Silver-protecting dishwashing detergent

Abstract

Machine dishwashing detergents containing galactaric acid have an improved silver protection effect and reduce tarnishing of a cleaning load that consists of silver.

Description

[0001] Silver-protecting dishwashing detergent

[0002] The present patent application relates to automatic dishwashing detergents containing galactaric acid, automatic dishwashing processes using these dishwashing detergents, and the use of galactaric acid or the dishwashing detergents containing it to reduce the tarnishing of silver ware, such as silver cutlery, and / or to facilitate the polishing of silver ware.

[0003] Dishwashing detergents are available to consumers in a wide variety of forms. In addition to traditionally liquid hand dishwashing detergents, automatic dishwashing detergents have gained considerable importance with the proliferation of household dishwashers. These automatic dishwashing detergents are typically offered to consumers in solid form, for example, as powder or tablets, but increasingly also in liquid form. Dishwashing detergents packaged in water-soluble foils, ready for individual dosage, may also contain solid, for example, powder, and liquid or gel preparations, which in these cases are normally contained in separate compartments within the foil-like packaging.

[0004] The primary purpose of automatic detergents is their cleaning and rinsing performance, although recently there has been increased emphasis on performance in low-temperature cleaning cycles and in cleaning cycles with reduced water consumption. In addition to the cleaning and rinsing performance of these detergents, however, it is also desirable for the detergents to perform other functions.

[0005] When washing silver dishes, the problem that can arise is that the silver dishes oxidize or tarnish, especially when strong bleaching agents are used. Tarnishing often appears in the form of a golden to bluish-brown discoloration. Traditionally, these side effects of the dishwashing process can be eliminated by polishing after dishwashing, although this polishing can be time-consuming. By adding special silver protective agents to the dishwashing detergent composition, oxidation and tarnishing can be reduced, thus making polishing the silver dishes easier. However, these silver protective agents do not always completely prevent tarnishing of the silver dishes. Protection against corrosion and tarnishing is particularly challenging with silver alloys that contain large amounts of copper.

[0006] N-containing heterocycles, such as triazole derivatives and polyvinylpyrrolidone, and sulfur-containing carbonic or amino acids are known as silver protective agents in automatic dishwashing detergents.

[0007] Surprisingly, it has now been found that galactaric acid leads to improved silver protection properties in automatic dishwashing.

[0008] A first object of the invention is therefore an automatic dishwashing detergent containing galactaric acid.

[0009] Galactaric acid is preferably contained in agents according to the invention in an amount of 0.05 wt.% to 2 wt.%, in particular 0.1 wt.% to 1 wt.%, whereby the percentages by weight given here and below refer to the total weight of the agents, unless otherwise stated.

[0010] The present invention further provides an automatic dishwashing process using a dishwashing detergent containing galactaric acid, in particular for protecting the treated silver ware, especially for preventing oxidation and / or tarnishing of the treated silver ware and / or for improving the polishability of the treated silver ware. The automatic dishwashing detergent is preferably dosed into the interior of a dishwasher before a dishwashing program is run, before the start of the main wash cycle, or during the main wash cycle. The dishwashing process can be carried out at any temperature.

[0011] A further object of the present invention is the use of galactaric acid or a dishwashing detergent according to the invention containing galactaric acid as a silver preservative, in particular for preventing the oxidation and / or tarnishing of silver ware and / or for facilitating the polishing of silver ware, in particular in machine dishwashing.

[0012] Within the scope of the method according to the invention and the use according to the invention, it is preferred if the concentration of galactaric acid in the aqueous dishwashing liquid which acts on the items to be washed within the dishwasher is at least temporarily in the range from 1 mg / l to 30 mg / l, in particular from 2 mg / l to 20 mg / l.

[0013] Compared to many other known silver protection agents, galactaric acid has the advantage of being a renewable raw material that is sustainably available and readily biodegradable. For all embodiments of the invention, galactaric acid can be present as a free acid or in the form of its alkali or ammonium salts.

[0014] According to this invention, automatic dishwashing detergents are compositions that can be used to clean soiled dishes in an automatic dishwashing process. This distinguishes the automatic dishwashing detergents according to the invention, for example, from automatic rinse aids, which are always used in combination with automatic dishwashing detergents and generally do not have any cleaning effect of their own.

[0015] The automatic dishwashing detergents according to the invention can be in solid or liquid form. In preferred embodiments, they are in powder, granulated, or compressed form. In further preferred embodiments, they are presented in ready-to-use, single-dose portions in water-soluble packaging, especially film-like packaging.

