EP2727986A2 - Polymers for allergen adhesive equipment - Google Patents

Abstract

Use of polymers comprising at least two of polyethylene glycol, polyvinyl pyrrolidone, vinylpyrrolidone-vinyl imidazole copolymers, polyvinylpyridine-nitrogen-oxide, reaction products of diethylenetriamine with cyano guanidine, or reaction products of dimethylamine with epichlorohydrin for coating allergen-adhesive equipments including textile surface (comprising cotton) or hard household surface is claimed. An independent claim is also included for use of detergents or cleaning agents, comprising the polymer for coating the allergen-adhesive equipments including textile surface or hard household surface.

Description

The present invention relates to the use of certain polymers for allergen-adhesive finishing of textiles or hard household surfaces.

Sensitivity to allergens is a problem for an increasing number of people, which has become more difficult in recent years due to the increased incidence of asthma. Asthma sufferers are particularly sensitive to allergens present in the air.

Allergens lead to an exaggerated immune reaction of the human or even animal body. Allergic reactions occur upon contact of allergens with, in particular, the human organism and can be caused in various ways, in particular via the inhalation of airborne allergens or by direct contact of the allergen with a moist surface of the human body, where they stick and with react to the surrounding body tissue. This can happen, for example, when a person is lying in bed and is in contact with allergenic dust that is on the pillow or comforters, and this is absorbed, for example, by the eyes of the person. This usually leads to an allergic reaction as the allergens are gradually absorbed by the mucous membranes around the eye.

Many allergens are protein-based molecules that can come from many different sources, with homes being one of the most common sources of dust mite allergens. Dust mites thrive in carpets, upholstered furniture, comforters, furniture covers, curtains and the like, but also in garments. Physicians specializing in the treatment of allergies often recommend removal of these items from the homes of people suffering from house-dust allergies. However, this is often an impractical and unworkable solution to the problem of house dust allergies.

Another method for removing mite allergens from a household is the use of means to kill the mites. However, the proteins which cause the allergic reactions are also found in the bodies of dead mites and in the remaining faeces of the mites, so that the mite killing does not solve the problem. In addition, mite killing agents may also be toxic or at least unpleasant to other organisms so that their use is not possible everywhere.

An increasing number of people are allergic to pollen, that is, to the pollen of plants. Pollen from trees such as hazel, alder, beech, oak, ash, hornbeam, pine, poplar, elm, willow and birch as well as some herbs, such as plantain, nettle, mugwort, sorrel, are particularly responsible for allergic reactions and ambrosia.

One method of neutralizing allergens in the home involves spraying surfaces with compositions that either denature or simply cover the allergens. The denaturing sprays are said to render the protein molecules inactive for causing an allergy reaction. This can be achieved by the formation of chemical complexes between the allergen protein and the denaturing chemical so that the allergen can no longer cause an allergic reaction in a human. Furthermore, sprays can be used to cover or trap allergens or allergenic particles. The covered allergens become too heavy to float in the air, so they sink to the bottom and can not be inhaled or otherwise come in contact with the human body, thus causing no allergic reaction. However, these two approaches have not yet proven to be entirely satisfactory for allergy patients. Allergen neutralization sprays usually contain a tannin or a related polyphenol as the active ingredient. These are known for their rich yellow color so they can not be sprayed on textile surfaces without significant risk of staining. Materials for covering or enclosing allergenic materials, such as dust, typically stick to dust and other airborne particles, making them too heavy to stay in the air. However, the sticky spray also makes the covered particles sticky which, when deposited, results in surfaces that feel sticky. This is particularly undesirable in bedspreads and pillows, for example. In addition, spraying a surface with a sticky material results in the increased attraction of dust and other airborne particles to the surface, so that the surface becomes more quickly dirty.

