Note: Descriptions are shown in the official language in which they were submitted.
CA 02314648 2000-07-27
BLEACHING COMPOSITIONS
Field of the Invention
This invention relates to bleaching compositions which may be used
for pretreating soiled textiles or as a washing additive and to a process for
pretreating textiles by which the protection of the fibers and of dyes on the
fibers is improved.
Background of the Invention
Bleaching compositions are known from the prior art as detergents,
detergent additives and even as laundry pretreatment compositions.
Bleach-containing compositions are used in the pretreatment of
laundry to improve the removal of encrusted soil or stains or "problem
stains", such as fat, coffee, tea, grease, mud- and clay-containing soils,
which are difficult to remove by washing with normal laundry detergents.
However, the treatment of laundry with bleach-containing compositions has
the disadvantage that the bleaching agent can destroy or at least impair the
dye on the textile and can also lead to a reduction in the tensile strength of
the textile fibers, particularly when the bleaching agent is applied to the
textile in undiluted form and remains thereon for a relatively long time
before washing. This effect on the textile dye and on the fibers is generally
intensified if metal ions, such as copper, iron, manganese or chromium, are
present. It is assumed that these metal ions catalyze the decomposition of
the peroxygen bleaching agent, such as hydrogen peroxide, on the surface
of the textiles, more particularly on cellulose fibers, which can lead to
destruction of the dye andlor the fibers.
In European patent application EP 0 829 533 A1, the problem
outlined above is allegedly avoided by adding aminotrimethylene
phosphoric acid to the bleach-containing composition. Unfortunately, the
results obtained are unsatisfactory.
CA 02314648 2000-07-27
2
Summary of the Invention
The problem addressed by the present invention was to provide a
bleaching composition containing a peroxy bleaching agent, a component
which protects the textile fibers and thus reduces destruction of the fibers
andlor the dye being added to the composition.
It has surprisingly been found that this is possible if copolymers of
an a,~i-unsaturated 1,3-dicarboxylic acid and an alkylene containing 3 to 8
carbon atoms is added to bleaching agents with otherwise a largely typical
composition which contain a peroxygen component. The destruction of the
strength of the textile and also the dye can be considerably reduced if
these textiles are pretreated in a step before the actual washing process.
In particular, textiles which also contain metal ions are protected.
Accordingly, the present invention relates to a bleach-containing
composition containing bleaching agents, optionally surfactants and
solvents, characterized in that a copolymer of an a,a-unsaturated 1,3
dicarboxylic acid and an alkylene containing 3 to 8 carbon atoms is present
as an additional component.
The compositions according to the invention are preferably used for
the pretreatment of soiled textiles or as a washing additive. However, they
may also be used as a perborate-containing detergent or as a detergency
booster and as a domestic cleaner for bathrooms and in the kitchen as a
dishwashing detergent or for cleaning carpets. They may be present in
liquid or gel-like form or in powder form.
Detailed Description of the Invention
The expression "pretreatment of soiled textiles" used herein means
that the generally water-containing composition is applied to the soiled
fibers and left thereon until the textile fibers are washed. The composition
may also be applied to the textile substrate together with sufficient water in
order to wet the textile.
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3
The term "washing" used herein means the usual cleaning of textiles
with at least one surfactant either in a washing machine or simply by hand.
The copolymer of an a,~3-unsaturated 1,3-dicarboxylic acid and an
alkylene containing 3 to 8 carbon atoms used in accordance with the
invention preferably contains malefic acid or malefic anhydride and
isobutylene as monomers. Particularly effective dye and fiber protection is
achieved with copolymers having a molecular weight of 7,000 to 15,000. A
particularly suitable copoymer is commercially obtainable, for example,
under the name of Norasol~ 460N from NorsoHaas.
Another key component of the composition according to the
invention is the bleaching agent. Preferred bleaching agents are H202 and
compounds which yield H202 in water, such as sodium perborate
tetrahydrate, sodium perborate monohydrate, sodium percarbonate or
corresponding percarbonate salts, persilicate, peroxypyrophosphates,
persulfates, such as monopersulfate, urea peroxy hydrate, citrate
perhydrates and H202-yielding peracidic salts or peracids, such as
perbenzoates, peroxophthalates, diperoxyazelaic acid,
phthaloiminoperacids or diperoxydodecanedioic acid, H2O2 being
particularly preferred.
The bleaching component is present in the compositions according
to the invention in such a quantity that a measurable improvement is
obtained in the removal of soils or stains from the soiled textile substrate
by
comparison with a composition containing no peroxygen compound when
the soiled substrate is washed in the usual way. The compositions
according to the invention normally contain from 0.5 to 25% by weight,
preferably from 0.5 to 15% by weight and more preferably from 1 to 10% by
weight of the bleaching component.