[0016] In a particularly preferred embodiment, the automatic dishwashing detergents according to the invention are in the form of shaped bodies, preferably as compacts, in particular as tablets. However, they can also be presented in other forms, in particular in solid forms such as powders, granules, or extrudates, or in liquid or gel forms based on water and / or organic solvents.

[0017] Detergents according to the invention can be formulated as single-phase or multi-phase products. Particular preference is given to automatic dishwashing detergents with one, two, three, or four phases. Automatic dishwashing detergents in the form of a prefabricated dosage unit with two or more phases are particularly preferred. Also particularly preferred are two- or multi-phase tablets, for example, bilayer tablets, especially bilayer tablets with a depression and a shaped body located in the depression.

[0018] Dishwashing detergents according to the invention are preferably pre-packaged into dosage units. These dosage units preferably contain the amount of cleaning agents required for one cleaning cycle. Preferred dosage units have a weight in the range of 12 g to 30 g, in particular from 14 g to 26 g, and particularly preferably from 15 g to 22 g.

[0019] The volume of the aforementioned dosing units and their spatial shape should be selected to ensure dosability of the pre-assembled units, for example, via the dosing chamber of the dishwasher. The volume of the dosing unit is therefore preferably in the range of 10 ml to 35 ml, in particular from 12 ml to 30 ml, and particularly preferably from 15 ml to 25 ml.

[0020] In particular, the prefabricated dosing units of the automatic dishwashing detergents according to the invention particularly preferably have a water-soluble coating. The dishwashing detergent according to the invention can also be a dishwashing detergent portion that is present in a water-soluble coating with one or more compartments. If multiple compartments are present, an agent composed according to the invention is contained in at least one compartment; this means that all or some of the remaining compartments can also be filled with compositions that do not contain galactaric acid.

[0021] The water-soluble coating is preferably formed from a water-soluble film material made of polymers or polymer blends. The coating can be formed from one or two or more layers of water-soluble film material. The water-soluble film material of the first layer and the further layers can be the same or different. It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, particularly cold water solubility. Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 g / mol to 1,000,000 g / mol, preferably from 20,000 g / mol to 500,000 g / mol, particularly preferably from 30.000 g / mol to 100,000 g / mol and in particular from 40,000 g / mol to 80,000 g / mol. Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are normally produced accordingly from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble casing comprises a polyvinyl alcohol whose degree of hydrolysis is 70 mol% to 100 mol%, preferably 80 mol% to 90 mol%, particularly preferably 81 mol% to 89 mol% and in particular 82 mol% to 88 mol%. In a preferred embodiment, the water-soluble packaging consists of at least 20 wt.%, particularly preferably at least 40 wt.%, very particularly preferably at least 60 wt.% and in particular at least 80 wt.-% of a polyvinyl alcohol whose degree of hydrolysis is 70 mol% to 100 mol%, preferably 80 mol% to 90 mol%, particularly preferably 81 mol% to 89 mol% and in particular 82 mol% to 88 mol%. A polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers can additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble wrapping. A preferred additional polymer is polylactic acids. Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.Likewise preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof. It may be preferred for the film material to contain further additives. The film material may, for example, contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol, or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents, or mixtures thereof.

[0022] Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example, under the designation M8720, M8630, M8312, M8440, M7062, C8400, or M8900. Also suitable are films sold under the designation SH2601, SH2504, SH2707, or SH2701 by Nippon Gohsei. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL from Aicello Chemical Europe GmbH, or the VF-HP films from Kuraray.

[0023] The water-soluble coating preferably comprises at least partially a bittering agent with a bitterness value between 1,000 and 200,000, in particular those selected from quinine sulfate (bitterness value = 10,000), naringin (bitterness value = 10,000), sucrose octaacetate (bitterness value = 100,000), quinine hydrochloride, and mixtures thereof. In particular, the outer surface of the water-soluble coating is at least partially coated with a bittering agent with a bitterness value between 1,000 and 200,000. In this context, it is particularly preferred that the water-soluble coating is coated to at least 50%, preferably to at least 75%, and most preferably to at least 90% with the bittering agent with a bitterness value between 1,000 and 200,000. The bittering substance with a bitterness value between 1,000 and 200,000 can be applied, for example, by printing, spraying or coating.