The international patent application WO 99/115206 describes deactivating compositions for dust mite allergens comprising a large amount of deactivating compounds. From the international patent application WO 02/28179 A1 are starch, polyvinyl alcohol, carboxymethylcellulose, polyacrylic acids, polyethylene glycols having molecular weights above 5000, polyethylene, polypropylene glycols having molecular weights above 8000, the polyquaternium compounds 1 to 14 and polyvinylpyrrolidone known as allergen-neutralizing agents. The international patent application WO 02/28187 A1 discloses agents containing allergen-neutralizing metal ions such as Zn, Sn, Mg, Ca, Mn, Ti, Fe, Co and / or Ni and additionally optionally polyphenol compounds, hydrogen peroxide, salicylic acid, citric acid, lactic acid, glycolic acid, ascorbic acid, gallic acid and / or gluconic acid contain. From the international patent application WO 03/006030 A1 is the allergen-neutralizing effect of salts, such as aluminum, calcium and / or magnesium sulfate, nitrate and / or chloride, known. The European patent application EP 1 550 705 relates to agents containing allergen-neutralizing polysaccharide derivatives. From the international patent application WO 2004/007658 A2 Allergen-binding lectins are known. The patent US Pat. No. 6,013,139 discloses aqueous carpet cleaning solutions suitable for allergen removal which contain certain amounts of sodium tripolyphosphate, boric acid, sodium bicarbonate, ethanol, isopropanol, sodium borate or tetraborate, and hydrogen peroxide. From the patent application CA 2 329 296 A1 is a method for immobilizing allergens by contacting with an aqueous agent containing water-soluble or -dispersible polymer and water-soluble or -dispersible volatile solvent, the polymer of the polysaccharides, polycarboxylates, polystyrene sulfates, acrylate polymers, optionally ethoylated and propoxylated Polyethyleniminen, polyvinylpyrrolidones, methyl vinyl ethers and polyvinyl alcohols and mixtures thereof is selected; the agent is sprayed on an allergen-coated surface and allowed to dry. The patent application US 2002/0176854 A1 discloses the allergen protein-cleaving action of subtilisin-type proteases. The patent application GB 2 300 122 A discloses a means for covering and surrounding dust mite allergens containing polysaccharide.

In garments, especially when worn on the body, the application of denaturing sprays or allergen-immobilizing agents to their already allergenic surface is uncomfortable for the wearer of the fabric, also leads to generally visible changes in the textile surface and is therefore, no acceptable solution to prevent or reduce allergies.

Surprisingly, it has been found that surfaces which have been brought into contact with certain polymeric active substances subsequently hold the allergens in contact with the surfaces so strongly that their effect on the organism of allergy sufferers is markedly reduced.

The invention relates to the use of polymers selected from polyethylene glycol, polyvinylpyrrolidone, N-vinylimidazole-N-vinylpyrrolidone copolymers, polyvinylpyridine-N-oxide, the reaction products of diethylenetriamine with cyanoguanidine, the reaction products of dimethylamine with epichlorohydrin, and mixtures of two or several of these, for allergen-adhesive finishing of textiles or hard household surfaces.

The average molecular weight (weight average) of the polymers used according to the invention is preferably in the range from 1000 g / mol to 1,000,000 g / mol, in particular from 2,000 g / mol to 500,000 g / mol and particularly preferably in the range from 5,000 g / mol to 250,000 g / mol. N-vinylimidazole-N-vinylpyrrolidone copolymers preferably have the monomers N-vinylamine and N-vinylpyrrolidone in molar ratios in the range from 50:50 to 1:99, in particular from 30:70 to 2:98.

Reaction products of diethylenetriamine with cyanoguanidine are commercially available, for example, under the trade name Tinofix® CL. Reaction products of dimethylamine with epichlorohydrin are commercially available, for example, under the trade name Texcare® DFC 6.

The polymers mentioned are particularly effective against the allergens associated with pollens, especially birch pollen, but also other common allergens such as mites, especially house dust mites, cockroaches and molds, animal dander and dander of cats or dogs and the like and / or fungal spores ,

The use according to the invention may preferably be realized by allowing a detergent containing a named polymer to act on a textile in the course of a machine or hand washing operation. After rinsing and drying, the textile has a binding effect against allergens, that is, allergens that have subsequently reached the textile, are released only in a very small extent even under mechanical stress, as occurs for example when wearing the textile. This reduces the risk of allergy to the wearer of the textile and to persons staying in its environment. The use according to the invention can also be implemented analogously by allowing a cleaning agent containing a named polymer to act on a hard surface in the course of a mechanical or manual cleaning process. Another object of the invention is therefore the use of detergents or cleaners containing a named polymer for the allergen-adhesive finish of textiles or hard household surfaces.