In order to obtain an improved bleaching effect where washing is
carried out at temperatures of 60°C or lower and particularly in the
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4
pretreatment of laundry, bleach activators may be incorporated in the
detergent tablets. Suitable bleach activators are compounds which form
aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms
and more preferably 2 to 4 carbon atoms andlor optionally substituted
perbenzoic acid under perhydrolysis conditions. Substances bearing O-
andlor N-acyl groups with the number of carbon atoms mentioned and/or
optionally substituted benzoyl groups are suitable. Preferred bleach
activators are polyacylated alkylenediamines, more particularly tetraacetyl
ethylenediamine (TAED), acylated triazine derivatives, more particularly
1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycol-
urils, more particularly 1,3,4,6-tetraacetyl glycoluril (TAGU), N-acylimides,
more particularly N-nonanoyl succinimide (NOSI), acylated phenol
sulfonates, more particularly n-nonanoyl or isononanoyloxybenzene-
sulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as
triethyl-O-acetyl citrate (TEOC), carboxylic anhydrides, more particularly
phthalic anhydride, isatoic anhydride andlor succinic anhydride, carboxylic
acid amides, such as N-methyl diacetamide, glycolide, acylated polyhydric
alcohols, more particularly triacetin, ethylene glycol diacetate, isopropenyl
acetate, 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from
German patent applications DE 196 16 693 and DE 196 16 767, acetylated
sorbitol and mannitol and the mixtures thereof (SORMAN) described in
European patent application EP 0 525 239, acylated sugar derivatives,
more particularly pentaacetyl glucose (PAG), pentaacetyl fructose,
tetraacetyl xylose and octaacetyl lactose, and acetylated, optionally N-
alkylated glucamine and gluconolactone, triazole or triazole derivatives
and/or particulate caprolactams andlor caprolactam derivatives, preferably
N-acylated lactams, for example N-benzoyl caprolactam and N-acetyl
caprolactam, which are known from International patent applications WO-
A-94/27970, WO-A-94128102, WO-A-94!28103, WO-A-95100626, WO-A-
CA 02314648 2000-07-27
95/14759 and WO-A-95!17498. The substituted hydrophilic acyl acetals
known from German patent application DE-A-196 16 769 and the acyl
lactams described in German patent application DE-A-196 16 770 and in
International patent application WO-A- 95!14075 are also preferably used.
5 The combinations of conventional bleach activators known from German
patent application DE-A-44 43 177 may also be used. Nitrite derivatives,
such as cyanopyridines, nitrite quats and/or cyanamide derivatives may
also be used. Preferred bleach activators are sodium-4-(octanoyloxy)-
benzene sulfonate, undecenoyloxybenzenesulfonate (UDOBS), sodium
dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid
(DOBA, OBC 10) and/or dodecanoyloxybenzenesulfonate (OBS 12).
Bleach activators such as these are present in the usual quantities of 0.01
to 20% by weight, preferably in quantities of 0.1 % by weight to 15% by
weight and more preferably in quantities of 1 % by weight to 10% by weight,
based on the composition as a whole.
The compositions according to the invention may contain surfactants
selected from anionic, nonionic, cationic andlor amphoteric surfactants or
mixtures thereof as further components. The surfactants are present in a
quantity of preferably 0.1 to 50% by weight, more preferably 0.1 to 35% by
weight and most preferably 0.1 to 15% by weight, based on the
composition.
Preferred nonionic surfactants are alkoxylated, advantageously
ethoxylated, more particularly primary alcohols preferably containing 8 to
18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO)
per mole of alcohol, in which the alcohol radical may be linear or,
preferably, 2-methyl-branched or may contain linear and methyl-branched
radicals in the form of the mixtures typically present in oxoalcohol radicals.
However, alcohol ethoxylates containing linear radicals of alcohols of native
origin with 12 to 18 carbon atoms, for example coconut alcohol, palm
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6
alcohol, tallow alcohol or oleyl alcohol, and an average of 2 to 8 EO per
mole of alcohol are particularly preferred. Preferred ethoxylated alcohols
include, for example, C~2_~4 alcohols containing 3 EO to 7 EO, C9_~, alcohol
containing 7 EO, 03_15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO,
C~2_~8 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such
as mixtures of C~2_~4 alcohol containing 3 EO and C,2_~$ alcohol containing
7 EO. The degrees of ethoxylation mentioned are statistical mean values
which, for a special product, may be either a whole number or a broken
number. Preferred alcohol ethoxylates have a narrow homolog distribution
(narrow range ethoxylates, NRE). In addition to these nonionic surfactants,
fatty alcohols containing more than 12 EO may also be used, as described
above. Examples of such fatty alcohols are tallow alcohols containing 14
EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO
groups together in the molecule may also be used in accordance with the
invention. Block copolymers containing EO-PO block units or PO-EO block
units and also EO-PO-EO copolymers or PO-EO-PO copolymers may be
used. Mixed-alkoxylated nonionic surfactants in which EO and PO units
are distributed statistically and not in blocks may of course also be used.
Such products may be obtained by the simultaneous action of ethylene and
propylene oxide on fatty alcohols.
In addition, alkyl glycosides with the general formula RO(G)x where
R is a primary, linear or methyl-branched, more particularly 2-methyl-
branched, aliphatic radical containing 8 to 22 and preferably 12 to 18
carbon atoms and G is a glycose unit containing 5 or 6 carbon atoms,
preferably glucose, may be used as further nonionic surfactants. The
degree of oligomerization x, which indicates the distribution of
monoglycosides and oligoglycosides, is a number of 1 to 10 and preferably
a number of 1.2 to 1.4.
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7
Another class of preferred nonionic surfactants which are used in
particular in solid compositions are alkoxylated, preferably ethoxylated or
ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1
to 4 carbon atoms in the alkyl chain, more particularly the fatty acid methyl
esters which are described, for example, in Japanese patent application JP
581217598 or which are preferably produced by the process described in
International patent application WO-A-90113533.
