EP2727986B1 - Polymères pour équipement adhésif pour les allergènes - Google Patents

Polymères pour équipement adhésif pour les allergènes Download PDF

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Publication number
EP2727986B1
EP2727986B1 EP13190046.6A EP13190046A EP2727986B1 EP 2727986 B1 EP2727986 B1 EP 2727986B1 EP 13190046 A EP13190046 A EP 13190046A EP 2727986 B1 EP2727986 B1 EP 2727986B1
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weight
acid
allergen
agents
mol
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German (de)
English (en)
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EP2727986A3 (fr
EP2727986A2 (fr
Inventor
Roland Breves
Rainer Simmering
Mirko Weide
Noelle Wrubbel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to the use of certain polymers for the allergen-adhesive finishing of textiles or hard household surfaces.
  • Sensitivity to allergens is a problem for an increasing number of people, which has been made more difficult in recent years by the increased incidence of asthma. Asthma sufferers are particularly sensitive to allergens in the air.
  • Allergens lead to an excessive immune reaction in the human or animal body. Allergy reactions occur when allergens come into contact with the human organism in particular and can be caused in various ways, in particular through inhalation of allergens in the air or through 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 lies in bed and comes into contact with allergenic dust that is on the pillow or duvet and is absorbed into the person's eyes, for example. This usually leads to an allergy reaction as the allergens are gradually absorbed into the mucous membranes around the eye.
  • allergens are protein-based molecules that can come from many different sources, with dust mites being one of the most common sources of allergens in homes. House dust mites thrive in carpets, upholstered furniture, bedspreads, furniture covers, curtains and the like, but also in clothing. Health professionals who specialize in the treatment of allergies often recommend removing these items from the homes of people with house dust allergies. However, this is often an impractical and impractical solution to the problem of house dust allergies.
  • mite killing agents Another way to remove mite allergens from a household is to use mite killing agents.
  • the proteins that cause the allergy reactions are also found in the bodies of dead mites and in remaining feces of the mites, so killing the mites does not solve the problem.
  • Mites killers can also be toxic or at least unpleasant for other organisms, so that their use is not possible everywhere.
  • pollen A growing number of people are allergic to pollen, the pollen from 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 and dock are particularly often responsible for allergic reactions and ambrosia.
  • One method of neutralizing allergens in the home involves spraying surfaces with compositions that either denature or simply mask the allergens.
  • the denaturing sprays are intended to render the protein molecules inactive with regard to 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 person.
  • Sprays can also be used to cover or capture allergens or allergen-containing particles. The covered allergens become too heavy to float in the air and therefore sink to the ground and cannot be inhaled or otherwise come into contact with the human body, and thus do not cause an allergy reaction.
  • these two approaches have so far not proven entirely satisfactory for allergy sufferers.
  • Allergen neutralization sprays usually contain a tannin or a related polyphenol as an active ingredient. These are known for their strong yellow color, so they cannot be sprayed onto textile surfaces without the considerable risk of staining. Materials used to cover or enclose 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, resulting in surfaces that are sticky to the touch after they have settled. This is particularly undesirable for duvets and pillows, for example. In addition, spraying a surface with a sticky material tends to attract dust and other airborne particles to the surface, causing the surface to become dirty more quickly.
  • 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 Starch, polyvinyl alcohol, carboxymethyl cellulose, polyacrylic acids, polyethylene glycols with molecular weights above 5000, polyethylene, polypropylene glycols with molecular weights above 8000, the polyquaternium compounds 1 to 14 and polyvinylpyrrolidone are known as allergen-neutralizing agents.
  • the international patent application WO 02/28187 A1 discloses agents that contain allergen-neutralizing metal ions such as Zn, Sn, Mg, Ca, Mn, Ti, Fe, Co and / or Ni and, in addition, optionally polyphenol compounds, hydrogen peroxide, salicylic acid, citric acid, lactic acid, glycolic acid, ascorbic acid, gallic acid and / or gluconic acid contain.
  • allergen-neutralizing metal ions such as Zn, Sn, Mg, Ca, Mn, Ti, Fe, Co and / or Ni
  • hydrogen peroxide hydrogen peroxide
  • salicylic acid citric acid
  • lactic acid glycolic acid
  • ascorbic acid ascorbic acid
  • gallic acid gallic acid and / or gluconic acid contain
  • the European patent application EP 1 550 705 relates to agents containing allergen-neutralizing polysaccharide derivatives.
  • the patent application US 2002/0176854 A1 discloses the allergen-protein-cleaving effect of proteases of the subtilisin type.
  • the patent application GB 2 300 122 A discloses a means for covering and enclosing dust mite allergens that includes polysaccharide. From the European patent application EP 1 703 014 A1 allergen-suppressing agents in combination with hydrophilic polymers such as polyvinylpyrrolidone are known.
  • the patent application CA 2 329 296 discloses liquid allergen immobilizing compositions containing water soluble polymers such as (co) polymers of vinyl pyrrolidone, sprayed onto tissue where solvent and water evaporate.
  • the invention relates to the use of polymers selected from N-vinylimidazole-N-vinylpyrrolidone copolymers with the monomers N-vinylamine and N-vinypyrrolidone in molar ratios in the range from 50:50 to 1:99, for the allergen-adhesive finishing of textiles or hard household surfaces.
  • the mean molecular weight (weight average) of the polymers used according to the invention is preferably in the range from 1,000 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-vinypyrrolidone in molar ratios in the range from 30:70 to 2:98.
  • the polymers mentioned are particularly effective against the allergens associated with pollen, especially birch pollen, but also other common allergens such as those from mites, especially house dust mites, cockroaches and molds, animal hair and dander from cats or dogs and the like, and / or fungal spores .
  • the use according to the invention can preferably be implemented in such a way that a detergent which contains a named polymer is allowed to act on a textile in the context of a washing process carried out by machine or by hand. After rinsing and drying, the textile has a binding effect on allergens, i.e. allergens that have subsequently reached the textile are only released to a very small extent even under mechanical stress, such as occurs when the textile is worn, for example. This reduces the risk of allergies for the wearer of the textile and for people in the vicinity.
