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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2093—Esters; Carbonates
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/667—Neutral esters, e.g. sorbitan esters
• • 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
  • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
  • 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 detergents and cleaners, in particular to automatic dishwashing compositions containing glycerol esters for preventing the discoloration of plastic dishes, to dishwashing methods using these dishwashing detergents, and to the use of dishwashing agents for preventing the discoloration of plastic dishes.
• the object of the present invention was therefore to provide alternative compounds which at least reduce the occurrence of discoloration on plastics in the course of automatic dishwashing as a result of colored food residues.
• washing or cleaning agents containing at least one glycerol ester characterized in that the glycerol is esterified in the glycerol ester with one or two branched or unbranched, saturated or unsaturated C 12-20 fatty acids, wherein at least one further hydroxy group of glycerol esterified with a C 2-6 carboxylic acid.
• the mono- and diesters of glycerol are, for example, as degradation products of dietary fats in fat digestion (lipolysis).
• Glycerol esters are used primarily as emulsifiers in the production of pastry and confectionery, chocolate products, margarine, baby food, cocoa powder, milk powder, mashed potatoes, rice and pasta.
• a first object of the present invention are therefore detergents and cleaners containing glycerol esters, wherein the glycerol esterified in the glycerol ester with one or two branched or unbranched, saturated or unsaturated C 12-20 fatty acids, preferably C 16-20 fatty acids is.
• At least one further hydroxy group of the glycerol ester preferably exactly one hydroxyl group of the glycerol ester, esterified with a C 2-6 carboxylic acid.
• the C 2-6 -carboxylic acid to be used according to the invention preferably comprises further hydrophilic groups, in particular carboxy groups and / or hydroxyl groups, preferably up to two further carboxy groups - in addition to the carboxy group which forms the ester bond with the glycerol - and / or up to 5 hydroxy groups.
• the C 2-6 carboxylic acid is particularly preferably selected according to the invention from acetic acid, propionic acid, lactic acid, oxalic acid, citric acid, isocitric acid, tartaric acid, tartronic acid, glycolic acid, malic acid and gluconic acid.
• the glycerol ester is a compound in which the glycerol is reacted firstly with a branched or unbranched, saturated or unsaturated C 12-20 fatty acid, preferably C 16-20 fatty acid, in particular C 18 -fatty acid, and secondly is esterified with a previously described hydrophilically modified C 2-6 carboxylic acid.
• both ester bonds are terminal.
• Esters of glycerol which can be used according to the invention are commercially available, for example, under the trade name Grindsted (Danisco), in particular under the trade names Grindsted® Acetem, Grindsted® Citrem, Grindsted® Mono-Di and Grindsted® Lactem.
• the glycerol ester is preferably present in detergents and cleaners according to the invention in an amount of from 0.05 to 30% by weight, in particular from 0.1 to 10% by weight, particularly preferably from 0.5 to 5% by weight.
• the washing or cleaning agent according to the invention in a preferred embodiment is a machine dishwashing detergent.
• the washing and cleaning agent according to the invention in particular the machine dishwashing detergent according to the invention, preferably contains at least one further constituent, preferably at least two further constituents selected from the group consisting of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration auxiliaries, Perfumes and perfume carriers.
• Another object of the present invention is the use of a detergent or cleaning agent according to the invention, in particular a machine dishwasher according to the invention, for preventing and / or reducing the staining of plastic and / or to avoid the change in the color impression of plastic dishes, especially when it is cleaned in an automatic Dishwasher.
• Another object of the present invention is a machine dishwashing process, characterized in that a washing or cleaning agent according to the invention, in particular a machine dishwashing agent according to the invention, is used, in particular for the purpose of reducing and / or preventing the discoloration of plastics.
• plastic materials are in a preferred embodiment of polyethylene or polypropylene.
• an agent according to the invention may optionally contain, in addition to the active ingredients mentioned, another known color transfer inhibitor, preferably then in amounts of from 0.01% by weight to 5% by weight, in particular from 0.1% by weight to 1% by weight. %, contain.
• another known color transfer inhibitor e.g. a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer of these can be used.
• polyvinylpyrrolidones having molecular weights of from 15,000 to 50,000 and also polyvinylpyrrolidones having molecular weights of more than 1,000,000, in particular from 1,500,000 to 4,000,000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyl oxazolidones, polyamine N-oxide Polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids.
• Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention.
• those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.
• porous polyamide particles and / or synthetic sheet silicates As further known color transfer inhibitors, it is possible to use porous polyamide particles and / or synthetic sheet silicates.
• enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water.
• a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, with the above-mentioned conventional polymeric color transfer inhibiting agents can additionally be used.
• the dishwashing compositions according to the invention which may be solid or liquid and in particular as pulverulent solids, in nachverêtter particle form, as homogeneous solutions or suspensions
• ingredients used according to the invention in principle all known ingredients customary in such compositions may be present, with substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers being particularly preferred become.
