CA2314660A1 - Bleaching compositions - Google Patents

Abstract

The invention relates to a bleach-containing composition which contains bleaching agent, optionally surfactants and solvents and which is characterized in that a water-miscible liquid component selected from the group of mono- or polyhydric alcohols containing 2 to 4 carbon atoms and polyalkylene glycols liquid at room temperature is present as an additional component.

Description

' CA 02314660 2000-07-27 BLEACHING COMPOSITIONS
Field of the Invention This invention relates to bleaching compositions which may be used as pre- or after-treatment compositions for textiles 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 the dye 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-phosphonic acid to the bleach-containing composition. Unfortunately, the results obtained are unsatisfactory.

' CA 02314660 2000-07-27 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 a water-soluble liquid component selected from the group of monohydric and dihydric alcohols containing 2 to 4 carbon atoms and polyalkylene glycols liquid at room temperature is added to bleaching agents with otherwise a largely typical composition which contain a peroxygen component. The addition of these compounds considerably reduces the destruction of the strength of the textile and also the dye 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 water-miscible soluble liquid component selected from the group of monohydric and polyhydric alcohols containing 2 to 4 carbon atoms and polyalkylene glycols liquid at room temperature 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 solid 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 water-containing composition may also be applied to the textile substrate together with sufficient water in order to wet the textile.
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 water-soluble liquid component used in accordance with the invention is preferably selected from mono- and polyhydric alcohols and polyalkylene glycols which have a vapor pressure lower than that of water.
In one particularly preferred embodiment, the liquid component is selected from the group consisting of ethylene glycol, 1,2-propylene glycol, glycerol, polyethylene glycol liquid at room temperature and mixtures thereof. The liquid water-miscible component is preferably present in the composition according to the invention in a quantity of 1 to 25% by weight, based on the final composition.
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, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid, H202 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 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 andlor 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 andlor particulate caprolactams andlor caprolactam derivatives, preferably N-acylated lactams, for example N-benzoyl caprolactam and N-acetyl 5 caprolactam, which are known from International patent applications WO-A-94127970, WO-A-94128102, WO-A-94/28103, WO-A-95100626, WO-A-95114759 and WO-A-95117498. 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- 95114075 are also preferably used.
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 andlor 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) andlor dodecanoyloxybenzenesulfonate (OBS 12).
Bleach activators such as these are present in the usual quantities of 0.~1 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 and/or 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 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_~a alcohols containing 3 EO to 7 EO, C9_~~ alcohol containing 7 EO, C~3_~5 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.
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
58!217598 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:
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~_4 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 02_18 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 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_~$ 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 C~4_~5 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 Cg~~ alcohols containing on average 3.5 moles of ethylene oxide (EO) or C~2_~g fatty alcohols containing 1 to 4 EO, are also suitable. In view of their 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 C$_~$ 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.
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. 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 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.
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 ' CA 02314660 2000-07-27 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 ~3-D-glucose, D-mannose, D-glucuronic acid; Schoner GmbH), Deuteron~
XN (nonionic polysaccharide; Schoner GmbH), Dicrylan~ Verdicker-O
(ethylene oxide adduct, 50% in waterlisopropanol; Pfersse Chemie), EMA~
81 and EMA~ 91 (ethylenelmaleic anhydride copolymer; Monsanto), Verdicker-QR-1001 (polyurethane emulsion, 19-21 % in water/diglycol ether; Rohm & Haas), Mirox~-AM (anionic acrylic acidlacrylate copolymer dispersion, 25% in water; Stockhausen), SER-AD-FX-1100 (hydrophobic 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 ~i-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:
r CH20H CH~OH
E
O
OH
n off O
OH
HO
M+ COO-O O
O OH
M+ - OOC O O
off HO pH M+ = Na,K,112 Ca H3C \O
M+ = Na, K, 1/2 Ca Basic unit of xanthan 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-NH-R2-NH-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 and/or polyether diols and, for example, from 2,4- or 2,6-toluene diisocyanate (TDI, R2 = C6H3-CH3), 4,4'-methylene di(phenyl isocyanate) (MDI, R2 =
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 present invention are derived, for example, from acrylic acid or methacrylic acid and may be described by general formula II:

[ CH2 i -]n (ll) 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 5 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 10 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
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- i -]n Ila C-(O-CH-CHZ)a0-R4 in which R4 is a preferably unbranched, saturated or unsaturated C8_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%
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 NaMSiXO~+~. 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 (i- and 8-sodium disilicates Na2Si205A 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 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 andlor 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:
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, C12-14 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 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-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 ~3-glucosidases, 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 invention into the required range, it may be advisable to use pH regulators.
5 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.
In order to improve their aesthetic impression, the compositions 10 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.