Nonionic surfactants of the amine oxide type, for example N
cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl
amine oxide, and the fatty acid alkanolamide type are also suitable. The
quantity in which these nonionic surfactants are used is preferably no more,
in particular no more than half, the quantity of ethoxylated fatty alcohols
used.
Other suitable surfactants are polyhydroxyfatty acid amides cor-
responding to formula III:
R'
R-CO-N-[Z] I I I
in which RCO is an aliphatic acyl radical containing 6 to 22 carbon atoms,
R' is hydrogen, an alkyl or hydroxyalkyl radical containing 1 to 4 carbon
atoms and [Z] is a linear or branched polyhydroxyalkyl radical containing 3
to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid
amides are known substances which are normally obtained by reductive
amination of a reducing sugar with ammonia, an alkylamine or an
alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl
ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds
corresponding to formula IV:
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8
R'-O-R2
IV
R-CO-N-[Z]
in which R is a linear or branched alkyl or alkenyl group containing 7 to 12
carbon atoms, R' is a linear, branched or cyclic alkyl group or an aryl group
containing 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl
group or an aryl group or a hydroxyalkyl group containing 1 to 8 carbon
atoms, C~.~ alkyl or phenyl groups being preferred, and [Z] is a linear
polyhydroxyalkyl group, of which the alkyl chain is substituted by at least
two hydroxyl groups, or alkoxylated, preferably ethoxylated or
propoxylated, derivatives of such a group.
[Z] is preferably obtained by reductive amination of a sugar, for
example glucose, fructose, maltose, lactose, galactose, mannose or
xylose. The N-alkoxy or N-aryloxy-substituted compounds may then be
converted into the required polyhydroxyfatty acid amides by reaction with
fatty acid methyl esters in the presence of an alkoxide as catalyst, for
example in accordance with the teaching of International patent application
WO-A-95107331.
Suitable anionic surfactants are, for example, those of the sulfonate
and sulfate type. Preferred surfactants of the sulfonate type are C9_~3 alkyl
benzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxy-
alkane sulfonates, and the disulfonates obtained, for example, from C~2_~8
monoolefins with an internal or terminal double bond by sulfonation with
gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the
sulfonation products. Other suitable surfactants of the sulfonate type are
the alkane sulfonates obtained from C~2_~8 alkanes, for example by
sulfochlorination or sulfoxidation and subsequent hydrolysis or
neutralization. The esters of a-sulfofatty acids (ester sulfonates), for
CA 02314648 2000-07-27
9
example the a-sulfonated methyl esters of hydrogenated coconut oil, palm
kernel oil or tallow fatty acids, are also suitable.
Preferred alk(en)yl sulfates are the alkali metal salts and, in
particular, the sodium salts of the sulfuric acid semiesters of C~2_~s fatty
alcohols, for example coconut alcohol, tallow alcohol, lauryl, myristyl, cetyl
or stearyl alcohol, or C~o_2o oxoalcohols and the corresponding semiesters
of secondary alcohols with the same chain length. Other preferred
alk(en)yl sulfates are those with the chain length mentioned which contain
a synthetic, linear alkyl chain based on a petrochemical and which are
similar in their degradation behavior to the corresponding compounds
based on oleochemical raw materials. C~2_~6 alkyl sulfates and C~2_~5 alkyl
sulfates and also 04_15 alkyl sulfates are particularly preferred from the
washing performance point of view. Other suitable anionic surfactants are
2,3-alkyl sulfates which may be produced, for example, in accordance with
US 3,234,258 or US 5,075,041 and which are commercially obtainable as
products of the Shell Oil Company under the name of DAN~.
Other suitable anionic surfactants are sulfonated fatty acid glycerol
esters, i.e. the monoesters, diesters and triesters and mixtures thereof
which are obtained where production is carried out by esterification of a
monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of
triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid
glycerol esters are the sulfonation products of saturated fatty acids
containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid,
myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
The sulfuric acid monoesters of linear or branched C~_2~ alcohols
ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched
C9_~~ alcohols containing on average 3.5 moles of ethylene oxide (EO) or
C~2_~$ fatty alcohols containing 1 to 4 EO, are also suitable. In view of
their
CA 02314648 2000-07-27
high foaming capacity, they are only used in relatively small quantities, for
example in quantities of 1 to 5% by weight, in detergents.
Other suitable anionic surfactants are the salts of alkyl sulfosuccinic
acid which are also known as sulfosuccinates or as sulfosuccinic acid
5 esters and which represent monoesters andlor diesters of sulfosuccinic
acid with alcohols, preferably fatty alcohols and, more particularly,
ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cg_~g fatty
alcohol molecules or mixtures thereof. Particularly preferred
sulfosuccinates contain a fatty alcohol molecule derived from ethoxylated
10 fatty alcohols which, considered in isolation, represent nonionic
surfactants
(for a description, see below). Of these sulfosuccinates, those of which the
fatty alcohol molecules are derived from narrow-range ethoxylated fatty
alcohols are particularly preferred. Alk(en)yl succinic acid preferably
containing 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof may
also be used.
Other suitable anionic surfactants are, in particular, soaps which are
used in particular in powder-form compositions and at relatively high pH
values. Suitable soaps are saturated and unsaturated fatty acid soaps,
such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid,
hydrogenated erucic acid and behenic acid, and soap mixtures derived in
particular from natural fatty acids, for example coconut, palm kernel, olive
oil or tallow fatty acids.