  • the use according to the invention can analogously also be realized in such a way that a cleaning agent which contains a named polymer is allowed to act on a hard surface in the course of a cleaning process carried out by machine or by hand.
  • the invention therefore also relates to the use of detergents or cleaning agents which contain a named polymer for the allergen-adhesive finishing of textiles or hard household surfaces.
  • the allergen-adhesive effect of the polymers mentioned and of the agents containing them is particularly pronounced when treating textiles at least partially made of cotton.
  • 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 made of cotton or containing 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 ingredient mentioned, in addition to the usual compatible ones Ingredients.
  • These agents which in particular can be in the form of pulverulent solids, in redensified particle form, as homogeneous solutions or as suspensions or dispersions, can in principle include, apart from the polymer used according to the invention, all known agents and agents contain usual ingredients.
  • the detergents and cleaning agents can in particular 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, color transfer inhibitors, foam regulators and dyes and fragrances , contain.
  • the agents can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof.
  • Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Soaps that can be used are preferably the alkali salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the sulfate-type surfactants which can be used include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the sulfonate-type surfactants that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed when corresponding monoolefins are reacted with sulfur trioxide, as well as alpha-sulfo fatty acid esters, which are formed during the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are contained in cleaning or washing agents in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while disinfectants and detergents for cleaning dishes are preferred 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight of 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 glycine diacetic acid, methylglycine diacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamin-N, N'-disuccinic acid, ethylenediamine-N, n'-disuccinic acid, and especially methyl-phosphonosuccinic acid, and especially poly-phospho-phosuccinic acid, and, in particular, poly-phospho-phosphonosuccinic acid, and also aminotra-phosphonosuccinic acid, and, in particular, poly-phosphonosuccinic acid.
  • the relative average molecular weight (here and below: 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, based in each case 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, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • the acid makes up at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as a third monomer can also be used as water-soluble organic builder substances.
  • 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, maleic acid being particularly preferred.
  • the third monomeric unit is formed by vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C 1 -C 4 carboxylic acids, with vinyl alcohol are particularly preferred.
  • Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and also 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, vinyl alcohol and / or vinyl acetate.
  • 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, are very particularly preferred , 5: 1. 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 40% by weight to 60% by weight, in particular 45 to 55% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight %, preferably 15% by weight to 25% by weight methallyl sulfonic acid or methallyl sulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Especially sucrose is preferred.
  • 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 acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used, in particular for the production 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 salts.
  • Such organic builder substances can, if desired, 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 upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.
  • Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate.
  • the water-insoluble inorganic builder materials used are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts from 5% by weight to 15% by weight. -% used.
  • the crystalline sodium aluminosilicates in detergent quality in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a particle size greater than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size less than 10 ⁇ m.
  • Their calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.
  • water-soluble inorganic builder materials can be contained.
  • polyphosphates such as sodium triphosphate
  • these include in particular the water-soluble crystalline and / or amorphous alkali silicate builders.
  • Such water-soluble inorganic builder materials are contained in the agents preferably in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight.
  • the alkali metal silicates which can be used as builder materials preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 y H 2 O, in which x, the so-called module, is a number 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 sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disitics are preferred.
  • Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, which are produced from amorphous alkali silicates, can also be used in the agents.
  • a crystalline layered sodium silicate with a module of 2 to 3, as can be produced from sand and soda is used.
  • Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment.
  • 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 lower alkaline and contain the usual alkali carriers such as alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 30 wt. %, based on the total agent, be included
  • the use of the highly alkaline metasilicates as alkali carriers is preferably not used at all.
  • the alkali carrier system preferably used in the agents is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight.
  • the ratio of carbonate used and hydrogen carbonate used varies depending on which pH value is ultimately desired, but an excess of sodium hydrogen carbonate is usually used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.
  • water-soluble organic builders in particular alkali citrate, 5% by weight to 15% by weight alkali metal carbonate and 20% by weight to 40 wt .-% alkali disilicate contain.
  • Suitable bleaching agents are those based on chlorine, such as, in particular, alkali hypochlorite, dichloroisocyanuric acid, trichloroisocyanuric acid and their salts, as well as those based on peroxygen.
  • Suitable peroxygen compounds include, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecanedioic acid, as well as their salts such as magnesium monoperoxyphthalate, hydrogen peroxide and, under the cleaning conditions, hydrogen peroxide-releasing inorganic salts, or peroxide and peroxide peroxide, such as perborate, Inclusion compounds, such as H 2 O 2 urea adducts, are considered. Hydrogen peroxide can also be used with the help of an enzymatic system, i.e. an oxidase and its substrate, be generated.
  • organic peracids or peracid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecanedioic acid, as well as their salts such as magnesium monoperoxyphthalate, hydrogen
  • solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated 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 agents containing them, which in principle can contain all conventional detergent, cleaning or disinfecting agent components.
  • Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight hydrogen peroxide are particularly preferably used.
  • a detergent or cleaning agent contains peroxygen compounds, these are preferably used in amounts of up to 25% by weight, in particular from 1% by weight to 20% by weight and particularly preferably from 7% by weight to 20% by weight. % present, while disinfectants preferably contain from 0.5% by weight to 40% by weight, in particular from 5% by weight to 20% by weight, of peroxygen compounds.
  • 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- are preferred Acylimides, especially N-nonanoyl succinimide (NOSI), acylated phenol sulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroyloxybenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate (DOBA), their formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) ), acy
  • bleach-activating compounds such as, for example, nitriles, from which perimidic acids are formed under perhydrolysis conditions.
  • nitriles include in particular aminoacetonitrile derivatives with a quaternized nitrogen atom according to the formula in which R 1 stands for -H, -CH 3 , a C 2-24 -alkyl or -alkenyl radical, a substituted C 1-24 -alkyl or C 2-24 -alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN and -N (+) -CH 2 -CN, an alkyl or alkenylaryl radical with a C 1-24 -alkyl group, or for a substituted alkyl or alkenylaryl radical with at least one, preferably two, optionally substituted C 1-24 -alkyl group (s)
  • transition metal complexes are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes.
  • Both inorganic and organic compounds can be used as ligands in such transition metal complexes, including, in addition to carboxylates, especially compounds with 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-pyridine, pyridazine,
  • 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 monodentate or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO 2 ) - group, i.e. a nitro ligand or a nitrito ligand.
  • the (NO 2 ) - group can also be bound to a transition metal in a chelating manner, or it can bridge two transition metal atoms asymmetrically or ⁇ 1 -O-.
  • the transition metal complexes can also carry further ligands, as a rule of a simpler structure, in particular monovalent or polyvalent anion ligands.
  • ligands for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate are possible.
  • the anion ligands are intended to balance the charge between the central transition metal atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible.
  • Such ligands in particular can also have a bridging effect, so that polynuclear complexes are formed.
  • both metal atoms in the complex do not have to be the same. It is also possible to use binuclear complexes in which the two central transition metal atoms have different oxidation numbers. If anion ligands are absent or the presence of anion ligands does not lead to a charge equalization in the complex, anionic counterions are present in the transition metal complex compounds to be used according to the invention, which neutralize the cationic transition metal complex.
  • 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.
  • transition metal complex compounds that can be used 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-nitrophenyl) 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-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl)
  • the enzymes that may be contained in the detergents or cleaning agents are in particular those from the class of 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% by weight to 1.5% by weight, in particular 0.5% by weight to 1% by weight.
  • the enzymes can be adsorbed on carrier substances in the usual way and / or embedded in coating substances or incorporated as concentrated liquid formulations which are as water-free as possible.
  • Suitable graying inhibitors or soil release active ingredients are cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers such as methyl hydroxyethyl cellulose, methylhydroxypropyl cellulose and methyl carboxymethyl cellulose. Sodium carboxymethyl cellulose and mixtures thereof with methyl cellulose are preferably used.
  • the soil release active ingredients usually used include copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
  • the proportion of graying inhibitors and / or soil release active ingredients in the agents is generally not more than 2% by weight and is preferably 0.5% by weight to 1.5% by weight.
  • detergents can contain, for example, derivatives of diaminostilbene disulfonic acid or its alkali metal salts.
  • diaminostilbene disulfonic acid or its alkali metal salts.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or similarly structured compounds are suitable instead of the morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • brighteners of the substituted 4,4'-distyryl-diphenyl type can be present, for example 4,4'-bis- (4-chloro-3-sulfostyryl) -diphenyl. Mixtures of brighteners can also be used.
  • Brighteners of the 1,3-diaryl-2-pyrazoline type for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and similarly structured compounds are particularly suitable for polyamide fibers.
  • the content of optical brighteners or brightener mixtures in the agent 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 from such active ingredients.
  • the customary foam regulators that can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanized or otherwise hydrophobized.
  • the polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof.
  • Further defoamers are paraffinic hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps with in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali salts of phosphoric acid mono- and / or dialkyl esters in which the alkyl chains each have 12 to 22 carbon atoms.
  • sodium monoalkyl phosphate and / or dialkyl phosphate having C 16 to C 18 alkyl groups is preferably used.
  • the proportion of foam regulators can preferably be 0.2% by weight to 2% by weight.
  • the agents can contain water as a solvent.
  • the organic solvents that can be used in the agents include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, as well as their Gemisehe and the ethers which can be derived from said classes of compounds.
  • Such water-miscible solvents are present in the agents in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight.
  • the agents can use acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
  • acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
  • Such pH regulators are preferably not contained above 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • Agents in the form of aqueous solutions or solutions containing other customary solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the agents are preferably in the form of pulverulent, granular or tablet-shaped preparations which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally stressable components and admixing the more sensitive components, to which in particular enzymes, bleaches and bleach-activating agents Active ingredients can be expected to be produced.
  • a method comprising an extrusion step is preferred.
  • a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (9)

