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WO2003104368A1 - Utilisation de matrices polymeres contenant une matiere active pour le lavage de la vaisselle en machine - Google Patents

Utilisation de matrices polymeres contenant une matiere active pour le lavage de la vaisselle en machine Download PDF

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Publication number
WO2003104368A1
WO2003104368A1 PCT/EP2003/005603 EP0305603W WO03104368A1 WO 2003104368 A1 WO2003104368 A1 WO 2003104368A1 EP 0305603 W EP0305603 W EP 0305603W WO 03104368 A1 WO03104368 A1 WO 03104368A1
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Prior art keywords
acid
polymer matrix
copolymers
salts
preferred
Prior art date
Application number
PCT/EP2003/005603
Other languages
German (de)
English (en)
Inventor
Arnd Kessler
Ingo Hardacker
Original Assignee
Henkel Komanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Henkel Komanditgesellschaft Auf Aktien filed Critical Henkel Komanditgesellschaft Auf Aktien
Priority to AU2003274090A priority Critical patent/AU2003274090A1/en
Publication of WO2003104368A1 publication Critical patent/WO2003104368A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the present invention relates to the use of active ingredient-containing polymer matrices for the corrosion protection of glassware in cleaning and / or rinsing operations of a dishwasher, compositions for use in a dishwasher for the stated purpose and methods for inhibiting the corrosion of glassware in cleaning and / or rinsing operations Dishwasher.
  • Corrosion of glassware during the cleaning and / or rinsing processes of a dishwasher has been a problem which has been known for a long time, based on the one hand on the emergence of minerals from the glass composition, accompanied by hydrolysis of the silicate network, and on the other hand due to the deposition of silicate material the glassware. Both phenomena can lead to damage to the glass surfaces when washed several times in a dishwasher, with clouding, scratches, streaks or the like causing consumer dissatisfaction.
  • European patent application EP 0 383 482 (Procter & Gamble) describes machine dishwashing detergents containing insoluble zinc salts which are distinguished by improved glass corrosion protection.
  • the insoluble zinc salts must have a particle size below 1.7 millimeters in order to achieve such an effect.
  • the international patent application WO 00/39259 discloses water-soluble glasses according to DIN ISO 719, which contain at least one glass corrosion-inhibiting active ingredient, the proportion by weight of which in the glass is not more than 85% by weight and which under the conditions of cleaning and / or Rinse cycle is released from this glass.
  • the present invention was based on the object of providing a machine dishwashing detergent which, even when used repeatedly, does not corrosively change the surfaces of glassware, in particular does not cause clouding, streaks or scratches but also does not cause the glass surfaces to become iridescent.
  • the disadvantages of the prior art should be largely avoided.
  • a product should be provided that can be used universally in different program programs, is characterized by a simple and inexpensive production method and can contain varying amounts of active agent.
  • the widest possible variety of forms should be feasible in order to take changing consumer habits into account.
  • the present invention relates in a first embodiment to the use of an active substance-containing polymer matrix containing an agent which can be released from the matrix and which is able to provide corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher, for releasing the (the) agent for the corrosion protection of the glassware from the polymer matrix in the cleaning and / or rinsing processes of the dishwasher.
  • a product tailored to each application can be produced using the type of polymer, the type of anti-corrosion agent and the composition of the polymer matrix containing the active ingredient in order to release only such a concentration of active agents that the agents are effective for protecting the glassware against corrosion, but not in such a concentration that the undesirable formation of insoluble salt occurs to a significant extent.
  • the use according to the invention has the advantage that the active ingredient-containing polymer matrices can be produced much more cheaply and in a greater variety of shapes.
  • the composition according to the invention can even be formulated as packaging for automatic dishwashing detergents or as a basket into which the detergents are introduced.
  • a carrier basket made of water-insoluble, active substance-containing polymer matrix contains a polymer body made of water-soluble, active substance-containing polymer matrix. Products of this type can release the active agents to different extents from the various matrices at different times, which leads to an optimal concentration of active substance at any time during the cleaning program.
  • the use according to the invention can be achieved both with water-insoluble and with water-soluble polymers or mixtures thereof.
  • Preferred uses are characterized in that the polymer matrix comprises one or more water-soluble polymer (s).
  • the polymers which can form the polymer matrix individually or as a mixture with one another are described below.
  • the active ingredient-containing polymer matrices used according to the invention contain at least one agent which can be released from the matrix and which is able to provide corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher.
  • the agent (s) effective for corrosion protection comes from the group of compounds of zinc, aluminum, silicon, tin, magnesium, calcium, strontium, titanium, zirconium, manganese and / or lanthanum.
  • Uses which are particularly preferred according to the invention are characterized in that the agent (s) active for corrosion protection, from the group of the water-insoluble compounds of zinc, aluminum, silicon, tin, magnesium, calcium, strontium, titanium, zirconium, Manganese and / or lanthanum is (are) preferred, the oxides of the metals mentioned being preferred and zinc oxide being particularly preferred among these.
  • the agent (s) active for corrosion protection from the group of the water-insoluble compounds of zinc, aluminum, silicon, tin, magnesium, calcium, strontium, titanium, zirconium, Manganese and / or lanthanum is (are) preferred, the oxides of the metals mentioned being preferred and zinc oxide being particularly preferred among these.
  • the invention relates to a composition for use in a dishwasher, containing an active ingredient-containing polymer matrix, with a content of at least one agent that can be released from the matrix and that is able to provide corrosion protection for glassware during cleaning and / or rinsing processes To provide the dishwasher for releasing the agent (s) effective for the corrosion protection of the glassware from the polymer matrix in the cleaning and / or rinsing processes of the dishwasher.
  • compositions according to the invention can be formulated universally. For example, it is possible to provide pre-soaking agents, pre-rinsing agents, cleaning agents for the main rinse cycle or rinse aid according to the invention.
  • compositions according to the invention can also be combination products which combine two or more of the aforementioned agents.
  • the formulation of compositions according to the invention as an addition product, which is, for example, suspended in the dishwasher, is also possible without problems.
  • the active ingredient-containing polymer matrix can be incorporated into the compositions according to the invention in particulate form, but it can also be a compact shaped body, which is, for example, either a core which fills a depression in a detergent tablet, or a shaped body which, as an addition product, is like a deodorant hanger in the dishwasher is introduced. Baskets that are suitable for holding detergent tablets can also be made from the active ingredient-containing polymer matrix.
  • the polymer matrix containing the active ingredient can also be used as packaging for automatic dishwashing detergents. This is particularly attractive in the case of completely water-soluble active substance-containing polymer matrices, since the consumer does not have to unpack the product, avoids direct contact with the product, which is perceived as undesirable, and also saves other packaging materials.
  • compositions according to the invention are particularly preferably characterized in that the polymer matrix a) 5 to 99.5% by weight of one or more polymers, b) 0.5 to 95% by weight of one or more agents which are capable of corrosion protection to provide for glassware during cleaning and / or rinsing processes of a dishwasher, c) comprises 0 to 30% by weight of further active ingredients and / or auxiliaries.
  • the polymer matrix of the compositions according to the invention comprises 5 to 99.5% by weight of one or more polymers.
  • polymers designates substances that result from a collective based on the IUPAC definition Macromolecules with a chemically uniform structure, but usually differing in terms of degree of polymerization, molecular weight and chain length.
  • a polymer is “a substance that is composed of a large number of molecules in which one type or more types of atoms or groupings of atoms (so-called constitutive units, basic building blocks or repeating units) are repeated
  • constitutive units basic building blocks or repeating units
  • the different macromolecules of a polymer are made up of so many identical or similar low molecular weight building blocks (monomers) that the physical properties of the substance, especially the viscoelasticity, do not change noticeably with a slight increase or reduction in the number of building blocks
  • the size of the macromolecules means that the end groups have relatively little effect on the properties of the polymers, so that they are usually not explicitly stated in the structural formulas given below.
  • the polymers forming the matrix of the compositions according to the invention can be of both natural and synthetic origin.
  • Preferred compositions according to the invention are characterized in that the polymer matrix is 7.5 to 95% by weight, preferably 10 to 90% by weight, particularly preferably 12.5 to 85% by weight, further preferably 15 to 82.5% by weight. -% and in particular 20 to 80 wt .-% of one or more polymers, the weight data relating to the active ingredient-containing polymer matrix.
  • the average molecular weight of the polymers contained in the compositions according to the invention is preferably at least 5000 g / mol, particularly preferably at least 10,000 g / mol and in particular at least 12,000 g / mol.
  • compositions according to the invention can contain both water-insoluble and water-soluble polymers and mixtures of these polymers.
  • Preferred compositions according to the invention based on water-insoluble polymer matrices are characterized in that the polymer matrix comprises one or more water-insoluble polymers from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, polycarbonate, polyvinyl chloride, the polyurethanes, the polyamides and mixtures thereof.
  • silicones are also preferably suitable as the polymer matrix.
  • the silicone rubbers are again particularly preferred: these are masses which can be converted into the rubber-elastic state and which, as base polymers, contain polydiorganosiloxanes which have groups accessible to crosslinking reactions.
  • groups accessible to crosslinking reactions mainly H atoms, OH and vinyl groups come into question, which are located at the chain ends, but can also be built into the chain.
  • fillers can also be incorporated into this system as amplifiers, the type and amount of which increase the mechanical and influence the chemical behavior of the vulcanizates significantly.