• Another object of the invention is the use of the previously described glycerol esters for preventing the discoloration of plastic materials during the automatic dishwashing process.
• Preventing the discoloration of plastic materials during the automatic dishwashing process means that the extent of discoloration of plastic materials is at least reduced, in the best case, the discoloration of plastic materials is completely suppressed.
• Another object of the invention is the use of the above-described glycerol esters to prevent the transfer of dyes resulting from colored food residues on plastic dishes during its cleaning in an automatic dishwasher. Avoiding the transfer of dyes to plastic dishes here means that the extent of the transfer of dyes to plastic dishes is at least reduced, in the best case, the transfer of dyes on plastic dishes is completely suppressed.
• Another object of the invention is the use of the glycerol esters described above to avoid the change in the color impression of plastic dishes during its cleaning in an automatic dishwasher. Avoiding the change in the color impression of plastic dishes here means that the extent of the change in the color impression is at least reduced, in the best case, the change in the color impression is completely suppressed.
• builders can be used.
• the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
• the crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
• silicates Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
• crystalline phyllosilicates of the formula NaMSi x O 2x + 1 .yH 2 O, in which x is 2.
• x is 2.
• both .beta.- and ⁇ -sodium Na 2 Si 2 O 5 ⁇ y H 2 O and further in particular Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5), Na-SKS-7 (.beta.-Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 ⁇ H 2 O), Na-SKS-10 (NaHSi 2 O 5 ⁇ 3 H 2 O, kanemite), Na-SKS-11 ( t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ).
• Machine dishwashing detergents preferably comprise a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2 + 1 .yH 2 O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0, 4 to 10 wt .-%, each based on the total weight of these agents.
• amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
• the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
• amorphous is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.
• X-ray-amorphous silicates whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
• the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
• Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
• the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
• phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
• sodium potassium tripolyphosphates Preferably usable according to the invention are the sodium potassium tripolyphosphates.
• phosphates are used as washing or cleaning substances in machine dishwashing detergent in the present application
• preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate ), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the automatic dishwashing detergent.
• alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali silicates, alkali metal silicates and mixtures of the abovementioned substances, it being possible to use the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention.
• a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
• a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
• the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent.
• Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
• compositions which, based on the weight of the automatic dishwashing detergent, are less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate (e) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.
• organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
• Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
• the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents.
• citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
• machine dishwashing detergents are preferred according to the invention, characterized in that the automatic dishwashing agent contains citric acid or a salt of citric acid and that of the Weight fraction of citric acid or the salt of citric acid is preferably more than 10 wt .-%, preferably more than 15 wt .-% and in particular between 20 and 40 wt .-% is.
• polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
• the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
• Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
• Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
• the content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
• the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
• biodegradable polymers of more than two different monomer units for example those containing as monomers, salts of acrylic acid and the Maleic acid and vinyl alcohol or vinyl alcohol derivatives or containing as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
• copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which can be used with particular preference.
• sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
• the automatic dishwashing agents according to the invention contain methylglycinediacetic acid or a salt of methylglycinediacetic acid, wherein the proportion by weight of methylglycinediacetic acid or of the salt of methylglycinediacetic acid is preferably between 0.5 and 15% by weight, preferably between 0.5 and 10% by weight and in particular between 0.5 and 6 wt .-% is.
• compositions of the invention may contain surfactants, wherein the nonionic, the anionic, the cationic and the amphoteric surfactants are counted among the group of surfactants.
• nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
• Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
• nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
• surfactants are also the polyhydroxy fatty acid amides known as PHFA.
• Low-foaming nonionic surfactants can be used as preferred surfactants.
• the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
• EO ethylene oxide
• alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
• the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• Nonionic surfactants which have a melting point above room temperature.
• surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
• surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
• nichionic surfactants of the general formula in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; 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 stand for integers from 1 to 6.
• R 1 is -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A '" O) z -R 2 , in the R 1 and R 2 independently represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 alkyl or alkenyl radical;
• A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferred according to the invention.
• Very particularly preferred nonionic surfactants in a preferred embodiment have the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH ( OH) R 2 in which R 1 is 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, in particular 4 to 20 carbon atoms, or mixtures thereof and x and z are values between 0 and 40 and y is a value of at least 15.
• R 1 is a linear or branched aliphatic hydrocarbon radical 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 is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units [CH 2 CH (CH 3 ) O] and [CH 2 CH 2 O] randomized, ie in the form of a random random distribution.
• the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
• Anionic surfactants can also be used as a component of automatic dishwashing detergents. These include in particular alkylbenzenesulfonates, (fatty) alkyl sulfates, (fatty) alkyl ether sulfates and alkanesulfonates.
• the content of the anionic surfactant is usually 0 to 10% by weight.
• the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents, which do not contain cationic or amphoteric surfactants are particularly preferred.
• the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
• the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
• cationic, anionic and amphoteric polymers can be used in machine dishwashing detergents in addition to nonionic polymers.
