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
  • C11D3/39—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
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

• the present invention relates to a solid particulate detergent containing certain acylhydrazones as a discrete particle bleach catalyst in combination with discrete particles of a tower powder as well as other components such as percarbonate, bleach activators, enzymes and other standard detergent ingredients. Also included is its use for improving stain removal, especially bleachable, hydrophilic stains such as red wine stains, tea stains, red fruit stains or beverages and foodstuffs therefrom or those containing appropriate colorants when washing fabrics or cleaning hard surfaces.
• Detergents especially those intended for household use, are generally not marketed as simple mixtures of their ingredients but in the form of granular preparations in which all or most of the ingredients are intimately mixed in the individual grains available.
• This form has several advantages in the use of detergents, of which only the most dust-free and safety against segregation during transport should be mentioned.
• Such granular detergents can be prepared in various ways. Thus, processes are known to convert the individual components of the detergent by compacting granulation, for example by means of extruders in the granular form. In addition, there are processes in which the finely divided constituents are agglomerated to larger particles with the aid of liquids, for example alkali silicate solutions.
• the registrations DE102014218805 and DE102014218807 disclose how corresponding particulate tower powders can be made.
• the detergent contains further constituents, in particular percarbonate, bleach activators, in particular TAED, builder substances, in particular soda, and enzymes, likewise in the form of discrete particles.
• Another object of the invention is the use of the herein described combination of particulate detergent ingredients to enhance the cleaning performance of peroxygen-containing detergents.
• 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.
• cleaning performance is understood to mean the removal of one or more soiling, in particular laundry soiling, which are pale-sensitive.
• the distance can be measured by a brightening of the soiling measured as well as assessed visually.
• 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 give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge. Among the latter, i.a. calculated the fabric softener.
• particle sizes can be determined by sieving the particles by means of a VE1000 sieve (Retsch GmbH, Haan) for 2 minutes with an interval of 10 seconds and an amplitude of 2 mm and determining the proportion of particles per sieve gravimetrically.
• 100 g sample are given by means of the top sieve of a sieve set, which is assembled in such a way that the mesh size decreases towards the bottom, and which is provided with a closure bottom.
• the proportion of particles per sieve is determined gravimetrically by transferring and weighing the different fractions, including the particles stuck in the sieve meshes, into weighing dishes.
• 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, a C 1-18 alkyl sulfate, especially methosulfate, or a corresponding alkanesulfonate, inorganic anions such as halide, especially chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, bisulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.
• the bleach catalysts of the formula (I) are present in the detergents according to the invention as discrete particles.
• the particles have a particle size distribution in which at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the particles have a particle size between 0.2 and 2.0 mm, preferably between 0 , 4 and 1.5 mm.
• the particles are preferably approximately spherical, the shape being not limited thereto.
• Discrete particles as used herein means that the particles are separate from other particles also included in the formulation.
• the particles may consist of the bleach catalyst of formula (I) or may contain this in combination with other ingredients. However, it is preferred that the particles consist of the bleach catalyst and the remaining constituents are contained in the composition in the form of further discrete particles, these further particles each containing one or more of the further constituents.
• the particulate further ingredients of the detergent are defined more fully below.
• the particles can each be coated (co-coated) to interact with others Components of the formulation. Suitable coating agents and methods of coating such particles are known in the art.
• particulate bleach catalysts formulated in tower powder-containing particulate detergents have better bleaching performance. Without wishing to be bound by any particular theory, it is believed that this finding is due to the balanced combination of various measures and effects.
• the spatial separation of the bleach catalyst from other ingredients prevents the bleach catalyst from being inactivated by the other ingredients.
• the bleach catalyst is available more quickly as an individual particle after adding the detergent to the water, so its performance in the wash liquor starts faster.
• the metering as a particle in particular after adjustment of the particle sizes, in particular of the bleach catalyst and the tower powder as an essential component of the washing and cleaning agent, ensures a homogeneous, stable and storable mixture.
• the homogeneous distribution of the bleach catalyst in the detergent ensures uniform metering in washing and cleaning processes via the consumption of the entire detergent and cleaner pack.
• the bleach catalyst particles are finely distributed in the wash liquor due to the presence of the particulate tower powder and, if appropriate, further particulate constituents, so that a homogeneous concentration of the bleach catalyst in the wash liquor is quickly achieved.
• a satisfactory bleaching performance can be achieved.