  • finely divided silicas, diatomaceous earth (diatomaceous earth), titanium dioxide, calcium carbonate or iron oxide are used as fillers.
  • the matrix can also be colored using inorganic pigments.
  • Both hot and cold vulcanizing silicone rubbers can be used in the context of the present invention.
  • the HTV silicone rubbers are mostly plastically deformable, just yet flowable materials, which contain highly disperse silica and as crosslinking catalysts organic peroxides [benzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, t-butyl peroxybenzoate, dicumyl peroxide, organometallic salts such as dibutyltin) and after vulcanization at temperatures> 100 ° C heat-resistant, between -100 ° C and +250 ° C elastic silicone elastomers ,.
  • Another crosslinking mechanism consists in an addition of SiH groups to Si-bonded vinyl groups, which is usually catalyzed by noble metal compounds, both of which are incorporated into the polymer chains or at the end thereof.
  • LSR Liquid Silicone Rubber
  • RTV-1 The first group (RTV-1) polymerizes slowly at 20 ° C under the influence of atmospheric humidity, the crosslinking taking place by condensation of SiOH groups with the formation of Si.O bonds.
  • RTV-2 crosslinker
  • z. B. mixtures of silicic acid esters (z. B. ethyl silicate) and organotin compounds are used, with the formation of a Si-O-Si bridge from ° Si-OR and ° Si-OH as a crosslinking reaction by alcohol elimination.
  • a silicone which can preferably be used in the context of the present invention is, for example, Dow Corning 3110 RTV, which can be crosslinked at room temperature with Dow Corning RTV Catalyst No. 4.
  • P 'olyethylene are associated with the polyolefins polymers having groups of the type - [CHz-CHz] - as a characteristic basic unit of the polymer chain.
  • Polyethylenes are produced by polymerizing ethylene using two fundamentally different methods, the high-pressure and the low-pressure process. The resulting products are accordingly often referred to as high-pressure polyethylene or low-pressure polyethylene; they differ mainly in their degree of branching and, related to this, in their degree of crystallinity and density. Both processes can be carried out as solution polymerization, emulsion polymerization or gas phase polymerization.
  • HMW-LDPE high molecular weight.
  • the pronounced degree of branching of the polyethylenes produced by the high-pressure process can be reduced by copolymerization of the ethylene with longer-chain olefins, in particular with butene and octene; the copolymers have the code LLD-PE (linear low density polyethylene).
  • the macromolecules of the polyethylenes from low-pressure processes are largely linear and unbranched. These polyethylenes (HDPE) have degrees of crystallinity of 60-80% and a density of approx. 0.94-0.965 g / cm 3 .
  • Polypropylenes are thermoplastic polymers of propylene with basic units of the type
  • Polypropylenes can be prepared by stereospecific polymerization of propylene in the gas phase or in suspension to give highly crystalline isotactic or less crystalline syndiotactic or amorphous atactic polypropylenes.
  • Polypropylene is characterized by high hardness, resilience, rigidity and heat resistance.
  • the mechanical properties of the polypropylenes can be improved by reinforcement with talc, chalk, wood flour or glass fibers, and the application of metallic coatings is also possible, which expands the possibilities for the aesthetic design of the compositions according to the invention.
  • Polytetrafluorethylene (PTFE, Teflon ® ) are polymers of tetrafluoroethylene with the general formula: - [CF 2 -CF 2 ] n -
  • PTFE are thermoelastic polymers with high linearity, a relatively high (up to 70%) degree of crystallinity and a melting point of approx. 327 ° C.
  • Polytetrafluorethylenes have an extremely high chemical resistance and are insoluble in all solvents below 300 ° C.
  • PTFE can be used in a very wide temperature range (-200 ° C to 250 ° C).
  • Polystyrene polyphenylethylene, polyvinylbenzene
  • abbreviation PS thermoplastic polymers of the structure
  • PS is almost exclusively produced by radical polymerization of styrene.
  • the methods of suspension or peripolymerization, emulsion, bulk and solution polymerization are most frequently used for this purpose.
  • the polystyrenes Depending on the polymerization conditions, the polystyrenes have molar masses of 170,000 to 1,000,000 g / mol. Depending on the type of polymerization, a powdery product (by emulsion, solution and peripolymerization) or a melt (bulk polymerization) is obtained.
  • Amorphous PS is crystal clear, stiff and quite brittle; it is resistant to acids, alkalis, alcohol and mineral oil, but is resistant to most solvents (tension cracking) or soluble in them. The light resistance is also low due to the ease of photooxidation, as is the water absorption.
  • PET Polyethylene terephthalates
  • PET have a density of approx. 1.38 g / cm 3 , a melting point of approx. 260 ° C and are semi-crystalline products with high strength, rigidity and dimensional stability, good sliding and wear properties as well as high chemical resistance.
  • the degree of crystallinity (30-40%) is reduced by incorporating foreign building blocks (isophthalic acid and / or 1,4-cyclohexanedimethanol).
  • the resulting copolyesters have high transparency, toughness, dimensional stability and favorable creep, sliding, wear and stress cracking properties.
  • PC Polycarbonates
  • polyester polycarbonates are u. a. accessible by reacting bisphenols with phosgene and aromatic dicarboxylic acid dichlorides.
  • Aromatic. Polycarbonates have molar masses in the range of approx. 10,000-200,000 g / mol, which can be adjusted using regulators during the polycondensation process.
  • Sje have a low density (approx. 1.2 g / cm 3 ), relatively high glass transition temperatures (-150 ° C) and melting points (150-300 ° C) and are in a wide temperature range (- 150 ° C to 150 ° C) can be used. They are resistant to water, neutral salt solutions, mineral acids, aqueous solutions of oxidizing agents, hydrocarbons, oils and fats, but are dissolved by certain chlorinated hydrocarbons, especially methylene chloride.
  • PVC Polyvinylchloride
  • the macromolecules are not strictly linear: depending on the monomer conversion and the polymerization temperature, they have approx. 3-20 short side chains per 1000 carbon atoms.
  • Technical polyvinyl chlorides have molar masses of approx. 30,000-130000 g / mol.
  • Polyamides are high-molecular compounds that consist of building blocks linked by peptide bonds.
  • the synthetic polyamides (PA) are thermoplastic, chain-like polymers with recurring acid amide groups in the main chain.
  • AS aminocarboxylic acid types
  • AA-SS diamine dicarboxylic acid types
  • A denotes amino groups and S carboxy groups.
  • the former are formed from one building block by polycondensation (amino acid) or polymerization ( ⁇ -lactam), the latter from two building blocks by polycondensation (diamine and dicarboxylic acid).
  • the polyamides are coded from unbranched aliphatic building blocks according to the number of carbon atoms.
  • PA 6 is the polyamide and ⁇ -aminocaproic acid or ⁇ -caprolactam.
  • PA 12 is a poly ( ⁇ -lauric lactam) made from ⁇ -lauric lactam.
  • PA 66 polyhexamethylene adipamide
  • PA 610 polyhexamethylene sebacinamide
  • PA 612 polyhexamethylene dodecanamide
  • Polyurethanes are polymers (polyadducts) with groupings of the type that are accessible through polyaddition from dihydric and higher alcohols and isocyanates
  • TDI 2,4- or 2,6-toluenediisocyanate
  • MDI C 6 H 4 -CH Z -C 6 H 4
  • water-soluble polymers of natural or synthetic origin can also form the polymer matrix.
  • compositions according to the invention are characterized in that the polymer matrix comprises one or more water-soluble polymers, the water-soluble polymer (s) preferably being selected from: i) polyacrylic acids and their salts ii) polymethacrylic acids and their salts iii) polyvinylpyrrolidone, iv) vinylpyrrolidone / vinyl ester copolymers, v) cellulose ethers vi) polyvinyl acetates, polyvinyl alcohols and their copolymers vii) graft copolymers of polyethylene glycols and vinyl acetate viii) alkylacrylamide / acrylic acid copolymers and their salts ix) methacrylic acrylamide copolymer x) alkyl acrylamide / methyl methacrylic acid copolymers and their salts xi) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their
  • Copolymers and their salts xv) Copolymers of xv-i) unsaturated carboxylic acids and their salts xv-ii) cationically derivatized unsaturated carboxylic acids and their salts xvi) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers as well as their alkali and ammonium salts xvii) acrylamidoalkyltrialkylacidic acid / ammonium chloride
  • Carboxylic acids xxiii-i) unsaturated carboxylic acids, xxiii-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or
  • Esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C 8 - ⁇ alcohol are saturated or unsaturated, straight-chain or branched C 8 - ⁇ alcohol.
  • Polyvinylpyrrolidones iii) are for example sold under the name Luviskol ® (BASF). Polyvinylpyrrolidones are preferred polymers in the context of the present invention. Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)
  • polyvinylpyrrolidones which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators.
  • free-radical formers peroxides, azo compounds
  • the ionic polymerization of the monomer only provides products with low molecular weights.
  • Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered.
  • Vinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.). Vinylpyrrolidone / Vinylester copolymers IV) are for example sold under the trademark Luviskol ® (BASF). Luviskol ® VA 64 and Luviskol ® VA 73, both vinyl pyrrolidone / vinyl acetate copolymers, are particularly preferred polymers.
  • the vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (II)
  • the vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization).
  • Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)
  • cellulose ethers v) are particularly hydroxypropyl cellulose, hydroxyethyl cellulose and methyl as, for example, sold under the trademark Culminal.RTM ® and Benecel ® (Aqualon), into consideration.
  • Cellulose ethers can be described by the general formula (III)
  • R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical.
  • at least one R in formula (III) 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 have reacted with the etherification reagent or how many moles of etherification reagent have been added to an anhydroglucose unit on average , Hydroxy-ethyl celluloses are water-soluble from a DS of approx. 0.6 or an MS of approx. 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 - propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.
  • water-soluble polymers are polyvinyl acetals, polyvinyl alcohols and their copolymers.
  • homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers are preferred, so that compositions according to the invention in which the water-soluble polymer (s) is selected / are composed of homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers, are preferred embodiments of the present invention.
  • These polymers are therefore primarily produced from polyvinyl esters, in particular polyvinyl acetates, via polymer-analogous reactions such as hydrolysis, but technically in particular by alkaline-catalyzed transesterification with alcohols (preferably methanol) in solution.
  • polyvinyl alcohols are particularly preferred as water-soluble polymers.
  • Polyvinyl alcohols abbreviated as PVAL, are polymers of the general structure
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups.
  • the manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable.
  • the water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water.
  • reaction products made of PVAL and starch are extremely advantageous to use. Furthermore, the solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.
  • Polyvinyl alcohol is largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through.
