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
  • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
• • 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
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

• the present invention relates to coated bleach activators, to a process for their preparation and to their use, preferably in dyed detergents or cleaners, in particular detergent tablets, which are used for cleaning dishes in dishwashers.
• bleach activators are widely described in the art. Usually, the agents contain bleaches which are to be enhanced by the activators in their effect.
• An important field of use of bleach and bleach activator-containing agents are detergents or cleaners. Usually, these agents contain one or more builders, bleaches, bleach activators, corrosion inhibitors and surfactants. To provide the consumer with a typical and distinctive product, these agents are usually both perfumed and colored. There are quite a number of requirements placed on the dyes: they have to dye the cleaning agent to be colored permanently and visually even at low use concentrations, and they must not fade or discolor even on prolonged storage or at elevated temperatures.
• the dyes used are chemically inert to the sometimes aggressive ingredients (e.g., bleach, alkali carriers) and do not degrade themselves or other ingredients. Since the detergent tablets on the market are often designed bicolor for aesthetic reasons, no fading of the colored phase or a transfer of color into lighter or uncolored areas may result at the phase boundary of differently colored areas.
• EP 482 807 B1 discloses the common granulation of TAED with binders and the subsequent coating of the granule particles with inorganic salts.
• the object was therefore to find coated bleach activators and a preparation process for these bleach activators, which make it possible to be used even in the presence of non-bleach-stable dyes without having to accept the aforementioned disadvantages.
• the present invention is in a first embodiment, a method for producing coated bleach activators, characterized by the steps of a) granulation of at least one bleach activator with a binder; b) coating the granules from step a) with a solution or dispersion of at least one complex image; c) drying the coated granules.
• at least one bleach activator is granulated with at least one binder. This step can be carried out easily in a wide variety of granulation systems.
• a Lödige mixer for example a ploughshare mixer from Lödige, or a Schugi mixer
• at mixing speeds of the mixing devices preferably between 2 and 7 m / s (ploughshare mixer) or 3 to 50 m / s (Eirich, Schugi), in particular between 5 and 20 m / s submitted a solid bed and then granulated with the addition of a granulating liquid.
• a predetermined grain size of the granules can be adjusted simultaneously in a conventional manner.
• the granulation and mixing process requires only a very short period of, for example, about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) for homogenizing the mixture to form the flowable granules.
• a residence time of 0.5 to 10 seconds is normally sufficient to obtain free-flowing granules.
• Suitable for carrying out this process step mixers include for example Eirich ® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ® Flexomix, the Fukae ® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co.
• - Lödige CB / Lödige KM / Schugi Flexomix Granulation can be carried out by initially introducing bleach activator and binder as a solid bed and granulating them with the addition of a granulating liquid, preferably an aqueous solution.
• a granulating liquid preferably an aqueous solution.
• the bleach activator is introduced as a solid and granulated with the addition of a solution of the binder.
• bleach activators which may be used according to the invention are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes.
• Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
• bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
• Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
• polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
• Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
• Combinations of conventional bleach activators can also be used.
• so-called bleach catalysts can also be used.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
• a further preferred bleach activator which can be used according to the invention is a cationic nitrile of the formula (I)
• R 2 is -N (+) - (CH 2 ) -CN X H (I),
• R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3) -CH ( CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 - CH (OH
• the general formula (I) includes a variety of cationic nitrites useful in the present invention.
• cationic nitriles are used in which R 1 is methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
• R 2 and R 3 are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.
• Preferred cationic nitriles of the formula (I) are characterized by their radicals R 1 , R 2 and R 3 :
• R 5 is -N (+) - (CH 2 ) -CN X ° (la),
• X " is an anion selected from the group Chloride, bromide, iodide, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate or xylenesulfonate or mixtures thereof.
• Suitable binders which are either mixed in the form of solids with the bleach activators and then granulated with the addition of a granulating liquid, or which may be part of the granulating liquid, are, for example, natural or synthetic polymers. Among these, for example, polyethylene or polypropylene glycols are preferable. Also preferred are non-ionic polymers such as, for example:
• Polyvinylpyrrolidones as sold for example under the name Luviskol ® (BASF).
• Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (II)
• Polyvinylpyrrolidones are prepared by radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators.
