0.01 ~ to 1.0
by weight of the deter~ellt composition herein.
Suitable lipase enzymes for detergent usage include those produced
by microor~nicm~ of the Pseudomonas group, such as Pseudomonas
stutzeri ATCC 19.154, as disclosed in GB 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 i~rom 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
,
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WO 97/05Z25 PCT~US96/12242
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 EP 341,947) is a l,refell~d lipase for use herein.
Prefe~ed levels of lipases are from 0.01 ~ to 2.0% by weight of the
dt;telgent composition herein.
Peroxidase enzymes are used in combination with oxygen sources,
e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They
are used for "solution ble~chin~, " i.e. to prevent transfer of dyes or
piPm~ tc 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, li~nin~se, and
haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-
cont~inin~ detergent compositions are disclosed, for example, in PCT
International Application WO 89/099813, published October 19, 1989, by
0. Kirk, ~si~n~ to Novo Tntlustries A/S.
A wide range of enzyme materials and means for their
incorporation into synthetic deLergellt compositions are also disclosed in
U.S. Patent 3,553,139. Enzymes are further disclosed in U.S. Patent
4,101,457 and in U.S. Patent 4,507,219. Enzyme materials useful for
liquid deter~ent formulations, and their incorporation into such
form~ tions, are disclosed in U.S. Patent 4,261,868. Enzymes for use in
detergents can be stabilized by various techniques. Enzyme stabilisation
techniques are disclosed and exemplified in U.S. Patent 3,600,319 and EP
0 199 405. Enzyme stabilisation systems are also described, for example,
in U.S. Patent 3,519,570.
Fn7~rme Stabilisers - The enzymes employed herein are stabilized
by the presence of water-soluble sources of calcium and/or m~nesjum
ions in the ftni~hed compositions which provide such ions to the enzymes.
(Calcium ions are generally somewhat more effective than m~nesium
ions and are prere,led herein if only one type of cation is being used.)
Additional stability can be provided by the presence of various other art-
disclosed stabilisers, especially borate species: see Severson, U.S.
4,537,706. Typical detergents, especially liquids, will comprise from 1
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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 litre of finiched
composition. This can vary somewhat, depending on the amount of
enzyme present and its response to the calcium or m~nesium ions. The
level of calcium or magnesium ions should be selected so that there is
always some mini~llm level available for the enzyme, after allowing for
complexation with builders, fatty acids, etc., in the composition. Any
water-soluble calcium or m~nesium salt can be used as the source of
calcium or m~nesium ions, including, but not limiteA to, calcium
chloride, calcium sulfate, calcium malate, calcium m~le~te, calcium
hydroxide, calcium formate, and calcium acetate, and t~e corresponding
m~n~sium salts. A small amount of calcium ion, generally from 0.05 to
0.4 millimoles per litre, is often also present in the con~position due to
calcium in the enzyme slurry an~ 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 sl~ffice.
It is to be unLderstood that the foregoing levels of calcium and/or
m~f~nesium ions are sufficient to provide enzyme stability. More calcium
and/or m~nesi~lm 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
m~gnesillm ions~ or both. The amount can vary, of course, with the
amount and type of enzyme employed in the composition.
The compositions herein may also optionally, but preferably,
contain various additional stabilizers, especially borate-type stabilizers.
Typically, such stabilizers will be used at levels in the compositions from
0.25% to 10%, preferably from 0.5% to 55~, 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. Substinlte-i boric
acids (e.g., phenylboronic acid, butane boronic acid, andl p-bromo
phenylboronic acid) can also be used in place of boric acid.
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24
Polymeric Dispersin~ Agents - Polymeric dispersing agents can
advantageously be ~ltili~e-l at levels from 0.5% to 8%, by weight, in the
compositions herein, especially in the presence of zeolite and/or layered
silicate builders. Suitable polymeric dispersing agents include polymeric
polycarboxylates and polyethylene glycols, although others known in the
art can also be used. It is believed, though it is not intended to be limited
by theory, that polymeric dispersing agents enh~nce overall detergent
builder pelrol,llance, when used in combination with other builders
(including lower molecular weight polycarboxylates) by particulate soil
release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by
polymerizing or copolymerizing suitable l~n~ rated 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, meS~conic acid, citraconic acid and methylenemalonic acid.
The presence in the polymeric polycarboxylates herein or monomeric
se~ment~, cont~inin~ no carboxylate radicals such as vinylmethyl ether,
styrene, ethylene, etc. is suitable provided that such segments do not
con~tihlte more than 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived
from acrylic acid. Such acrylic acid-based polymers which are useful
herein are the water-soluble 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 ~refelably 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.
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
CA 02227884 1998-01-23
WO 97~a~22~; PCT/US96/12242
preferably ranges from 2,000 to 100,000, more preferably 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
1:1, more preferably from 10:1 to 2:1. Water-soluble salts of such
acrylic acid/maleic acid copolymers can include, for example, the alkali
metal, ammonium and substit~lte~l 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/vinyll alcohol terpolymers. Such materials are also
disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer
of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be inclll~le-l 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.
Polyaspartate and polyglllt~m~te dispersing agents may also be
used, especially in conjunction with zeolite builders. Dispersing agents
such as polyaspartate prefe~dbly have a molecular weight (avg.) of
10,000.