  • compositions preferred in the context of the present invention are characterized in that the water-soluble polymer is a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -%.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used, compositions according to the invention being preferred in which the water-soluble polymer is a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol "1 , preferably from 11,000 to 90,000 gmol " 1 , particularly preferably from 12,000 to 80,000 gmol "1 and in particular from 13,000 to 70,000 gmol " 1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Erkol ® (Fa. Erkol). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example Erkol ® 3-83, 4-88 Erkol ®, Erkol ® 5-88 and 8-88 Erkol ®. Further polyvinyl alcohols which are particularly suitable as material for the polymer matrix can be found in the table below:
  • ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
  • ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
  • Gohsenol ® NK-05, A-300, AH-22, C- 500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM1 1 Q, KZ-06 (trademark of Nippon Gohsei KK).
  • graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols are also suitable as water-soluble polymers a).
  • Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds on polyalkylene glycols are obtained by polymerization in the heat in a homogeneous phase in that the polyalkylene glycols are converted into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid In the presence of radical formers.
  • Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.
  • Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols.
  • Polyethylene glycols are polymers of ethylene glycol which have the general formula IV
  • n can take on values between 1 (ethylene glycol) and several thousand.
  • polyethylene glycols There are various nomenclatures for polyethylene glycols that can lead to confusion. It is technically common to specify the average relative molecular weight after the Specification "PEG", so that "PEG 200" characterizes a polyethylene glycol with a relative molar mass of approx. 190 to approx. 210.
  • PEG the average relative molecular weight after the Specification
  • PEG 200 characterizes a polyethylene glycol with a relative molar mass of approx. 190 to approx. 210.
  • a different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above.
  • polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone -Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
  • PPG Polypropylene glycols
  • the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.
  • the polyethylene glycol used has a molecular weight of between 200 and several million, preferably between 300 and 30,000.
  • the monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.
  • the monomers of the second group can likewise be of very different types, with graft polymers particularly preferably containing crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid.
  • Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin.
  • the grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight, of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is.
  • Suitable water-soluble polymers are copolymers of alkyl acrylamide with acrylic acid, alkyl acrylamide with methacrylic acid, alkyl acrylamide with methyl methacrylic acid and also alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / Methyl methacrylic acid / alkylamino-alkyl (meth) acrylic acid copolymers, alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and
  • Copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids, optionally further ionic or nonionic monomers are also known as copolymers.
  • polymers suitable according to the invention are water-soluble amphopolymers.
  • Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -COOH or S0 3 H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - COO '-.
  • amphopolymer suitable is the acrylic resin commercially available as Amphomer ®, is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters.
  • Preferred amphopolymers are composed of unsaturated carboxylic acids (eg acrylic - and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally other ionic or nonionic monomers together.
  • Other suitable amphoteric polymers are for example sold under the names Amphomer ® and Amphomer ® LV-71 (DELFT NATIONAL) available octylacrylamide / methyl methacrylate / tert-Butylaminoethylmeth acrylate / 2-hydroxypropyl methacrylate copolymers.
  • Suitable zwitterionic polymers are, for example, acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts. Further suitable zwitterionic polymers are methacroyl ethylbe- Tdin / methacrylate copolymers, which are available under the name Amersette® ® (AMERCHOL).
  • Anionic polymers suitable according to the invention include a .:
  • Vinyl acetate-crotonic acid copolymers such as are commercially available for example under the names Resyn ® (National Starch), Luviset ® (BASF) and Gafset ® (GAF).
  • Resyn ® National Starch
  • Luviset ® BASF
  • Gafset ® GAF
  • these polymers also have monomer units of the general formula (VI):
  • Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers which are sold, for example, under the name Ultrahold ® strong (BASF).
  • Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds on polyalkylene glycols are obtained by polymerization in the heat in a homogeneous phase in that the polyalkylene glycols are converted into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid In the presence of radical formers.
  • Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.
  • the grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight, of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is.
  • Copolymers obtained by copolymerization of at least one monomer from each of the following three groups are also suitable according to the invention as ingredient a): i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or
  • Esters of short-chain saturated alcohols and unsaturated carboxylic acids ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C 8 _ 18 alcohol
  • Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, the carbon chains of these compounds being optionally interrupted by double-bonded hetero groups such as -O-, -NH-, -S-.
  • polyurethanes are water-soluble in the sense of the invention if they are more than 2.5% by weight soluble in water at room temperature.
  • the polyurethanes consist of at least two different types of monomers, a compound (A) with at least 2 active hydrogen atoms per molecule and a di- or polyisocyanate (B).
  • the compounds (A) can be, for example, diols, triols, diamines, triamines, polyetherols and polyesterols.
  • the compounds with more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds with 2 active hydrogen atoms.
  • Examples of compounds (A) are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, di-, tri-, tetra- and poly-ethylene and propylene glycols, copolymers of lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, Ethylenediamine, propylenediamine, 1, 4- Diaminobutane, hexamethylenediamine and ⁇ , ⁇ -diamines based on long-chain alkanes or polyalkylene oxides.
  • Polyurethanes in which the compounds (A) are diols, triols and polyetherols can be preferred according to the invention.
  • polyethylene glycols and polypropylene glycols with molecular weights between 200 and 3000, in particular between 1600 and 2500 have proven to be particularly suitable in individual cases.
  • Polyesterols are usually obtained by modifying compound (A) with dicarboxylic acids such as phthalic acid, isophthalic acid and adipic acid.
  • the compounds (B) used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate. These compounds can be described by the general formula VII:
  • R 1 represents a connecting group of carbon atoms, for example a methylene-ethylene-propylene, butylene, pentylene, hexylene, etc. group.
  • HMDI hexamethylene diisocyanate
  • R 4 (CH 2 ) 6
  • TDI 2,4- or 2,6-toluenediisocyanate
  • R 4 stands for C 6 H 3 -CH 3
  • MDI 4,4'-methylenedi (phenyl isocyanate)
  • MDI isophorone diisocyanate
  • R 4 represents the isophorone residue (3,5,5-trimethyl-2-cyclohexenone)
  • polyurethanes used according to the invention can also contain building blocks such as diamines as chain extenders and hydroxycarboxylic acids.
  • building blocks such as diamines as chain extenders and hydroxycarboxylic acids.
  • Dialkylolcarboxylic acids such as dimethylolpropionic acid are particularly suitable hydroxycarboxylic acids.
  • the other building blocks there is no fundamental restriction as to whether the building blocks are nonionic, anionic or cationic.
  • Polyurethanes which can be characterized as follows, have proven particularly suitable according to the invention in many cases:
  • compositions according to the invention contain at least partially polyalkylene glycol units in the molecule.
  • Compositions according to the invention are particularly preferred here in which the water-soluble polymer (s) is / are selected from polyurethanes from diisocyanates (VII) and diols (VIII).
  • H-0-R 2 -0-H VIII
  • the diols being selected at least in part from polyethylene glycols (IV) and / or polypropylene glycols (V)
  • CH 3 and R 1 and R 2 independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical with 1 to 24 carbon atoms and n each represent numbers from 5 to 2000.
  • the reaction mixtures can additionally contain further polyisocyanates. It is also possible for the reaction mixtures - and therefore the polyurethanes - to contain other diols, triols, diamines, triamines, polyetherols and polyesterols.
  • the compounds with more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds with 2 active hydrogen atoms.
  • Polyurethanes in which at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight and in particular at least 75% by weight of the diols reacted in the polyurethane are selected from polyethylene glycols (IV ) and / or polypropylene glycols (V).
  • n is a number between 6 and 1500, preferably between 7 and 1200, particularly preferably between 8 and 1000 , more preferably between 9 and 500 and in particular between 10 and 200.
  • Examples of compounds optionally further contained in the reaction mixtures for the preparation of the polyurethanes are ethylene glycol, 1, 2- and 1, 3-propylene glycol, butylene glycols, ethylenediamine, propylenediamine, 1, 4-diaminobutane, hexamethylenediamine and ⁇ , ⁇ -diamines based on long-chain Alkanes or polyalkylene oxides.
  • Compositions in which the polyurethanes contain additional diamines, preferably hexamethylenediamine and / or hydroxycarboxylic acids, preferably dimethylolpropionic acid, are preferred.
  • compositions which are particularly preferred in the context of the present invention are characterized in that the water-soluble polymer is a polyurethane composed of diisocyanates (I) and diols (II)
  • compositions according to the invention in which the water-soluble polymer is a polyurethane which has structural units of the formula (IX)
  • R 1 is for - (CH 2 ) 6 - or for 2,4- or 2,6-C 6 H 3 -CH 3 , or stands for Cs ⁇ -CHz-Ce ⁇
  • R 2 is selected from -CH 2 -CH 2 - (0-CH 2 -CH 2 ) n - or - CH (CH 3 ) -CH 2 - (0-CH (CH 3 ) -CH 2 ) n -, where n is a number from 5 to 199 and k is a number from 1 to 2000.
  • compositions according to the invention comprise polyurethanes which have one or more of the structural units (IX a) to (IX h):
  • n is a number from 5 to 199 and k is a number from 1 to 2000.
  • reaction mixtures can also contain further compounds from the group of polyisocyanates (in particular triisocyanates and tetraisocyanates) and from the group of polyols and / or di- or polymains.
  • polyisocyanates in particular triisocyanates and tetraisocyanates
  • Triols, tetrols, pentols and hexols as well as di- and triamines can be contained in the reaction mixtures.