[0024] In a further embodiment, the water-soluble packaging can consist of at least two packaging parts made of different materials, for example, different films or materials with two different properties (for example, hot- and cold-water-soluble films). In this embodiment, it is preferred that a water-soluble film and another packaging part produced by injection molding are combined. If the packaging parts from which the two or more compartments of a multi-compartment package are formed are made of differently soluble materials, their solubility can be used to regulate the release of the individual compartment contents, which can have different compositions and thus lead to a temporal change in the composition of the dishwashing solution.

[0025] According to a particularly preferred embodiment of the present invention, the water-soluble casing comprises at least one at least partially plastically deformed film. In particular, this plastic deformation of the film can be produced by methods known to those skilled in the art, such as deep drawing (with and without the application of a vacuum), blow molding, or stamp molding. In particular, the water-soluble casing comprises at least one at least partially plastically deformed film produced by deep drawing. Shaped bodies can be obtained from powders or granules containing the ingredients of the automatic dishwashing detergent, preferably using a pressing force of 40 to 65 kN, particularly preferably 48 to 60 kN, to form compacts with a hardness in the range of 150 to 250 N, in particular in the range of 200 to 230 N. The powders or granules can thus be compressed, preferably with a relatively low pressing force, to form compacts with a relatively high hardness.

[0026] Tablet-shaped products can contain disintegrants, which increase their volume upon contact with water. This increases their inherent volume (swelling), but also releases gases, generating pressure that causes the tablet to disintegrate into smaller particles. Possible disintegrants include, for example, carbonate in combination with organic acids, such as citric acid or the galactaric acid used in the invention, synthetic or natural polymers, or modified natural substances such as cellulose and starch and their derivatives, as well as alginates or casein derivatives.Preferred disintegrants according to the invention are gas-evolving effervescent systems consisting of at least two components which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution, the preferred acidifying agent being galactaric acid.

[0027] Preferred automatic dishwashing detergents according to the invention contain at least one bleaching agent as a further ingredient, with oxygen bleaching agents being preferred. Among the compounds serving as bleaching agents that yield H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate are particularly important. Other useful bleaching agents include, for example, peroxypyrophosphates, citrate perhydrates, and H2O2-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid, or diperdodecanedioic acid.

[0028] Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, with particular examples being alkyl peroxyacids and aryl peroxyacids, such as N-phthaloylaminoperoxycaproic acid. Preferred automatic dishwashing detergents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, particularly preferably a coated sodium percarbonate. The weight fraction of the bleaching agent, based on the total weight of the washing or cleaning agent, is in preferred embodiments in the range from 2 wt.% to 30 wt.%, in particular from 4 wt.% to 20 wt.%, and particularly preferably from 6 wt.% to 15 wt. Automatic dishwashing detergents according to the invention can further contain bleach activators.Under perhydrolysis conditions, these compounds yield aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those bearing O- and / or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups. Polyacylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) proving particularly suitable. Dishwashing detergents characterized by containing a bleach activator from the group of acetylated amines, in particular tetraacetylenediamine (TAED), as bleach activator are preferred. These bleach activators, in particular TAED, are preferably used in amounts of up to 10 wt.%, in particular in the range from 0.1 wt.% to 10 wt.%, in particular from 0.5 wt.% to 8 wt.%, and particularly preferably from 1 wt.% to 6 wt.%.

[0029] Alternatively, or preferably in addition to the conventional bleach activators, the automatic dishwashing detergents according to the invention preferably contain at least one bleach catalyst. These substances are bleach-enhancing transition metal salts or transition metal complexes, such as Mn, Fe, Co, Ru, or Mo salen 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 ammine complexes, can also be used as bleach catalysts. Particular preference is given to using complexes of manganese in oxidation state II, III, IV, or V, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O, and / or S. Preference is given to using ligands that have nitrogen donor functions.It is particularly preferred to use bleach catalyst(s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN) as macromolecular ligands. Suitable manganese complexes are, for example, [Mn. HI 2(pO)i(p-OAC)2(TACN)2](CIO4)2, [Mn lll Mn lv (pO)2(p-OAc)i(TACN)2](BPh4)2, [Mn lv 4(pO)6(TACN)4](CIO4)4, [Mn lll 2(pO)i(p-OAc)2(Me-TACN)2](CIO4)2, [Mn lll Mn lv (pO)i(p-OAc)2(Me-TACN)2](CIO4)3, [Mn lv 2(p- O)3(Me-TACN)2](PF6)2 and [Mn lv2(pO)3(Me / Me-TACN)2](PF6)2 (OAc = OC(O)CH3). Dishwashing detergents containing a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me4-TACN), are preferred according to the invention, since the aforementioned bleach catalysts can significantly improve the cleaning result in particular. Bleach-enhancing transition metal complexes, especially those with Mn or Co as central atoms, are used in conventional amounts, preferably in an amount of up to 5 wt.%, in particular from 0.0025 wt.% to 1 wt.%, and particularly preferably from 0.01 wt.% to 0.30 wt.%, in each case based on the total weight of the bleach catalyst-containing agents. In special cases, however, more bleach catalyst can also be used.

