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EP2727985A2 - Polymères pour équipement répulsif pour les allergènes - Google Patents

Polymères pour équipement répulsif pour les allergènes Download PDF

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Publication number
EP2727985A2
EP2727985A2 EP13190049.0A EP13190049A EP2727985A2 EP 2727985 A2 EP2727985 A2 EP 2727985A2 EP 13190049 A EP13190049 A EP 13190049A EP 2727985 A2 EP2727985 A2 EP 2727985A2
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EP
European Patent Office
Prior art keywords
vinylformamide
mol
cellulose
acid
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13190049.0A
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German (de)
English (en)
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EP2727985B1 (fr
EP2727985A3 (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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Publication of EP2727985A2 publication Critical patent/EP2727985A2/fr
Publication of EP2727985A3 publication Critical patent/EP2727985A3/fr
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Classifications

    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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

Definitions

  • the present invention relates to the use of certain polymers for allergenic repulsive 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 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.
  • mite allergens Another method for removing mite allergens from a household is the use of means to kill the mites.
  • 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.
  • mite killing agents may also be toxic or at least unpleasant to other organisms so that their use is not possible everywhere.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the invention relates to the use of polymers selected from polyvinylamine, poly-N-vinylformamide, the copolymers of vinylamine and N-vinylformamide, and cellulose derivatives obtainable by alkylation and optionally additional hydroxyalkylation of cellulose, and mixtures of two or more of this, for the allergen-repulsive finishing of textiles or hard household surfaces.
  • the average molecular weight (weight average) of the polyvinylamines, poly-N-vinylformamides and / or copolymers of vinylamine and N-vinylformamide used according to the invention is preferably in the range from 1000 g / mol to 1,000,000 g / mol, in particular from 5,000 g / mol to 500,000 g / mol and more preferably in the range of 10,000 g / mol to 400,000 g / mol.
  • the polymer is not completely composed of vinylamine monomers (corresponding to a fully hydrolyzed Poly-N-vinylformamide), it preferably has the monomers vinylamine and N-vinylformamide in molar ratios of 99: 1 to 80:20, in particular 98: 2 to 93: 7.
  • Polymerization products of N-vinylformamide and fully or partially hydrolyzed derivatives thereof are commercially available, for example, under the trade name Lupamin®.
  • Cellulose derivatives which are preferred according to the invention are those in which the cellulose is alkylated with C 1 to C 10 groups, in particular C 1 to C 3 groups and particularly preferably with methyl groups. You can, if desired, additionally C 2 - to C 10 -hydroxyalkyl, especially C 2 - to C 3 hydroxyalkyl groups, carry. They can be obtained in a known manner by reaction of cellulose with appropriate alkylating agents, for example alkyl halides or alkyl sulfates, and, if desired, subsequent reaction with corresponding alkylene oxides, such as, for example, ethylene oxide and / or propylene oxide.
  • appropriate alkylating agents for example alkyl halides or alkyl sulfates
  • alkylene oxides such as, for example, ethylene oxide and / or propylene oxide.
  • averaged in the cellulose derivative are 1 to 2.5, in particular 1.2 to 2, alkyl groups and, if present, 0.2 to 1.5, in particular 0 to 5, hydroxyalkyl groups per anhydroglucose monomer unit.
  • the average molecular weight (weight average) of the cellulose derivatives used according to the invention is preferably in the range from 1000 g / mol to 1,000,000 g / mol, in particular from 5,000 g / mol to 500,000 g / mol and particularly preferably in the range from 10,000 g / mol to 150,000 g / mol.
  • the determination of the degree of polymerization or of the molecular weight of the soil release-capable cellulose derivative is based on the determination of the limiting viscosity number of sufficiently dilute aqueous solutions by means of an Ubbelohde capillary viscometer (capillary 0c). Using a constant [H. Staudinger and F. Reinecke, “On Molecular Weight Determination on Cellulose Ethers", Liebigs Annalen der Chemie 535, 47 (1938)] and a Correction Factor [F.
  • 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 reduced binding effect against allergens, that is, allergens that subsequently reach the textile, are held there only to a very limited extent, so that they can not come into skin contact with the allergic person, for example when wearing the textile , This reduces the risk of allergy to the wearer of the textile.
  • 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. This ensures that allergens can only settle on the hard surface to a very limited extent.
  • Another object of the invention is therefore the use of detergents or cleaners containing a named polymer for allergen-repulsive finishing of textiles or hard household surfaces.
  • a preferred subject of the invention is therefore the use of the polymers and the agents containing them for the allergen-repulsive 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 may be in the form of particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may in principle contain, in addition to the polymer used according to the invention, all known ingredients customary in such agents.
  • 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 and 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.
  • N-alkyl-amines vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl part, as well as 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), Ethylenediamin tetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-di-phosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)
  • 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.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • terpolymers which contain, as monomers, two unsaturated acids and / or salts thereof and, as the 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.
  • 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.
  • 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.
  • 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. 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • water-soluble inorganic builder materials may be included.
  • 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 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.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • 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.
  • 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.
  • 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.
  • Alkali silicates may be present in amounts of up to 30% by weight. to be included in the total amount.
  • 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.
  • carbonate and bicarbonate preferably sodium carbonate and bicarbonate
  • 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.
  • 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 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. 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.
  • 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.
  • 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.
  • 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 phenolsulfonates or - carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), their formal carbonic ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy
  • 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
  • transition metal complexes 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)) - (2-pyridyl
  • 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 ⁇ 1 -O-bridge.
  • the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands.
  • anion ligands 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.
  • 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 anionic ligands are missing or the presence of anionic ligands does not lead to charge balance in the complex, anionic counterions are present in the transition metal complex compounds to be used according to the invention present, 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-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'-
  • 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 graying inhibitors or soil release agents are cellulose ethers such as carboxymethyl cellulose and methyl carboxymethyl cellulose. Preferably, sodium carboxymethyl cellulose is 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 .-%.
  • detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • 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.
  • brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl.
  • 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.
  • 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 of the invention, 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a process comprising an extrusion step is preferred.
  • 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.
  • 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.
  • Lupamin® 1595 is a copolymer of 95 mole% vinylamine and 5 mole% N-vinylformamide; Mw 15,000.
  • Lupamin® 9095 is a copolymer of 95 mole% vinylamine and 5 mole% N-vinylformamide; Mw 340,000.
  • Methocel® A40M is a medium substitution grade methylcellulose of 1.8 (viscosity 40,000 mPa.s in 2% aqueous solution at 20 ° C)
  • Methocel® J5MS is a hydroxypropylmethylcellulose with a mean degree of methoxylation of 1.3 and average hydroxypropylation degree of 0.82 (viscosity 5,000 mPa.s in 2% aqueous solution at 20 ° C).

