WO2001007557A1

WO2001007557A1 - Bleaching compositions

Info

Publication number: WO2001007557A1
Application number: PCT/EP2000/006837
Authority: WO
Inventors: Heinz-Manfred Wilsberg; Hans-Jürgen Riebe; Josef Penninger
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-07-27
Filing date: 2000-07-18
Publication date: 2001-02-01
Also published as: DE50010643D1; AU6275000A; CA2314660A1; DE19935259A1; EP1198551A1; EP1198551B1

Abstract

Disclosed is a composition containing bleaching agents, optionally surfactants and solvents, characterized in that it comprises a liquid which can be mixed with water as another other constituent, whereby said liquid is selected from the group of monovalent and multivalent alcohols with 2-4 carbon atoms and polyalkylene glycols which are liquid at room temperature.

Description

Bleaching compositions

The present invention relates to bleaching agent compositions which can be used as pretreatment or aftertreatment agents for textiles, and to a pretreatment process for textiles with which the protection of the fibers or the colors thereon is improved.

Bleaching agent compositions are known from the prior art as detergents, detergent additives and also as laundry pretreatment agents.

In laundry pretreatment, bleach-containing compositions of this type are used in order to improve the removal of encrusted dirt or stains or of "problem stains", such as grease, coffee, tea, grass, stains containing mud and clay, which are difficult to achieve by washing with conventional textile washing machines However, treating the laundry with bleach-containing agents has the disadvantage that the bleach can destroy the color and also lead to a reduction in the tensile strength of the textile fiber, especially if the bleach is applied undiluted to the textile and there via a This effect on the textile color and on the fiber is usually intensified if metal ions such as copper, iron, manganese or chromium are present. It is believed that these metal ions on the surface of the textiles, especially on cellulose fibers, the decomposition of the Persauer Catalyst bleaches, such as hydrogen peroxide, catalyze what can lead to the destruction of the color and / or the fiber.

In order to avoid the problem outlined above, European patent application EP 0 829 533 A1 proposes adding aminotrimethylenephosphonic acid to the bleach-containing composition. However, the results achieved are not satisfactory. The object of the present invention was to provide a bleaching agent composition which contains a peroxy bleaching agent, a component being added to the composition which protects the textile fiber and thus reduces the destruction of the fiber and / or of the dye.

Surprisingly, it was found that this succeeds if a water-soluble liquid component selected from the group of monohydric and dihydric alcohols having 2 to 4 carbon atoms and polyalkylene glycols which are liquid at room temperature is added to bleaching agents which otherwise have an essentially customary composition and contain a peroxygen component. The addition of these compounds considerably reduces the destruction of the strength of the textile and also of the color if these textiles are pretreated in one step before the actual washing. In particular, textiles that also contain metal ions are protected.

The present invention accordingly relates to a bleach-containing composition, containing bleach, optionally surfactants and solvents, characterized in that a water-miscible, soluble liquid component selected from the group of mono- and polyhydric alcohols with 2 to 4 carbon atoms and also as a further component Room temperature liquid polyalkylene glycols is included.

The compositions according to the invention are preferably used for the pretreatment of soiled textiles or as a washing additive. However, they can also be used as a heavy-duty detergent or as a detergent, as well as a household cleaner in wet rooms and in the kitchen as a dishwashing detergent or for carpet cleaning. They can be in liquid to gel form or in solid form.

The term "pretreatment of soiled textiles" used here means that the usually aqueous composition is applied to the soiled fiber and is left there before the textile fiber is washed. The aqueous composition can also be applied to the textile substrate together with sufficient water to moisten the textile. The term “washing” here means the usual cleaning process for textiles with at least one surfactant using a washing machine or simply by hand.

The water-soluble liquid component used according to the invention is preferably selected from monohydric and polyhydric alcohols and polyalkylene glycols which have a vapor pressure which is lower than that of water. The liquid component is particularly preferably selected from the group consisting of ethylene glycol, 1, 2-propylene glycol, glycerol, polyethylene glycol which is liquid at room temperature or from any mixtures of the foregoing. The liquid, water-miscible component is preferably contained in the composition according to the invention in an amount of 1 to 25% by weight, based on the finished composition.