Particularly pronounced is the allergen-adhesive effect of the polymers mentioned and the agents containing them in the treatment of at least partially made of cotton existing textiles. A preferred subject of the invention is therefore the use of the polymers and the agents containing them for the allergen-adhesive finishing of textiles which consist of cotton or contain cotton.

An agent for washing laundry or for cleaning hard household surfaces preferably contains 0.001% by weight to 10% by weight, in particular 0.1% by weight to 1% by weight, of the polymeric active substance mentioned besides customary, compatible with it Ingredients. These agents, which can be in the form of particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may in principle, in addition to the polymer used according to the invention, be all known and in such compositions contain usual ingredients. The detergents and cleaning agents may in particular be builders, surface-active surfactants, bleaches, bleach activators and catalysts, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators or other auxiliaries, such as optical brighteners, grayness inhibitors, dye transfer inhibitors, foam regulators and dyes and fragrances , contain.

The agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are in cleaning or washing agents in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while disinfectants as well as means for cleaning dishes preferably 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactants.

A washing or cleaning agent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediamine tetrakis (methylenephosphonic acid), Lysintetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, especially by oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized. The relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. As water-soluble organic builders terpolymers can also be used which contain as monomers two unsaturated acids and / or salts thereof and as a third monomer vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Especially preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. As water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.

In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O used _{2x + 1} · y H ₂ O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both .beta.- and δ-sodium (Na ₂ Si ₂ O _s · y H ₂ O) is preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in the compositions. In a further preferred embodiment, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Sodium silicates with a modulus in the range 1.9 to 3.5 are used in a further embodiment. In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Machine dishwashing detergents are preferably of low alkaline content and contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. The alkali carriers used conventionally include carbonates, bicarbonates and alkali silicates having a molar ratio of SiO ₂ / M ₂ O (M = alkali atom) of from 1.5: 1 to 2.5: 1. Alkali silicates may be used in amounts of up to 30% by weight. %, based on the total mean. The use of the highly alkaline metasilicates as alkali carriers is preferably completely dispensed with. The alkali carrier system preferably used in the compositions is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight. Depending on which pH is ultimately desired, the ratio of carbonate used and hydrogen carbonate used varies, but usually an excess of sodium bicarbonate is used, so that the weight ratio between bicarbonate and carbonate is generally from 1: 1 to 15: 1.

In a further embodiment of the means for cleaning dishes in these 20 wt .-% to 40 wt .-% of water-soluble organic builder, in particular alkali, 5 wt .-% to 15 wt .-% alkali carbonate and 20 wt .-% bis 40 wt .-% Alkalidisilikat included.

Suitable bleaching agents are those based on chlorine, in particular alkali hypochlorite, dichloroisocyanuric acid, trichloroisocyanuric acid and salts thereof, as well as those based on peroxygen. Suitable peroxygen compounds are, in particular, organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecanedioic acid and salts thereof, such as magnesium monoperoxyphthalate, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the cleaning conditions, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide. Inclusion compounds, such as H ₂ O ₂ -urea adducts, into consideration. Hydrogen peroxide can also be produced with the aid of an enzymatic system, ie an oxidase and its substrate, be generated. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. The peroxygen compounds can be added to the washing or cleaning liquor as such or in the form of these containing agents, which may in principle contain all conventional detergents, cleaners or disinfectant ingredients. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a washing or cleaning agent contains peroxygen compounds, these are in amounts of preferably up to 25 wt .-%, in particular from 1 wt .-% to 20 wt .-% and particularly preferably from 7 wt .-% to 20 wt .-%. % present, while in disinfectants preferably from 0.5 wt .-% to 40 wt .-%, in particular from 5 wt .-% to 20 wt .-%, of peroxygen compounds are included.