[0030] Preferred automatic dishwashing detergents according to the invention contain at least one anionic polymer as a further component. Preferred anionic polymers are the copolymers polycarboxylates and the copolymers polysulfonates. In preferred embodiments, the weight fraction of the anionic polymer in the total weight of the automatic dishwashing detergent according to the invention is in the range from 0.1 wt.% to 20 wt.%, preferably from 0.5 wt.% to 18 wt.%, particularly preferably from 1 wt.% to 15 wt.%, and in particular from 4 wt.% to 14 wt.%.

[0031] The inventive automatic dishwashing detergent, characterized in that the copolymer anionic polymer is selected from the group of hydrophobically modified polycarboxylates and polysulfonates, is a particularly preferred subject matter, since the hydrophobic modification of the anionic copolymers makes it possible to improve the rinsing and drying properties of these detergents while simultaneously reducing deposit formation.

[0032] The copolymers can have two, three, four or more different monomer units.

[0033] Preferred copolymer polysulfonates contain, in addition to monomer(s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.

[0034] As unsaturated carboxylic acid(s), particularly preferred unsaturated carboxylic acids are those of the formula R 1 (R 2 )C=C(R 3 )COOH is used, in the R 1 to R 3independently of one another represent -H, -CH3, 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 by -NH2, -OH or -COOH as defined above or -COOH or -COOR 4 where R 4 a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

[0035] Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof. Unsaturated dicarboxylic acids can, of course, also be used.

[0036] According to the invention, copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are particularly preferred as copolymeric polycarboxylates. Copolymers of acrylic acid with maleic acid containing 50 to 90 wt.% acrylic acid and 50 to 10 wt.% maleic acid have proven particularly suitable. Their relative molecular weight, based on free acids, is generally 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, and in particular 30,000 to 40,000 g / mol.

[0037] The monomers containing sulfonic acid groups are those of the formula R 5 (R 6 )C=C(R 7 )-X-SO3H is preferred, in which R 5 to R 7independently of one another represent -H, -CH3, 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 by -NH2, -OH or -COOH or -COOH or -COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group selected from -(CH2)n- where n = 0 to 4, -COO-(CH2)k- where k = 1 to 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- and -C(O)-NH-CH(CH3)-CH2-.

[0038] Preferred monomers are those of the formulas

[0039] H2C=CH-X-SO3H

[0040] H2C=C(CH3)-X-SO3H

[0041] HO3S-X-(R 6 )C=C(R 7 )-X-SO3H, in which R 6 and R 7are independently selected from -H, -CH3, -CH2CH3, -CH2CH2CH3 and -CH(CH3)2 and X represents an optionally present spacer group selected from - (CH2)n- with n = 0 to 4, -COO-(CH2)k- with k = 1 to 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- and -C(O)-NH-CH(CH3)-CH2-.

[0042] Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.

[0043] In the polymers, the sulfonic acid groups can be present entirely or partially in neutralized form, i.e., the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention. The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95 wt.% in the case of copolymers containing only carboxylic acid groups and sulfonic acid group-containing monomers; more preferably, the proportion of the sulfonic acid group-containing monomer is 50 to 90 wt.% and the proportion of the carboxylic acid group-containing monomer is 10 to 50 wt.%; the monomers are preferably selected from those mentioned above.

[0044] The molecular weight of the sulfo copolymers preferably used according to the invention can be varied to adapt the properties of the polymers to the desired application. Preferred automatic dishwashing detergents are characterized by the copolymers having molecular weights of 2000 g / mol to 200,000 g / mol, preferably of 4000 g / mol to 25,000 g / mol, and in particular of 5000 g / mol to 15,000 g / mol.

[0045] In a further preferred embodiment, the copolymers comprise, in addition to the carboxyl-containing monomer and the sulfonic acid-containing monomer, at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has been shown to improve, in particular, the rinse performance of automatic dishwashing detergents according to the invention.