Clay Soil Removal/Anti-redeposition ~ents - The compositions
according to the present invention can also optionally contain water-
soluble ethoxylated ~mine~ 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%.
The most preferred soil release and anti-redeposition agent is
ethoxylated tetraethylenepe~t~mine. Exemplary ethoxylated amines are
further described in U.S. Patent 4,~97,898, VanderMeer, issued July 1,
1986. Another group of preferred clay soil removal-antiredeposition
agents are the cationic compounds disclosed in EP 111,965. Other clay
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26
soil removal/antiredeposition agents which can be used include the
ethoxylated amine polymers disclosed in EP 111,984; the zwitterionic
polymers disclosed in EP 112,592; and the amine oxides disclosed in
U.S. Patent 4,548,744. Other clay soil removal and/or anti redeposition
agents known in the art can also be ~ li7e-1 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.
Polymeric Soil Release A~ent - 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 segmPnts, to hydrophilize the
surface of hydrophobic fibers, such as polyester and nylon, and
hydrophobic se~m~r~t~ 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 se mentS. This can enable
stains occurring subsequent to tre~tm~nt with the soil release agent to be
more easily cleaned in later washing procedures.
Soil release agents characterised by poly(vinyl ester)
hydrophobe sep:ments include graft copolymers of poly(vinyl ester), e.g.,
C1-C6 vinyl esters, preferably poly(vinyl ~cet~te) graf~ed onto
polyalkylene oxide backbones, sucb as polyethylene oxide backbones (see
EP 0 219 048). Commercially available soil release agents of this kind
include the SOKALAN type of material, e.g., SOKALAN HP-22,
available from BASF (West Germany).
One type of preferred soil release agent is a copolymer having
random blocks of ethylene terephth~l~te and polyethylene oxide (PEO)
terephth~l~te. The molecular weight of this polymeric soil release agent
is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to
Hays and U.S . Patent 3 ,893 ,929.
Another preferred polymeric soil release agent is a polyester with
repeat units of ethylene terephth~l~te units which contains 10-15 % by
weight of ethylene terephth~l~te units together with 90-80~ by weight of
polyoxyethylene terephth~l~te units, derived from a polyoxyethylene
glycol of average molecular weight 300-5,000. Examples of this polymer
CA 02227884 1998-01-23
W~97ra5225 PCT~US96/12Z4Z
include the commercially available material ZELCON 5126 (from
Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857.
- Another preferred polymeric soil release agent is a sulfonated
product of a subst~nti~lly linear ester oligomer comprised of an
oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat
units and terminal moieties covalently ~ chet1 to the backbone. These
soil release agents are described fully in U.S. Patent 4,968,451. Other
suitable polymeric soil release agents include the tereph~h~l~te polyesters
of U.S. Patent 4,711,730, the anionic end-capped oligorneric esters of
U.S. Patent 4,7219580 and the block polyester oligomeric compounds of
U.S. Patent 4,702,~57.
Preferred polymeric soil release agents also include the soil release
agents of U.S. Patent 4,877,896, which discloses anionic, especially sul-
foarolyl, end-capped terephth~l~te esters.
If l-tili7e~1, soil release agents will generally comprise from 0.01%
to 10.0~, by weight, of the compositions herein, typically from 0.1% to
5%, ~efelably from 0.2% to 3.0%.
Still another prerelred 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 termin~te~l with modified isethionate end-
caps. A particularly preferled soil release agent of this type comprises
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)-eth~n~sulfonate. Said soil release
agent also comprises from 0.5~ to 20%, by weight of the oligomer, of a
cryst~lline-reducing stabilizer, preferably selected from xylene sulfonate,
cllm.on~ sulfonate, ~oluene sulfonate, and mi~tures thereof.
Dye Transfer Inhibiting A~ents
The compositions according to the present invention may also include one
or more materials effective for inhibiting the transfer of dyes from one
fabric to another during the cle~nin~ process. Generally, such dye transfer
inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimi~1~701e,
m~ng~nPse phthalocyanine, peroxidases, and rnixtures thereof. If used,
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W O 97/05225 PCT~US96/12242
28
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%.
More specifically, the polyamine N-oxide polymers preferred for
use herein contain units having the following structural formula: R-AX-P;
wherein P is a 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. r~eferLed polyamine N-
oxides are those wherein R is a heterocyclic group such as pyridine,
pyrrole, imi-l~7ole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general
structures:
(R2)y; =N--(Rl)X
~R3)z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic
groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of
the N-O group can be ~ cheA or form part of any of the aforementioned
groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10,
~referably pKa ~7, more prefefred pKa <6.
Any polymer backbone can be used as long as the amine oxide
polymer formed is water-soluble and has dye transfer inhibiting
properties. Examples of suitable polymeric backbones are polyvinyls,
polyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and mixtures thereof. These polymers include random or
block copolymers where one monomer type is an amine N-oxide and the
other monomer type is an N-oxide. The amine N-oxide polymers typically
have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
However, the number of amine oxide groups present in the polyamine
oxide polymer can be varied by appropriate copolymerization or by an
a~propriate degree of N-oxidation. The polyamine oxides can be obtained
CA 02227884 1998-01-23
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29
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
S00,000; most pre~erred S,000 to 100,000. This preferred class of
materials can be referred to as "PVNO".