  • a content of compounds with more than two “active” H atoms leads to partial crosslinking of the polyurethane reaction products and can have advantageous properties such as, for example, control of the dissolution behavior, abrasion stability or flexibility of the polymer matrices according to the invention Process advantages in production, etc.
  • the content of such compounds with more than two “active” H atoms in the reaction mixture is less than 20% by weight of the total reactants used for the diisocyanates, preferably less than 15% by weight and in particular less than 5% by weight.
  • the polyurethanes in the compositions according to the invention have molar masses from 5000 to 150,000 gmol "1 , preferably from 10,000 to 100,000 gmol " 1 and in particular from 20,000 to 50,000 gmol "1 .
  • a particularly preferred polymer for the active substance-containing polymer matrix is a polymer which contains sulfonic acid groups.
  • Preferred compositions according to the invention are therefore characterized in that the polymer matrix comprises at least one copolymer of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers.
  • Preferred among these monomers are those of the formulas Xla, Xlb and / or Xlc,
  • H 2 C CH-X-S0 3 H (Xla),
  • H 2 C C (CHg) -X-S0 3 H (Xlb),
  • ionic or nonionic monomers that can be used are, in particular, ethylenically unsaturated compounds.
  • the group iii) monomer content of the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).
  • copolymers are made of
  • R 1 (R 2 ) C C (R 3 ) COOH (X), in which R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched , mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH 2 , -OH or - COOH as defined above or for -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or is a branched hydrocarbon radical having 1 to 12 carbon atoms,
  • Particularly preferred copolymers consist of
  • H 2 C CH-X-S0 3 H (Xla),
  • H 2 C C (CH 2 ) -X-S0 3 H (Xlb),
  • the copolymers can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • compositions according to the invention are preferred which are characterized in that they contain one or more copolymers, the structural units of the formula XII, as the polymer matrix
  • compositions according to the invention contain one or more copolymers as the polymer matrix, the structural units of the formula XII
  • acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • Compositions according to the invention which contain one or more copolymers as the polymer matrix, which structural units of the formula XIV
  • compositions according to the invention which are characterized in that they contain, as polymer matrix, one or more copolymers which have structural units of the formula XVI
  • compositions according to the invention which contain, as polymer matrix, one or more copolymers which have structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII
  • the sulfonic acid groups in the polymers can be wholly or partly in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • metal ions preferably alkali metal ions and in particular by sodium ions.
  • Corresponding compositions which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.
  • the monomer distribution of the copolymers used in the compositions according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,
  • compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred compositions are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol "1 , preferably from 4000 to 25,000 gmol " 1 and in particular from 5000 to 15,000 gmol "1 .
  • the active ingredient-containing polymer matrix which is contained in the compositions according to the invention has, in addition to the polymer (s), a content of at least one agent which can be released from the matrix and which is able to provide corrosion protection for glassware in cleaning and / or to provide dishwashing operations for a dishwasher.
  • Compositions preferred according to the invention are characterized in that the polymer matrix 1 to 90% by weight, preferably 1.5 to 80% by weight, particularly preferably 2 to 70% by weight, further preferably 2.5 to 60% by weight and in particular 3 to 50% by weight of one or more agents which are able to provide corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher, the weight information relating to the active ingredient-containing polymer matrix.
  • Preferred agents which are able to provide corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher come from the group of the compounds of zinc, aluminum, silicon, tin, magnesium, calcium, strontium, titanium, Zirconium, manganese and / or lanthanum. Of the compounds mentioned, the oxides are particularly preferred.
  • a preferred agent for providing corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher is zinc in oxidized form, i.e. Zinc compounds in which zinc is cationic.
  • Zinc compounds in which zinc is cationic are zinc in oxidized form.
  • magnesium salts are also preferred.
  • both soluble and poorly or insoluble zinc or magnesium compounds can be embedded in the polymer matrix.
  • Preferred compositions according to the invention contain one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid in the active ingredient-containing polymer matrix.
  • the acids in question preferably originate from the group of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the Amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acids with at least 8 carbon atoms and / or resin acids.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be contained in the polymer matrix, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.
  • the acids mentioned below are preferred within these groups:
  • benzoic acid 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3 , 5-Dicar boxybenzoic acid (trimesionic acid).
  • sugar acids galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.
  • hydroxy acids From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxy succinic acid (malic acid), 2,3-dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1, 2,3-propanetricarboxylic acid (citric acid), ascorbic acid , 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
  • oxo acids 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
  • amino acids From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.
  • polyacrylic acid polymethacrylic acid
  • alkyl acrylamide / acrylic acid copolymers alkyl acrylamide / methacrylic acid copolymers
  • alkyl acrylamide / methyl methacrylic acid copolymers copolymers of unsaturated carboxylic acids
  • vinyl acetate / crotonic acid copolymers vinyl pyrrolidone / vinyl acrylate.
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:
  • compositions according to the invention contain at least one zinc salt but no magnesium salt of an organic acid in the polymer matrix, it preferably being at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, Zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate can also be used with preference
  • the active substance-containing polymer matrix can consist exclusively of polymer (s) and the agents described above to achieve glass corrosion inhibition, but it can also contain other ingredients. Additives to be mentioned here in particular, as are customary in polymer production, for example plasticizers, antioxidants, rheology improvers or other processing aids. However, other ingredients from the field of washing or cleaning agents, for example colorants and fragrances, can also be part of the polymer matrix.
  • Hydrophilic, high-boiling liquids in particular, can be used as plasticizers in the compositions according to the invention, it also being possible, if appropriate, to use solids as a solution, dispersion or melt at room temperature.
  • Particularly preferred compositions according to the invention are characterized in that the plasticizer is one or more materials from the group consisting of glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, Dodecaethylene glycol, glycerin, neopentyl glycol, trimethylolpropane, pentaerythritol, mono-, di-, triglycerides, surfactants, in particular nonionic surfactants, and mixtures thereof are used.
  • compositions according to the invention can contain the active substance-containing polymer matrix in different amounts. Depending on whether the active ingredient-containing polymer matrix is contained in the compositions as a fine powder, granules, etc., or as part of a shaped body, or whether it encloses the composition as packaging, the proportions of the active ingredient-containing polymer matrix in the overall composition can vary. Compositions according to the invention are preferred here which, based on the total mass of the composition, 1 to 40% by weight, preferably 1.5 to 35% by weight, particularly preferably 2 to 30% by weight and in particular 2.5 to 20% % By weight of the active ingredient-containing polymer matrix.
  • compositions according to the invention Depending on the active substance content of the active substance-containing polymer matrix and on the amount of polymer matrix which is contained in the compositions according to the invention, the contents of the compositions according to the invention in the agent which can be released from the matrix and which is capable of providing corrosion protection for glassware Providing cleaning and / or rinsing processes of a dishwasher vary.
  • compositions according to the invention which are characterized in that, based on the total mass of the composition, they contain at least one from the group of the compounds of zinc, aluminum, silicon, tin, magnesium, calcium, strontium, titanium, zirconium, manganese and / or lanthanum Substances in amounts of 0.1 to 20% by weight, preferably 0.2 to 15% by weight and in particular 0.4 to 10% by weight, are preferred.
  • compositions which contain at least one zinc salt are particularly preferred, the composition preferably comprising zinc in oxidized form in amounts of from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0 , 04 to 0.2 wt .-%, each based on the total weight of the composition contains.
  • the incorporation of polymer matrices according to the invention into the compositions according to the invention does not impose any restriction on the forms of supply or the formulations of these compositions.
  • pre-rinse or pre-rinse products, rinse aids, machine cleaners or additional products can also be provided as the composition according to the invention.
  • a preferred embodiment of the composition according to the invention provides that the polymer matrix is provided as a molded part to be introduced separately into the dishwasher, which releases the agents from the polymer matrix over several rinse cycles. This molded part can either be a dosing basket for other products, such as the cleaner, but it can also be a separate and separate molded part Embody the additional benefit of protecting the glass.
  • Possible shapes are based, for example, on the known dishwasher dodorants.
  • the design of the plastic part in a translucent, opalescent or completely clear form, for example in the form of a stylized diamond, is visually appealing.
  • Such product designs make it possible to visualize the gloss resulting from the gentle use of glass in a consumer-friendly manner.
  • the active ingredient-containing polymer matrices can easily be reshaped using standard methods.
  • the shaping processing is carried out according to the methods customary in the plastics processing industry, with film production and further processing, blow molding and injection molding being preferred in particular. All processes have in common that a plastic granulate is melted with the help of an extruder and fed to shaping tools.
  • the plastic granulate may already contain the agents for inhibiting glass corrosion, but these can also be added during melting in the extruder, which enables the polymer matrices according to the invention to be produced particularly cost-effectively.
  • a melted polymer blend is then present on the extruder head and, depending on the desired molded part, is further processed using conventional methods of thermoforming polymers, deep-drawing, so-called rotary die processes, blow molding (blow extrusion) and injection molding being of particular importance.
