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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids

Definitions

• the present invention relates to a dishwashing detergent containing certain nitrogen-based complexing agents in combination with MGDA, their use in a machine dishwashing process for increasing the deposit inhibition on dishes and a corresponding method for automatic dishwashing. Furthermore, the present invention relates to the use of the nitrogen-based complexing agents described herein in combination with MGDA for increasing the deposit inhibition on items to be washed in a machine dishwashing process.
• the object of the present invention was therefore to provide a, preferably phosphate-free, machine dishwasher detergent which has improved coating inhibition.
• Another object of the present invention is the use of the described automatic dishwashing agents for increasing the deposit inhibition on dishes during its cleaning in an automatic dishwashing machine.
• Yet another aspect of the invention is a machine dishwashing process in which a machine dishwashing composition according to the invention is used, in particular for the purpose of improving coating inhibition.
• At least one includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more.
• fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
• oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.
• alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
• the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
• N-based complexing agents used according to the invention are compounds of the formula (I) XOOC- (CH 2 ) n -CH (R 1) -N (R 2 ) -CH (R 3) -C (R 4) (R 5) -COOX (I)
• X is H, an alkali metal or ammonium
• R1 is H, C1-C10 alkyl or C (R6) (R7) COOX
• R2 is H, C1-C10 alkyl or CH 2 COOX
• R3 is H, C1-C10 alkyl or COOX
• R4, R5, R6 and R7 are independently H, OH or C1-C10 alkyl
• n is 0 or 1.
• Alkyl refers to saturated straight or branched chain hydrocarbons of 1-10, preferably 1-4 carbon atoms and includes, but is not limited to, methyl, ethyl, n -propyl, iso -propyl, n -butyl , sec-butyl, iso-butyl and tert-butyl.
• R1 is H or C1-C10 alkyl, especially H or methyl.
• R 2 is CH 2 COOX
• R 3 is H or COOX
• R 4 is H or OH
• R1 is H or C1-C10 alkyl
• R2 is H
• R3 is COOX
• R4 is OH
• R1 is H or C1-C10 alkyl
• R2 is C1-C10 alkyl
• R3 is COOX
• R4 is OH
• R1 is H or C1-C10 alkyl
• R2 is CH2COOX
• R3 is H
• R4 is H
• R1 is H or C1-C10 alkyl
• R2 is CH2COOX
• R3 is COOX
• R4 is H
• R1 is H or C1-C10 alkyl
• R2 is CH2COOX
• R3 is H
• R4 is OH
• R1 is H or C1-C10 alkyl
• R2 is CH2COOX
• R3 is COOX
• R4 is OH
• N-based chelating agents useful in the present invention include, but are not limited to, N- (1,2-dicarboxy-2-hydroxyethyl) glycine (DHEG), N- (1,2-dicarboxy-2-hydroxyethyl) - alanine, N, N-biscarboxymethyl- ⁇ -alanine, N- (1,2-dicarboxy-2-hydroxyethyl) -sarcosine and N- (1,2-dicarboxy-2-hydroxyethyl) -iminodiacetic acid.
• DHEG N- (1,2-dicarboxy-2-hydroxyethyl) glycine
• DHEG N- (1,2-dicarboxy-2-hydroxyethyl) - alanine
• N, N-biscarboxymethyl- ⁇ -alanine N- (1,2-dicarboxy-2-hydroxyethyl) -sarcosine
• N-based chelating agents are chiral, all enantiomers or diastereomers may be employed, each as such, as racemates, or any mixtures.
• N-based complexing agents used according to the invention exhibit the property of increasing the deposit inhibition in the presence of methylglycine diacetic acid (MGDA) and therefore lead to an overall improved performance of the dishwashing detergent.
• MGDA methylglycine diacetic acid
• the improvement of the scale inhibition is generally to be understood that when using the dishwashing compositions according to the invention the formation of deposits on dishes during its cleaning in an automatic dishwashing machine in comparison to the use of dishwashing agents that do not contain the complexing agents according to the invention, is significantly reduced ,
• the complexing agents i. the complexing agents of formula (I) and MGDA, are usually used in total amounts of 0.1 to 40 wt .-%, based on the total formulation of the agent used. Preferred amounts are 2 to 35 wt .-% and in particular 5 to 30 wt .-%, more preferably 10 to 25 wt .-%.
• the weight ratio of MGDA to the at least one complexing agent of the formula (I) can be 1: 4 to 4: 1, preferably 1: 2 to 2: 1, more preferably about 1: 1.