The most prefe,led polyamine N-oxide useful in the compositions
herein is poly(4-vinylpyridine-N-oxide) which as an average molecular
weight of S0,000 and an amine to amine N-oxide ratio of 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimi~ ole polymers
(referred to as a class as "PVPVI") are also preferred for use herein.
Preferably the PVPVI has an average molecular weight range from S,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 PVPVI copolylmers typically have a molar ratio of N-vinylimic1~7ole
to N-vinylpyrrolidone from 1:1 to 0.2:1, more ~Lefeldbly from 0.8:1 to
0.3:1, most ~re~lably from 0.6:1 to 0.4:1. These copolymers can be
either linear or branched.
The present invention compositions also may employ a polyvinyl-
pyrrolidone ("PVP"~ having an average molecular weight of from 5,000 to
400,000, ~rerelably from 5,000 to 200,000, and more prereidbly 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
cont~inin~ PVP can also contain polyethylene glycol ("PEG") having an
average molecular weight fromL 500 to 100,000, plef~l~bly 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.
The detergent compositions herein may also optionally contain from
0.005 % to 5 % by weight of certain types of hydrophilic optical
bri~hteners which also provide a dye transfer inhibition action. If used,
the compositions herein will preferably comprise from 0.01% to 1.2~i by
weight of such optical brighteners.
The hydrophilic optical brighte~ers useful in the present invention
are those having the structural formula:
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Rl R2
N~O>~H IH~ I ~N
R2 SO3M SO3M Rl
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a
salt-forming cation such as sodium or pot~sillm.
When in the above formula, R1 is anilino, R2 is N-2-bis-
hydroxyethyl and M is a cation such as sodium, the bri~htener 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 bri~:ht~onP-r useful in the compositio~s herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-
N-2-methyl~mino and M is a cation such as sodium, the bri~htt-Iler is 4,4'-
bis[(4-~nilino-~(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-
yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular
bri~htener species is commercially marketed under the tradename Tinopal
5BM-GX by Ciba-Geigy Corporation.
When in the above formula, Rl is anilino, R2 is morphilino and M
is a cation such as sodium, the brightener is 4,4'-bist(4-~nilino-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.
Other specific optical briPhte~er species which may be used 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 SBM-GX and/or Tinopal AMS-GX) provides significantly better
dye transfer inhibition in aqueous wash solutions than does either of these
two detergent composition components when used alone. Without being
=
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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 brightPn~r concentration in the wash liquor. Brighteners
with relatively high exhaustion coefficients are the most suitable for
inhibiting dye transiFer in the context of the present invention.
Of course, it will be appreciated that other conventional optical
brightener types of compounds can optionally be used in the present
compositions to provide conventional fabric "brightness" benefits, rather
than a true dye transfer inhibiting effect. Such usage is conventional and
well-known to de~elgent formulations.
Conventional optical bri~htPners or other bri~ht~ning or whitenin~
agents known in the art can be incorporated at levels typically from
0.005 3Zo to S%, ~r~rerably from 0.01% to 1.2% and most preferably from
0.05% to 1.2%, by weight, into the detergellt compositions herein.
Commercial optical brighteners which may be useful in the present
invention can be cl~sifie~ into subgroups, which include, but are not
nP!cec.c~rily limitetl to, derivatives of stilbene, pyrazoline, coumarin,
carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles,
5- and ~membered-ring heterocycles, and other miscellaneous agents.
F.x~mrles of such brighteners are disclosed in "The Production and
Application of Fluorescent BriPhtening Agents", M. Zahradnik, Published
by Jo_n Wiley & Sons, New York (1982~. Further optical bri~htener
which may also be used in the present invention include naphth~limide,
benzoxazole, benzofuran, be~7imi~ole and any mixtures thereof.
Specific examples of optical brighteners which are useful in the
present compositions are those i~lentifiPd in U.S. Patent 4,790,856. These
brighteners include the PHORWHITE series of bri~htlonPrs from Verona.
Other brighteners disclosed in this reference include: Tinopal UNPA,
Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic White
CC and Artic White CWD; the 2-(4-styryl-phenyl)-2H-naptho[1,2-
d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-
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bis(styryl)bisphenyls; and the aminocoumarins. Specific examples of
these brighteners include 4-methyl-7-diethyl- amino coumarin; 1 ,2-bis(-
ben7imi~1~701-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-
2-yl)thiophene; 2-styryl-naptho-tl,2-d]oxazole; and 2-(stilbene-4-yl)-2H-
naphtho[1 ,2-d]triazole. See also U.S . Patent 3 ,646,015 .
Suds Suppressors - Compounds for reducing or suppressing the formation
of suds can be incorporated into the compositions of the present
invention. Suds ~u~ression can be of particular importance in the so-
called "high concentration cleaning process" and in front-loading
European-style washing machines.