Another essential component of the composition according to the invention is the bleach. Preferred bleaching agents are H ₂ O ₂ as well as providing compounds, in water H ₂ O ₂ as sodium perborate monohydrate, Natriumper- carbonate or equivalent percarbonate salts, persilicate, peroxypyrophosphates, persulfates such as monopersulfate, urea peroxyhydrate, citrate perhydrates and _H2 _O2 -yielding peracidic Salts or peracids, such as perbenzoates, peroxophthaiates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid, with H ₂ O _{2 being} particularly preferred.

The bleach component is included in the compositions of the invention in an amount such that there is a measurable improvement in the removal of stains from the soiled textile substrate compared to a composition which does not contain a peroxygen compound when the soiled substrate is washed in a conventional manner. The compositions according to the invention usually contain from 0.5 to 25% by weight, based on the overall composition, of bleach component, preferably from 0.5 to 15% by weight and particularly preferably from 1 to 10% by weight.

In order to achieve an improved bleaching action when washing at temperatures of 60 ° C. and below, and in particular during pretreatment of laundry, bleach activators can be incorporated into the detergent tablets. Bleach activators which can be used are compounds which, under perhydrolysis conditions, contain aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1,3,4, are preferred , 6-tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids such as triethylcarboxylic acids, acetyl citrate (TEOC), carboxylic acid anhydrides, in particular phthalic anhydride, isatoic anhydride and / or succinic anhydride, carboxylic acid amides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, isopropenyl acetate, 2,5-diacetate the enoiester known from German patent applications DE 196 16 693 and DE 196 16 767, as well as acetylated sorbitol and mannitol, or those in European patent application EP 0 525 Mixtures described (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate derivatives / caprol, preferably N-acylated lactams, for example N-benzoylcaprolactam and N-acetylcaprolactam, which are known from international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626 , WO-A-95/14759 and WO-A-95/17498 are known. The hydrophilically substituted acylacetals 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 international patent application WO-A-95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE-A-4443 177 can also be used. Nitrile derivatives such as cyanopyridines, nitriiquats and / or cyanamide derivatives can also be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate. Bleach activators of this type are in the customary quantitative range from 0.01 to 20% by weight, preferably in amounts from 0.1 to 15% by weight, in particular 1% by weight to 10% by weight, based on the total composition. contain.

As further constituents, the compositions according to the invention can comprise surfactants selected from anionic, nonionic, cationic and / or amphoteric surfactants. contain the and their mixtures. The surfactants are preferably present in an amount of 0.1 to 50% by weight, preferably 0.1 to 35% by weight and in particular 0.1 to 15% by weight, based on the composition.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 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 has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁₄ alcohols with 3 EO to 7 EO, C ^ alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ . ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C ₁₂ . _1B alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The oligomer degree of formation x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably nonionic surfactants used, which are used in particular in solid compositions, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as 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-90/13533.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula III,

R ¹

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be 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 polyhydroxy fatty acid amides also includes compounds of the formula IV, R ¹ -OR ²

I

R-CO-N- [Z] IV

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

[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 can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Cg. ₃ -Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12, are preferably used as sulfonate-type surfactants. ₁₈ -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkanesulfonates which are derived from C ₁₂ are also suitable. _1β- alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C _1B fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production 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 become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 1-4 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ . _1B fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain

or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other anionic surfactants that can be used are soaps, which are used in particular in powdery compositions and at higher pH values. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The bleaching agent composition according to the invention is preferably in a liquid to in a form.

Solvents that can be used in the liquid to gel compositions come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that 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, ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether , Dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Solvents can be used in the liquid to gel detergents according to the invention in amounts between 0.1 and 20% by weight, but preferably below 15% by weight and in particular below 10% by weight.

To adjust the viscosity, one or more thickeners or thickening systems can be added to the composition according to the invention. The viscosity of the Compositions according to the invention can be measured using customary standard methods (for example Brookfield viscometer RVD-VII at 20 rpm and 20 ° C., spindle 3) and are preferably in the range from 100 to 5000 mPas. Preferred compositions have viscosities of 200 to 4000 mPas, values between 400 and 2000 mPas being particularly preferred.

Suitable thickeners are usually polymeric compounds. These swelling agents are mostly organic, high-molecular substances that absorb liquids, swell and eventually convert into viscous real or colloidal solutions, come from the groups of natural polymers, modified natural polymers and fully synthetic polymers.