• the ionic polymerization of the monomer provides only low molecular weight products.
• commercial Polyvinylpyrrolidones have molecular weights in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on K value - have glass transition temperatures of 130-175 °. They are called white, hygroscopic powder or aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
• Vinylpyrrolidone / vinyl ester copolymers as sold, for example, under the trademark Luviskol ® (BASF). Luviskol ® VA 64 and Luviskol ® VA 73, each vinylpyrrolidone / vinyl acetate copolymers are particularly preferred non-ionic polymers.
• the vinyl ester polymers are vinyl ester-accessible polymers having the moiety of formula (III)
• Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (II) and (III)
• Cellulose ethers such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, as sold, for example, under the trademarks Culminal ® and Benecel ® (AQUALON).
• Cellulose ethers can be described by the following general formula
• R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula is -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH.
• Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit.
• Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1, 35 (DS) and 1, 5-3 (MS). Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.
• Polyvinyl alcohols referred to as PVAL for short, are polymers of the general structure
• polyvinyl alcohols are passed through polymer-analogous reactions Hydrolysis, technically but especially by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) prepared in solution.
• alcohols preferably methanol
• PVAL for example, Mowiol ® types from Clariant
• PVAL are as a white yellowish powders or granules having degrees of polymerization in the range of about 500-2500 (corresponding to molecular weights of about 20,000-100,000 g / mol) in the trade and have different degrees of hydrolysis of 98 -99 and 87-89 mol%, respectively. So they are partially hydrolyzed polyvinyl acetates with a residual content of acetyl groups of about 1-2 or 11-13 mol%.
• the water-solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
• Particularly preferred processes according to the invention are characterized in that natural polymers, preferably cellulose and / or starch and derivatives thereof, in particular carboxymethylcellulose (CMC) and / or hydroxypropylcellulose (HPC) and / or hydroxypropylmethylcellulose (HPMC) are used as binders.
• natural polymers preferably cellulose and / or starch and derivatives thereof, in particular carboxymethylcellulose (CMC) and / or hydroxypropylcellulose (HPC) and / or hydroxypropylmethylcellulose (HPMC) are used as binders.
• the granules from step a) are coated with a solution or dispersion of at least one complex image and the coated granules are dried.
• the coating can be carried out at the same time as drying (for example in a fluidized bed apparatus in which the granules are treated with a solution or dispersion of at least one complexing agent and dried at the same time), but it is also possible and preferred to dry after coating, ie in time subsequently to this, perform.
• Granules are substances that can complex metal ions.
• Preferred complexing agents are so-called chelate complexing agents, ie substances which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, ie at least "bidentate".
• chelate complexing agents ie substances which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, ie at least "bidentate".
• normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
• Common and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
• Complex-forming polymers ie polymers which carry functional groups either in the main chain itself or in a pendent position, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can be used according to the invention.
• the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
• Complexing groups (ligands) of conventional complexing polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific. Activities towards ions of different metals.
• Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
• one or more chelating agents from the groups of (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• diphosphonic acid the higher homologues of which have up to 8 carbon atoms, and hydroxy- or amino-containing derivatives thereof, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (meth ylenphosphonic acid) or nitrilotri (methylene phosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and f) cyclodextrins.
• aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (meth ylenphosphonic acid) or nitrilotri (methylene phosphonic acid
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and f) cyclodextrins.
• polycarboxylic acids a) are understood in the context of this patent application carboxylic acids - including monocarboxylic acids - in which the sum of carboxyl and in the Molecule-containing hydroxyl groups is at least 5.
• Complexing agents from the group of nitrogen-containing polycarboxylic acids in particular EDTA, are preferred.
• these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
• alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
• polymeric aminodicarboxylic acids their salts or their precursors.
• polyaspartic acids or their salts and derivatives which, in addition to co-builder properties, also have a bleach-stabilizing effect.
• polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
• hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
• Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
• the complexing agent used here is preferably HEDP from the class of phosphonates.
• the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, it may be preferred Aminoalkanphosphonate, in particular DTPMP use, or to use mixtures of said phosphonates.
