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
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds

Definitions

• the present invention relates to the use of a combination of fragrance capsules and certain acylhydrazones in detergents in the washing of textiles to improve the long-lasting scent of textiles, as well as detergents containing such a combination.
• fragrance capsules which attract to the laundry during the washing process.
• a first subject of the invention is therefore the use of a combination of fragrance capsules with an acylhydrazone of the general formula (I) in the R 1 is a CF 3 or a C 1-28 -alkyl, C 2-28 -alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 -cycloalkenyl- , phenyl, naphthyl, C 7-9 aralkyl, C 3-20 heteroalkyl, or C 3-12 -Cy C loheteroalkyl distr, R 2 and R 3 independently represent hydrogen or an optionally substituted C 1-28 alkyl C 2-28 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3-28 heteroalkyl, C 3-12 -cycloheteroalkyl, C 5-16 -heteroaralkyl, phenyl, nap
• Another object of the invention are detergents containing a peroxygen bleaching agent and a combination of fragrance capsules and a compound of formula (I).
• Yet another aspect of the invention relates to a process for washing textiles in which an agent according to the invention is used.
• At least one refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the nature of the ingredient.
• at least one anionic surfactant means, for example, one or more different anionic surfactants, i. one or more different types of anionic surfactants. Together with quantities, the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.
• the detergents described herein may be detergents for textiles or natural fibers.
• Detergents in the context of the invention also include washing aids which are metered into the actual detergent during manual or automatic textile washing in order to achieve a further effect or to enhance an effect.
• laundry detergents within the scope of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example for dissolving stubborn soiling, and also agents which are in a downstream of the actual textile laundry step the laundry more desirable features such as give a comfortable grip, crease resistance or low static charge.
• the fabric softeners are calculated.
• acylhydrazones of formula (I) may be in E or Z configuration; when R 2 is hydrogen, the compound of general formula (I) may be in one of its tautomeric forms or as a mixture of these.
• R 2 is preferably hydrogen.
• R 1 and / or R 3 is preferably an electron-withdrawing group-substituted methyl, phenyl or naphthyl group.
• R 4 is preferably hydrogen.
• an electron-withdrawing group is preferably an ammonium group in question, which optionally carries alkyl or hydroxyalkyl groups or is formed with the inclusion of the N-atom carrying an alkyl group as heterocycloalkyl optionally carrying further heteroatoms.
• the anion A - is preferably a carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, bromide, bicarbonate or carbonate, wherein in polyvalent anions, the charge balance can be achieved by the presence of additional cations such as sodium or ammonium ions.
• a carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphat
• the performance of compounds of general formula (I) may optionally be controlled by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II) - (III) - (IV) - (V), Cu ( I) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Ti (II) - (III) - (IV), and particularly preferably those selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III ), Fe (I) - (II) - (III) - (IV) and Co (I) - (II) - (III);
• the acylhydrazone can also be used in the form of complex compounds of said metal central atoms with ligands of general formula (I
• a bleach-enhancing complex which has a ligand with a skeleton of the formula (I) may have the corresponding ligand once or more than once, in particular twice. It may be one or possibly two or more nuclear. It may also contain other neutral, anion or cationic ligands such as H 2 O NH 3 , CH 3 OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C 2-18 carboxylate C 1-18 -alkyl sulfate, especially methosulfate, or a corresponding alkanesulfonate, inorganic anions such as halide, in particular chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, bisulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.
• fragrances By “encapsulated fragrances”, “fragrance capsules” or “encapsulated perfume” are meant in the context of the invention preferably fragrances, which are encapsulated in microcapsules.
• the microcapsules which can be used according to the invention may preferably be water-soluble and / or water-insoluble microcapsules. Preferably, however, they are water-insoluble microcapsules.
• the water insolubility of the microcapsules has the advantage that this allows a washing application lasting outward separation of active ingredients can be made, and that an active ingredient release can be made only after the washing application.