The anionic surfactants including the soaps may be present in the
form of their sodium, potassium or ammonium salts and as soluble salts of
organic bases, such as mono-, di- or triethanolamine. The anionic
surfactants are preferably present in the form of their sodium or potassium
salts and, more preferably, in the form of their sodium salts.
The bleaching composition according to the invention is preferably
present in liquid or gel form. It preferably contains water andlor a
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11
nonaqueous solvent to achieve the liquid or gel-form state.
Solvents which may be used in the liquid or gel-form compositions
belong, for example, to the group of monohydric or polyhydric alcohols,
alkanolamines and glycol ethers providing they are miscible with water in
the concentration range indicated. The solvents are preferably selected
from ethanol, n- or i-propanol, butanols, ethylene glycol methyl ether,
ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol
mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl
ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol
monomethyl or monoethyl ether, diisopropylene glycol monomethyl or
monoethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-
propanol, 3-methyl-3-methoxybutanol, propylene glycol-t-butyl ether and
mixtures of these solvents. These nonaqueous solvents may be used in
the liquid or gel-form compositions according to the invention in quantities
of 0.1 to 20% by weight, preferably below 15% by weight and more
preferably below 10% by weight.
One or more thickeners or thickening systems may be added to the
composition according to the invention to adjust its viscosity. The viscosity
of the compositions according to the invention can be measured by
standard methods (for example Brookfield RVD-VII viscosimeter at 20
r.p.m. and 20°C, spindle 3) and is preferably in the range from 100 to
5000
mPas. Preferred compositions have viscosities of 200 to 4000 mPas,
viscosities in the range from 400 to 2000 mPas being particularly preferred.
Suitable thickeners are typically polymeric compounds. These
generally organic high molecular weight compounds, which are also known
as swelling agents and which take up liquids and swell in the process and,
finally, change into viscous true or colloidal solutions, belong to the groups
of natural polymers, modified natural polymers and fully synthetic polymers.
The thickeners may be present in a quantity of up to 5% by weight and
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12
preferably in a quantity of 0.01 to 3% by weight, based on the final
composition.
Naturally occurring polymers used as thickeners are, for example,
agar agar, carrageen, tragacanth, gum arabic, alginates, pectins, polyoses,
guar gum, locust bean gum, starch, dextrins, gelatin and casein.
Modified natural materials belong above all to the group of modified
starches and celluloses, of which carboxymethyl cellulose and other
cellulose ethers, hydroxyethyl cellulose and hydroxypropyl cellulose and
also gum ethers are mentioned as examples.
A large group of thickeners which are widely used in various fields of
application are the fully synthetic polymers, such as polyacrylic and poly-
methacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers,
polyimines, polyamides and polyurethanes.
The thickeners may be present in a quantity of up to 5% by weight,
preferably in a quantity of 0.05 to 2% by weight and more preferably in a
quantity of 0.1 to 1.5% by weight, based on the final composition.
Thickeners from the classes of compounds mentioned are
commercially obtainable and are marketed, for example, under the names
of Acusol~ 820 (methacrylic acid (stearyl alcohol-20 EO) esterlacrylic acid
copolymer, 30% in water; Rohm & Haas), Dapral~ GT 282 S (alkyl poly-
glycol ether; Akzo), Deuterol~ Polymer-11 (dicarboxylic acid copolymer;
Schoner GmbH), Deuteron~ XG (anionic heteropolysaccharide based on
~i-D-glucose, D-mannose, D-glucuronic acid; Schoner GmbH), Deuteron~
XN (nonionic polysaccharide; Schoner GmbH), Dicrylan~ Verdicker-O
(ethylene oxide adduct, 50% in water/isopropanol; Pfersse Chemie), EMA~
81 and EMA~ 91 (ethylenelmaleic anhydride copolymer; Monsanto),
Verdicker-QR-1001 (polyurethane emulsion, 19-21 % in waterldiglycol
ether; Rohm & Haas), Mirox~-AM (anionic acrylic acidlacrylate copolymer
dispersion, 25% in water; Stockhausen), SER-AD-FX-1100 (hydrophobic
CA 02314648 2000-07-27
13
urethane polymer; Servo Delden), Shellflo~ S (high molecular weight poly-
saccharide, stabilized with formaldehyde; Shell) and Shellflo~ XA (xanthan
biopolymer, stabilized with formaldehyde; Shell), Kelzan~ and Keltrol~
(Kelco).
A polymeric thickener preferably used is xanthan, a microbial anionic
heteropolysaccharide which is produced by Xanthomonas campestris and
a few other species under aerobic conditions and which has a molecular
weight of 2 to 15 million dalton. Xanthan consists of a chain with ~-1,4-
glucose (cellulose) with side chains. The structure of the sub-groups
consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the
number of pyruvate units determining the viscosity of the xanthan.
Xanthan may be described by the following formula:
CH20H CH~OH
O
OH
n
OH
H3C-C-O-CH2 O
O
OH
HO
M+COO-
J--O O
vn
M+ - OOC O O
OH HO OH
HsC O
M+ = Na, K, 112 Ca
Basic unit of xanthan
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14
Examples of other preferably used synthetic thickeners are
polyurethanes and modified (meth)acrylates.