15 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 containing 15 to 30% by weight of methoxy groups and 1 to 15% by weight 20 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 ' CA 02314660 2000-07-27 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 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 ' CA 02314660 2000-07-27 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 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 and/or 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-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 water-soluble liquid component selected from the group of monohydric and dihydric alcohols containing 2 to 4 carbon atoms and polyalkylene glycols liquid at room temperature and optionally surfactants.
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 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 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 02314660 2000-07-27 A non-prewashed cotton cloth from the Wascheforschungsanstalt Krefeld (80 x 80 cm) was immersed in water containing 15 ppm Cu2+, spun 5 and wrung-dry. 30 ml of the bleaching agent with the composition shown in Table 1 was poured into the middle of the cloth. The bleaching agent was left to act overnight (16 hours) and was washed at 60°C in a domestic washing machine (Miele W 918) using a commercially available detergent (Persil Megaperls~).
10 After washing, 4.5 x 80 cm wide strips were cut out so that the edge zone of the bleaching agent applied was located in the middle of the strip.
The tensile strength results are set out in Table 2.
Examples 2 to 5 and 8 to 11 correspond to the invention while Examples 1, 6, 7 and 12 are Comparison Examples.
15 Tensile strength was determined to DIN 53857. The untreated cloth had tensile strengths of 884.9 N (dry) and 935.7 N (wet).
The Examples show that the loss of tensile strength of the cloth samples treated in accordance with the invention is distinctly lower than that of the samples pretreated with a conventional bleaching agent.

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D I- S I-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.

Claims (17)

1. A bleach-containing composition comprising bleaching agent, optionally surfactants and solvents, wherein a water-miscible liquid component selected from the group of mono- or polyhydric alcohols containing 2 to 4 carbon atoms and polyalkylene glycols liquid at room temperature is present as an additional component.

2. A composition as claimed in claim 1, wherein water-miscible liquid component is selected from the group consisting of ethylene glycol, 1, 2-propylene glycol, glycerol, polyethylene glycol liquid at room temperature or mixtures thereof.

3. A composition as claimed in claim 1 or 2, wherein the liquid water-soluble component is present in a quantity of 1 to 25% by weight, based on the final composition.

4. A composition as claimed in any of claims 1 to 3, wherein the bleaching agent is present in a quantity of 0.5 to 25% by weight.

5. A composition as claimed in claim 4, wherein the quantity is 0.5 to 15% by weight.

6. A composition as claimed in claim 4, wherein the quantity is 1 to 10% by weight.

7. A composition as claimed in any of claims 1 to 6, wherein the bleaching agent is H2O2.

8. A composition as claimed in any of claims 1 to 5, wherein the surfactants are present in a quantity of 1 to 50% by weight.

9. A composition as claimed in any of claims 1 to 8 is in liquid or gel form.

10. A composition as claimed in claim 9, wherein the composition has a viscosity of 500 to 5,000 mPas.

11. A composition as claimed in claim 10, wherein the viscosity is in the range of 1000 to 4000 mPas.

12 A composition as claimed in claim 10, wherein the viscosity is in the range of 2000 to 3500 mPas.

13. A composition as claimed in claims 10, 11 or 12, wherein the composition includes thickener in a quantity of up to 5% by weight based on the final composition.

14. A composition as claimed in claim 13, wherein the quantity is from 0.1 to 3% by weight.

15. A composition as claimed in claim 13 or 14, wherein the thickener is selected from agar agar, carrageen, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starch, dextrins, gelatin and casein, modified starches and celluloses and fully synthetic polymers.

16. A composition as claimed in any of claims 1 to 15 additionally comprising one or more substances from the group of builders, enzymes, electrolytes, pH regulators, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, soil release compounds, optical brighteners, redeposition inhibitors, shrinkage inhibitors, anti-crease agents, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxi-dants, corrosion inhibitors, swelling and non-slip agents and UV absorbers.

17. A process for pretreating soiled textiles with a bleach-containing composition containing a peroxygen compound and a water-soluble liquid component selected from the group of mono- or polyhydric alcohols containing 2 to 4 carbon atoms and polyalkylene glycols liquid at room temperature and optionally surfactants.