[0046] Automatic dishwashing detergents, characterized in that the automatic dishwashing detergent contains as anionic copolymer a copolymer comprising i) monomer(s) containing carboxylic acid groups, ii) monomer(s) containing sulfonic acid groups, iii) non-ionic monomer(s), are preferred according to the invention.

[0047] Non-ionic monomers are preferably monomers of the general formula R 1 (R 2 )C=C(R 3 )-XR 4 used in the R 1 to R 3 independently represents -H, -CH3 or -C2H5, X represents an optionally present spacer group selected from -CH2-, -C(O)O- and -C(O)-NH-, and R 4represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms. Particularly preferred non-ionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimehtylhexane-1, ethylcyclohexyne, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-Hexadecene, 1-Octadecene and C22-α-Olefin, 2-Styrene, α-Methylstyrene, 3-Methylstyrene, 4-Propylstyrene, 4-Cyclohexylstyrene, 4-Dodecylstyrene, 2-Ethyl-4-Benzylstyrene, 1-Vinylnaphthalene, 2-Vinylnaphthalene, Methyl acrylate, Ethyl acrylate, Propyl acrylate, Butyl acrylate,Pentyl acrylate, hexyl acrylate, methyl methacrylate, N-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N-(2-ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, N-(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, N-(lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, N-(stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or mixtures thereof.

[0048] In a preferred embodiment, dishwashing detergents according to the invention further contain at least one nonionic surfactant of the general formula R 1 O(AlkO)xM(OAlk) y OR 2 , where R 1 and R 2independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently of one another represent values ​​between 1 and 70; and M represents an alkyl radical from the group CH2, CHR 3 , CR 3 R 4 , CH2CHR 3 and CHR 3 CHR 4 where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.

[0049] In a further preferred embodiment, automatic dishwashing detergents according to the invention contain, as non-ionic surfactant, a surfactant of the general formula R 1 -CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R 2 , where R, R 1 and R 2independently of one another represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms; and x and y independently of one another represent values ​​from 1 to 40.

[0050] In particular, compounds of the general formula R 1 -CH(OH)CH2- O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R 2 in which R represents a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values ​​from 20 to 30. Corresponding compounds can be obtained, for example, by reacting alkyldiols HO-CHR-CH2-OH with ethylene oxide, followed by reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.

[0051] In a further preferred embodiment, automatic dishwashing detergents according to the invention contain, as nonionic surfactant, a surfactant of the general formula R1 -O(CH2CH2O)xCR 3 R 4 (OCH2CH2)yO-R 2 is used in the R 1 and R 2 independently of one another represent an alkyl radical or alkenyl radical having 4 to 22 carbon atoms; R 3 and R4 independently of one another represent H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and x and y independently of one another represent values ​​from 1 to 40. Preference is given in particular to compounds of the general formula R 1 -O(CH2CH2O)xCR 3 R 4 (OCH2CH2)yO-R 2 , in the R 3 and R 4 stands for H and the indices x and y independently take values ​​from 1 to 40, preferably from 1 to 15.

[0052] Particularly preferred are compounds of the general formula R 1 -O(CH2CH2O)xCR 3 R 4 (OCH2CH2)yO-R 2 , in which the residues R 1 and R 2independently of one another represent saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y independently of one another assume values ​​from 1 to 15 and in particular from 1 to 12.

[0053] Also preferred are compounds of the general formula R 1 -O(CH2CH2O)xCR 3 R 4 (OCH2CH2) y OR 2 , in which one of the residues R 1 and R 2 is branched.

[0054] Compounds of the general formula R are particularly preferred. 1 -O(CH2CH2O)xCR 3 R 4 (OCH2CH2) y OR 2 , in which the indices x and y independently take values ​​from 8 to 12.

[0055] The weight fraction of the nonionic surfactant of the general formula R 1 O(AlkO)xM(OAlk) y OR 2of the total weight of the automatic dishwashing detergent according to the invention is in a preferred embodiment between 0.05 and 10 wt.%, preferably between 0.1 and 8 wt.%, preferably between 0.5 and 5 wt.% and in particular between 1 and 3 wt.%.

[0056] Dishwashing detergents according to the invention preferably also contain builder(s) and enzyme(s) to ensure their cleaning effect.

[0057] As a further component, automatic dishwashing detergents according to the invention preferably contain one or more builders. The weight proportion of the builders in the total weight of the automatic dishwashing detergents according to the invention is preferably 15 to 80 wt.% and in particular 20 to 70 wt.%. The builders include, in particular, carbonates, phosphates, citrates, organic cobuilders, and silicates.