• Preferred processes according to the invention are characterized in that as complexing agents phosphonates, preferably hydroxyalkane or
• HEDP 1-hydroxyethane-1,1-diphosphonate
• ETMP ethylenediamine tetramethylenephosphonate
• DTPMP diethylenetriaminepentamethylenephosphonate
• the granules produced according to the invention contain at least the constituents bleach activator, binder and complexing agent.
• Preferred processes according to the invention are characterized in that the dried granules (including coating), based on their weight, 5 to 80 wt .-%, preferably 10 to 75 wt .-% and in particular 20 to 70 wt .-% bleach activator (s ) contains.
• preferred processes according to the invention are characterized in that the dried granules (including coating), based on their weight, 0.1 to 50 wt .-%, preferably 3 to 25 wt .-% and in particular 5 to 15 wt. Contains% complexing agents.
• step a) is carried out in a mixer granulator, wherein preferably bleach activator (s) and binder are initially introduced in solid form and are granulated with a granulating liquid.
• the granulation liquid is free of surfactant (s) and complexing agent (s).
• coated bleach activators which can be prepared for example by the process according to the invention.
• coated bleach activators comprising a particle core containing bleach activator (s) and a shell surrounding this core, the shell being at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight. % and in particular to 100 wt .-% of its weight of complexing agent (s).
• Coated bleach activators preferred according to the invention are characterized in that the shell contains as complexing agents phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1, 1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylene phosphonate (EDTMP ) or its hexasodium salt and / or diethylenetriaminepentamethylenephosphonate (DTPMP) or its hepta- or octasodium salt.
• phosphonates preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1, 1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylene phosphonate (EDTMP ) or its hexasodium salt and / or diethylenetriaminepentamethylenephosphonate
• the core of the coated bleach activators according to the invention does not consist exclusively of bleach activator.
• a content of binders in the core of the particles is preferred, in particular coated bleach activators, in which the core next to bleach activator (s) contains binders, which binders as natural polymers, preferably cellulose and / or starch and their derivatives, in particular carboxymethylcellulose (CMC) and or hydroxypropylcellulose (HPC) and / or hydroxypropylmethylcellulose (HPMC) are preferred and preferred amounts of the core of binder 1 to 50 wt .-%, preferably 5 to 40 wt .-% and in particular 10 to 30 wt .-% of binder (each relative to the uncoated core), preferred embodiments of the present invention.
• CMC carboxymethylcellulose
• HPMC hydroxypropylmethylcellulose
• coated bleach activators according to the invention or prepared according to the invention are characterized by a high storage stability and are suitable excellent for use in a variety of means, especially detergents or cleaners.
• Sensitive substances such as, for example, dyes have significantly higher stabilities in compositions with the coated bleach activators according to the invention or prepared according to the invention than in compositions with coated bleach activators not according to the invention or prepared according to the invention.
• a further subject of the present invention is therefore the use of the coated bleach activators according to the invention or inventively prepared in washing or cleaning agents, in particular in washing or cleaning agent tablets.
• the present invention also relates to detergents or cleaners containing at least one bleaching agent, at least one dye and at least one coated bleach activator according to the invention or prepared according to the invention.
• Particularly preferred detergents or cleaners according to the invention contain the dye in homogeneous distribution, i.
• Preferred washing or cleaning agents according to the invention contain, in addition to the above-mentioned bleach, dye and coated bleach activators according to the invention, substances from the groups of builders (builders, cobuiiders), surfactants, enzymes, dyes, fragrances, corrosion inhibitors, polymers , or another common ingredient of detergents and cleaners. These ingredients are described below. Builders, cobuiiders, surfactants, enzymes, dyes, fragrances, corrosion inhibitors, polymers , or another common ingredient of detergents and cleaners. These ingredients are described below. Builder
• all builders commonly used in detergents and cleaners in particular silicates, carbonates, organic cobuilders and also the phosphates, may be incorporated in the detergents and cleaners.
• Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
• Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 -yH 2 O are preferred.
• amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
• the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
• the term "amorphous” is also understood to mean "X-ray amorphous”.
• the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
• both the monoalkali metal salts and the dialkali metal salts of carbonic acid as well as sesquicarbonates may be included in the compositions be.
• Preferred alkali metal ions are sodium and / or potassium ions.
