WO2014079756A1

WO2014079756A1 - Antiadhesive polymers for microbe-repulsive textile finishing

Info

Publication number: WO2014079756A1
Application number: PCT/EP2013/073772
Authority: WO
Inventors: Paula Barreleiro; Mirko Weide; Martina Hutmacher; Rainer Simmering; Noelle Wrubbel
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2012-11-20
Filing date: 2013-11-14
Publication date: 2014-05-30
Also published as: DE102012221196A1

Abstract

Antimicrobial action in the use of washing compositions was to be improved. This was achieved essentially through the use of polymers formed from the monomers (I), (II) and (III).

Description

Anti-adhesive polymers for microbial-repulsive textile finishing

The present invention relates to the use of certain polymers to reduce the adhesion of microorganisms to textiles.

Microorganisms such as bacteria, fungi and viruses can colonize household and textile surfaces. Bacteria and fungi can also multiply on such surfaces. This can result in hygiene risks, but also lead to unaesthetic microbial deposits, so-called biofilms. The occurrence of microbially induced, especially bacterially caused bad odors is possible. Garments made of delicate materials such as silk or microfibers can only be washed at 30 ° C or 40 ° C. It is possible that thereby fungi, such as the human pathogenic Candida albicans, and bacteria are not always killed sufficiently. In particular, after a fungal infection can come by such adhering to garments, not killed fungi to a reinfection.

In order to prevent reinfection by adhering to clothing or other textile surfaces such as furniture upholstery or curtains microorganisms, so far mainly antimicrobial substances have been used, either inhibit the growth of microorganisms (biostatics) or kill them (biocides). The disadvantage is that such biocides or biostats used for example in detergents and cleaners enter the wastewater after use and may impair the function of the microbial treatment stages in the sewage treatment plants. In addition, the selection pressure on the microorganisms for resistance formation is greatly increased, so that after some time new antimicrobial substances must be found that act against resistant microorganisms. It is therefore desirable to have biorepulsive substances instead of biocidal or biostatic substances which prevent the adhesion of the microorganisms without physiologically impairing the microorganisms.

International patent application WO 2006/071452 A2 discloses the use of polyester amides for the temporary or permanent finishing of textile surfaces. International Patent Application WO 2006/071451 A2 relates to the reduction of the adhesion of microorganisms to textile surfaces by copolymers of 5% by weight to 95% by weight of anionic vinyl monomer and 5% by weight to 95% by weight of nonionic hydrophilic vinyl monomer, wherein vinyl monomers having a secondary or tertiary amino group or ammonium group, polyfunctional vinyl monomers, hydrophobic vinyl monomers and / or vinyl monomers having silicone groups may additionally be present. From the international patent application WO 2006/077049 A2 are polymers and copolymers from the groups of polyesters, polysaccharides, polyethers, polyurethanes, polyureas and polyamides or their copolymers known, which are suitable for reducing or preventing the adhesion of microorganisms to textiles.

Surprisingly, it has been found that on surfaces which have been brought into contact with certain polymeric active substances, the adhesion of microorganisms is prevented or at least significantly reduced.

The invention relates to the use of polymers composed of the monomers of the general formulas (I), (II) and (III),

in which

R and R ^4, independently of one another, denote H or linear or branched C 1 -C ₆ -alkyl,

R ² and R ³ independently of one another are linear or branched C ¹ -C 6 -alkyl or -hydroxyalkyl,

R ^{5 is} H or CH ₃ ,

R ^{6 is} H or dC ₂ alkyl and

R ⁷ and R ⁸ independently of one another are H or C 1 -C ⁸ -alkyl,

n and m for integers from 1 to 3 and

X ^" for a counterion

stand,

for the prevention of microbial colonization, in particular the colonization by bacteria, fungi and / or viruses, of textile surfaces.

Preferred monomers of the general formula (I) are diallyldimethylammonium chloride

(DADMAC), diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium monophosphate, di (methylallyl) dimethylammonium chloride, di (ethylallyl) dimethylammonium chloride, diallyldi (.beta.-hydroxyethyl) ammonium chloride and diallyldiethylammonium chloride. Particularly preferred is diallyldimethylammonium chloride (DADMAC).

Preferred monomers of the general formula (II) are acrylic acid (AA), methacrylic acid (MA), ethacrylic acid and dimethylacrylic acid and mixtures thereof. Particularly preferred is acrylic acid (AA). The acid groups of the monomers of the general formula (II) may also be wholly or partly in the form of alkali metal or ammonium salts, in particular sodium and / or potassium salts.