  • thermoforming polymers deep-drawing, so-called rotary die processes, blow molding (blow extrusion) and injection molding being of particular importance.
  • shaping can be carried out to form foils, which can then be further processed.
  • the material thickness of the film can vary. For foil bags, so-called pouches, lower material thicknesses are to be selected than for foils that will later be used for deep-drawing or rotary die processes. If the molded parts from the polymer matrix containing the active ingredient are to be used later as a type of packaging, they must of course be water-soluble in order to release the contents of the packaging and to leave no residues in the dishwasher.
  • the water-soluble film which forms the pouch has a thickness of 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, particularly preferably 5 to 75 ⁇ m and in particular 10 to 50 ⁇ m , having.
  • Films for deep-drawing processes preferably have thicknesses that are 1.5 times, preferably twice and in particular 2.5 times the values mentioned for pouches.
  • the foils are blown with air from a melt leaving the extruder via a blow mandrel to form a tube. This can then be cut, filled and sealed.
  • the raw materials plasticized by suitable additives are atomized to form the films. Here it may be necessary to connect drying to the atomizers.
  • the films obtained by this process can then also be shaped into bags and closed when filled.
  • melt leaving the extruder is blow-molded from water-soluble polymer blend.
  • Blow molding methods suitable according to the invention include extrusion blow molding, coextrusion blow molding, injection stretch blow molding and immersion blowing.
  • the wall thicknesses of the moldings can be produced differently in some areas by means of blow molding, by correspondingly varying the wall thicknesses of the preform, preferably along its vertical axis, preferably by regulating the amount of thermoplastic material, preferably by means of an adjusting spindle when the preform is removed from the extruder nozzle, formed.
  • the molded body can be blow-molded with areas of different outer circumference and constant wall thickness by changing the wall thicknesses of the preform, preferably along its vertical axis, correspondingly to different thicknesses, preferably by regulating the amount of thermoplastic material by means of an adjusting spindle when the preform is being removed from the extruder nozzle, formed.
  • bottles, balls, Santa Clauses, Easter bunnies or other figures can be blow-molded, which can be filled with agents, then sealed and then removed from the mold.
  • the molded body can be embossed and / or decorated in the blow mold during blow molding.
  • a motif can be transferred to the molded body in mirror image.
  • the surface of the molded body can be designed practically as desired.
  • information such as calibration marks, application instructions, hazard symbols, brands, weight, filling quantity, expiry date, pictures, etc. can be applied to the molded body in this way.
  • the preform, the shaped body and / or the liquid-tightly closed shaped body can be tubular, spherical or bubble-shaped.
  • the shape factor in the sense of the present invention can be precisely determined by modern particle measurement techniques with digital image processing.
  • a common method is, for example, the Camsizer® system from Retsch Technology or the KeSizer® from Kemira. These methods are based on the fact that the bodies are irradiated with a light source and the shaped bodies are recorded, digitized and processed by computer technology as projection surfaces.
  • the surface curvature is determined by an optical measuring method in which the “shadow cast” of the body to be examined is determined and converted into a corresponding form factor.
  • the basic principle for determining the form factor was described, for example, by Gordon Rittenhouse in “A Visual method of estimating two -dimensional sphericity "in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pages 79-81.
  • the measuring limits of this optical analysis method are 15 ⁇ m to 90 mm.
  • Methods for determining the shape factor for larger particles are known to the person skilled in the art. These are usually based on the principles of the
  • the walls of the molded articles produced by blow molding have a wall thickness of between 0.05 and 5 mm, preferably between 0.06 and 2 mm, preferably between 0.07 and 1.5 mm, more preferably between 0.08 and 1 , 2 mm, more preferably between 0.09-1 mm and most preferably between 0.1-0.6 mm.
  • the filling opening of the hollow body after filling can be closed in a liquid-tight manner, preferably by material closure, preferably by means of thermal treatment, particularly preferably by applying a hot melt.
  • the filling opening or openings of the hollow body can also advantageously be closed in a liquid-tight manner by thermal treatment, preferably by fusing the walls which adjoin the opening, in particular by means of clamping jaws.
  • blow molding process as a BFS (blow-fill-seal) process, so that the moldings produced are still filled and sealed in the blow mold.
  • BFS blow-fill-seal
  • the desired shape is first blown, then filled with the content and then closed in one operation.
  • a tube of plasticized water-soluble plastic material is extruded into an open blow mold, the blow mold is closed and by generating an am Effective pressure gradient expanded this hose and applied to the forming wall of the blow mold to form the container.
  • the melt of water-soluble polymer blend leaving the extruder is processed to give a shape by means of an injection molding process.
  • the injection molding is carried out according to methods known per se at high pressures and temperatures with the steps of closing the mold connected to the extruder for injection molding, injecting the polymer at high temperature and high pressure, cooling the injection-molded molding, opening the mold and removing the molded blank , Further optional steps such as the application of release agents, demolding etc. are known to the person skilled in the art and can be carried out using technology known per se.
  • injection molding is carried out at a pressure between 100 and 5000 bar, preferably between 500 and 2500 bar, particularly preferably between 750 and 1500 bar and in particular between 1000 and 1250 bar.
  • the temperature of the material to be injection molded is preferably above the melting or softening point of the material and thus also depends on the type and composition of the polymer blend. In preferred processes according to the invention, injection molding is carried out at temperatures between 100 and 250 ° C., preferably between 120 and 200 ° C. and in particular between 140 and 180 ° C.
  • the tools that hold the materials are preferably preheated and have temperatures above room temperature, temperatures between 25 and 60 ° C. and in particular from 35 to 50 ° C. being preferred.
  • the thickness of the wall can be varied.
  • the wall should be chosen so thin that a rapid dissolution or disintegration is achieved and the ingredients are quickly released into the application fleet, but is also a certain minimum thickness is required to give the hollow shape the desired stability, in particular shape stability.
  • the wall thickness of the injection molded body is 100 to 5000 ⁇ m, preferably 200 to 3000 ⁇ m, particularly preferably 300 to 2000 ⁇ m and in particular 500 to 1500 ⁇ m.
  • the molded body produced by injection molding regularly does not have closed walls on all sides and is open on at least one of its sides - in the case of a spherical or elliptical body in the region of part of its shell - due to the production process.
  • a or preparation (s) are / are filled into the compartment (s) formed in the interior of the molded body. This also takes place in a manner known per se, for example in the context of production processes known from the confectionery industry; Procedures that run in several steps are also conceivable.
  • a one-step procedure is particularly preferred if, in addition to solid preparations, preparations (dispersions or emulsions, suspensions) comprising liquid components or even preparations (foams) comprising gaseous components are to be introduced into moldings.
  • methods according to the invention are preferred in which the shaping processing is carried out by extrusion into an injection mold (by injection molding).
  • compositions according to the invention can also be realized as “normal” products which contain the active substance-containing polymer matrix as one of several substances.
  • Compositions according to the invention can therefore can also be provided as machine dishwashing detergents, rinse aid or machine cleaners in both solid and liquid form.
  • Liquid cleaning agents in the context of the present invention, are aqueous and non-aqueous agents based on liquid constituents, with dynamic viscosities in the range between 0.2 and 1000 mPa-s, but also more viscous agents with viscosities above 1000 mPa-s up to cut-resistant and dimensionally stable gels are possible forms of offer.
  • Preferred non-aqueous liquid cleaning agents contain solvents from the group consisting of ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol -n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl
  • these typically also contain one or more thickeners.
  • Preferred thickeners are agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,
  • Hydroxypropylmethylcellulose Kemmehlether, Polyacryl- u.
  • Polymethacrylic compounds vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas.
  • hydrotropes Another typical component of liquid aqueous cleaning agents are hydrotropes.
  • the addition of such substances causes a poorly soluble substance to become water-soluble in the presence of the hydrotrope, which is not itself a solvent.
  • Substances that bring about such an improvement in solubility are referred to as hydrotropes or hydrotropes.
  • Typical hydrotropes e.g. xylene and cumene sulfonate are used in the assembly of liquid detergents or cleaning agents.
  • Other substances e.g. Urea or N-methylacetamide, increase the solubility through a structure-breaking effect, in which the water structure in the vicinity of the hydrophobic group of a poorly soluble substance is broken down.
  • Solid forms of the automatic dishwashing agent according to the invention are, for example, fine to coarse-grained powders, such as are obtained, for example, by spray drying or granulation, compacted substance mixtures from roller compaction, but also solidified melts or moldings obtained by extrusion or tableting.
  • shaped bodies of this type can have practically all expediently manageable configurations, for example in the form of a table, in the form of bars or bars, a cube, a cuboid and a corresponding spatial element with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section ,
  • This last embodiment encompasses the form of presentation from the actual tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • Preferred tableted or extruded agents have two or more phases in the context of the present invention, which can be determined, for example, by their composition Share in the total volume of the molded body and / or their visual appearance.
  • the phases of such multiphase molded articles can additionally be distinguished by a different dissolution behavior in the aqueous phase.
  • Shaped bodies of this type are suitable for the time-controlled release of certain ingredients (controlled release), for example in certain rinse cycles of the automatic washing program.
  • one of the phases of the molded body has meltable or softenable substances from the group of waxes, paraffins and / or polyalkylene glycols as the main constituent.
  • the molded body or molded body component containing these meltable or softenable substances is at least largely water-insoluble.