• Compounds of, for example, carbonate, silicate and optionally other auxiliaries such as, for example, anionic surfactants or other, in particular organic builders, may be present as a separate component in the finished compositions.
• the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the washing and cleaning agent industry.
• Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO in addition to higher molecular weight representatives.
• the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.
• Sodium dihydrogen phosphate, NaH 2 PO 4 exists as dihydrate (density 1, 91 like “3 , melting point 60 °) and as monohydrate (density 2.04 like “ 3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
• NaH 2 PO 4 is acidic; It is formed when phosphoric acid is adjusted to pH 4.5 with narcotic eye and the mash is sprayed.
• Potassium dihydrogen phosphate (potassium phosphate primary or monobasic phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33, like "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) ⁇ ] and is light soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt.
• Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with sodium carbonate solution prepared using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) a density of 2.536 "3 iron.
• Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
• Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, in the detergent industry, the more soluble, hence highly effective, potassium phosphates are often preferred over corresponding sodium compounds.
• Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 like " 3 , melting point 94 ° with loss of water) ,
• decahydrate density 1.815-1.836 like " 3 , melting point 94 ° with loss of water
• Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
• the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
• Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% "3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH 2 PO 4 or KH 2 PO 4 results in higher mol.
• Sodium and potassium phosphates where one can distinguish cyclic representatives, the sodium or Kaliummetaphoshate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
• pentasodium triphosphate Na 5 P 3 O ⁇ o (sodium tripolyphosphate)
• P (O) (ONa) -O] n - Na with n 3.
• 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
• pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
• organic cobuilders which may be used in the washing or cleaning compositions are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates.
• the polymers may also be part of the active ingredient-containing polymer matrix, but they may also be contained completely independently of these in the inventive compositions. The mentioned classes of substances are described below.
• Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.
• the acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
• citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
• Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
• the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and more preferably from 1,200 to 4,000 g / mol, may again be preferred from this group.
• Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention.
• the sulfonic acid-containing copolymers will be described in detail below.
• the sulfonic acid group-containing polymers described above may also be present in the compositions according to the invention, without necessarily having to be part of the active ingredient-containing polymer matrix zuu.
• polyacrylates As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers.
• the polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons.
• Such polyacrylates are commercially available under the trade name Sokalan ® PA15 and Sokalan ® PA25 (BASF).
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
• Their molecular weight relative to free acids is generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 30,000 to 80,000 g / mol.
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
• the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
• biodegradable polymers of more than two different monomer units for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
• copolymers have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• other preferred builder substances are polymers of amino dicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.
• Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
• it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
• a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
• DE dextrose equivalent
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
• Ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
• EDDS Ethylenediamine-N, N'-disuccinate
• glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be present in lactone form. and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
• hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
• Aminoalkanphosphonate are preferably
• Ethylenediamine tetramethylene phosphonate (EDTMP)
• Diethylenetriaminepentamethylenephosphonate and their higher homologues in question. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
• the builder used here is preferably HEDP from the class of phosphonates.
• the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
• agents according to the invention are characterized in that they comprise builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates, in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95% Wt .-%, particularly preferably from 5 to 90 wt .-% and in particular from 10 to 80 wt .-%, each based on the composition.
• surfactants preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates, in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95% Wt .-%, particularly preferably from 5 to 90 wt .-% and in particular from 10 to 80 wt .-%, each based on the composition.
• preferred cleaners comprise one or more surfactants from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.
• 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 obtained for example from C 12 - ⁇ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration , Also suitable are alkanesulfonates consisting of C 12 .
• esters of ⁇ -sulfo fatty acids for example, the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettcicren are suitable.
• sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
• Fatty acid glycerol esters are the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• 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, straight-chain alkyl radical which is prepared on a petrochemical basis and which comprises have similar degradation behavior as the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 - alkyl sulfates and C 12 -C 15 alkyl sulfates and C 4 -C 15 alkyl sulfates are preferred.
• 2,3-Alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
• 2 alcohols such as 2-methyl-branched Cg-u-alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8 - ⁇ 8 fatty alcohol radicals or mixtures of these.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
• Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
• alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the Al k (en) yl chain or salts thereof.
• 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 including the soaps may be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di-triethanolamine.
• the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
• Another group of detergent substances are the nonionic surfactants.