Preferred monomers of the general formula (III) are (meth) acrylamide which contain N, N-dialkyl (meth) acrylamides, such as N, N-dimethyl (meth) acrylamide, N, N-methylethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N, N-methylpropyl (meth) acrylamide, N, N-ethylpropyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-methylbutyl (meth) acrylamide, N, N- Ethylbutyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N, N-propylbutyl (meth) acrylamide, N, N-dipentyl (meth) acrylamide, N, N-methylpentyl (meth) acrylamide, N, N- Ethylpentyl (meth) acrylamide, N, N-propylpentyl (meth) acrylamide, N, N-butylpentyl (meth) acrylamide, N, N-dihexyl (meth) acrylamide, N, N-methylhexyl (meth) acrylamide, N, N- Ethylhexyl (meth) acrylamide, N, N-propylhexyl (meth) acrylamide, N, N-butylhexyl (meth) acrylamide, N, N-pentylhexyl (meth) acrylamide, N, N-diheptyl (meth) acrylamide, N, N- Methylheptyl (meth) acrylamide, N, N-ethylheptyl (meth) acrylamide, N, N-propylheptyl (meth) acrylamide, N, N-butylheptyl (meth) acrylamide, N, N-pentylheptyl (meth) acrylamide, N, N-dioctyl (meth) acrylamide, N, N-methyl-octyl L (meth) acrylamide, N, N-ethyloctyl (meth) acrylamide, N, N-propyloctyl (meth) acrylamide, N, N-butyl octyl (meth) acrylamide, N, N-pentyloctyl (meth) acrylamide and N, N-Heptyloctyl (meth) acrylamide, and the corresponding N-monoalkyl (meth) acrylamides and mixtures of these. Particularly preferred is acrylamide.

The polymers used according to the invention have no monomers other than those of the general formulas (I), (II) and (III). The stated monomers can be randomly distributed in the polymer or in the form of interconnected blocks of only one monomer at a time. It is possible to polymerize a second monomer onto a homopolymer of one of the monomers and then to copolymerize the third monomer onto the block copolymer, or to polymerise a mixture of second and third monomer to a homopolymer of one of the monomers. The molar ratio of monomer of the formula (I) to monomer of the formula (II) is preferably in the range from 1: 100 to 10: 1, in particular from 10:25 to 4: 1, and / or the molar ratio of monomer in the polymer used according to the invention according to formula (I) to monomer according to formula (III) in the range of 1: 200 to 10: 1, in particular from 1:10 to 4: 1. Particularly preferred is a terpolymer of diallyldimethylammonium chloride (DADMAC), acrylic acid and acrylamide. The average molar mass of the polymers used according to the invention is preferably in the range from 200 g / mol to 500,000 g / mol, in particular from 500 g / mol to 100,000 g / mol and more preferably from 1000 g / mol to 50,000 g / mol. The average molecular weights given here and, if appropriate, for other polymeric ingredients are weight-average molar masses M _w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard.

Preferably, a polymer used according to the invention has a solubility in water at 25 ° C over the entire range of pH 7 to pH 9, more preferably over the entire range of pH 2 to pH 1 1, of at least 0.01 g / l, in particular of at least 0.1 g / l and more preferably from 1 g / l to 15 g / l.

The polymers mentioned are able to furnish textiles in such a way that microbial growth on them is avoided because bacteria, fungi and / or viruses do not adhere to the textile surface treated with them or only to a lesser extent. Another object of the invention is therefore the use of said polymers for preventing or reducing the adhesion of microorganisms, in particular of bacteria, fungi and / or viruses, to textiles.

For the treatment of the textile surface, preference is given to using an aqueous liquor which contains 1 mg / l to 5000 mg / l, in particular 10 mg / l to 500 mg / l of the polymer used according to the invention.

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. Further objects of the invention are therefore the use of a detergent containing a named polymer to prevent the microbial colonization of textile surfaces, and the use of a detergent containing a said polymer to prevent or reduce the adhesion of microorganisms to textiles.

A detergent, which is understood here to mean a means for washing laundry or a laundry pre-treatment agent used before the actual washing process, such as, for example, a stain remover or a laundry after-wash, such as a fabric softener, preferably contains 0.01% by weight .-% to 2 wt .-%, in particular 0.05 wt .-% to 1, 5 wt .-% and particularly preferably 0.5 wt .-% to 1, 2 wt .-% of said polymeric active ingredient in addition to conventional , with this compatible ingredients. These agents, which may be present in particular as pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may, in addition to the polymer used in the invention Principle contain all known and customary in such agents ingredients. The detergents may, in particular, be builder substances, 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, graying inhibitors, dye transfer inhibitors, foam regulators and dyes and fragrances, contain. If they are liquid and hydrous, they preferably have a pH in the range of 8 to 12, especially 9 to 12; otherwise, the pH ranges mentioned apply to 0.47% by weight aqueous solutions of the agents.