• “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
• Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
• amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be e.g. to act carboxylic acids, sulfonic acids or phosphonic acids.
• Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or non
• Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
• Machine dishwashing detergents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of from 0.01 to 10% by weight, based in each case on the total weight of the automatic dishwashing detergent.
• the bleaching agents are a substance which can be used with particular preference for washing or cleaning.
• sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
• Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
• bleaching agents from the group of organic bleaching agents can also be used.
• Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
• peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ - phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)] , o-Carboxybenzamidoperoxycapronsäure, N-Nonenylamidoperadipinklare and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-Diperoxy carboxylic acid, 1,9-dip
• chlorine or bromine releasing substances can be used.
• suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
• DICA dichloroisocyanuric acid
• Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
• automatic dishwashing agents which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, preferably sodium percarbonate , contain.
• the active oxygen content of the automatic dishwashing agents in each case based on the total weight of the composition, is preferably between 0.4 and 10% by weight, more preferably between 0.5 and 8% by weight and in particular between 0.6 and 5% by weight. %.
• Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1.0 wt .-% to.
• Bleach activators are used in automatic dishwashing detergents, for example, to achieve improved bleaching performance when cleaned at temperatures of 60 ° C and below.
• As bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
• Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
• polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
• Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
• Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.
• Enzymes can be used to increase the washing or cleaning performance of automatic dishwashing detergents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in automatic dishwasher detergents, which can be used correspondingly preferred.
• Machine dishwashing detergents preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
• the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
• the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as 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.
• a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as 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.
• further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
• Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
• such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating. Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.
• one or more enzymes and / or enzyme preparations preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agent used.
• Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
• Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
• the content of zinc salt in dishwasher detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt the content of zinc in oxidized form (calculated as Zn 2+) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. %, in each case based on the total weight of the glass corrosion inhibitor-containing agent.
• disintegration aids so-called tablet disintegrants
• tablet disintegrants or disintegrants excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.
• Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
• perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
• perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.
• the preparation of automatic dishwashing agents according to the invention can take place in different ways.
• the agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, in particular tablets, are particularly suitable as firm supply forms.
• the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
• Inventive agents can be formulated in the form of single-phase or multi-phase products.
• automatic dishwashing detergents with one, two, three or four phases are preferred.
• Machine dishwashing detergent characterized in that it is in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
• the individual phases of multiphase agents may have the same or different states of aggregation.
• Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase are preferred.
• Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.
• the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
• the subject matter of the present application is furthermore a method for cleaning dishes in a dishwashing machine, in which the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle.
• the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.
• a typical frame formulation for a machine dishwashing detergent which can preferably be used, for example in tablet form, comprises the following substances: Na tripolyphosphate 20-50% by weight sodium 10-30% by weight sodium 5-18% by weight bleach 0.5-5% by weight bleach catalyst 0.01-1% by weight sulfopolymer 2.5-15% by weight polycarboxylate 0.1-10% by weight nonionic surfactant 0.5-10% by weight phosphonates 0.5-5% by weight amylase 0.1-5% by weight protease 0.1-5% by weight % By weight, based in each case on the total agent.
• Example 1 Inhibition of staining of plastic in automatic dishwashing using dishwasher tablets
• ballast dirt 15 g olive oil, 5 g vinegar essence, 80 g tomato ketchup, 3.7 g paprika spice, 3.7 g curry spice, 10 g salt.
• a commercial dishwashing tablet was used on the one hand, and the same commercial dishwashing tablet in combination with 2 grams of Grindsted Lactem P22 or in combination with 2 grams of Grindsted Acetem 70 on the other hand.
• Example 2 Inhibition of staining of plastic in automatic dishwashing using dishwashing powder
• Polypropylene breakfast slices were subjected to a machine dishwashing process (Bosch SGS 57M22 dishwasher, program 70 ° C (time-cut), water hardness 21 ° dH).
• the following ballast dirt was used: 15 g olive oil, 5 g vinegar essence, 80 g tomato ketchup, 3.7 g paprika spice, 3.7 g curry spice, 10 g salt.
• a commercial dishwashing detergent powder was used as well as the same commercial dishwasher detergent powder in combination with 2 grams of Grindsted Lactem P22 or in combination with 2 grams of Grindsted Acetem 70.

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• 2012
  • 2012-01-12 DE DE102012200402A patent/DE102012200402A1/de not_active Withdrawn
  • 2012-08-03 WO PCT/EP2012/065253 patent/WO2013104434A1/de not_active Ceased
  • 2012-08-03 PL PL12745480T patent/PL2802640T3/pl unknown
  • 2012-08-03 HU HUE12745480A patent/HUE032316T2/hu unknown
  • 2012-08-03 EP EP12745480.9A patent/EP2802640B1/de not_active Not-in-force
  • 2012-08-03 ES ES12745480.9T patent/ES2625801T3/es active Active
• 2014
  • 2014-07-11 US US14/328,918 patent/US20140323379A1/en not_active Abandoned

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