• 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.
• Preferred ethoxylated alcohols include, for example, C 12th 14- alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, C 3 . 15- alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 . ⁇ 8 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 2 . ⁇ 4 -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 rank ethoxylates, NRE).
• NRE narrow rank ethoxylates
• fatty alcohols with more than 12 EO can also be used. Examples of these are 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
• Useful alkypolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular 2-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 Glycosid istsgrad 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 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.
• 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.
• surfactants are polyhydroxy fatty acid amides of the formula (XVIII),
• RCO is an aliphatic acyl radical having 6 to 22 carbon atoms
• R ⁇ is hydrogen
• [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (XIX), R 1 -OR 2 I R-CO-N- [Z] (XIX)
• R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
• R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein C ⁇ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives thereof residue.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• nonionic surfactants in detergents and cleaners for automatic dishwashing come as surfactants in general all surfactants in question.
• the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose.
• Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols.
• alkoxylated alcohols as the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C 10 to C 8 , preferably between C 12 and C ⁇ e, such as C ⁇ - , C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 8 -alcohols).
• C 10 to C 8 preferably between C 12 and C ⁇ e, such as C ⁇ - , C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 8 -alcohols.
• n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation.
• a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
• nonionic surfactants have been low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
• surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
• R 1 is -O- (CH 2 -CH 2 -O) w - (CH 2 -CH-O) x - (CH 2 -CH 2 -O) y - (CH 2 -CH-O) z -H (XX )
• R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 .
• the preferred nonionic surfactants of formula XX can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
• the radical R 1 in the formula I above may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
• Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals.
• R 1 in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
• alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
• R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
• Preferred automatic dishwashing agents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
• nonionic surfactants which have a Cg. 15 alkyl having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
• the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature.
• preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.
• Suitable nonionic surfactants in addition to the nonionic surfactants according to the invention which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
• Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
• a particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16th 20 alcohol), preferably a C 18 alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Of these, the so-called “narrow rank ethoxylates" (see above) are particularly preferred.
• particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) which are prepared from C 6 . 2 Q monohydroxyalkanols or C 6 . 2 o-alkylphenols or C 16-20 - fatty alcohols and more than 12 mol, preferably more than 15 mol and was recovered in particular more than 20 moles of ethylene oxide per mole of alcohol (s).
• ethoxylated nonionic surfactant s
• the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
• such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
• Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
• the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
• Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule comprise up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.
• nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25 Wt .-% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
• Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
• a further preferred machine dishwashing detergent according to the invention contains nonionic surfactants of the formula
• R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
• R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15.
• nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
• R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R 3 is H is methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl
• x is values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5 stand. If the value x ⁇ 2, each R 3 in the above formula may be different.
• R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
• R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
• each R 3 in the above formula may be different if x ⁇ 2.
• the alkylene oxide unit in the square bracket can be varied.
• the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
• R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15. Summarizing the latter statements, dishwashing agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula
• R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R 3 is H or a methyl, ethyl, n-propyl, iso Is propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
• x are values between 1 and 30
• k and j are values between 1 and 12, preferably between 1 and 5
• x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
• anionic, cationic and / or amphoteric surfactants in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in automatic dishwashing detergents, and in most cases only in amounts below 10% by weight, in most cases even below 5 Wt .-%, for example, from 0.01 to 2.5 wt .-%, each based on the agent used.
• the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.
• the automatic dishwashing detergents comprise surfactant (s), preferably nonionic surfactant (s), in amounts of from 0.5 to 10% by weight, preferably from 0.75 to 7.5 Wt .-% and in particular from 1, 0 to 5% by weight, each based on the total agent included.
• surfactant preferably nonionic surfactant (s)
• s nonionic surfactant
• bleach Bleaching agents are important constituents of detergents and cleaning agents, and a washing and cleaning agent may in the context of the present invention contain one or more substances from the group mentioned.
• sodium percarbonate has particular significance.
• Further useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
• Sodium percarbonate is a term used in unspecific terms for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate.
• the commercial product has the average composition 2 Na 2 CO 3 -3 H 2 O 2 and is therefore not peroxycarbonate.
• Sodium percarbonate forms a white, water-soluble powder of density 2.14 "3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.