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  • 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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP13190049.0A 2012-10-31 2013-10-24 Polymères pour équipement répulsif pour les allergènes Active EP2727985B1 (fr)

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DE201210219954 DE102012219954A1 (de) 2012-10-31 2012-10-31 Polymere zur allergen-repulsiven Ausrüstung

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EP2727985A2 true EP2727985A2 (fr) 2014-05-07
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2300122A (en) 1995-04-25 1996-10-30 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
CA2329296A1 (fr) 1999-12-22 2001-06-22 The Clorox Company Methode pour immobiliser les allergenes
WO2002028187A1 (fr) 2000-09-29 2002-04-11 The Procter & Gamble Company Compositions de neutralisation d'allergene
WO2002028179A1 (fr) 2000-09-29 2002-04-11 The Procter & Gamble Company Compositions de neutralisation d'allergenes
US20020176854A1 (en) 2001-05-25 2002-11-28 Payton Hugh W. Method for reducing allergenicity in indoor spaces
WO2003006030A1 (fr) 2001-07-11 2003-01-23 Smith C Steven Nouvelle composition et procede de modification de proteine allergene dans l'environnement
WO2004007658A2 (fr) 2002-07-10 2004-01-22 Kimberly-Clark Worldwide, Inc. Tampon de nettoyage pour le controle et l'elimination d'allergenes
EP1550705A1 (fr) 2002-07-03 2005-07-06 Kao Corporation Inactivateur d'allergenes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO802143L (no) * 1979-09-14 1981-03-16 Charles Edward Johnson Preparat og fremgangsmaate for bekjempelse av stoev-allergener
WO2005066410A1 (fr) * 2004-01-07 2005-07-21 Sekisui Chemical Co., Ltd. Suppresseur d'allergene, fibre traitee de suppression d'allergene et procede de production correspondant
JP4953582B2 (ja) * 2005-03-25 2012-06-13 フマキラー株式会社 ハウスダスト処理剤

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Publication number Priority date Publication date Assignee Title
GB2300122A (en) 1995-04-25 1996-10-30 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
CA2329296A1 (fr) 1999-12-22 2001-06-22 The Clorox Company Methode pour immobiliser les allergenes
WO2002028187A1 (fr) 2000-09-29 2002-04-11 The Procter & Gamble Company Compositions de neutralisation d'allergene
WO2002028179A1 (fr) 2000-09-29 2002-04-11 The Procter & Gamble Company Compositions de neutralisation d'allergenes
US20020176854A1 (en) 2001-05-25 2002-11-28 Payton Hugh W. Method for reducing allergenicity in indoor spaces
WO2003006030A1 (fr) 2001-07-11 2003-01-23 Smith C Steven Nouvelle composition et procede de modification de proteine allergene dans l'environnement
EP1550705A1 (fr) 2002-07-03 2005-07-06 Kao Corporation Inactivateur d'allergenes
WO2004007658A2 (fr) 2002-07-10 2004-01-22 Kimberly-Clark Worldwide, Inc. Tampon de nettoyage pour le controle et l'elimination d'allergenes

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Title
F. RODRIGUEZ; L. A.GOETTLER: "The Flow of Moderately Concentrated Polymer Solutions in Water", TRANSACTIONS OF THE SOCIETY OF RHEOLOGY, vol. VIII, 1964, pages 3 17
H. STAUDINGER; F. REINECKE: "Über Molekulargewichtsbestimmung an Celluloseethern", LIEBIGS ANNALEN DER CHEMIE, vol. 535, 1938, pages 47

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EP2727985A3 (fr) 2017-08-23
DE102012219954A1 (de) 2014-04-30

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