Polymers derived from nature that are used as thickeners are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, carob bean flour, starch, dextrins, gelatin and casein.

Modified natural products primarily come from the group of modified starches and celluloses, examples include carboxymethyicellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.

A large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

The thickeners can be present in an amount of up to 5% by weight, preferably from 0.05 to 2% by weight, and particularly preferably from 0.1 to 1.5% by weight, based on the finished composition ,

Thickening agents from the substance classes mentioned are commercially available and, for example, under the trade names Acusol ^® -820 (methacrylic acid (stearyl alcohol-20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® -GT -282-S (alkyl polyglycol ether, Akzo), DeuteroP polymer-l 1

(Dicarboxylic acid copolymer, Schönes GmbH), Deuterorf -XG (anionic Heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron ^® -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ^® -Dickener-O (ethylene oxide adduct, 50% in water / Isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride copolymer, Monsanto), thickener QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas) , Mirox ^® -AM (anionic acrylic acid-acrylic ester copolymer dispersion, 25% in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^β -S (high-molecular polysaccharide, stabilized with formaldehyde , Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell), Kelzarf and Keltrol ^® (Kelco).

A preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons. Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.

Xanthan can be described by the following formula:

Basic unit of xanthan

Examples of other preferred synthetic thickeners are polyurethanes and modified (meth) acrylates.

Polyurethanes (PUR) are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula I.

[-OR ¹ -OC-NH-R ² -NH-C-] _n I,

II II o o

in which R ^{1 is} a low molecular weight or polymeric diol radical, R ^{2 is} an aliphatic or aromatic group and n is a natural number. R ¹ is preferably a linear or branched C _2-12 alk (en) yl group, but can also be a residue of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from the above formula I in that the R ¹ further -O-CO-NH groups are bound. Technically important PUR are made from polyester and / or polyether diols and, for example, from 2,4- or 2,6-toluenediisocyanate (TDI, R ² = C ₆ H ₃ -CH ₃ ), 4,4'-methylene di ( phenyl isocyanate) (MDI, R ² = C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ² = (CH ₂ ) ₆ ].

Commercial polyurethane-based thickeners are, for example, under the names Acrysol ^® PM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel ^® L75-N (nonionic PU dispersion, 50% in water, Borchers), Coatex ^® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco ^® DSX-1514 (PUR dispersion, 40% in water / Butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% PUR emulsion in water / digylcol ether, Rohm & Haas) and Rilanit ^® VPW-3116 (PUR dispersion, 43% in water, Henkel) available.

Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula II

I

[-CH ₂ -C-] _n

CXR ⁴

in which R ^{3 is} H or a branched or unbranched C ₁ ^ -alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C ₈ . ₂₂ -alk (en) yl radical, R ^{5 is} H or R ⁴ and n is a natural number. Such modified polyacrylates are generally esters or amides of acrylic acid or an α-substituted acrylic acid. Preferred among these polymers are those in which R ^{3 represents} H or a methyl group. In the case of the polyacrylamides (X = NR ⁵ ), both single (R ⁵ = H) and double (R ⁵ = R ⁴ ) N-substituted amide structures are possible, the two hydrocarbon radicals which are bonded to the N atom being independent of one another from optionally alkoxylated branched or unbranched C ₈ . ₂₂ -Alk (en) yl residues can be selected. Among the polyacrylic esters (X = O) are preferred those in which the alcohol was obtained from natural or synthetic fats or oils and is additionally alkoxylated, preferably ethoxylated. Preferred degrees of alkoxylation are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.

Since the polymers that can be used are technical compounds, the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of alkoxylation. Formula II only provides formulas for idealized homopolymers. However, copolymers in which the proportion of monomer units which satisfy the formula II is at least 30% by weight can also be used in the context of the present invention. For example, copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO groups can also be used.

Modified polyacrylates which are preferably used in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula Ha

R ⁷

I [-CH ₂ -C-] _n lla,

I C- (O-CH-CH ₂ ) _a OR ⁴

II IOR ⁶

in which R ^{4 represents} a preferably unbranched, saturated or unsaturated Cg- - alk (en) yl radical, R ⁶ and R ⁷ independently of one another represent H or CH ₃ , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number between 2 and 30, preferably between 10 and 20. R ⁴ is preferably a fatty alcohol residue obtained from natural or synthetic sources, the fatty alcohol in turn preferably being ethoxylated (R ⁶ = H).