• the microcapsules usable according to the invention are water-insoluble microcapsules, the wall material of the microcapsules being polyurethanes, polyolefins, polyamides, polyesters, polysaccharides, epoxy resins, silicone resins and / or polycondensation products of carbonyl compounds and compounds containing NH groups includes.
• the water-insoluble microcapsules are drivable.
• drittable microcapsules means those microcapsules which by mechanical rubbing or by pressure, as e.g. when the hands are dried with a towel, can be opened or wiped so that a release of content results only as a result of a mechanical action, for example, when one dries hands with a towel on which such microcapsules are deposited.
• Preferred microcapsules which can be used according to the invention have average diameters in the range from 0.05 to 500 ⁇ m, preferably between 5 and 150 ⁇ m, in particular between 10 and 100 ⁇ m, e.g. 10-80 ⁇ m.
• the shell of the microcapsules surrounding the core or (filled) cavity has an average thickness in the range between advantageously about 0.01 and 50 ⁇ m, preferably between about 0.1 ⁇ m and about 30 ⁇ m, in particular between about 0.5 ⁇ m and about 8 ⁇ m.
• microcapsules which have the aforementioned diameter and shell thickness, are drivable in the context of the invention.
• microcapsule preparation as such is well known to those skilled in the art. Suitable methods for producing microcapsules are familiar to the person skilled in the art and are described, for example, in US Pat US 3,870,52 , in US 3,516,941 , in US 3,415,758 or in EP 0 026 914 A1 described. The latter describes, for example, the production of microcapsules by acid-induced condensation of melamine-formaldehyde precondensates and / or their C1-C4-alkyl ethers in water, in which the hydrophobic material forming the capsule core is dispersed, in the presence of a protective colloid.
• melamine-urea-formaldehyde microcapsules or melamine-formaldehyde microcapsules or urea-formaldehyde microcapsules can be used, for example obtainable from 3M Corporation or BASF. Suitable microcapsules are also in WO 2001/049817 A2 described.
• the water-insoluble microcapsules usable according to the invention in particular the e.g. Aminoplast capsules, during the normal washing process, apply it very well to the textile. After the washing process, these capsules then usually have a certain brittleness, so that a targeted release of fragrance from the capsule can take place by the action of mechanical force, e.g. while rubbing the skin with a towel which has been washed with a suitable detergent or cleaner. In this way, even after prolonged storage of the laundry targeted a fragrance can be caused. The consumer is enabled to produce specific fragrances.
• At least one, preferably two or more fragrances are encapsulated in the fragrance capsules. It can be used as fragrances but also natural fragrance mixtures.
• the present invention is not limited with regard to the choice of fragrances, it is possible to use all customary fragrances and fragrance mixtures which are available in microcapsule form. In this respect, the following list of exemplary fragrances and fragrance mixtures is to be understood as exemplary only and not as a limitation.
• Natural perfume mixtures as available from plant sources include, but are not limited to, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
• perfume mixtures are essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, champa blossom oil, fir oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil , Cajuput oil, calamus oil, camomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, copaiba balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk kernel oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, oregano oil , Palmarosa oil, Patchoul
• fragrance aldehydes such as, for example, adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropylphenyl) -2-methylpropanal), ethylvanillin, florhydral ( 3- (3-isopropylphenyl) butanal]), helional (3- (3,4-methylenedioxyphenyl) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy-4-methylpentyl) 3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3- (4-tert-butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenealdehyde, vanillin, 2,6,
• Suitable perfume ketones include, but are not limited to, methyl-betanaphthyl ketone, muskedanone-1-one (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one).
• fragrances include but are not limited to: ambrettolide, ambroxan, anethole, anisalcohol, anisole, methyl anthranilate, ethyl benzoate, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, Boisambrene forte, ⁇ -bromostyrene, eugenol, eugenol methyl ether , Eucalyptol, farnesol, fenchyl acetate, geranyl acetate, geranyl formate, heptincarboxylic acid methyl ester, hydroquinone dimethyl ether, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, camphor, Karvakrol, Karvon, p-
• fragrances are diphenyloxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl-n-heptenone, pinene, terpinyl acetate, citral, citronellal.