Polyurethanes (PUR) are produced by polyaddition from dihydric
and higher alcohols and isocyanates and may be described by general
formula I:
[-O-R'-O-C-N H-R2-N H-C-]" I
O O
in which R' is a low molecular weight or polymeric diol residue, R2 is an
aliphatic or aromatic group and n is a natural number. R' is preferably a
linear or branched C2_~2 alk(en)yl group, although it may also be a residue
of a higher alcohol, so that crosslinked polyurethanes are formed which
differ from general formula I above in the fact that other -O-CO-NH groups
are attached to the substituent R'.
Technically important PURs are produced from polyester andlor
polyether diols and, for example, from 2,4- or 2,6-toluene diisocyanate
(TDI, R2 = C6H3-CH3), 4,4'-methylene di(phenyl isocyanate) (MDI, RZ =
C6H4-CH2-C6H4) or hexamethylene diisocyanate [HMDI, R2 = (CH2)6].
Commercially available polyurethane-based thickeners are market-
ed, for example, under the names of Acrysol~PM 12 V (mixture of 3-5%
modified starch and 14-16% PUR resin in water; Rohm & Haas),
Borchigel~ L75-N (nonionic PUR dispersion, 50% in water; Borchers),
Coatex~ BR-100-P (PUR dispersion, 50% in waterlbutyl glycol; Dimed),
Nopco~ DSX-1514 (PUR dispersion, 40% in waterlbutyl triglycol; Henkel-
Nopco), Verdicker QR 1001 (20% PUR emulsion in water/diglycol ether;
Rohm & Haas) and Rilanit~ VPW-3116 (PUR dispersion, 43% in water;
Henkel).
Modified polyacrylates which may be used in accordance with the
CA 02314648 2000-07-27
present invention are derived, for example, from acrylic acid or methacrylic
acid and may be described by general formula II:
R3
5
[-CH2- i -]~ (II)
C-X-R4
II
10 O
in which R3 represents H or a branched or unbranched C~~ alk(en)yl group,
X represents N-R5 or O, R4 is an optionally alkoxylated, branched or
unbranched, optionally substituted C&22 alk(en)yl group, R5 represents H or
15 has the same meaning as R4 and n is a natural number. Modified poly-
acrylates such as these are generally esters or amides of acrylic acid or of
an a-substituted acrylic acid. Of these polymers, those in which R3
represents H or a methyl group are preferred. Among the polyacrylamides
(X = N-R5), both mono- (R5 = H) and di- (R5 = R4) -N-substituted amide
structures are possible, the two hydrocarbon radicals attached to the
nitrogen atom being selected independently of one another from optionally
alkoxylated branched or unbranched C8_22 alk(en)yl radicals. Among the
polyacrylates (X = 0), those in which the alcohol was obtained from natural
or synthetic fats or oils and is additionally alkoxylated, preferably
ethoxylated, are preferred. Preferred degrees of alkoxylation are from 2 to
30, degrees of alkoxylation of 10 to 15 being particularly preferred.
Since the polymers suitable for use in accordance with the invention
are technical compounds, the designation of the groups attached to X
represents a statistical mean value which, in the individual case, can vary
in regard to chain length or degree of alkoxylation. Formula II merely
indicates formulae for idealized homopolymers. However, copolymers in
which the percentage content of monomer units corresponding to formula II
CA 02314648 2000-07-27
16
is at least 30% by weight may also be used in accordance with the present
invention. For example, copolymers of modified polyacrylates and acrylic
acid or salts thereof which also contain acidic H atoms or basic -COO-
groups may also be used.
According to the invention, preferred modified polyacrylates are
polyacrylatelpolymethacrylate copolymers which correspond to formula Ila:
R'
[-CH2-C-]~ I la
C-(O-CH-CH2)a0-R4
II
O R6
in which R4 is a preferably unbranched, saturated or unsaturated C&22
alk(en)yl group, R6 and R' independently of one another represent H or
CH3, the degree of polymerization n is a natural number and the degree of
alkoxylation a is a natural number of 2 to 30 and preferably 10 to 20. R4 is
preferably a fatty alcohol moiety obtained from natural or synthetic sources,
the fatty alcohol in turn preferably being ethoxylated (R6 = H).
Products corresponding to formula Ila are commercially obtainable,
for example, under the name of Acusol~ 820 (Rohm & Haas) in the form of
30% by weight dispersions in water. In the commercial product mentioned,
R4 is a stearyl group, R6 is a hydrogen atom, R' is H or CH3 and the degree
of ethoxylation a is 20.
In addition, complexing agents may be used in combination with the
thickeners mentioned above to stabilize viscosity. Examples of complexing
agents are low molecular weight hydroxycarboxylic acids, such as citric
acid, tartaric acid, malic acid or gluconic acid and salts thereof, citric
acid
and sodium citrate being particularly preferred. The complexing agents
may be present in a quantity of 1 to 8% by weight, preferably 3.0 to 6.0%
CA 02314648 2000-07-27
17
by weight and more preferably 4.0 to 5.0% by weight, based on the final
composition.
The compositions according to the invention may contain other
ingredients which further improve their performance andlor aesthetic
properties. According to the invention, preferred compositions may
additionally contain one or more substances from the group of builders,
enzymes, electrolytes, pH regulators, perfumes, perfume carriers,
fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, soil release
compounds, optical brighteners, redeposition inhibitors, shrinkage
inhibitors, anti-crease agents, dye transfer inhibitors, antimicrobial agents,
germicides, fungicides, antioxidants, corrosion inhibitors, swelling and non-
slip agents and UV absorbers.