A wide variety of materials may be used as suds ~u~ressors, and
suds ~u~l~ressors are well known to those ~kille~l 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 ~up~ressor of particular interest encompasses
monocarboxylic fatty acid and soluble salts therein. See U.S. Patent
2,954,347. The monocarboxylic fatty acids and salts thereof used as suds
suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,
preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal
salts such as sodium, pot~ssi~lm, and lithium salts, and ammonium and
alkanolammonium salts.
The dete~ t compositions herein may also contain non-surf~ct~nt
suds ~u~pressors. These include, for example: high molec~ r weight
hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid
triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1g-C40
ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated
amino tri~7in~s such as tri- to hexa-alkylmelamines or di- to tetra-
alkyltli~min~ c~lortriazines formed as products of cyanuric chloride with
two or three moles of a primary or secondary amine cont~ining 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 paraffLn and haloparaffin can be l-tili7etl 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
. .
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a miniml-m 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 con~tit~lte a preferred category of
suds ~u~pressor for detergent compositions. Hydrocarbon suds
suppressors are described, for example, in U.S. Patent 4,265,779. The
hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and
heterocyclic saturated or lln~hlrated hydrocarbons having from 12 to 70
carbon atoms. The term "paraffin, " as used in this suds suppressor
discussion, is intton~1e~1 to include mixtures of true paraffins and cyclic
hydrocarbons.
Another preferred category of non-surfactant suds su~pressors
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
k~own in the art and are, for example, disclosed in U.S. Patent 4,265,779
and EP 354016.
Other silicone suds suppressors are disclosed in U.S. Patent
3,455,839 which relates to compositions and processes for defoaming
aqueous solutions by incorporating therein small amounts of
polydimethylsiloxane fluids.
Mixtures of silicone and sil~n~t~l silica are described, for instance,
in German Patent Application DOS 2,124,526. Silicone defoamers and
suds controlling agents in granular deter~ellt compositions are disclosed in
U.S. Patent 3,933,672 and in U.S. Patent 4,652,392.
An exemplary silicone based suds ~u~l3ressor for use herein is a
suds ~u~ressing amount of a suds controlling agent consisting essentiall
of:
(i) polydimethylsiloxane fluid having a viscosity of from 20 cs. to
1,500 cs. at 25~C;
(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane
resin co~posed of (CH3)3SiOl/2 units of SiO2 units in a ratio
of from (CH3)3 SiOl/2 units and to SiO2 units of from 0.6: 1
to 1.2:1; and
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34
(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the preferred silicone suds suppressor used herein, the solvent
for a continuous phase is made up of certain polyethylene glycols or
polyethylene-polypropylene glycol copolymers or mixtures thereof
(preferred), or polypropylene glycol. The primary silicone suds
suppressor is branched/crosslinke~ and preferably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions with controlled suds will optionally comprise from 0.001 to
ereiably from 0.01 to 0.7, most ~referably from Q.05 to 0.5, weight
% of said silicone suds ~lppressor, 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 surf~ct~nt; and (3)
polyethylene glycol or a copolymer of polyethylene-polypropylene glycol
having a solubility in water at room temperature of more than 2 weight
~; and without polypropylene glycol. Similar amounts can be used in
granular compositions, gels, etc. See also U.S. Patents 4,978,471 and
4,983,316; 5,288,431 and U.S. Patents 4,639,489 and 4,749,740, Aizawa
et al at column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises
polyethylene glycol and a copolymer of polyethylene
glycol/poly~ro~ylene glycol, all having an average molecular weight of
less than 1,000, prefelably 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 ~refelLed 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, plefeldbly PPG 200/PEG 300.
Pleferred is a weight ratio of between 1: 1 and 1: 10, most ~Lerelably
between 1 :3 and 1 :6, of polyethylene glycol:copolymer of polyethylene-
polypropylene glycol.
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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.
Other suds suppressors useful herein comprise the secondary
alcohols (e.g., 2-alkyl aL~canols) and mixtures of such alcohols with
silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118
and EP 150,872. The secondary alcohols include the C6-C16 alkyl
alcohols having a C1-C16 chain. A ~referled alcohol is 2-butyl octanol,
which is available from Condea under the trademark ISOFOL 12.
Mixtures of secondary alcohols are available under the tr~-lem~rk
ISALCHEM 123 from Enichem. Mixed suds ~u~ressors typically
comprise mixtures of alcohol + silicone at a weight ratio of 1:~ to 5:1.
For any deter~ent compositions to be used in automatic laundry
washing machines, suds should not form to the extent that they overflow
the washing m~c.hine. Suds ~u~p~essors, when lltili7ecl, are preferably
present in a "suds ~uppLessing amount. By "suds suppressing amount'l is
meant that the form~ tor of the composition can select an amount of this
suds controlling agen~ that will sufficiently control the suds to result in a
low-sll~lsinE laundry detergent for use in automatic laundry washing
machines.