  • the solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C. and should preferably be below 5 mg / l.
  • the meltable or softenable substances should have the lowest possible solubility in water, even in water at an elevated temperature, in order to largely avoid a temperature-independent release of the active substances. The active substance is released in this way when the melting or softening point is reached.
  • an agent containing the active ingredient-containing polymer matrix to the rinsing process in addition to a commercially available cleaning agent, for example in the form of a special glass protective agent.
  • a dosage can take place both before the start of each washing program and in the form of a depot product which brings about a continuous release of the zinc and / or magnesium salts according to the invention over several washing cycles.
  • preferred automatic dishwashing agents In addition to the builders (builders, cobuilders) and the polymer matrix containing active ingredients, preferred automatic dishwashing agents according to the invention furthermore contain one or more substances from the group of surfactants, bleaching agents, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors, polymers, or another conventional constituent of detergents. and detergents. These ingredients are described below.
  • all builders usually used in detergents and cleaning agents can be incorporated into the washing and cleaning agents, in particular silicates, carbonates, organic cobuilders and also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula H 2 0, 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 are 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 yH 2 0 are preferred.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments.
  • This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • Both monoalkali metal salts and dialkali metal salts of carbonic acid as well as sesquicarbonates can be included in the compositions as carbonates.
  • Preferred alkali metal ions are sodium and / or potassium ions.
  • Compounds made of, for example, carbonate, silicate and optionally other auxiliaries such as anionic surfactants or other, in particular organic builder substances, can also be present as separate components in the finished compositions.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one Metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 4 can distinguish in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale deposits on the wash ware and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 P0 exists as a dihydrate (density 1.91, preferably “3 , melting point 60 °) and as a monohydrate (density 2.04, preferably " 3 ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 0 7 ) at 200 ° C, and at higher temperature in sodium trimetaphosphate (Na 3 P 3 0 9 ) and Maddrell's salt (see below).
  • NaH 2 P0 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with a Naronauge and the mash is sprayed.
  • Potassium dihydrogen phosphate primary or monobasic potassium phosphate, potassium biphoshate, KDP
  • KH 2 P0 4 is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) J and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0, is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly " 3 , melting point 48 ° with loss of 5 H 2 0) and 12 mol. Water ( Density 1, 52 like '3 , melting point 35 ° with loss of 5 H 2 0), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 0 7 when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HP0 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 are colorless crystals, which like 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 0 5 ) a melting point of 100 ° C. and in anhydrous form (corresponding to 39-40% P 2 0 5 ) a density of 2.536 iron 3 .
  • Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or three-base potassium phosphate), K 3 P0 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, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 0 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like " 3 , melting point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P 2 0 7 is formed by heating 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 formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), 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 of the 1% solution at 25 ° being 10.4.
  • Sodium and potassium phosphates in which one can differentiate between cyclic representatives, the sodium and potassium metaphoshates and chain-like types, the sodium and potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O ⁇ 0 (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P 2 0 5 , 25% K 2 0) on the market.
  • the potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
  • Automatic dishwashing detergents preferred in the context of the present invention contain no sodium and / or potassium hydroxide. Dispensing with sodium and / or potassium hydroxide as the alkali source has proven to be particularly advantageous if zinc gluconate, zinc formate and zinc acetate are used as zinc salts.
  • Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates.
  • the polymers can also be a component of the active substance-containing polymer matrix, but they can also be contained in the agents according to the invention completely independently of this. The substance classes mentioned are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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 of these.
  • 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 value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, can in turn be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
  • the copolymers containing sulfonic acid groups are described in detail below.
  • the sulfonic acid group-containing polymers described above can also be present in the agents according to the invention without necessarily having to be part of the active ingredient-containing polymer matrix.
  • polyacrylates As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention.
  • the polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred.
  • Such polyacrylates are commercially available under the trade names Sokalan ® PA15 or 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.
  • Your relative molecular mass on free acids is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 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 agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • copolymers preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 can also be used so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
  • 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 at C ⁇ of the saccharide ring can be particularly advantageous.
  • Ethylenediamine-N, N'-disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be 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 aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • Agents according to the invention are characterized in the context of the present application in that they contain builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates in amounts of 0.1 to 99.5% by weight, preferably of 1 to 95 % By weight, particularly preferably from 5 to 90% by weight and in particular from 10 to 80% by weight, in each case based on the composition.
  • preferred cleaning agents contain one or more surfactant (s) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 . 13- Alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, as obtained, for example, from C 12 . ⁇ 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products , into consideration.
  • Alkanesulfonates which are derived from C 12 are also suitable.
  • esters of cc-sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerin esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerin with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol 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, acidic acid, palmitic acid, stearic acid or behenic acid.
  • the alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from 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 this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based, straight-chain alkyl radical which have an analogous degradation behavior like the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 4 -C 15 alkyl sulfates are preferred from a washing-technical point of view.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 21 alcohols such as 2-methyl-branched Cg-n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 .
  • EO ethylene oxide
  • 1 ⁇ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 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 which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alkyl (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • non-ionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly or preferably 2-branched methyl or linear and methyl branched residues in the mixture can contain, as they are usually present in oxo alcohol residues.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 . 14 - alcohols with 3 EO or 4 EO, C 9. -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 ⁇ . 2 14 -alcohol with 3 EO and C 12 _ 18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides which can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for 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.
  • Linear alkyl polyglucosides, ie alkyl polyglycosides, which consist of a glucose residue and an n-alkyl chain, are preferably used.
  • nonionic surfactants which are 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 with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Other suitable surfactants are polyhydroxy fatty acid amides of the formula (XVIII),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 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)
  • [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.
  • surfactants are generally suitable as surfactants.
  • the nonionic surfactants described above, and above all the low-foaming nonionic surfactants are preferred for this purpose.
  • the alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols.
  • alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide Alcohols, preferably the longer-chain alcohols (C 10 to C 18 , preferably between C 12 and C 16 , such as, for example, Cn-, C 12 -, C 13 -, C 14 -, C 15 -, C 16 , C 17 and C 18 alcohols).
  • ethylene oxide Alcohols preferably the longer-chain alcohols (C 10 to C 18 , preferably between C 12 and C 16 , such as, for example, Cn-, C 12 -, C 13 -, C 14 -, C 15 -, C 16 , C 17 and C 18 alcohols).
  • a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • final etherification with short-chain alkyl groups can also give the class of "closed" alcohol ethoxylates, which can also be used in the context of the invention.
  • Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.
  • Nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants within the scope of the present invention.
  • surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups.
  • automatic dishwashing agents according to the invention are preferred which contain surfactants of the general formula XX as nonionic surfactant (s)
  • R 1 for a straight-chain or branched, saturated or mono- or polyunsaturated C 6 .
  • 24 is alkyl or alkenyl; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • the preferred nonionic surfactants of the formula XX can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R in the above formula I can 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 generally not shown, the linear radicals being from alcohols of native origin with 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, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • preferred dishwasher detergents according to the invention are those in which R 1 in formula I for an alkyl radical having 6 to 24 preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 and R 3 are selected independently of one another 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 for a radical -CH 3 , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.