[0058] Particular preference is given to the use of carbonate(s) and / or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of 2% to 30% by weight, preferably 4% to 28% by weight, and in particular 8% to 24% by weight. If phosphates are used as builder substances in the automatic dishwashing detergents, they are preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of up to 60% by weight, preferably 15 to 45% by weight.

[0059] Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins, and organic cobuilders. Suitable organic builders include, for example, polycarboxylic acids, which can be used in the form of the free acid and / or their sodium salts. Polycarboxylic acids are understood to be monomeric carboxylic acids that carry more than one acid function. Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is acceptable on ecological grounds, and mixtures thereof. In addition to their builder effect, the free acids typically also possess the property of an acidifying component and are thus also used to adjust 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 are particularly suitable. Particularly preferred automatic dishwashing detergents according to the invention contain citric acid or alkali metal citrate as one of their essential builders. Automatic dishwashing detergents containing 2 to 40 wt.%, preferably 5 to 30 wt.%, and in particular 7 to 20 wt.% citrate are preferred according to the invention.

[0060] Citrates are preferably used in combination with carbonates and / or bicarbonates. Preferred dishwasher detergents are therefore characterized by a builder combination of citrate and carbonate / bicarbonate. However, builder combinations of phosphate, citrate, and carbonate / bicarbonate are also possible.

[0061] Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 g / mol to 70,000 g / mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular mass of 2,000 g / mol to 20,000 g / mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular masses of 2,000 g / l to 10,000 g / mol, and particularly preferably of 3,000 to 5,000 g / mol, may be preferred. The content of (homo)polymeric polycarboxylates in the automatic dishwashing detergents is preferably in the range of 0.5 wt.% to 20 wt.% and in particular of 3 wt.% to 10 wt.%.

[0062] Dishwashing detergents according to the invention can contain crystalline layered

[0063] Silicates of the general formula NaMSixO2x+i ■ y H2O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values ​​for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a modulus of Na2 can also be used. <D : SiÜ2 von 1 :2 bis 1 :3,3, vorzugsweise von 1 :2 bis 1 :2,8 und insbesondere von 1 :2 bis 1 :2,6, welche vorzugsweise löseverzögert sind und Sekundärwascheigenschaften aufweisen. In bevorzugten erfindungsgemäßen maschinellen Geschirrspülmitteln wird der Gehalt an Silikaten, bezogen auf das Gesamtgewicht des maschinellen Geschirrspülmittels, auf Mengen unterhalb 10 Gew.-%, vorzugsweise unterhalb 5 Gew.-% und insbesondere unterhalb 2 Gew.-% begrenzt. Besonders bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel sind Silikat-frei.

[0064] Other suitable builders that can be used as sole builders, but especially in combination with citrate, are methylglycinediacetic acid (MGDA) and glutamic acid-N,N-diacetic acid (GLDA). These builders are preferably used in amounts of 5 wt.% to 60 wt.%, in particular 10 wt.% to 40 wt.% in automatic dishwashing detergents according to the invention.

[0065] In addition to the aforementioned builders, the detergents according to the invention may contain alkali metal hydroxides. These alkali carriers are preferably used in the detergents only in small amounts, preferably in amounts below 10 wt.%, preferably below 6 wt.%, preferably below 5 wt.%, particularly preferably between 0.1 and 5 wt.%, and especially between 0.5 and 5 wt.%, each based on the total weight of the detergent. Alternative automatic dishwashing detergents are free of alkali metal hydroxides.

[0066] Dishwashing detergents according to the invention preferably contain enzyme(s) as a further ingredient. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are essentially of natural origin; based on the natural molecules, improved variants are available for use in detergents or cleaning agents and are therefore preferably used. Detergents or cleaning agents preferably contain enzymes in total amounts of 1 x 10' 6 Up to 5% by weight based on active protein. The protein concentration can be determined using known methods, such as the BCA method or the biuret method.

[0067] Among the proteases, those of the subtilisin type are preferred. Examples of these are the subtilisins BPN' and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which can be classified as subtilases but no longer as subtilisins in the narrower sense. Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which have been improved for use in detergents and cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) are particularly noteworthy.

[0068] Lipases or cutinases can also be used according to the invention, particularly for their triglyceride-cleaving activities, but also for the in situ generation of peracids from suitable precursors. These include, for example, lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed lipases, especially those with the amino acid substitution D96L.

[0069] Enzymes collectively known as hemicellulases can also be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases, and ß-glucanases.