The use of the above-mentioned polymers in a detergent, when used, both inhibits or at least reduces the adhesion of microorganisms to textiles and also achieves easier detachment of microbial soiling from the textiles.

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 products of alkyl glycosides or linear or branched alcohols having in each case 12 to 18 C 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 present in detergents in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight. A detergent 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 hydroxyimidodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) carboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids , Methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative average molecular weight 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 acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. 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 of 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 may 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 of benzene or benzene derivatives derives, 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. Particularly 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 contain, as monomers, acolein 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. Of these, preference is given to the detergent-grade crystalline sodium aluminosilicates, in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X. 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 μm, and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding inhibitor is usually 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 contained in the compositions preferably in amounts of 1 wt .-% to 20 wt .-%, in particular from 5 wt .-% to 15 wt .-%. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to Si0 ₂ below 0.95, in particular from 1: 1, 1 to 1: 12 and may be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ 0: Si0 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 0 ₂ x ₊ iy H ₂ 0 used in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 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 β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ y H ₂ O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali silicates of the above 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 of 1.9 to 3.5 are used in another embodiment. In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15.

Suitable bleaching agents are those based on chlorine, in particular alkali hypochlorite, dichloroisocyanic acid, trichloroisocyanuric acid and salts thereof, but especially those based on persuurs. Suitable peroxygen compounds are, in particular, organic peracids or persaltic 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 conditions of use, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide. Inclusion compounds, such as H ₂ 0 ₂ -Harnstoffaddukte, into consideration. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. 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. 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 detergent contains peroxygen compounds, they are present in amounts of preferably up to 25% by weight, more preferably from 1% to 20% and most preferably from 7% to 20% by weight. As a bleach-activating under perhydrolysis conditions peroxycarboxylic acid-yielding compound, in particular compounds which give under perhydrolysis conditions optionally substituted perbenzoic acid and / or aliphatic peroxycarboxylic acids having 1 to 12 C-atoms, in particular 2 to 4 C-atoms, alone or in mixtures, are used. 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroyl oxybenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate ( DOBA), whose formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benzene sulfonate (DECOBS), acylated polyhydric alcohols, in particular 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), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose, a cetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam.

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

R ¹

R ² -N ( ⁺ ) - (CR ⁴ R ⁵ ) -CN Xf)

in the R is -H, -CH ₃ , a C ₂ -24-alkyl or alkenyl radical, a substituted Ci_ ₂ 4-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 Alkenylarylrest with a C |. ₂₄ -alkyl group, or represents a substituted alkyl or Alkenylarylrest having at least one, preferably two, optionally substituted Ci_ 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 -0) _n H with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have the meaning given above for R, R ² or R ³ , where at least 2 of the radicals mentioned, in particular R ² and R ³ , also including the Nitrogen atom and optionally further heteroatoms may be linked to one another in a ring-closing manner and then preferably form a morpholino ring, and X ( ^- ) is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, the C 9-15 -alkylbenzenesulfonates, the Ci_ ₂ o-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, 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 , amine 2,2 ^{'-Bispyridyl-} triazole, 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, Ν, Ν, Ν ^' , Ν ^' - 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 g optionally substituted salene, porphins and porphyrins. 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 attached to a transition metal be chelate-bound or it may have two transition metal atoms asymmetrically or r | -0-verb zurück. 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. It is also possible to use binuclear complexes in which the two transition-metal central atoms have different oxidation numbers. If anion ligands are missing or the presence of anion ligands does not lead to charge balance in the complex, anionic counterparts in the transition metal complex compounds to be used according to the invention are anionic. present, which neutralize the cationic transition metal complex. 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 useful transition metal complex compounds are Mn (IV) ₂ ^ -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) methyl] -1,2-phenylenediamine] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] 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] manganese (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-0-0 Co (NH ₃ ) 5] Cl 4.

Suitable enzymes in the detergents 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 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 active ingredients in the compositions is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight.