  • nonionic surfactants which have a C 9 . 15 alkyl group 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 dishwashing agents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.
  • Suitable, in addition to the nonionic surfactants contained in the compositions according to the invention, which have melting or softening points in the temperature range mentioned, are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous 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 that have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex 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 with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.
  • 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 16-2 alcohol), a C preferably 18 alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won.
  • C 16-2 alcohol straight chain fatty alcohol having 16 to 20 carbon atoms
  • C preferably 18 alcohol and at least 12 mole preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won.
  • the so-called “narrow ranks ethoxylates” are particularly preferred.
  • the / preferred inventive ethoxylated (s) nonionic surfactant selected from C 6 - 2 o-monohydroxy alkanols 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).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly 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 contain 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 make up nonionic surfactant.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight. -% 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 automatic dishwashing agent according to the invention contains nonionic surfactants of the formula
  • R 1 0 [CH 2 CH (CH 3 ) 0] x [CH 2 CH 2 0] y [CH 2 CH (OH) R 2 ], in which R 1 represents a linear or branched aliphatic carbon hydrogen radical with 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 stands for values between 0.5 and 1, 5 and y stands for 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 preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH 3 or - CH 2 CH 3 are particularly preferred for the radical R 3 . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • the value 3 for x has been chosen here by way of example and may well be larger, the range of variation 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 stands for numbers 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 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
  • dishwashing detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • anionic, cationic and / or amphoteric surfactants can also be used, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent.
  • the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.
  • Bleaching agents and bleach activators are important constituents of washing and cleaning agents and a washing and cleaning agent can contain one or more substances from the groups mentioned within the scope of the present invention.
  • Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H 2 0 2 in water.
  • Other usable bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate.
  • Sodium percarbonate is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate.
  • the merchandise has the average composition 2 Na 2 C0 3 -3 H 2 0 2 and is therefore not peroxycarbonate.
  • Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 "3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.
  • the industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process).
  • aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg 2+ ions).
  • the precipitated salt which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried at 90 ° C. in fluid bed dryers.
  • the bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process.
  • the percarbonate is stabilized by an additional coating.
  • Typical organic bleaching agents that can be used as ingredients in the context of the present invention are the diacyl peroxides, such as, for example, dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • 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, ⁇ -phthalimidoxy acid perooxyperoxy (poxy) hexaproacid acid ( ⁇ ) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid,
  • Diperoxybrassylic acid the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.
  • chlorine or bromine-releasing substances can also be used as bleaching agents for automatic dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanic acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanic acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • Advantageous agents in the context of the present invention contain one or more bleaching agents, preferably from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40% by weight .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
  • one or more bleaching agents preferably from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40% by weight .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
  • bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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 number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • bleach catalysts can also be incorporated into the cleaning agents according to the present invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • agents are preferred, one or more substances from the group of bleach activators, in particular from the groups of polyacylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.1 to 20% by weight, preferably 0.5 to 15% by weight % and in particular from 1 to 10 wt .-%, each based on the total agent.
  • TAED tetraacetylethylene diamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI)
  • NOSI N-nonanoylsuccin
  • the bleach activators preferred in the context of the present invention also include the “nitrile quats”, cationic nitriles of the formula (XXI), R 1
  • 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
  • General formula (XXI) includes a large number of cationic nitriles which can be used in the context of the present invention.
  • the laundry detergent tablets according to the invention particularly advantageously contain cationic nitriles 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 radical.
  • R 2 and R 3 are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical.
  • radicals R 1 to R 3 are identical, for example (CH 3 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH 2 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH 2 CH 2 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH (CH 3 )) 3 N (+) CH 2 -CN X “ , or (HO -CH 2 -CH 2 ) 3 N (+) CH 2 -CN X " , where X " preferably represents an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is selected.
  • Detergents and cleaning agents preferred in the context of the present invention are characterized in that they contain the cationic nitrile of the formula (XXI) in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular from 0.5 to 10% by weight, based in each case on the weight of the shaped body.
  • Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases carry in the laundry to remove stains such as protein, grease or starchy stains and graying. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases carry in the laundry to remove stains such as protein, grease or starchy stains and graying. Cellulases and other glycosyl hydrolases can also help to retain color
  • Bacillus subtilis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include, in particular alpha-amylases, iso-amylases, pullulanases and P ektinasen '.
  • Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight. , each based on the total mean.
  • dyes within the scope of the present invention, the selection of which is not difficult for the person skilled in the art, have a high Storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers, so as not to stain them.
  • Preferred for use in the washing and cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the cleaning process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances.
  • anionic colorants for example anionic nitroso dyes, are suitable.
  • 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 ® Blue 6900 (Cl 74160), Pigmosol ® Green 8730 (Cl 74260), Basonyl ® Red 545 FL (Cl 45170), Sandolan ® Rhodamine EB400 (Cl 45100), Basacid ® Yellow 094 (Cl 47005), Sicovit ® Patentblau 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol ® Blau 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).
  • colorants When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against 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 washing or cleaning agents 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 in the context of the present invention in order to improve the aesthetic impression of the products and to the consumer in addition to the performance of the To provide a visually and sensorially “typical and distinctive” product.
  • fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propalate and benzylate propionate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g.
  • the Jonone, o -somethylionon and methyl-cedrylketone to the alcohols anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly the terpenes like limonen and pinene belong.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • Detergents for machine dishwashing can contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing.
  • the known substances of the prior art can be used.
  • silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • transition metal salts which are selected from the group of the 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 manganese sulfate, as well as the manganese complexes
  • Me-MeTACN Mn III (m-0) (m-0Ac) 2 Mn III (Me-MeTACN)] 2+ (PF 6 -) 2
  • Me-TACN is 1, 4,7-trimethyl-1, 4,7-triazacyclononane
  • Me-MeTACN stands for 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • automatic dishwashing agents which additionally have at least one silver protective agent selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1% by weight. %, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, in each case based on the total composition.
  • at least one silver protective agent selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1% by weight. %, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, in each case based on the total composition.
  • the agents according to the invention can be provided, for example, as powders, granules or tablets. Such agents preferably contain the active substance-containing polymer matrix in particulate form, which is admixed with the agent or the premixes to be pressed.
  • Compositions preferred according to the invention are characterized in that they contain the active substance-containing polymer matrix in particulate form, the active substance-containing polymer matrix preferably having an average particle size of at most 500 ⁇ m.
  • compositions according to the invention which contain the active substance-containing polymer matrix as a shaped body which is preferably produced by extruding, casting, injection molding, blow molding or drawing the active substance-containing polymer matrix.
  • the active ingredient-containing polymer matrix can also be used as packaging for machine dishwashing detergents or part thereof.
  • Compositions are preferred here which contain the active substance-containing polymer matrix as a coating, which preferably is produced by injection molding, blow molding, deep drawing, calendering, cold rolling or by coating the composition by means of the coating process.
  • the present invention furthermore relates to a method for inhibiting the corrosion of glassware in cleaning and / or rinsing operations in a dishwasher, characterized by bringing the glassware into contact with washing and / or rinsing water which contains an effective amount of a composition according to the invention , and a method for inhibiting the corrosion of glassware in cleaning and / or rinsing operations of a dishwasher, which is characterized in that a composition according to the invention is provided in the interior of the dishwasher at a location accessible to the washing and / or rinsing water