Builders which may be present in the compositions according to the
invention include, in particular, silicates, aluminium silicates (more
particularly zeolites), carbonates, salts or organic di- and polycarboxylic
acids and mixtures thereof.
Suitable crystalline layer-form sodium silicates correspond to the
general formula NaMSiX02X+~. y H20, where M is sodium or hydrogen, x is a
number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x
being 2, 3 or 4. Crystalline layer silicates such as these are described, for
example, in European patent application EP-A-0 164 514. Preferred
crystalline layer silicates corresponding to the above formula are those in
which M is sodium and x assumes the value 2 or 3. Both ~3- and 8-sodium
disilicates Na2Si205~ y H20 are particularly preferred, ~i-sodium disilicate
being obtainable, for example, by the process described in International
patent application WO-A- 91108171.
Other useful builders are amorphous sodium silicates with a
modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more
preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash
CA 02314648 2000-07-27
18
cycle properties. The delay in dissolution in relation to conventional
amorphous sodium silicates can have been obtained in various ways, for
example by surface treatment, compounding, compacting or by overdrying.
In the context of the invention, the term "amorphous" is also understood to
encompass "X-ray amorphous". In other words, the silicates do not
produce any of the sharp X-ray reflexes typical of crystalline substances in
X-ray diffraction experiments, but at best one or more maxima of the
scattered X-radiation which have a width of several degrees of the
diffraction angle. However, particularly good builder properties may even
be achieved where the silicate particles produce crooked or even sharp
diffraction maxima in electron diffraction experiments. This may be
interpreted to mean that the products have microcrystalline regions
between 10 and a few hundred nm in size, values of up to at most 50 nm
and, more particularly, up to at most 20 nm being preferred. So-called X-
ray amorphous silicates such as these, which also dissolve with delay in
relation to conventional waterglasses, are described for example in
German patent application DE-A-44 00 024. Compacted amorphous
silicates, compounded amorphous silicates and overdried X-ray-amorphous
silicates are particularly preferred.
The finely crystalline, synthetic zeolite containing bound water used
in accordance with the invention is preferably zeolite A and/or zeolite P.
Zeolite MAP~ (Crosfield) is a particularly preferred P-type zeolite.
However, zeolite X and mixtures of A, X andlor P are also suitable.
According to the invention, it is also possible to use, for example, a
commercially obtainable co-crystallizate of zeolite X and zeolite A (ca. 80%
by weight zeolite X) which is marketed by CONDEA Augusta S.p.A. under
the name of VEGOBOND AX~ and which may be described by the
following formula:
CA 02314648 2000-07-27
19
nNa20 ~ (1-n)K20 ~ A1203 ~ (2 - 2.5)Si02 ~ (3.5 - 5.5) H20.
The zeolite may be used as a spray-dried powder or even as an undried
suspension still moist from its production. If the zeolite is used in the form
of a suspension, the suspension may contain small additions of nonionic
surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite,
of ethoxylated C~2_~$ fatty alcohols containing 2 to 5 ethylene oxide groups,
C~2_~4 fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated
isotridecanols. Suitable zeolites have a mean particle size of less than 10
~m (volume distribution, as measured by the Coulter Counter Method) and
contain preferably 18 to 22% by weight and more preferably 20 to 22% by
weight of bound water.
The generally known phosphates may of course also be used as
builders providing their use should not be avoided on ecological grounds.
The sodium salts of the orthophosphates, the pyrophosphates and, in
particular, the tripolyphosphates are particularly suitable.
Suitable enzymes are hydrolases, such as proteases, esterases,
lipases or lipolytic enzymes, amylases, cellulases or other glycosyl
hydrolases and mixtures thereof. All these hydrolases contribute to the
removal of stains, such as protein-containing, fat-containing or starch-
containing stains, and discoloration in the washing process. Cellulases
and other glycosyl hydrolases can contribute towards color retention and
towards increasing fabric softness by removing pilling and microfibrils.
Oxidoreductases may also be used for bleaching and for inhibiting dye
transfer. Enzymes obtained from bacterial strains or fungi, such as Bacillus
subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens
are particularly suitable. Proteases of the subtilisin type are preferably
used, proteases obtained from Bacillus lentus being particularly preferred.
Of particular interest in this regard are enzyme mixtures, for example of
CA 02314648 2000-07-27
protease and amylase or protease and lipase or lipolytic enzymes or
protease and cellulase or of cellulase and lipase or lipolytic enzymes or of
protease, amylase and lipase or lipolytic enzymes or protease, lipase or
lipolytic enzymes and cellulase, but especially protease- andlor lipase-
5 containing mixtures or mixtures with lipolytic enzymes. Examples of such
lipolytic enzymes are the known cutinases. Peroxidases or oxidases have
also been successfully used in some cases. Suitable amylases include in
particular a-amylases, isoamylases, pullanases and pectinases. Preferred
cellulases are cellobiohydrolases, endoglucanases and ~i-glucosidases,
10 which are also known as cellobiases, and mixtures thereof. Since the
various cellulase types differ in their CMCase and avicelase activities, the
desired activities can be established by mixing the cellulases in the
appropriate ratios.