The compositions herein will generally comprise from 0% to 5% of
suds suppressor. When lltili7~.1 as suds suppressors, monocarboxylic fatty
acids, and salts thereim, will be present typically in amounts up to 5 %, by
weight, of the detelgellt composition. Preferably, from 0.5 % to 3 % of
fatty monocarboxylate suds ~u~plessor is lltili7e~1. Silicone suds
~u~yr~SOrS are typically ~ltili7ell 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 minimi7e~ and effectiveness of lower amounts for effectively
controlling slld~in~. 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
tili7e-l in combination with polyorganosiloxane, as well as any adjunct
materials that may be l~ltili7e~1. Monostearyl phosphate suds suppressors
are generally lltili7e~1 in amounts r~ngin~ from 0.1% to 2%, by weight, of
,
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36
the composition. Hydrocarbon suds suppressors are typically lltili7e~1 in
amounts r~nging from 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.
Fabric Softeners - Various through-the-wash fabric softeners,
especially the imr~l~able smectite clays of U.S. Patent 4,062,647, as well
as other softener clays known in the art, can optionally be used typically
at levels of from 0.5% to 10%, preferably from 0.5% to 2~ 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 and U.S. Patent 4,291,071.
Other In~redients - A wide variety of other functional ingre-lientc useful
in detergent compositions can be included in the compositions herein,
including other active ingredients, carriers, hydrotropes, processin~ aids,
dyes or pigm.ont~, solvents for liquid formulations, solid fillers for bar
compositions. If high s~lsin~ is desired, suds boosters such as the Clo-
C16 alkanol~mi~1es can be incorporated into the compositions, typically at
1%-10% levels. The C1o-C14 monoethanol and diethanol amides
illustrate a typical class of such suds boosters. Use of such suds boosters
with high s~ ing adjunct surfactants such as the amine oxides, betaines
and slllt~inp!~ noted above is also advantageous. If desired, soluble
m~n~sj~lm salts such as MgC12, MgSO4, and the like, can be added at
levels of, typically, 0.1%-2%, to provide ~ litional suds and to enhance
grease removal pelrolmance.
Various delelsive ingre-lient~ 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 surf~ct~nt 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 int~n~le~l detersive function.
To illustrate this technique in more detail, a porous hydrophobic
silica (trademark SIPERNAT D10, DeGussa) is admixed with a
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proteolytic enzyme solution cont~ining 3%-5% of C13 15 ethoxylated
alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surf~,ct~nt
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 delergent matrix. By this
means, ingredients such as the aforementioned enzymes, bleaches, bleach
activators, bleach catalysts, photoactivators, dyes, fluor~scers, fabric
conditioners and hydrolyzable surfactants can be "protected" for use in
detergents.
The detergent compositions herein will preferably be form~ te-3
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.
n~lry products are typically at pH 9-11. Techniques for controlling pH
at recommen~1ecl usage levels include the use of burre~, alkalis, acids,
etc., and are well known to those skilled in the art.
Other oI~tional ingredients
Other optional ingredients suitable for inclusion in the compositions of the
invention include perfumes, colours and filler salts, with sodium sulfate
being a preferred filler salt.
Form of the compositions
The detergellt compositions of the invention can be form~ te~1 in any
desirable form such as powders, gr~n~ tes, pastes, liquids, and gels.
Liquid compositions
The detergent compositions of the present invention may be form~ ted as
liquid de~el~;ellt compositions. Such liquid delergent compositions
typically comprise from 94% to 35% by weight, preferably from 90% to
40% by weight, most preferably from 80% to 50% by weight of a liquid
carrier, e.g., water, prefer~bly a mixture of water and organic solvent.
Gel compositions
The detergent compositions of the present invention may also be in the
form of gels. Such compositions are typically form~ te~ with polyakenyl
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38
polyether having a molecular weight of from about 750,000 to about
4,000,000.
Solid compositions
The detergent compositions of the invention may also be in the form of
solids, such as powders and granules.
The mean particle size of the components of granular compositions in
accordance with the invention should preferably be such that no more that
5 % of particles are greater than 1 .4mm in diameter and not more than 5 %
of particles are less than 0.15mm in diameter.
The term mean particle size as defined herein is calc~ tecl by sieving a
sample of the composition into a number of fractions (typically 5
fractions) on a series of Tyler sieves. The weight fractions thereby
obtained are plotted ~in~t the aperture size of the sieves. The mean
particle size is taken to be the aperture size through which 50% by weight
of the sample would pass.
The buL~ density of granular detergent compositions in accordance with
the present invention are particularly useful in concentrated granular
dele~gellt compositions that are characterised by a relatively high density
in comparison with conventional laundry detergent compositions. Such
high density compositions typically have a buL~ density of at least 400
g/litre, more ~leferdbly from 650 g/litre to 1200 g/litre, most preferably
from 800g/litre to lOOOg/litre.
Bulk density is me~red by means of a simple funnel and cup device
concietin~ of a conical funnel moulded rigidly on a base and provided
with a flap valve at its lower extremity to allow the contents of the funnel
to be emptied into an axially ~ ned cylindrical cup disposed below the
funnel. The funnel is 130 mm high and has internal diameters of 130
mm and 40 mm at its respective upper and lower extremities. It is
mounted so that the lower extremity is 140 mm above the upper surface
of the base. The cup has an overall height of 90 mm, an internal height
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39
of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500
ml.
To carry out a measurement, the fimnel is filled with powder by hand
pouring, the flap valve is opened and powder allowed to over~lll the cup.