Products of the formula IIa are commercially strength, for example, under the name Acusol ^® 820 (Rohm & Haas) in the form of 30 wt .-% dispersions in water available. In the commercial product mentioned, R ^{4 is} a stearyl radical, R ⁶ is a hydrogen atom, R ⁷ is H or CH ₃ and the degree of ethoxylation a is 20. In combination with the above-mentioned thickeners, additional complexing agents can be used to stabilize the viscosity. Examples of complexing agents are low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid, or gluconic acid or salts thereof, citric acid or sodium citrate being particularly preferred. The complexing agents can be contained in an amount of 1 to 8% by weight, preferably 3.0 to 6.0% by weight and in particular 4.0 to 5.0% by weight, based on the finished composition ,

The compositions according to the invention can contain further ingredients which further improve the application technology and / or aesthetic properties of the composition. In the context of the present invention, preferred compositions can additionally contain one or more substances from the group of builders, enzymes, electrolytes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, soil release compounds, optical brighteners, graying inhibitors, Anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, swelling and anti-slip agents and UV absorbers.

The builders that can be contained in the compositions according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Suitable crystalline, layered sodium silicates have the general formula NaMS O ^ ^• y H ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O _s yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171. Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “roentgenamoφh”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O (1-n) K ₂ O ^• AI ₂ O ₃ ^• (2 - 2.5) SiO ₂ ^■ (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, this contain ge additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups, C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, it is also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned are suitable as enzymes. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing piliing and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures are, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and Celiulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Celiobiohydrolases, endoglucanases and β-glucosidases, which are also cellobia- Sen are called, or mixtures of these are used. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

In order to bring the pH of the compositions according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation.

In order to improve the aesthetic impression of the compositions according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other constituents of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

Foam inhibitors that can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils.

Suitable soil release compounds are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and the Polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the compositions according to the invention to reduce graying and yellowing of the treated Eliminate textiles. These substances absorb on the fiber and bring about a brightening and fake bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and pure with the yellow tone of the grayed or yellowed laundry White results. Suitable compounds for example, originate from the substance classes of the 4,4 ^'diamino-2,2 - stilbenedisulfonic (flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, Benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles. The optical brighteners are usually used in amounts between 0.01 and 0.3% by weight, based on the finished composition.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or 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 can also be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, preference is given to cellulose ethers, such as carboxymethylceliulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylceliulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the Means used.

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers are sensitive to bending, kinking, pressing and squeezing across the fiber direction, the compositions according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, most of which contain Ethylene oxide are implemented, or products based on lecithin or modified phosphoric acid esters.

To control microorganisms, the compositions according to the invention can contain antimicrobial active ingredients. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, haiogenophenols and phenolmericuriacetate, these compounds also being dispensed with entirely in the compositions according to the invention can.

An increased wearing comfort can result from the additional use of antistatic agents which are additionally added to the compositions according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are described, for example, in patent applications FR 1, 156.513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, silicon derivatives, for example, can be used in the compositions according to the invention. These additionally improve the rinsing behavior of the compositions according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are partially or completely fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are around 25 ° C. rich between 100 and 100,000 mPas, the silicones in amounts between 0.2 and 5 wt .-%, based on the entire composition.

Finally, the compositions according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position which are effective by radiation-free deactivation. Substituted benzotriazoles, 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 urocanoic acid are also suitable.

In order to avoid the decomposition of certain detergent ingredients catalyzed by heavy metals, substances can be used which complex heavy metals. Suitable heavy metal complexing agents are, for example, ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) in the form of the free acids or as alkali metal salts and derivatives thereof, and also the alkali salts of anionic polyelectrolytes, such as polymaleates and polysulfonates.

A preferred class of complexing agents are the phosphonates, which in preferred compositions in amounts of 0.01 to 2.0 wt .-%, preferably 0.05 to 1.5 wt .-% and in particular 0.1 to 1.0 % By weight are included. These preferred compounds include, in particular, organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic 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 batchwise by simply mixing the constituents, water, solvent and surfactant (s) advantageously being introduced and the further constituents being added in portions. There is no separate heating during manufacture required, if desired, the temperature of the mixture should not exceed 80 ° C.