• all of these benefits are particularly pronounced at low wash temperatures, e.g. at 20 ° C.
• the subject invention leads to a surprisingly improved detergent.
• 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.
• the solid peroxygen compounds used may be used in the form of powders or granules, which may also be coated in a manner known in principle.
• 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.
• the peroxygen compounds may preferably be used in the form of discrete particles in the agents described herein.
• a conventional bleach activator is used together with the acylhydrazone of the general formula (I), the general formula (II) and in particular the formula (III).
• such bleach activators are preferably present in amounts of up to 10 wt .-%, in particular from 1.5 wt .-% to 5 wt .-%.
• the bleach activators may also preferably be employed in the form of discrete particles in the agents described herein.
• 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 particulate form 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-trimethyl-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-tetraazacyclotetrade
• 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.
• binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands lacking 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
• the detergents which may be present in particulate form, in particular as pulverulent solids or in densified particulate form, may contain, in principle, all known ingredients customary in such compositions, in addition to the bleach catalyst according to formula (I), the tower powder and optionally the abovementioned bleaching agents and bleach activators.
• the compositions may include other ingredients selected from 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 actives, and shape-retaining polymers Active ingredients, and other auxiliaries, such as optical brighteners, foam regulators, dyes and fragrances included.
• the tower powder contains at least one surfactant and at least one builder.
• the tower powder is in the form of discrete particles in the composition, wherein the particles of the tower powder have a particle size distribution at which at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the particles Particle size between 0.1 and 2.0 mm, preferably between 0.1 and 1.6 mm.
• the proportion of turpentine in the composition is at least 20% by weight, more preferably at least 30% by weight, even more preferably at least 50% by weight.
• 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.
• the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products 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, more preferably a fatty alcohol radical.
• 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 NH 4 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 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 3 EO or 4 EO, C 9-11 -alcohol 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, in particular 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 Is a 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, especially citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, especially glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and Hydroxyiminodisuccinate, ethylenediaminetetraacetic acid and Polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), lysintetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) carboxylic acids, in particular polycarboxylate
• 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 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.
• 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 amounts of from 5% by weight to 15% by weight, are used as water-insoluble inorganic builder materials. % 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 included in the compositions in amounts of 1% to 20% by weight, especially 5% to 15% by weight.
• the alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline.
• Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
• the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na 2 Si x O used 2x + 1 ⁇ y H 2 O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4.
• Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
• 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 acid-acting 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.
• 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.
• the detergent contains the above-mentioned other ingredients at least partially also in the form of discrete particles.
• agents which contain part of the constituents in the form of tower powder particles.
• the amount of such tower powder particles in the composition is typically 20 to 70% by weight, preferably 45-55% by weight, based on the total weight of the composition.
• Such tower powders are typically granulated by spray drying from a slurry and contain various detergent ingredients such as surfactants, builders, chelants and binders, each of which may be as defined above.
• tower powders which comprise (1) surfactants, in particular linear alkylbenzenesulfonates and / or salts thereof, in particular sodium salts, (2) water-soluble builder systems which contain complexing agents, in particular HEDP, polycarboxylates, in particular polyacrylates, alkali silicate and alkali metal carbonate, and optionally (3 ) Sodium sulfate and / or (4) a binder such as carboxymethyl cellulose.
• a suitable tower powder contains, for example, 20-25 wt.% LAS-Na, 2-4 wt.% 1-hydroxyethane-1,1-diphosphonic acid (HEDP), 3-10 wt.% Polycarboxylate, 10-15 wt.
• Alkali metal silicate in particular sodium silicate 2.1, 5 to 10% by weight alkali metal carbonate, in particular sodium carbonate, 2-3% by weight CMC and ad 100% by weight alkali metal sulphate, in particular sodium sulphate.
• all other ingredients i. in addition to the bleach catalyst and the above-mentioned tower powder ingredients, may be used in the form of discrete particles.
• Their proportion of the agent is usually also 20 to 70 wt .-%, preferably 35-55 wt .-%.
• these ingredients are the above-described bleaching agents, bleach activators and bleach catalysts, especially percarbonate and TAED, as well as enzymes which may each be formulated as separate discrete particles.
• the total agent consists of 70% by weight, preferably 80% by weight, more preferably 90% by weight, of particles having a particle size distribution of 0.1 to 2 mm.
• the particles of the composition Preferably, 85 to 100% of the particles of the composition have a particle size in the range of 0.1 to 1.6 mm.