• the industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process).
• aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium by salting-out agent (mainly sodium chloride), Kristallisierangesstoff (for example, polyphosphates, polyacrylates) and stabilizers (for example, Mg 2+ ions).
• the precipitated salt which still contains 5 to 12 wt .-% mother liquor is then removed by centrifugation and dried in fluidized bed driers at 90 ° C.
• the bulk density of the finished product may vary between 800 and 1200 g / l, depending on the manufacturing process.
• the percarbonate is stabilized by an additional coating. Coating methods and materials used for coating are widely described in the patent literature. In principle, all commercially available percarbonate types can be used according to the invention, as offered for example by the companies Solvay Interox, Degussa, Kemira or Akzo.
• Dishwashing detergents may also contain bleaches from the group of organic bleaches.
• Typical organic bleaching agents which can be used as ingredients in the present invention are the diacyl peroxides, e.g. Dibenzoyl.
• Other typical organic bleaching agents are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.
• chlorine or bromine releasing substances can also be used according to the present invention.
• suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid,
• Tribromoisocyanuric acid Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
• DICA dichloroisocyanuric acid
• Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
• Advantageous agents in the context of the present invention comprise one or more bleaches, preferably from the group of the oxygen or halogen bleaches, in particular the chlorine bleaches, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40 Wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25% by weight and in particular from 5 to 20 wt .-%, each based on the total agent.
• Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases can contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
• subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
• enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
• lipolytic enzymes are the known cutinases.
• Peroxidases or oxidases have also proved suitable in some cases.
• Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
• Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also cellobiases, or mixtures thereof. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
• the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
• Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight. , in each case based on the total mean.
• Dyes which are preferred in the context of the present invention and whose selection does not present any difficulty to a person skilled in the art have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to textile fibers so as not to stain them.
• Preferred for use in the detergents and cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the cleaning process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
• One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes.
• Pigmosol come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ® GLW (CAS 12219-32-8, Cl Acidblue 221 )), Nylosan ® Yellow N- 7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ® (Cl Acid Blue 182, CAS 12219-26-0) is used.
• the first name indicates the name of the dye
• the second name is the generic name in the Color Index (Cl.generic name)
• the five-digit number is the number of the relevant dye in the Color Index (Cl.
• Cosmenyl Yellow 10G Cosmenyl Yellow 10G; Pigment yellow 3; 11710;
• Liquitint Yellow LP (Disperse yellow 31); (48000); E110 Sunset Yellow; Food Yellow 3; 15985; 2783-94-0
• Basacid Blue 762 liquid Basacid Blue 762 liquid; Direct blue 199; 74190; 12222-04-7
• Patent Blue 85 E 131; E 131 Patent Blue 85%; Acid Blue 3,
• Liquitint Blue MC (Acid blue 9); (42090);
• the colorant When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For highly soluble dyes, for example, the above-mentioned Basacid ® Green or the above-mentioned Sandolan Blue ®, are typically selected dye concentrations in the range of some 10 "2 to 10" 3 wt .-%.
• the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 "3 to 10" 4 wt .-% ,
• Fragrances are added to the compositions within the scope of the present invention in order to improve the aesthetics of the products and to provide the consumer, in addition to the performance of the product, with a visually and sensory "typical and unmistakable" product.
• fragrance compounds for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention.
• Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
• the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, and Lilial Bourgeonal, to the ketones, for example, the Jonone, oc-lsomethylionon and methyl cedrylketon to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene.
• fragrance oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
• Detergents for automatic dishwashing may contain corrosion inhibitors to protect the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
• chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
• transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and the manganese sulfate and the manganese complexes
• Me-MeTACN is 1,2,4,7-tetramethyl-1,4,7-triazacyclononane.
• zinc compounds can be used to prevent corrosion on the items to be washed.
• automatic dishwashing detergents which additionally contain at least one silver protectant selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of from 0.001 to 1% by weight are preferred.
• % preferably from 0.01 to 0.5 wt .-% and in particular from 0.05 to 0.25 wt .-%, each based on the total agent.

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• 2004
  • 2004-03-12 DE DE102004012568A patent/DE102004012568A1/de not_active Ceased
• 2005
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