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Abstract

L'invention concerne l'utilisation d'une matrice polymère à matière active, ayant une teneur en au moins un agent chimique qui peut être libéré de la matrice et qui est capable de fournir une protection contre la corrosion pour des objets en verres lors de cycles de lavage ou de rinçage d'un lave-vaisselle, aux fins de libérer de la matrice polymère cet ou ces agents chimiques agissant pour la protection contre la corrosion des objets en verre pendant les cycles de lavage ou de rinçage du lave-vaisselle.
PCT/EP2003/005603 2002-06-06 2003-05-28 Utilisation de matrices polymeres contenant une matiere active pour le lavage de la vaisselle en machine WO2003104368A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003274090A AU2003274090A1 (en) 2002-06-06 2003-05-28 Use of polymer matrices containing an active substance for washing dishes in a dishwasher

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10225115A DE10225115A1 (de) 2002-06-06 2002-06-06 Verwendung wirkstoffhaltiger Polymermatrizes beim maschinellen Geschirrspülen
DE10225115.0 2002-06-06

Publications (1)

Publication Number Publication Date
WO2003104368A1 true WO2003104368A1 (fr) 2003-12-18

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PCT/EP2003/005603 WO2003104368A1 (fr) 2002-06-06 2003-05-28 Utilisation de matrices polymeres contenant une matiere active pour le lavage de la vaisselle en machine

Country Status (3)

Country Link
AU (1) AU2003274090A1 (fr)
DE (1) DE10225115A1 (fr)
WO (1) WO2003104368A1 (fr)

Cited By (3)

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Publication number Priority date Publication date Assignee Title
EP1571198A1 (fr) * 2004-03-02 2005-09-07 Dalli-Werke GmbH & Co. KG. Composés au manganèse liés à des polymères dans des compositions détergentes
DE102010030021A1 (de) 2010-06-14 2011-12-15 Henkel Ag & Co. Kgaa Maschinelles Reinigungsverfahren
EP3075832A1 (fr) * 2015-03-30 2016-10-05 Dalli-Werke GmbH & Co. KG Composés d'acide aminé de manganèse dans des compositions de nettoyage

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
DE102004020720A1 (de) * 2004-04-28 2005-12-01 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln
DE102005033158B4 (de) * 2005-07-13 2010-06-24 Henkel Ag & Co. Kgaa Reinigungsmittel und Verfahren zu seiner Herstellung
GB0805904D0 (en) 2008-04-01 2008-05-07 Reckitt Benckiser Nv Injection moulding process
DE102018205971A1 (de) 2018-04-19 2019-10-24 Henkel Ag & Co. Kgaa Korrosionsschutz für Glaswaren in einer Geschirrspülmaschine

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Publication number Priority date Publication date Assignee Title
EP0383480A1 (fr) * 1989-02-13 1990-08-22 The Procter & Gamble Company Compositions additives de rinçage apportant une protection pour les objets en verre
EP0383482A2 (fr) * 1989-02-13 1990-08-22 The Procter & Gamble Company Compositions détergentes granulaires pour le lavage automatique de la vaisselle protégeant les articles en verre

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DE19710009A1 (de) * 1997-03-12 1998-09-24 Knoll Ag Mehrphasige wirkstoffhaltige Zubereitungsformen
DE19961661A1 (de) * 1999-06-25 2000-12-28 Henkel Kgaa Wirkstoffportionspackung
DE19960096A1 (de) * 1999-12-14 2001-07-05 Henkel Kgaa Teilchenförmiger Klarspüler und maschinelle Geschirrspülmittel

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0383480A1 (fr) * 1989-02-13 1990-08-22 The Procter & Gamble Company Compositions additives de rinçage apportant une protection pour les objets en verre
EP0383482A2 (fr) * 1989-02-13 1990-08-22 The Procter & Gamble Company Compositions détergentes granulaires pour le lavage automatique de la vaisselle protégeant les articles en verre

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1571198A1 (fr) * 2004-03-02 2005-09-07 Dalli-Werke GmbH & Co. KG. Composés au manganèse liés à des polymères dans des compositions détergentes
WO2005095570A1 (fr) * 2004-03-02 2005-10-13 Dalli-Werke Gmbh & Co. Kg Composes de manganese lies par un polymere dans des compositions de nettoyage
US7754672B2 (en) 2004-03-02 2010-07-13 Dalli-Werke Gmbh & Co. Kg Polymer bound manganese compounds in cleaning composition
DE102010030021A1 (de) 2010-06-14 2011-12-15 Henkel Ag & Co. Kgaa Maschinelles Reinigungsverfahren
WO2011157630A1 (fr) 2010-06-14 2011-12-22 Henkel Ag & Co. Kgaa Procédé de lavage en machine
EP3075832A1 (fr) * 2015-03-30 2016-10-05 Dalli-Werke GmbH & Co. KG Composés d'acide aminé de manganèse dans des compositions de nettoyage

Also Published As

Publication number Publication date
AU2003274090A1 (en) 2003-12-22
DE10225115A1 (de) 2003-12-24

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