• the particles are preferably approximately spherical, the shape being not limited thereto.
• any of the detergents described herein may be any method known in the art.
• the preparation of the agents 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 by spray-drying the thermally stable components and admixing them more sensitive components, which in particular enzymes, bleaching agents and bleach-activating agents are to be expected, can 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 invention also relates to the use of the above-described combination of particulate detergent ingredients comprising bleach catalyst and tower powder, each in the form of discrete particles, to enhance the cleaning performance of peroxygen-containing detergents.
• the compound of formula (I) when using the combination, is in the form of discrete particles, the discrete particles having a particle size distribution at least 70%, preferably at least 80%, even more preferably at least 90% Wt .-% of the particles have a particle size between 0.2 and 2.0 mm, preferably between 0.4 and 1.5 mm, and wherein the combination comprises discrete particulate tower powder, wherein the particles of the tower powder have a particle size distribution, in which at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the particles have a particle size between 0.1 and 2.0 mm, preferably between 0.1 and 1.6 mm, wherein preferably the proportion of turpentine in the combination is at least 20% by weight, more preferably at least 30% by weight, even more preferably at least 50% by weight.
• the concentration of the bleach catalysts according to formula (I) in aqueous liquor, as used for example in washing machines or dishwashers 0.5 .mu.mol / l to 500 .mu.mol / l, in particular 5 .mu.mol / l to 100 .mu.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.
• 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 present invention is preferably carried out by subjecting a peroxygen compound and a detergent containing an acylhydrazone of the general formula (I) in the form of discrete particles in combination with a particulate tower powder to a contaminated by a machine or hand washing operation Textile can act.
• the use according to the invention can be realized particularly simply by the use of a detergent containing peroxygen compound, tower powder, a compound of formula (I) or a bleach catalyst obtainable therefrom by complexing 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 tower powder may also be added separately to a wash liquor which has a detergent without the respective stated ingredient.
• the compound of formula (I) may also be used in the form of a bleach catalyst obtainable by complexing with a said transition metal ion therefrom in the composition.
• Another object of the invention is a method for washing textiles in which an agent according to the invention is used.
• Washing processes ie in particular processes for cleaning textiles, are generally distinguished by the fact that cleaning-active substances are applied to the cleaning product in one or more process steps and washed off after the exposure time, or the cleaning product is otherwise treated with a detergent or a solution of this agent is treated.
• 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 A according to the invention and its structure from the various discrete particles (all data in% by weight, unless stated otherwise): Table 1: Detergent compositions ingredient A tower powder 53.0 alkylbenzenesulfonate 0.9 FA7EO 3.0 sodium 20.0 sodium carbonate peroxyhydrate 14.0 TAED 4.0 Acylhydrazone 1) 0.29 carboxymethylcellulose 2.5 defoamers 0.5 Soil-release polymer 0.25 enzymes + Optical brightener 0.3 Perfume 0.16 perfume capsules 0.1 Balance (sodium sulfate, etc.) Ad 100 1) Morpholinium 4- (2- (2 - ((2-hydroxyphenylmethyl) methylene) hydrazinyl) -2-oxoethyl) -4-methyl chloride (Tinocat LT B200, BASF SE)
• the composition of the tower powder is shown in Table 2.
• Table 2 Tower powder ingredient A LAS-Na 23.0 HEDP-Na 4 2.2 polycarboxylate 5.2 Sodium silicate 2.1 13.9 sodium 7.1 sodium sulphate 40.0 Carboxymethylcellulose, Na salt 2.2 rest Ad 100
• Table 3 shows the particle sizes of the particles used in the powder detergent. Since these are within a narrow range between 0.1 and 2 mm, segregation is prevented and ensures a homogeneous distribution of the active ingredients in the powder detergent. Thus, the desired dosage of active ingredients per wash load is secured by the consumer.
• Soil-release polymer > 1.6 mm: ⁇ 1% > 0.4mm: 50-80% > 0.1mm: 15-45% ⁇ 0.1 mm: ⁇ 5% enzymes ⁇ 600 ⁇ m: ⁇ 5% > 1500 ⁇ m: ⁇ 5% brighteners > 0.8 mm: ⁇ 1% ⁇ 0.1 mm: ⁇ 32% perfume capsules > 2.0 mm: 2% ⁇ 2.0 -> 0.2 mm: 90% ⁇ 0.2mm: 8%
• Example 3 Improved stability by discrete particles

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