  1. Utilisation de polymères choisis parmi les copolymères N-vinylimidazole-N-vinylpyrrolidone comportant les monomères N-vinylamine et N-vinypyrrolidone dans des rapports molaires dans la plage allant de 50:50 à 1:99, pour l'apprêt, adhésif pour les allergènes, de textiles ou de surfaces domestiques dures.
  2. Utilisation de polymères choisis parmi les copolymères N-vinylimidazole-N-vinylpyrrolidone comportant les monomères N-vinylamine et N-vinypyrrolidone dans des rapports molaires dans la plage allant de 50:50 à 1:99, pour l'apprêt, adhésif pour les allergènes, de textiles composés de coton ou contenant du coton.
  3. Utilisation d'agents détergents ou nettoyants contenant un polymère choisi parmi les copolymères de N-vinylimidazole-N-vinylpyrrolidone comportant les monomères N-vinylamine et N-vinypyrrolidone dans des rapports molaires dans la plage allant de 50:50 à 1:99, pour l'apprêt, adhésif pour les allergènes, de textiles ou de surfaces domestiques dures.
  4. Utilisation selon la revendication 1 ou 2, caractérisée en ce que l'on laisse agir, sur un textile, un agent détergent contenant le polymère, dans le cadre d'une opération de lavage en machine ou à la main, ou en ce que l'on laisse agir, sur une surface dure, un agent nettoyant contenant le polymère, dans le cadre d'une opération de nettoyage en machine ou à la main.
  5. Utilisation selon l'une des revendications 3 à 4, caractérisée en ce que l'agent contient 0,001 à 10 % en poids, en particulier 0,1 à 1 % en poids de la substance active polymère.
  6. Utilisation selon l'une des revendications 3 à 5, caractérisée en ce que l'agent contient en outre des adjuvants, des tensioactifs, des agents de blanchiment, des activateurs et des catalyseurs de blanchiment, des solvants organiques miscibles à l'eau, des enzymes, des agents séquestrants, des électrolytes, des régulateurs de pH ou d'autres excipients.
  7. Utilisation selon l'une des revendications 1 à 6, caractérisée en ce que la masse molaire moyenne (moyenne en poids) du polymère est située dans la plage allant de 1 000 g/mol à 1 000 000 g/mol, en particulier de 2 000 g/mol à 500 000 g/mol.
  8. Utilisation selon l'une des revendications 1 à 7, caractérisée en ce que le polymère est un copolymère de N-vinylimidazole-N-vinylpyrrolidone comportant les monomères N-vinylamine et N-vinypyrrolidone dans des rapports molaires dans la plage allant de 30:70 à 2:98.
  9. Utilisation selon l'une des revendications 1 à 8, caractérisée en ce que les allergènes sont liés à des pollens, en particulier à des pollens de bouleau, ou à des acariens, à des cafards, à des poils d'animaux et/ou à des spores fongiques.
EP13190046.6A 2012-10-31 2013-10-24 Polymères pour équipement adhésif pour les allergènes Active EP2727986B1 (fr)