• MGDA and DHEG are used, in particular in weight ratios of 2: 1 to 1: 2, preferably about 1: 1, and amounts of 10 to 25 wt .-% based on the total weight of the composition.
• the automatic dishwashing compositions herein containing MGDA and the at least one N-based chelating agent can be solid or liquid in nature and, in particular, as powdered solids, in densified particulate form, as homogeneous solutions or suspensions.
• the automatic dishwashing detergent is present in a pre-portioned form.
• the automatic dishwashing detergent comprises a plurality of spatially separate compositions, whereby it is possible to separate incompatible ingredients from one another, or to offer compositions in combination, which are used at different times in the dishwasher. This is particularly advantageous if the automatic dishwashing detergents are present in pre-portioned form.
• At least one of the compositions is solid and / or at least one of the compositions is liquid, the complexing agents and MGDA being present in at least one of the compositions, but may also be present in several compositions.
• the agents according to the invention preferably contain at least one further constituent, in particular at least two further constituents selected from the group consisting of Builders, including other complexing agents, surfactants, polymers, enzymes, enzyme stabilizers, bleaches, bleach activators, bleach catalysts, especially manganese or cobalt based catalysts, corrosion inhibitors and glass corrosion inhibitors, disintegrants, perfumes and perfume carriers.
• Builders including other complexing agents, surfactants, polymers, enzymes, enzyme stabilizers, bleaches, bleach activators, bleach catalysts, especially manganese or cobalt based catalysts, corrosion inhibitors and glass corrosion inhibitors, disintegrants, perfumes and perfume carriers.
• additional builders can be used.
• the additional builders that can be used include in particular the zeolites, silicates, carbonates and organic cobuilders.
• the agents are phosphate-free.
• Phosphate-free as used in this context means that the compositions contain less than 1% by weight, based on the total mass of phosphates, in particular less than 0.5% by weight, more preferably less than 0.1% by weight. -%.
• phosphonates such as HEDP, are explicitly excluded and are not included in the context of the present invention under the term "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).
• Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi x O 2x + 1 .yH 2 O, in which 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 .3H 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 contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 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 to conventional amorphous sodium silicates can in various ways, for example by surface treatment, compounding, compaction / densification or by over-drying.
• 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.
• alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, it being possible to use alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention.
• 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 wt .-% and in particular below 2 wt .-%, in each case based on the total weight of the automatic dishwashing detergent used.
• Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
• 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 citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
• NTA nitrilotriacetic acid
• 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.
• citric acid and / or citrates in these compositions has proved to be particularly advantageous for the cleaning and rinsing performance of agents according to the invention. Therefore, according to the invention, preference is given to automatic dishwasher detergents, characterized in that the automatic dishwashing agent contains citric acid or a salt of citric acid and the weight proportion of citric acid or of the salt of citric acid is preferably more than 10% by weight, preferably more than 15% by weight 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.
• 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.
• copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• 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 is a primary straight-chain or methyl-branched, in particular 2-methyl-branched 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 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 May contain residues in the mixture, 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.
• 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 containing no 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 automatic 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 furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, 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
• Preferred zwitterionic polymers are 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 agents of the present invention contain at least one enzyme preparation or enzyme composition containing one or more enzymes.
• Suitable enzymes include, but are not limited to, proteases, amylases, lipases, hemicellulases, cellulases, Perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are preferably used accordingly.
• the agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein.
• the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
• proteases are among the most technically important enzymes of all. They cause the degradation of protein-containing stains on the items to be cleaned.
• proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range.
• Subtilases are naturally produced by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
• subtilisin type proteases preferably used in washing and dishwashing detergents are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the the subtilases, but not the subtilisins in the narrower sense attributable enzyme thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of said proteases, which have a relation to the parent protease modified amino acid sequence.
• Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.
• amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the improved for use in dishwashing further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
• DSM 12368 Bacillus sp. A 7-7
• CTTase cyclodextrin glucanotransferase
• lipases or cutinases in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
• suitable precursors include, for example, those originally available from Humicola lanuginosa (Thermomyces lanuginosus ), or further developed lipases, in particular those with the amino acid exchange D96L.
• 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 to increase the bleaching effect.
• peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
• phenol oxidases, polyphenol oxidases can be used to increase the bleaching effect.
• organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
• An enzyme can be particularly protected during storage against damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage.
• damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage.
• inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
• Dishwashing agents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
• Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
• Such prefabricated preparations 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, low in water and / or added with stabilizers or further auxiliaries.
• 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.
• in superimposed layers may additionally contain other active ingredients, such as stabilizers, emulsifiers, pigments, bleaches or dyes be applied.
• Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
• the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
• preferred protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 10% by weight of the enzyme protein.
• dishwashing detergents which, based in each case 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.
• compositions described herein may also include enzyme stabilizers.
• stabilizers are reversible protease inhibitors.
• Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned.
• peptide aldehydes that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose.
• the peptidic reversible protease inhibitors include ovomucoid and leupeptin.
• specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.
• enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art.
• 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.
• Further useful bleaching agents are, for example, peroxypyrophosphates, Citrate perhydrates and H 2 O 2 supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, Phthaloiminopertica Acid or Diperdodecandiklare. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.
• 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.
• 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.
• polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are 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) are particularly preferably used.
• TAED tetraacetylethylenediamine
• DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
• TAGU tetraacet
• 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.
• 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 .-%, each 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, patchouli, rose or ylang-ylang oil.
• the preparation of automatic dishwashing agents described herein can be carried out 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.
• the 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 matter. 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.
• the automatic dishwashing agents described herein are preferably prefabricated into dosage 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 dishwashing agents in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
• the water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
• the wrapper may be formed of one or two or more layers of the water-soluble film material.
• the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
• the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
• Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
• 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 of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
• polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
• polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
• a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above can be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers.
• a preferred additional polymer is polylactic acids.
• Preferred polyvinyl alcohol copolymers include, 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.
• polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
• Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
• the film material contains further additives.
• the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
• Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
• Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
• Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
• the corresponding use of the automatic dishwasher detergents according to the invention is likewise an object of the invention.
• the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used.
• the subject matter of the present application is therefore furthermore a process for the cleaning of 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 framework formulation for a machine dishwashing detergent preferably used, for example in tablet form comprises the following substances: citrate 10-50% 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 phosphonate 0.5-5% by weight protease 0.1-5% by weight amylase 0.1-5% by weight, the data in% by weight are based on the total agent.
• the combinations of MGDA and the at least one further N-based complexing agent described herein can be used.
• Phosphate-free, solid dishwashing detergent formulation (Tab): raw material Amount (wt%) Na citrate 15.00 to 20.00 Phosphonate (eg HEDP) 0.00 to 7.50 MGDA / N-based complexing agent 5.00 to 25.00 silicate 10.00 to 35.00 soda 12.50 to 25.00 Na Percarbonate 10.00 to 15.00 bleach catalyst 0.02-0.50 TAED 2.00-3.00 nonionic surfactant 2.50 to 10.00 polycarboxylate 5.00 to 10.00 Cationic acrylate copolymer 0.25-0.75 PVP (cross-linked) 0.00 to 1.50 protease 1.50 to 5.00 amylase 0.50 to 3.00 Benzotriazole (silver protection) 0.00 to 0.50 Perfume 0.05-0.15 dye 0.00-1.00 Zn acetate anhydrous 0.10-0.30 Na sulfate 0.00 to 25.00 water 0.00 to 1.50
• the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used.
• the subject matter of the present application is therefore furthermore a process for the cleaning of 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.
• Table 1 Composition of the automatic dishwashing detergent raw materials P-free total % g / job citric acid 1.60 0.32 Na citrate 20.00 4.00 HEDP 5.00 1.00 MGDA 16.00 3.20 Soda heavy 15.50 3.10 Na Percarbonate 15.00 3.00 bleach catalyst 1.00 0.20 TAED 2.90 0.58 nonionic surfactants 6.00 1.20 benzotriazole 0.30 0.06 Polyacrylate polymer 5.00 1.00 sulfopolymer 5.00 1.00 acrylic copolymer 0.50 0.10 protease 3.90 0.78 amylase 0.80 0.16 Perfume 0.07 0.01 dyes 0.74 0.15 Zn acetate anhydrous 0.20 0.04 PEG 4000 scales 0.50 0.10 100.01 20.00
• the mixture of the two complexing agents shows an improvement in the scale inhibition.
• the performance is stronger when replacing part of the MGDA compared to the complete replacement.

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• 2015
  • 2015-04-10 DE DE102015206485.9A patent/DE102015206485A1/de not_active Withdrawn
• 2016
  • 2016-04-05 EP EP16163860.6A patent/EP3078732A1/fr not_active Withdrawn

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