In order to bring the pH value of the compositions according to the
15 invention into the required range, it may be advisable to use pH
regulators.
Suitable pH regulators are any known acids and alkalis providing their use
is not inappropriate for applicational or ecological reasons or on consumer
protection grounds. The pH regulators are normally used in quantities of
no more than 2% by weight of the total formulation.
20 In order to improve their aesthetic impression, the compositions
according to the invention may be colored with suitable dyes. Preferred
dyes, which are not difficult for the expert to choose, have high stability in
storage, are not affected by the other ingredients of the compositions or by
light and do not have any pronounced substantivity for textile fibers so as
not to color them.
Foam inhibitors suitable for use in the compositions according to the
invention are, for example, soaps, parafins and silicone oils.
Suitable soil-release compounds are, for example, nonionic cellulose
ethers, such as methyl cellulose and methyl hydroxypropyl cellulose
CA 02314648 2000-07-27
21
containing 15 to 30% by weight of methoxy groups and 1 to 15% by weight
of hydroxypropoxyl groups, based on the nonionic cellulose ether, and the
polymers of phthalic acid andlor terephthalic acid known from the prior art
or derivatives thereof, more particularly polymers of ethylene terephthalates
andlor polyethylene glycol terephthalates or anionically andlor nonionically
modified derivatives thereof. Of these, the sulfonated derivatives of
phthalic acid and terephthalic acid polymers are particularly preferred.
Optical brighteners (so-called "whiteners") may be added to the
compositions according to the invention to eliminate discoloration and
yellowing of the treated laundry. These substances are absorbed onto the
fibers and produce a brightening and fake bleaching effect by converting
invisible ultraviolet radiation into visible longer-wave light, the
ultraviolet
radiation absorbed from the sunlight being reflected as a pale bluish
fluorescence and giving pure white with the yellow of the discolored or
yellowed laundry. Suitable compounds belong, for example, to the classes
of 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyryl
biphenyls, methyl umbelliferones, coumarins, dihydroquinolines, 1,3-diaryl
pyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole and
benzimidazole systems and the heterocycle-substituted pyrene derivatives.
The optical brighteners are normally used in quantities of 0.01 to 0.3% by
weight, based on the final composition.
The function of redeposition inhibitors is to keep the soil detached
from the fibers suspended in the wash liquor and thus to prevent the soil
from being re-absorbed by the washing. Suitable redeposition inhibitors
are water-soluble, generally organic colloids, for example glue, gelatine,
salts of ether sulfonic acids of starch or cellulose or salts of acidic
sulfuric
acid esters of cellulose or starch. Water-soluble polyamides containing
acidic groups are also suitable for this purpose. Soluble starch
preparations and other starch products than those mentioned above, for
CA 02314648 2000-07-27
22
example degraded starch, aldehyde starches, etc., may also be used.
Polyvinyl pyrrolidone is also suitable. However, cellulose ethers, such as
carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl
cellulose, and mixed ethers, such as methyl hydroxyethyl cellulose, methyl
hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures
thereof, in quantities of 0.1 to 5% by weight, based on the composition, are
preferably used.
Since flat textiles, particularly of rayon, rayon staple, cotton and
blends thereof, can show a tendency to crease because the individual
fibers are sensitive to sagging, folding, pressing and squeezing
transversely of the fiber direction, the compositions according to the
invention may contain synthetic anti-crease agents. These include, for
example, synthetic products based on fatty acids, fatty acid esters, fatty
acid amides, alkylol esters, alkylol amides or fatty alcohols mostly reacted
with ethylene oxide or products based on lecithin or modified phosphoric
acid esters.
For protection against microorganisms, the compositions according
to the invention may contain antimicrobial agents. Depending on the anti-
microbial spectrum and the action mechanism, antimicrobial agents are
classified as bacteriostatic agents and bactericides, fungistatic agents and
fungicides, etc. Important representatives of these groups are, for
example, benzalkanolium chlorides, alkylaryl sulfonates, halophenols and
phenol mercury acetate. However, the compositions according to the
invention may also be completely free from these compounds.
Increased wearing comfort can be obtained from the additional use
of antistatic agents which may be additionally incorporated in the
compositions according to the invention. Antistatic agents increase surface
conductivity and thus provide for the improved dissipation of any charges
developed. External antistatic agents are generally substances containing
CA 02314648 2000-07-27
23
at least one hydrophilic molecule ligand and form a more or less
hygroscopic film on the surface. These generally interfacially active anti-
static agents may be divided into nitrogen-containing antistatics (amines,
amides, quaternary ammonium compounds), phosphorus-containing
antistatics (phosphoric acid esters) and sulfur-containing antistatics (alkyl
sulfonates, alkyl sulfates). External antistatics are described, for example,
in patent applications FR 1 156 513, GB 873,214 and GB 839.407. The
lauryl (or stearyl) dimethyl benzylammonium chlorides disclosed therein are
suitable as antistatics for textiles or as a detergent additive, a
conditioning
effect additionally being obtained.