Compounds which give peroxocarboxylic acid under perhydrolysis conditions can in particular be compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures. Suitable bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular no-nanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), whose formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benzenesulfonate (DECOBS), acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran; and acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives , in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose, acetylated , optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_1-24-Alkyl- oder C_2-24-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN und -N⁽⁺⁾-CH₂-CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C_1-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃,-CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6, R⁴ und R⁵ unabhängig voneinander eine voranstehend für R¹, R² oder R³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R² und R³, auch unter Einschluss des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X(^-) ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C_9-15-Alkylbenzolsulfonaten, den C_1-20-Alkylsulfaten, den C_8-22-Carbonsäuremethylester-sulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden. Auch sauerstoffübertragende Sulfonimine und/oder Acylhydrazone können eingesetzt werden.In addition to the compounds that form peroxycarboxylic acids under perhydrolysis conditions, other bleach-activating compounds, such as nitriles, from which perimide acids form under perhydrolysis conditions may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or alkenyl radical, a substituted C _1-24 -alkyl or C _2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN and -N ⁽⁺⁾ -CH ₂ -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C _1-24 alkyl group (s) and optionally further substituents on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have the meaning given above for R ¹ , R ² or R ³ , where at least 2 of the radicals mentioned, in particular R ² and R ³ , also include the Nitrogen atom and optionally further heteroatoms ring-closing linked together and then preferably form a morpholino ring, and X ( ^- ) a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumenesulfonate, the C _9-15 -alkylbenzenesulfonates, the C _1-20 Alkyl sulfates, the C _{8-22 -carboxylic} acid _methyl ester sulfonates, sulfate, hydrogen sulfate and mixtures thereof, can be used. Oxygen-carrying sulfonimines and / or acylhydrazones can also be used.

The presence of bleach-catalyzing transition metal complexes is also possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Suitable ligands in such transition metal complexes are both inorganic and organic compounds, which in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , Triazole, 2,2'-bispyridylamine, tris- (2-pyridylmethyl) amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9 Trimethyl-1,5,9-triazacyclododecane, (bis ((1-methylimidazol-2-yl) -methyl)) - (2-pyridylmethyl) -amine, N, N '- (bis (1-methylimidazole) 2-yl) -methyl) -ethylenediamine, N-bis (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ', N'-tetrakis (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3-bis (bis (2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and optionally substituted Salene, porphins and porphyrins belong. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic, and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO ₂ ) ^- group, that is, a nitro ligand or a nitrito ligand. The (NO ₂ ) ^- group may also be chelated to a transition metal, or it may bridge two transition metal atoms asymmetrically or η ¹ -O-bridge. In addition to the ligands mentioned, the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands. In question, for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands should provide charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise. In the case of bridged, dinuclear complexes, both metal atoms in the complex need not be the same. The use of binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate. Examples of transition metal complex compounds that can be used are Mn (IV) ₂ (μ-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) -di-hexafluorophosphate, [N, N'-bis [(2 -hydroxy-5-vinylphenyl) -methylene] -1,2-diaminocyclohexane] -manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitro-phenyl) -methylene] -1 , 2-diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N '- bis [(2-hydroxyphenyl) methylene] -1,2-diamino-cyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2 -diaminoethane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-sulfonatophenyl) methylene] -1,2-diaminoethane] -man-gan (III) chloride, Manganese oxalato complexes, nitropentammine cobalt (III) chloride, nitrite pentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride, and the peroxo complex [(NH ₃ ) ₅ CO-]. OO-Co (NH ₃ ) ₅ ] Cl ₄ .

Suitable enzymes contained in the washing or cleaning agents are, in particular, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, Amylase, lipase and / or cellulase is particularly preferred. The proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.

Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and / or soil-release agents in the compositions is generally not more than 2 wt .-%, and is preferably 0.5 wt .-% to 1.5 wt .-%.

As optical brighteners for particular textiles made of cellulose fibers (for example cotton), detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Further, brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. Brighteners of the 1,3-diaryl-2-pyrazolines type, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable for polyamide fibers. The content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%. In a preferred embodiment, the agent is free of such agents.