• the detergents described in the context of the use according to the invention usually contain the encapsulated fragrances in amounts of between 0.001-0.5% by weight, preferably 0.05-0.15% by weight, in each case based on the total agent.
• the agents may additionally contain non-encapsulated fragrances or perfume mixtures.
• the level of fragrance contained, which are not encapsulated is typically between 0.001-5.0 weight percent, preferably 0.05-0.5 weight percent, based on the total agent.
• the concentration of the compound of the formula (I) in an aqueous liquor, as used, for example, in washing machines is 0.5 ⁇ mol / l to 500 ⁇ mol / l, in particular 5 ⁇ mol / l to 100 ⁇ mol / l ,
• the above-mentioned complex-forming metal ions are preferably not intentionally added, but they may be present from possible sources of such metal ions, which include, in particular, the tap water, the washing machine itself, adhesions to textiles, and stains on the fabrics.
• metal ions inadvertently introduced with other detergent ingredients may also be considered.
• Preferred peroxygen concentrations (calculated as H 2 O 2 ) in the liquor are in the range from 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l and particularly preferably from 0.2 g / l to 0.5 g / l.
• the use according to the invention is preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 20 ° C. to 40 ° C., and particularly preferably at temperatures below 30 ° C.
• the water hardness of the water used for preparing the aqueous liquor is preferably in the range from 0 ° dH to 21 ° dH, in particular 0 ° dH to 3 ° dH.
• the water hardness is preferably in the range of 0 ° dH to 16 ° dH, in particular 0 ° dH to 3 ° dH, which can be achieved for example by the use of conventional builder materials or water softeners.
• the use according to the invention is preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.
• the use according to the invention is preferably carried out by allowing a peroxygen compound and a detergent containing an acylhydrazone of the general formula (I) and fragrance capsules to act on a contaminated textile in the course of a machine or hand washing operation.
• the use according to the invention can be realized particularly simply by the use of a detergent containing peroxygen compound, perfume capsules and a compound of formula (I) or a bleach catalyst obtainable therefrom by complex formation with a transition metal ion mentioned in the laundry of textiles requiring cleaning.
• the peroxygen compound and / or the compound of the formula (I) and / or a complex obtainable therefrom and / or the fragrance capsules may also be added separately to a wash liquor which has a detergent without the respective stated ingredient.
• Another object of the invention is a detergent containing a peroxygen bleaching agent and a combination of fragrance capsules and a compound of formula (I).
• the compound of formula (I) may also be present in the form of a bleach catalyst obtainable by complexation with a transition metal ion thereof from said agent.
• the agent additionally comprises a manganese, titanium, cobalt, nickel or copper salt and / or a manganese, titanium, cobalt, nickel or copper complex without a ligand which corresponds to a compound according to formula (I).
• the molar ratio of said transition metal or the sum of said transition metals to the compound of formula (I) is preferably in the range of 0.001: 1 to 2: 1, especially 0.01: 1 to 1: 1.
• Preferred transition metal is Mn.
• peroxygen compounds contained in the agents are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxoacid salts, such as alkali metal or peroxodisulfates or caroates, or diacyl or tetraacyldiperoxides, hydrogen peroxide and among the Washing conditions hydrogen peroxide-releasing substances, such as alkali metal perborates, alkali metal peroxides, alkali metal peracidates and urea perhydrate, into consideration.
• organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxoacid salts, such as alkali metal or peroxodisulfates or caro
• Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate.
• solid peroxygen compounds ie an oxidase and its substrate.
• solid peroxygen compounds can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
• alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide.
• peroxygen compounds are present in the compositions in amounts of up to 50% by weight, more preferably from 2% to 45% and more preferably from 5% to 20% by weight.
• a conventional bleach activator together with the acylhydrazone the general formula (I), the general formula (II) and in particular the formula (III).
• bleach activators are preferably present in amounts of up to 10 wt .-%, in particular from 1.5 wt .-% to 5 wt .-%.
• Compounds which give peroxocarboxylic acid under perhydrolysis conditions can in particular be compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures.
• Suitable are bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups.