[0070] To increase the bleaching effect, oxidoreductases, for example, oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose-, or manganese-peroxidases, dioxygenases, or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention. Advantageously, organic compounds, particularly aromatic ones, that interact with the enzymes are also added to enhance the activity of the respective oxidoreductases (enhancers) or to ensure electron flow in the event of significantly different redox potentials between the oxidizing enzymes and the soils (mediators).

[0071] An enzyme can be protected against damage such as inactivation, denaturation, or degradation, for example, due to physical influences, oxidation, or proteolytic cleavage, particularly during prolonged storage of the agent containing it. Inhibition of proteolysis is particularly preferred when the proteins and / or enzymes are obtained microbially, especially if the agents also contain proteases. Detergents or cleaning agents can contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.

[0072] Enzymes with washing or cleaning activity are generally not supplied in the form of pure protein, but rather in the form of stabilized, storable, and transportable preparations. These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably as concentrated as possible, with little water content, and / or containing stabilizers or other additives.

[0073] Alternatively, the enzymes can be encapsulated for both solid and liquid dosage forms, for example by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a water-, air-, and / or chemical-impermeable protective layer. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shake or roll granulation or in fluid-bed processes. Such granules, for example by applying polymeric film formers, are advantageously low in dust and, due to the coating, are stable in storage.

[0074] Furthermore, it is possible to package two or more enzymes together so that a single granulate has multiple enzyme activities.

[0075] As can be seen from the above, the enzyme protein constitutes only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, particularly preferably between 0.4 and 20 wt.%, and especially between 0.8 and 10 wt.% of the enzyme protein.

[0076] Particularly preferred are those automatic dishwashing detergents which, based on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations.

[0077] In addition to the aforementioned non-ionic surfactants to be used according to the invention, the automatic dishwashing detergents according to the invention may also contain other non-ionic surfactants.

[0078] In a preferred embodiment, the weight proportion of the further non-ionic surfactant in the total weight of the automatic dishwashing detergent according to the invention is between 0.1 and 30 wt.%, preferably between 0.5 and 20 wt.%, preferably between 1 and 10 wt.% and in particular between 2 and 6 wt.%.

[0079] In a preferred embodiment, further preferred nonionic surfactants have the general formula R 1 O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(CH3)O]zCH2CH(OH)R 2 on, in the R 1 represents a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R 2denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x and z represent values ​​between 0 and 40 and y represents a value of at least 15.

[0080] The addition of these nonionic surfactants has proven particularly advantageous with regard to rinse performance and drying. In a preferred embodiment, the automatic dishwashing detergent contains, based on its total weight, a nonionic surfactant of the general formula R 1 O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(CH3)O]zCH2CH(OH)R 2 in amounts of 0.1 to 15 wt.%, preferably 0.2 to 10 wt.%, particularly preferably 0.5 to 8 wt.% and in particular 1.0 to 6 wt.%.

[0081] Particularly preferred are those end-capped poly(oxyalkylated) nonionic surfactants which, according to the formula R 1 O [CH2CH2O] y CH2CH(OH)R 2 contains, in the R 1represents a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and y stands for a value between 15 and 120, preferably 20 to 100, in particular 20 to 80. The group of these non-ionic surfactants includes, for example, hydroxy mixed ethers of the general formula C6-22-CH(OH)CH2O-(EO)20-i20-C2-26 , for example the C5-12 fatty alcohol (EO)22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO)4o-8o-2-hydroxyalkyl ethers.

[0082] An automatic dishwashing detergent according to the invention, characterized in that a surfactant of the general formula

[0083] R 1 CH(OH)CH2O-(CH2CH2O)20-i20- R 2 is used, where R 1 and R 2independently of one another represent a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms, are particularly preferred.

[0084] Surfactants of the formula R are also preferred. 1 O[CH2CH(CH3)O]x[CH2CH2O] y CH2CH(OH)R 2 , in the R 1 represents a linear or branched aliphatic hydrocarbon radical having 4 to 22 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 4, preferably 0.5 to 1.5, and y stands for a value of at least 15.

[0085] According to the invention, surfactants of the general formula R 1 O[CH2CH(CH3)O]x[CH2CH2O] y CH2CH(OH)R 2 preferred, in the R 1represents a linear or branched aliphatic hydrocarbon radical having 4 to 22 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 a value between 1 and 40 and y for a value between 15 and 40, wherein the alkylene units [CH2CH(CH3)O] and [CH2CH2O] are randomized, ie in the form of a statistical, random distribution.