The customary foam regulators that can be used in particular detergents include, for example, polysiloxane-silica mixtures, wherein the fine-particle silica contained therein is preferably silanated or otherwise rendered hydrophobic. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C ₁₆ - to C ₁₈ -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.

The agents may contain water as a solvent. Among the organic solvents which can be used in the compositions, in particular if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said compound classes ethers. Such water-miscible solvents are present in the compositions in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight.

To establish a desired, by the mixture of the other components not automatically resulting pH, the agents can system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but Also, mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, included.

The preparation of solid compositions presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, thermally-sensitive ingredients optionally being added separately later.

Compositions in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

The compositions are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and bleach-activating agents Active ingredients are expected to be produced. For the production of compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions in tablet form, the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200 10 ⁵ Pa to 1 500 10 ⁵ Pa pressed. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strength of usually over 150 N. Preferably, a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

example

The polymers indicated in the table below were force-applied to cotton lobes in 1% strength by weight solution, and the lobules were dried and then dusted with equal amounts of birch pollen. After briefly shaking off the loosely adherent pollen, the adhered pollen allergens were determined by means of an ELISA test. The amounts of adhered pollen allergen are given as compared to the amount (100%) which adhered to the untreated lobe under the same conditions. Polyethylene glycol 12000 510% Polyvinylpyrrolidone I (Sokalan® HP53) 520% Polyvinyl pyridine-N-oxide 550% Tinofix® CL 30 560% Polyvinylpyrrolidone II (Sokalan® HP56) 650% Texcare® DFC 6 700%

It can be seen that the allergens have been bound to the treated lobules more than 5 times stronger than to the untreated lobules.

Claims (9)

Use of polymers selected from polyethylene glycol, polyvinylpyrrolidone, vinylimidazole-vinylpyrrolidone copolymers, polyvinylpyridine-N-oxide, the reaction products of diethylenetriamine with cyanoguanidine, the reaction products of dimethylamine with epichlorohydrin and mixtures of two or more of these, for allergenic adhesive finishing of Textiles or hard household surfaces. Use of polymers selected from polyethylene glycol, polyvinylpyrrolidone, vinylimidazole-vinylpyrrolidone copolymers, polyvinylpyridine-N-oxide, the reaction products of diethylenetriamine with cyanoguanidine, the reaction products of dimethylamine with epichlorohydrin and mixtures of two or more of these, for allergenic adhesive finishing of Textiles made of cotton or containing cotton. Use of detergents or cleaners comprising a polymer selected from polyethylene glycol, polyvinylpyrrolidone, vinylimidazole-vinylpyrrolidone copolymers, polyvinylpyridine-N-oxide, the reaction products of diethylenetriamine with cyanoguanidine, the reaction products of dimethylamine with epichlorohydrin and mixtures of two or more of these , included, for allergen-adhesive finishing of textiles or hard household surfaces. Use according to claim 1 or 2, characterized in that a detergent containing the polymer is allowed to act on a textile in the course of a machine or hand washing operation, or in that a cleaning agent containing the polymer is used in a mechanical or manual cleaning action on a hard surface. Use according to claim 3 or 4, characterized in that the agent contains 0.001 wt .-% to 10 wt .-%, in particular 0.1 wt .-% to 1 wt .-% of the polymeric active ingredient. Use according to any one of claims 3 to 5, characterized in that the agent additionally contains builder substances, surface-active surfactants, bleaches, bleach activators and catalysts, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators or other auxiliaries. Use according to one of claims 1 to 6, characterized in that the average molecular weight (weight average) of the polymer in the range of 1000 g / mol to 1,000,000 g / mol, in particular from 2,000 g / mol to 500,000 g / mol. Use according to one of claims 1 to 7, characterized in that the polymer is an N-vinylimidazole-N-vinylpyrrolidone copolymer with the monomers N-vinylamine and N-vinylpyrrolidone in molar ratios in the range from 50:50 to 1:99, in particular of Is 30:70 to 2:98. Use according to one of claims 1 to 8, characterized in that the allergens are associated with pollens, in particular birch pollen, or with mites, cockroaches, animal hair and / or fungal spores.