In order to improve the water absorption capacity and the
rewettability of the treated textiles and to make them easier to iron,
silicone
derivatives for example may be used in the compositions according to the
invention. These silicone derivatives additionally improve the rinse-out
behavior of the compositions according to the invention by virtue of their
foam-inhibiting properties. Preferred silicone derivatives are, for example,
polydialkyl and alkylaryl siloxanes where the alkyl groups contain 1 to 5
carbon atoms and are completely or partly fluorinated. Preferred silicones
are polydimethyl siloxanes which may optionally be derivatized and are
then aminofunctional or quaternized or bear Si-OH, Si-H andlor Si-CI
bonds. The preferred silicones have viscosities at 25°C of 100 to
100,000
mPas and may be used in quantities of 0.2 to 5% by weight, based on the
composition as a whole.
Finally, the compositions according to the invention may also contain
UV filters which are adsorbed onto the treated textiles and which improve
the fastness of the fibers to light. Compounds which show these desirable
properties are, for example, the compounds and derivatives of benzo-
phenone with substituents in the 2- andlor 4-position which act through
radiationless deactivation. Also suitable are substituted benzotriazoles, 3-
CA 02314648 2000-07-27
24
phenyl-substituted acrylates (cinnamic acid derivatives), optionally with
cyano groups in the 2-position, salicylates, organic Ni complexes and
natural substances, such as umbelliferone and the body's own urocanic
acid.
In order to avoid the decomposition of certain detergent ingredients
catalyzed by heavy metals, heavy metal complexing agents may be used.
Suitable heavy metal complexing agents are, for example, the alkali metal
salts of ethylenediamine tetraacetic acid (EDTA) or nitrilotriacetic acid
(NTA) in the form of the free acids or as alkali metal salts and derivatives
thereof and alkali metal salts of anionic polyelectrolytes, such as
polymaleates and polysulfonates.
A preferred class of complexing agents are the phosphonates which
are present in preferred compositions in quantities of 0.01 to 2.0% by
weight, preferably 0.05 to 1.5% by weight and more preferably 0.1 to 1.0%
by weight. These preferred compounds include in particular organo-
phosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic
acid (HEDP), aminotri(methylene phosphonic acid) (ATMP), diethylenetri-
amine penta(methylene phosphonic acid) (DTPMP or DETPMP) and 2-
phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), which are mostly
used in the form of their ammonium or alkali metal salts.
The compositions according to the invention are prepared
continuously or in batches simply by mixing the ingredients, water, solvent
and surfactants) preferably being introduced first and the other ingredients
being subsequently added in portions. There is no need for separate
heating during the production process. If heating is required, the
temperature of the mixture should not exceed 80°C.
The present invention also relates to a process for pretreating soiled
textiles with a bleach-containing composition which contains a peroxygen
compound and a copolymer of an a,~i-unsaturated 1,3-dicarboxylic acid
CA 02314648 2000-07-27
and an alkylene containing 3 to 8 carbon atoms and optionally surfactants)
and solvent.
For pretreating the fibers, the composition according to the invention
is applied to the fibers for up to 24 hours, preferably for 1 minute to 1 hour
5 and more preferably for 5 minuites to 30 minutes. The period should be
selected so that the liquid composition does not dry on the fibers. The
textiles are normally soiled with dried-on stains or soil which are generally
very difficult t remove. The liquid compositions may simply be applied to
the textiles and left thereon although the soil removal process may also be
10 mechanically assisted, for example by rubbing with a towel or by treatment
with a sponge or a brush.
In general, the compositions according to the invention are applied
to the textiles or to the substrate to be treated or are used as an additive
with a commercially available detergent.
CA 02314648 2000-07-27
26
The following compositions were used in the Examples:
Invention Comparison
Component Quantity Quantity
[% by weight][% by weight]
Hydrogen peroxide 7.5 7.5
1-Hydroxyethane-1,1-diphosphonic 0.1 0.1
acid
C12I14 fatty alcohol ether sulfate2.0 2.0
x 2 EO
Cw~a fatty alcohol x 2.5 EO 0.5 0.5
Copolymer' 0.1 --
Ethanol 0.2 0.2
Butyl hydroxytoluene 0.03 0.03
Perfume + +
Dye ~ + +
Water to 100 to 100
' Norasol~ 460N, a product of NorsoHaas
The formulations shown above were tested using the following test
arrangement:
A textile strip (15 x 40 cm) was placed over a watch glass (20 cm in
diameter) in such a way that the middle of the strip was located in the
"basin" of the watch glass. 10 ml of the test formulation were pipetted onto
the textile. The curvature of the watch glass prevented the product from
spreading too quickly and too far over the textile. The liquid was gradually
absorbed by the textile. The contact time on the textile was 16 hours. The
test fabric was then washed at 60°C in the normal program of a domestic
washing machine (Miele W 918) using a commercially available detergent
CA 02314648 2000-07-27
27
(Persil~ Megaperls) and dried in air.
The damage to the textile was visually evaluated using a scoring
system. No damage to the textile corresponded to a score of 1; in the
event of complete fiber damage with the formation of a hole in the treated
area, a score of 6 was awarded.
A commercially available olive-brown corduroy with a heavy metal
content of 400 ppm Cu and 11 ppm Fe was used as the test fabric.
The composition according to the invention was given a score of 3.5.
The copolymer-free composition tested for comparison produced complete
fiber damage and was given a score of 6.
The invention may be varied in any number of ways as would be
apparent to a person skilled in the art and all obvious equivalents and the
like are meant to fall within the scope of this description and claims. The
description is meant to serve as a guide to interpret the claims and not to
limit them unnecessarily.