[0086] The group of preferred end-capped poly(oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula R 1 O[CH2CH2O]x[CH2CH(R 3 )O] y CH2CH(OH)R 2 , in the R 1 and R 2 independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2, but preferably represents -CH3, and x and y independently represent values ​​between 1 and 32, wherein nonionic surfactants with R 3 = -CH3 and values ​​for x from 15 to 32 and y from 0.5 to 1.5 are particularly preferred.

[0087] By using the previously described non-ionic surfactants with a free hydroxyl group on one of the two terminal alkyl residues, the rinsing performance and drying can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

[0088] The stated carbon chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned nonionic surfactants represent statistical averages, which can be a whole or fractional number for a specific product. Due to the manufacturing processes, commercial products of the above-mentioned formulas usually do not consist of a single representative, but of mixtures, which can result in averages and, consequently, fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.

[0089] Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures consisting of two, three, four, or more surfactants. Surfactant mixtures do not refer to mixtures of nonionic surfactants that, as a whole, fall under one of the general formulas mentioned above, but rather to mixtures containing two, three, four, or more nonionic surfactants that can be described by different ones of the above-mentioned or other general formulas.

[0090] Particularly preferred are nonionic surfactants having a melting point above room temperature. Nonionic surfactant(s) having a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C, and especially between 26.6 and 43.3°C, are particularly preferred.

[0091] In addition to the ingredients described above, the agents according to the invention may contain other substances commonly found in dishwashing detergents, such as glass corrosion inhibitors, fragrances, and perfume carriers. Examples

[0092] A dishwashing detergent M1 according to the invention and, for comparison, a galactaric acid-free, otherwise identically composed detergent V1 of the compositions given in Table 1 below were prepared.

[0093] Table 1 : Composition of dishwashing detergents (wt.%)

[0094] In a Miele® GSL2 dishwasher, 30 dishwashing cycles were run with the same load in a 65°C wash program with a 10-minute hold time and a subsequent 65°C rinse cycle. Using water with a hardness of 21° dH and 400 mg / l NaHCO3, the dishwasher was loaded with a representative sample of glasses, plates, knives, stainless steel serving utensils, and silverware. 17 g of M1 or V1 detergent and 50 g of standardized artificial soil were added per wash cycle. The door was left open for 30 minutes after each wash cycle. The evaluation was performed visually in a black box under constant artificial daylight (Philips® TLD 36 W / 965, natural daylight 6500 fluorescent tubes mounted approximately 65 cm above the work surface).The tarnish resistance of the treated silverware was visually assessed on a scale of 1 to 5 (with 5 being the best value), followed by its polishability on a scale of 0.5 to 5 (with 5 being the best value) by a trained panel. The results are presented in Table 2 below. Table 2: Evaluation of the silver protection results.

[0095] It was shown that the silver protection behavior could be significantly improved by the addition of galactaric acid.

Claims

Patent claims 1 . Dishwashing detergent containing galactaric acid.

2. Agent according to claim 1, characterized in that it contains 0.05 wt.% to 2 wt.%, in particular from 0.1 wt.% to 1 wt.% of galactaric acid.

3. Agent according to claim 1 or 2, characterized in that it is in the form of a pressed shaped body, in particular as a compact, especially as a tablet.

4. Agent according to one of the preceding claims, characterized in that it is in the form of a prefabricated dosing unit with two or more phases.

5. Agent according to claim 4, characterized in that it has a weight in the range from 12 g to 30 g, in particular from 14 g to 26 g.

6. Agent according to claim 4 or 4, characterized in that its volume is in the range from 10 ml to 35 ml, in particular from 12 ml to 30 ml.

7. Agent according to one of the preceding claims, characterized in that it has a water-soluble coating formed from a water-soluble film material made of polymers or polymer mixtures.

8. A machine dishwashing method, characterized in that a machine dishwashing detergent according to one of the preceding claims is used, in particular for providing silver protection, especially for preventing and / or reducing the oxidation and / or tarnishing of silver dishes and / or for facilitating the polishing of silver dishes.

9. Use of galactaric acid or a dishwashing detergent according to the invention containing galactaric acid as a silver preservative, in particular for preventing and / or reducing the oxidation and / or tarnishing of silver ware and / or for facilitating the polishing of silver ware.

10. The method according to claim 8 or use according to claim 9, characterized in that the concentration of galactaric acid in the aqueous dishwashing liquid which acts on the items to be washed within the dishwasher is at least temporarily in the range from 1 mg / l to 30 mg / l, in particular from 2 mg / l to 20 mg / l.

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