Applications Claiming Priority (1)

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DE102012219948.9A DE102012219948A1 (de) 2012-10-31 2012-10-31 Polymere zur allergen-adhäsiven Ausrüstung

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EP2727986A2 EP2727986A2 (fr) 2014-05-07
EP2727986A3 EP2727986A3 (fr) 2017-08-16
EP2727986B1 true EP2727986B1 (fr) 2021-01-13

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CN111117795A (zh) * 2019-12-31 2020-05-08 长沙如洋环保科技有限公司 一种杀菌除螨的环保浓缩型洗衣液及其制备方法

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GB9508409D0 (en) 1995-04-25 1995-06-14 Sinclair Animal & Household Ca House dust mite allergen control
WO1999015206A1 (fr) 1997-09-23 1999-04-01 Megabios Corporation Procedes de preparation de complexes de transfection lipidiques/polynucleotidiques
US6013139A (en) 1999-04-19 2000-01-11 Tarkinson; Edward G. Method of cleaning carpets
US6627591B2 (en) * 1999-12-17 2003-09-30 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Dye fixing composition
CA2329296A1 (fr) 1999-12-22 2001-06-22 The Clorox Company Methode pour immobiliser les allergenes
WO2002028179A1 (fr) 2000-09-29 2002-04-11 The Procter & Gamble Company Compositions de neutralisation d'allergenes
JP2004510717A (ja) 2000-09-29 2004-04-08 ザ　プロクター　アンド　ギャンブル　カンパニー アレルゲン中和組成物
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EP1550705B1 (fr) 2002-07-03 2015-09-09 Kao Corporation Inactivateur d'allergenes
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EP2727986A3 (fr) 2017-08-16
EP2727986A2 (fr) 2014-05-07
DE102012219948A1 (de) 2014-04-30

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