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. Furthermore, brighteners of the type of substitution 4,4'-distyryl-diphenyl, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. For polyamide fibers are particularly well brighteners of the type of 1, 3-diaryl-2-pyrazolines, for example, 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similarly structured compounds. The content of the composition in optical brighteners or brightener mixtures is generally not more than 1% by weight, preferably 0.05% by weight to 0.5% by weight. In a preferred embodiment, the agent is free of such agents.

The customary foam regulators which can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein being preferably signed 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 cis-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 classes of compounds 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, not by itself resulting from the mixture of the other components of the pH, the agents systemic and environmentally friendly acids, especially 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 agents in tablet form, the procedure is preferably such that all components 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

Statistical polymers P1, P2 and P3 were prepared from the monomers diallyldimethylammonium chloride, acrylic acid and acrylamide (P1: molar ratio 1: 1: 1; P2: molar ratio 1: 2: 1; P3: molar ratio 6: 3: 58 were added in each case to 1 wt. % solution applied to cotton or polyester pads, the pads were dried and then challenged with the test bacteria Pseudomonas aeruginosa or Staphylococcus aureus by cultivating the test bacteria overnight on TSA agar medium and then with tryptone-NaCl from the agar plates The final dilution step was carried out in PBS buffer (1 ×) After incubation of the test microbial suspension on the test specimens, these were then rinsed repeatedly with buffer solution to wash off non-adherent test microbes the Textilprüflppchen adherent microorganisms was determined by the textile p Rüpflppchen in sterile tubes with PBS + 0.05% Tween 80 and glass beads were transferred to replace firmly adhering test germs. Subsequently, the lobes were placed in sterile Petri dishes, covered with Caso agar and incubated aerobically for 48 h at 37 ° C. In addition, a germ count of the shaking solution was carried out. In the table below, the amount of adhered microorganism is given as compared to the amount (100%) adhered to an untreated lobe under the same conditions.

It can be seen that the microorganisms have been bound to the treated lobules significantly less than to the untreated lobules.

Claims

claims

1. Use of polymers composed of the monomers of the general formulas (I), (II) and (III),

in which

R ¹ and R ⁴ independently of one another are H or linear or branched C ₁ -C ₆ -alkyl,

R ² and R ³ independently of one another represent linear or branched C ₁ -C ₆ -alkyl or

hydroxyalkyl,

R ^{5 is} H or CH ₃ ,

R ^{6 is} H or CC ₂ alkyl and

R ⁷ and R ⁸ independently of one another are H or C 1 -C ₈ -alkyl,

n and m for integers from 1 to 3 and

X ^" for a counterion

stand,

for the prevention of microbial colonization of textile surfaces.

2. Use of polymers composed of the monomers of the general formulas (I), (II) and (III),

(I)

in which

R ² and R ³ independently of one another represent linear or branched C 1 -C ₆ -alkyl or

hydroxyalkyl,

R ^{5 is} H or CH ₃ ,

R ^{6 is} H or dC ₂ alkyl and

R ⁷ and R ⁸ independently of one another are H or C 1 -C ⁸ -alkyl,

n and m for integers from 1 to 3 and

X ^" for a counterion

stand,

for preventing or reducing the adhesion of microorganisms to textiles.

Use according to claim 1 or 2, characterized in that the polymer is part of a detergent.

Use according to one of claims 1 to 3, characterized in that it is the colonization by bacteria, fungi and / or viruses.

Use according to any one of Claims 1 to 4, characterized in that a washing agent containing the polymer is allowed to act on a textile in the course of a machine or hand washing operation.

Use according to any one of claims 3 to 5, characterized in that the agent contains from 0.01% to 2% by weight, in particular from 0.05% to 1%, by weight of the polymer.

Use according to one of claims 1 to 6, characterized in that one uses an aqueous liquor containing 1 mg / l to 5000 mg / l, in particular 10 mg / l to 500 mg / l of the polymer.

8. Use according to one of claims 1 to 7, characterized in that the average molecular weight (weight average) of the polymer in the range of 200 g / mol to 500,000 g / mol, in particular from 500 g / mol to 100000 g / mol.

9. Use according to one of claims 1 to 8, characterized in that the monomer of the general formula (I) diallyldimethylammonium chloride, the monomer of the general formula (II) acrylic acid, and / or the monomer of the general formula (III) is acrylamide.

10. Use according to one of claims 1 to 9, characterized in that in the polymer, the molar ratio of monomer of formula (I) to monomer of formula (II) in the range of 1: 100 to 10: 1, in particular 10:25 to 4: 1, and / or the molar ratio of monomer according to formula (I) to monomer according to formula (III) in the range from 1: 200 to 10: 1, in particular from 1:10 to 4: 1.