The filled cup is removed from the frame and excess powder removed
from the cup by p~ssing a straight edged implement eg; a knife, across its
upper edge. The filled cup is then weighed and the value obtained for the
weight of powder doubled to provide a bulk density in g/litre. Replicate
measurements are made as required.
In a further embodiment of the invention is provided a method for
reducing heater encrustation, which comprises contacting the heater with
an effective amount of an aqueous solution of a deterge~t composition
comprising an hydroxyacid component in accordance with the present
invention.
Makin processes - ~ranular compositions
In general, granular detergent compositions in accordance with the
present invention can be made via a variety of methods including dry
mixing, spray drying, agglomeration and gr~n~ tion.
The invention is illustrated in the following non limitin~ examples, in
which all percentages are on a weight basis unless other~,vise stated.
,
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In the bleaching compositions of the invention, the abbreviated component
identifications have the following me~nin~
C12LAS : Sodium linear C12 alkyl benzene
sulphonate
TAS : Sodium tallow alcohol sulphate
C45AS : Sodium C14-C1s linear alkyl sulphate
C45E3S Sodium C14-C1s branched alkyl sulphate
condensed with 3 moles of ethylene oxide.
Soap : Sodium linear alkyl carboxylate derived from an
80/20 mixture of tallow and a coconut oils.
C45E7 : A C14 15 predomin~ntly linear primary alcohol
condensed with an average of 7 moles of
ethylene oxide
C25 E3 : A C12 15 branched primary alcohol condensed
with an average of 3 moles of ethylene oxide
C25E5 : A C12 15 branched primary alcohol condensed
with an average of 5 moles of ethylene oxide
TFAA : C16-Clg alkyl N-methyl gl~lc~mi-le
Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0
ratio)
NaSKS-6 : Crystalline layered silicate of formula
~ -Na2Si205
Carbonate : Anhydrous sodium carbonate with a particle size
between 200~m and 900~m
Bicarbonate : An~ydrous sodium bicarbonate with a particle
size distribution between 400~1m and 1200~m
Sulphate : Anhydrous sodium sulphate
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(Alo2sio2)l2 27H20
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41
having a primary particle size in the range from
0.1 to 10 micrometers
STPP : Anhydrous sodium tripolyphosphate
Citrate : Tri-sodium citrate dihydrate oiF activity 86.4%
with a particle size distribution between 425~m
and 850~m
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000.
PB4 : Sodium perborate tetrahydrate of nominal
formula NaBO2.3H2O-H2o2
PBl : Anhydrous sodium perborate bleach of
nominal formula NaBo2.H2o2
Percarbonate : Sodium Percarbonate of nominal formula
2Na2C03.3H202
NOBS : Nonanoylo~yl,e~ene sulfonate in the form of
the sodium salt.
TAED : Tetraacetyl ethylene ~ mine
CMC : Sodium carboxymethyl cellulose
Brightener 1 : Disodium4,4'-bis(4-~nilino-6-morpholino-1.3.5-
triazin-2-yl)amino stilbene-2:2'-disulphonate.
Bri~htener 2 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
DTPMP : Diethylene tri~mine penta (methylene
phosphonate), marketed by Monsanto under the
Trade name Dequest 2060
EDDS : Ethylene~ minç -N, N'- disuccinic acid, [S,S]
isomer in the form of the sodium salt.
Silicone antifoam: Polytlim-othyldiloxane foam controller with
Siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to said
dispersing agent of 10:1 to 100:1.
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42
Photoactivated: Sulphonated Zinc Phthalocyanin
encapsulated in bleach dextrin soluble polymer
Savinase : proteolytic enzyme of activity 4KNPU/g
Alcalase : proteolytic enzyme of activity 3AU/g
Carezyme : cellulytic enzyme of activity 1000 SCEVU/g
Termamyl : Amylolytic enzyme of activity 60KNU/g
Lipolase : Lipolytic enzyme of activity 100kLU/g
all sold by NOVO Tncll.lstries A/S
PVP : polyvinylpyrrolidone of MWt 13000
SRP : Sulfobenzoyl end capped esters with oxyethylene
oxy and terephtaloyl backbone
F.xample l-Comparative Pelr~ ance Testins~
The following laundry deterge.lt compositions A and F having a ratio of
carbonate producing compounds to calcium binding capacity compounds
of 0.55 were prepared, where F is a comparative composition and A is in
accord with the invention:
Formulations A F
C45AS 11.0 11.0
Zeolite A 15.0 15.0
Carbonate 4.0 4.0
MA/AA 4.0 4.0
CMC 0.5 0.5
DTPMP 0.4 0.4
C25E5 5.0 5 0
Perfume 0.5 0.5
NaSKS-6 13.0 13.0
Citrate 3.0 3.0
TAED 7.0 7.0
Percarbonate 20.0 20.0
SRP 0.3 0.3
-
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Savinase 1.4 1.4
Lipolase 0.4 0.4
Carezyme 0.6 0.6
Termamyl 0.6 0.6
Silicone antifoam 5.0 5.0
Brightener 2 0.2 0.2
Glycolic acid (neutralised 1.25
form)
Balance (moisture & 100.0 100.0
miscellaneous)
Test protocol - Hea~er encrustation testir~
A test was made using two Bosch automatic dishwashing machines SMS
9022. The 65~C normal cycle programme was selected and water of 25~
German Hardness was used. The detergent was poured in the automatic
dispenser located in the door of the machine in amount sufficient to obtain
a ratio of Sg of detergent per litre of solution. With this amount, the
laundry conditions were reproduced and easier access than in a laundry
washing machine to the heater for observation was obtained.