The present invention further relates to a process for the pretreatment of soiled textiles with a bleach-containing composition, which comprises a peroxygen compound and a water-soluble liquid component selected from the group of mono- and dihydric alcohols with 2 to 4 carbon atoms and polyalkylene glycols which are liquid at room temperature, and if appropriate Contains surfactants.

For the pretreatment of the fiber, the composition according to the invention is usually applied to the fiber over a period of up to 24 hours, in particular from one minute to one hour and particularly preferably from five minutes to 30 minutes. The period should be chosen so that the liquid composition does not dry on the fiber. The textiles are usually contaminated with dried-on stains or dirt, which are usually very difficult to remove. The liquid compositions can simply be applied to the textiles and left there, the dirt removal can also be done by mechanical support, e.g. B. be supported by rubbing or by treatment with a sponge or a brush.

As a rule, the compositions according to the invention are applied in undiluted form to the textiles or to the substrate to be treated or used as an additive with a commercially available detergent.

Examples

A non-prewashed cotton fabric from the Krefeld laundry research institute (80 × 80 cm) was immersed in water containing 15 ppm of Cu ²⁺ , spun and ironed dry. In the middle of the fabric, 30 ml of a bleaching agent with the composition shown in Table 1 was added. The bleach was left to act overnight (16 hours), then it was washed with a commercial detergent (Persil Megaperls®) in a household washing machine (Miele W 918) at 60 ° C.

After washing, strips 4.5 × 80 cm wide were cut out so that the edge zone of the applied bleaching agent was in the middle of the strip. The results on tensile strength are shown in Table 2.

Examples 2 to 5 and 8 to 11 represent examples according to the invention, Examples 1, 6, 7 and 12 are comparative examples.

The tensile strength was determined in accordance with DIN 53857. The untreated fabric had a tear strength of dry: 884.9 N wet 935.7 N

The examples show that the tensile strength loss of the fabric samples treated according to the invention is significantly less than that of the samples pretreated with a conventional bleaching agent.

Table 1

Table 2

Claims

claims

1. Bleach-containing composition, containing bleach, optionally surfactants and solvents, characterized in that a water-miscible liquid component selected from the group of mono- and polyhydric alcohols with 2 to 4 carbon atoms and the liquid polyalkylene glycols at room temperature is contained as a further component.

2. Composition according to claim 1, characterized in that the 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 from any mixtures of the above.

3. Composition according to one of claims 1 or 2, characterized in that the liquid water-soluble component is contained in an amount of 1 to 25 wt .-%, based on the finished composition.

4. Composition according to one of claims 1 to 3, characterized in that the bleaching agent in an amount of 0.5 to 25 wt .-%, based on the total composition, preferably from 0.5 to 15 wt .-% and particularly is preferably contained from 1 to 10 wt .-%.

5. Composition according to one of claims 1 to 4, characterized in that H ₂ O _{2 is} contained as the bleaching agent.

6. Composition according to one of claims 1 to 5, characterized in that surfactants are contained in an amount of 1 to 50 wt .-%.

7. Composition according to one of claims 1 to 6, characterized in that it is in liquid to gel form.

8. The composition according to claim 7, characterized in that it has a viscosity of 500 to 5000 mPas, preferably from 1000 to 4000 mPas and in particular from 2000 to 3500 mPas.

9. The composition according to claim 8, characterized in that it contains thickeners in an amount of up to 5 wt .-%, preferably from 0.1 to 3 wt .-%, based on the finished composition.

10. The composition according to claim 9, characterized in that the thickener is selected from agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein , modified starches and celluloses as well as fully synthetic polymers.

11. The composition according to any one of claims 1 to 10, further comprising one or more substances from the group of builders, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, soil release compounds, optical Brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, swelling and anti-slip agents as well as UV absorbers.

12. Process for the pretreatment of soiled textiles with a bleach-containing composition which contains a peroxygen compound and a water-soluble liquid component selected from the group of mono- and dihydric alcohols with 2 to 4 carbon atoms as well as polyalkylene glycols which are liquid at room temperature and optionally surfactants.