• 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, especially nonanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), their formal carbonic ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benz
• bleach-activating compounds such as, for example, nitriles, from which perimides acids are formed under perhydrolysis conditions, may be present.
• R 11 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 12 and R 13 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH)
• the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1.5% by means of carboxymethylcellulose.
• Diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile is particularly preferred.
• customary bleach-activating 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 and its substituted derivatives, such as 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-triazacyclododecane and its substituted derivatives such as 1,5,9-tri-methyl-1,5,9-triazacyclododecane 1,4,8,11-tetraazacyclotetradecane and its substituted derivatives such as 5,5,7,12 , 12,14-hexamethyl-1,4,8,11-tetraazacyclote
• 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 anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention.
• 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) m
• fragrance capsules are included in the compositions of the invention in the amounts disclosed above in the context of use.
• Detergents which may be in particular pulverulent solids or in densified particulate form, may contain, in addition to the combination of perfume capsules and compound according to formula (I) to be used according to the invention and optionally also the said bleach activators and catalysts, in principle all known ingredients customary in such agents.
• the agents may include, in particular, builders, surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, special effect polymers such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle reducing polymeric agents, and formulating polymeric actives, and other adjuvants such as optical brighteners, foam regulators, dyes and other, in particular non-encapsulated fragrances.
• An agent may be used to further enhance the disinfecting effect, for example against specific germs, in addition conventional antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bound to organic frameworks O-acetates and O.
• conventional antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bound to organic frameworks O-acetates and O.
• benzamidines isothiazolines, phthalimide derivatives, pyridine derivatives, amines, quaternary ammonium compounds, guanidines, amphoteric compounds, quinolines, benzimidazoles, IPBC, dithiocarbamates, metals and metal compounds such as silver and silver salts, halogens such as chlorine, iodine and theirs Compounds, other oxidizing agents and inorganic nitrogen compounds.
• Such antimicrobial additives are preferably present in amounts of up to 10 wt .-%, in particular from 0.01 wt .-% to 5 wt .-%, each based on the total agent included; in a preferred embodiment, however, they are free of such additional disinfecting agents.
• the agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be included.
• anionic surfactants for example, those of the sulfonate type and sulfates are used.
• surfactants of the sulfonate type are preferably C 9-13 alkylbenzenesulfonates, Olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C 12-18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
• alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
• Suitable alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula in which R 'and R "are independently H or alkyl and together contain from 6 to 19, preferably from 7 to 15, and in particular from 9 to 13, carbon atoms
• a particularly preferred representative is sodium dodecylbenzylsulfonate.
• Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
• EO ethylene oxide
• Fatty alcohols with 1 to 4 EO are suitable.
• Suitable alkyl ether sulfates are, for example, compounds of the formula R 1 is -O- (AO) n -SO 3 - X +
• R 1 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol residue.
• Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with an even number of carbon atoms Atoms are preferred.
• radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols.
• AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
• EO ethylene oxide
• PO propylene oxide
• n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
• X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + including Na, with Na + being extremely preferred.
• Other cations X + may be selected from NHa + , Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof.
• the stated degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product.
• the indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
• Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• anionic surfactants are particularly soaps into consideration.
• Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the anionic surfactants are preferably in the form of their sodium, potassium or magnesium salts, in particular in the form of the sodium salts.
• anionic surfactants are the freedom from formulation no conditions to be observed in the way.
• Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, in particular the alkylbenzenesulfonates.
• Anionic surfactants including the soaps i. in particular alkylbenzenesulfonates, alkyl ether sulfates and soaps, are preferably present in the detergent at a certain proportion by weight, namely from 5 to 25% by weight, based on the total weight of the detergent formulation. Preference is given to amounts of from 7 to 20% by weight of anionic surfactants, based on the total weight of the detergent formulation. Regardless of whether the detergent contains one or more of the anionic surfactants, the amounts given refer to the total amount of all anionic surfactants contained in the detergent.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
• alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
• the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
• alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
• APG alkyl polyglycosides
• Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, especially in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
• the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
• 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 hydroxyiminodisuccinates, 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 polymeric (poly) carboxylic acids,
• 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 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 monoethylenic 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.
• vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C 1 -C 4 carboxylic acids, with vinyl alcohol.
• Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
• 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. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
• Such organic builders may optionally be present in amounts of up to 40% by weight, more preferably up to 25% by weight, and preferably from 1% to 8% by weight.
• Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. 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 water, are used as the water-insoluble inorganic builder materials Amounts of 5 wt .-% to 15 wt .-% used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
• 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.
• the soluble builder system consists of a) an alkali silicate having a modulus M 2 O: SiO 2 , wherein M is an alkali metal ion, in the range of 1: 1.9 to 1: 3.3, b) an alkali carbonate , c) a polymeric polycarboxylate having a molecular weight of less than 10,000 g / mol, and d) a phosphonate capable of complexing, and e) optionally an acidic component.
• the soluble builder system constitutes less than 40% by weight of the total composition.
• Suitable enzymes in the detergents are, in particular, those from the class of proteases, cutinases, amylases, lipases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipases 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.
• cellulose ethers such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose.
• sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used.
• Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
• the proportion of graying inhibitors and / or soil-release agents in the compositions is generally not more than 2 wt .-%, and is preferably 0.5 wt .-% to 1.5 wt .-%.
• 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 for polyamide fibers.
• the content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, and preferably in the range of 0.05 wt .-% to 0.5 wt .-%.
• the customary foam regulators which can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being 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.
• preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C 16 - to C 18 -alkyl groups.
• the proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.
• the agents 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.
• any of the detergents described herein may be any method known in the art.
• the preparation of solid compositions can be carried out in a manner known in principle, for example by spray-drying or granulation, with thermally sensitive ingredients optionally being added separately later.
• 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.
• Another object of the invention is a method for washing textiles in which an agent according to the invention is used.
• Such washing methods for cleaning textiles are generally distinguished by the fact that cleaning-active substances are applied to the items to be cleaned and washed off after the action time in one or more method steps, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent.
• temperatures of up to 95 ° C or less, 90 ° C or less, 60 ° C or less, 50 ° C or less, 40 ° C or less, 30 ° C or less, or 20 ° C or less used. These temperature data refer to the temperatures used in the washing steps.
• the uses, compositions and methods described above in connection with detergents are also applicable to hard surface cleaners.
• the invention thus also encompasses the use of the described combinations for improving the cleaning performance of hard surface cleaners, corresponding cleaning agents and methods in which such cleaners are used.
• Table 1 shows a powder detergent B according to the invention in comparison with a powder detergent A not according to the invention (all data in% by weight, unless stated otherwise): Table 1: Detergent compositions ingredient A B LAS - Well 12.5 12.5 FA 7 EO 3.0 3.0 HEDP-Na 4 1.1 1.1 polyacrylate 2.7 2.7 Sodium silicate 2.1 7.0 7.0 sodium 20.0 20.0 sodium carbonate peroxyhydrate 14.0 14.0 TAED 4.0 4.0 Acylhydrazone 1 ) - 0.29 carboxymethylcellulose 2.5 2.5 defoamers 0.5 0.5 Soil-release polymer 0.25 0.25 enzymes + + Optical brightener 0.3 0.3 Perfume 0.16 0.16 perfume capsules 0.1 0.1 Balance (sodium sulfate, etc.) Ad 100 Ad 100 1 ) Morpholinium 4- (2- (2 - ((2-hydroxyphenylmethyl) methylene) hydrazinyl) -2-oxoethyl) -4-methyl chloride
• the measured pH in the wash liquor is 8.9 for Formula A and 9.8 for Formula B.
• Table 2 The values given (Table 2) are mean values of 6 determinations. The soiled textiles were bought or self-made. The differences between the remission values and the standard detergent are shown. The use of the acylhydrazone bleach catalyst in Detergent Formulation B, as compared to Detergent Formulation A, exhibits improvements in leachability, especially on bleachable stains. Table 2: Wash results soiling Origin / Art Diff.

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