One machine was run with formulation A and the other with formulation
F. After 27 wash cycles, the heater was removed for visual observation.
A white deposit was observed on the heater where Formulation F was
used while for the heater which was using form~ tion A according to the
invention at 1.25% of glycolic acid, no white deposit was observed.
The visual observation test is made for determining the presence of
calcium and/or m~nesi~lm carbonate. The heater is im~ersed in an
acidified water solution (2N sulfuric acid). The observation of an
effervescence on top of the heater indicates the presence of calcium
and/or m~nesi~lm carbonate encrustation.
Using the above test, an effervescence was observed on the heater where
formulation F was used while the heater using formulation A according to
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44
the invention at 1.25 % of glycolic showed a significantly reduced
effervescence versus formulation F.
Thus, encrustation was observed on the heater using formulation F while
retl~ce~l encrustation was observed on the heater using formulation A
according to the invention.
Exam~le 2
The following laundry detergent compositions B to F having a ratio of
carbonate producing compounds to calcium binding capacity compounds
of 0.55 were prepared, where F is a comparative composition and B to E
are in accord with the invention.
Formulations B C D E F
C45AS 11.0 11.0 11.0 11.0 1 1.0
Zeolite A 15.0 15.0 15.0 15.0 15.0
Carbonate 4.0 4.0 4.0 4.0 4.0
MA/AA 4.0 4.0 4.0 4.0 4.0
CMC 0.5 0.5 0.5 0.5 0.5
D T P M P 0.4 0.4 0.4 0.4 0.4
C25E5 S.0 5.0 5.0 5.0 S.0
Perfume 0.5 0.5 0.5 0.5 0.5
NaSKS-6 13.0 13.0 13.0 13.0 13.0
Citrate 3.0 3.0 3.0 3.0 3.0
TAED 7.0 7.0 7.0 7.0 7.0
Percarbonate 20.0 20.0 20.0 20.0 20.0
SRP 0.3 0.3 0.3 0.3 0.3
Savinase 1.4 1.4 1.4 1.4 1.4
Lipolase 0.4 0.4 0.4 0.4 0.4
Carezyme 0.6 0.6 0.6 0.6 0.6
Termamyl 0.6 0.6 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0 5.0 5.0
Bri~htener 2 0.2 0.2 0.2 0.2 0.2
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Glycolic acid 0.45 0.9 1.34 - -
(neutralised form)
Glycolic acid - - - 1.34
R~l~nce (moisture & 100 100 100 100 100
miscellaneous)
Compositions B to E in accordance with the invention were all seen by
the visual observation test, to produce appreciably less heater encrustation
than composition F.
Fxample 3
The following laundry detergent compositions G to X were prepared in
accord with the invention:
Formulations G H
Blown powder STPP - 24
Zeolite A 24
Sulfate 6 13
MA/AA 4 2
LAS 8 11
Silicate 3 3
CMC 1 0.5
Bri~hten~r 1 0.2 0.2
Soap 1.0 1.0
DTPMP 0.4 0.2
Spray-on C45E7 2.5 2.0
C25E3 2.5 2.0
Silicon antifoam 0.3 0.3
Perfume 0.3 0.3
Dry additives Carbonate 13.0 1~.0
PB4 18.0 10.0
PBl 4.0 ~
TAED 3.0 1.0
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46
Photoactivated 0.02 0.02
bleach
Savinase 1.0 1.0
Lipolase 0.4 0.4
Sulfate 3.0 5 0
Glycolic acid 1.25 1.25
(neutralised form)
Balance (moisture & miscellaneous)
Formulations I J K
Blown Zeolite A 15 15
powder
Sulfate - 5 0
LAS 3.0 3.0
DTPMP 0.4 0.5
CMC 0.4 0.4
MA/AA 4.0 4.0
Agglomerate C45AS - - 11.0
s
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
ZeoliteA 10.0 15.0 13.0
CMC - - o 5
MA/AA - - 2.0
Carbonate 9.0 7.0 7.0
¦ Spray on Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0
¦ Dry additives MA/AA - - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
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PVP 0.5 0.50.5
Savinase 1.0 1.01.30
Lipolase 0.4 0.40.4
Termamyl 0.6 0.60.6
Carezyme 0.6 0.60.6
Siliconeantifoam 5.0 5.05.0
Sulfate - 9.0
Glycolic acid 1.25 1.25 1.25
(neutralised
form)
Balance (moisture & miscellaneous)
Formulations L M
¦ Blownpowder Zeolite A 22 6.0
Sulfate 10 7.0
MA/AA 3.0 6.0
LAS 12.0 22.0
C45AS 7.0 7.0
Silicate 1.0 5.0
Soap - 2.0
Brightener 2 0.2 0.2
Carbonate 16.0 20.0
DTPMP 0.4 0.4
Spray-on C45E7 1.0 1.0
Dry additives PVP 0.5 0.5
Savinase 1.0 1.0
Lipolase 0.4 0.4
NOBS 6.1 4.5
PB 1 5.0 6.0
Sulfate 6.0
Glycolic acid 1.25 1.25
(neutralised form)
Balance (moisture & miscellaneous)
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48
Formulations Q
¦ Agglomerate C45AS 14.0
Zeolite A 6.0
Carbonate 8.0
MA/AA 8.0
CMC 0.5
DTPMP 0.4
¦ Spray-on C25E5 5.0
Perfume 0.5
¦ Dry additives NaSKS-6 10.0
Citrate 1.0
TAED 7.0
Percarbonate 20.0
(14.0% AvOx)
SRP 0.3
Savinase 1.4
Lipolase 0.4
Carezyme 0.6
Termamyl 0.6
Silicone antifoam 5.0
Bri~htener 2 0.2
Glycolic acid 1.25
(neutralised form)
R~l~nce (moisture & miscellaneous)
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49
Formulations N O P
- ¦ Blown powder Zeolite A 15.0 15.0 15.
Sulfate 5.0
LAS 3.0 3.0 3.0
Mixture of N,N-dimethyl-N-(2- - 1.5 1.5
hydroxyethyl)-N-dodecyl/N,N-
t1im~t~yl-N-(2-hydroxyethyl)-N
tetradecyl annnnoniu m bro ~ de
D TP M P 0.4 0.4 0.4
C M C 0.4 0.4 0.4
M A/A A 4.0 2.0 2.0
¦ Agglomerates LAS 5.0 5.0 5.0
T AS 2.0 2.0 2.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
¦ Spray-on relrunle 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0
¦ Dry additives Citrate 5.0 - 2.0
Bicarbonate - 3.0
Carbonate 8.0 15.0 10.
T A E D 6.0 2.0 5.0
PBl 14.0 7.0 10.
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite - - 10.
Savinase 1.0 1.0 1.0
Lipolase 0.4 0.4 0.4
Termamyl 0.6 0.6 0.6
Carezyme 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Sulfate 3.0
Glycolic acid (neutralised form)1.25 1.25 1.25
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¦ Balance (moisture & miscellaneous)
Formulations Q
A~lomerate C45AS 14.0
Zeolite A 6.0
Carbonate 8.0
MA/AA 8.0
CMC 0.5
DTPMP 0.4
¦ Spray-on C25E5 5.0
Perfume 0.5
¦ Dry additives NaSKS-6 10.0
Citrate 1.0
TAED 7.0
Percall,onate 20.0
(14.0% AvOx)
SRP 0.3
Savinase 1.4
Lipolase 0.4
Carezyme 0.6
Termamyl 0.6
Silicone antifoam 5.0
Bri~:h'Lel~er 2 0.2
Glycolic acid 1.25
(neutralised form)
Balance (moisture & miscellaneous)
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51
R S T
.
Blown STPP 24 24
Powder
Zeolite A - 30.0
Sulfate 9 13 19.0
MA/AA 2 2 3.0
LAS 6 11 14.0
TAS 2 - -
C45AS - - 8.0
Silicate 7 3
CMC 1 0.5
Brightener 1 0.2 0.2
Brightener 2 - - 0.2
Soap 1.0 1.0
Carbonate - - 8.0
DTPMP 0.4 0.2
¦ Spray On C45E7 2.5 2.0 1.0
C25E3 2.5 2.0
Silicone antifoam 0.3 0.3
P~,rul-,e 0.3 0-3
Dry Carbonate 6.0 15.0
additives
PB4 18.0 10
PBl 4.0 0 0.1
TAED 3.0 1.0
Photoactivated 0.02 0.02
bleach
PVP - - 0.5
Savinase 1.0 1.0 1.0
Lipolase 0.4 0.4 0.4
Termamyl 0.25 0.15 0.1
Carezyme - - 0.1
Sulfate 3.0 5.0
Glycolic acid 1.25 1.25 1.25
(neutralised
form)
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Balance 100.0 100.0 100
(Moisture &
Miscellaneous)
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WO 97/~SZZ5
Formulations U V W X
LAS 20.0 14.0 24.0 22.0
Mixture of N,N-tlimçtltyl-N-(2- 0.7 1.0 - 0.7
hydroxyethyl) -N-dodecyl/N,N-dimethyl-N-
(2-hydroxyethyl) -N-tetradecyl ammonium
bromide
N-Cocoyl N-Methyl Glllc~minP 1.0 - -
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5
STPP 30.0 18.0 30.0 22.0
Silicate (2.0R) 9.0 5.0 10.0 7.6
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5
DTPMP 0.7 1.0
SRP 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Savinase 0.8 1.0 0.5 0.5
Termamyl 0.8 0.4 - 0.25
Lipolase 0.2 0.1 0.2 0.1
Carezyme (5T) 0.15 0.05
Photoactivated bleach (ppm) 70 45 - 10
Bri~htener 2 0.2 0.2 0.08 0.2
PBl 6.0 2.0
NOBS 2.0 1.0
Glycolic acid (neutralised form) 1.25 1.25 1.25 1.25
R~l~nce (Moisture & Miscellaneous) 100 100 100 100
