Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
  • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
• • 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
  • C11D3/34—Organic compounds containing sulfur
  • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
• • 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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • 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
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38609—Protease or amylase in solid compositions only
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3942—Inorganic per-compounds
• • 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
  • C11D3/395—Bleaching agents
  • C11D3/3951—Bleaching agents combined with specific additives
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds

Definitions

• the present invention relates to dishwashing detergents which are particularly suitable for removing hydrophobic red and yellow stains from dishes, as well as the use of these detergents, in particular in machine dishwashing.
• Modern automatic dishwashing detergents must meet a wide range of requirements. They should demonstrate improved cleaning and rinsing performance, even during low-temperature cleaning cycles or in cleaning cycles with reduced water consumption. Particular attention is paid to the drying properties of the automatic dishwashing detergents used. The need for additional manual drying of the cleaned dishes is undesirable; the formation of drops and residues on the treated dishes should be avoided.
• WO 2022/069468 A1 a detergent for removing stains or bad odors from textiles.
• This detergent contains a bleach, a bleach activator, a protease and an oxygen transfer agent such as 3-methyl-1,2-benzisothiazol-1,1-dioxide. The use of this agent for cleaning dishes is not described.
• Cogranulates are known that are used in washing and cleaning agents. These cogranulates are coated with cellulose ether and contain cyclic sulfonimine, bleach activator and cellulose ether as a binding agent. The use in dishwashing detergents is not disclosed.
• Granules are disclosed that can be used in washing and cleaning agents as well as in dishwashing detergents. These granules contain sulfonimines or quaternary iminium salts and acids that are solid at 25°C. The granules are characterized by high storage stability, contain highly active bleaching catalysts and develop a very good bleaching effect even at low temperatures. Examples of use for dishwashing detergents are not included in this document.
• Detergents and cleaning agents and dishwashing detergents differ in their composition. Although a number of components with the same composition can be used in these agents, they differ significantly from one another. For example, only non-ionic surfactants are used in dishwashing agents, whereas detergents generally contain anionic and non-ionic surfactants. Dishwashing detergents also often contain special additives such as glass corrosion inhibitors, silver corrosion inhibitors or foam regulators.
• the aim of the present invention was to provide dishwashing detergents which are ideal for removing red and yellow stains from dishes. In addition to their excellent cleaning performance, these detergents also have an excellent bleaching effect, which means that objects which have already been dyed red or yellow can be freed of color residues.
• dishwashing detergents containing sulfonimines and other selected ingredients show particularly good cleaning performance in removing red and yellow stains from dishes.
• all compounds previously used in dishwashing detergents can be used as builders or structural agents.
• phosphates such as pentasodium triphosphate. Since phosphates contribute to the eutrophication of water bodies, water-soluble organic compounds are now preferably used. These do not replace all the functions of phosphates and are therefore often used together with polycarboxylates, nitriloacetic acid, phosphonates, soda or complexing carboxylic acids such as citric acid salts.
• Preferably used builders contain at least 10% by weight, based on the total amount of builders, of crystalline sodium layer silicate of the formula (la) Na 2 Si x O 2x+1 ⁇ y H 2 O (Ia) where x is a number from 1.9 to 4 and y is a number from 0 to 20,
• Crystalline layered silicates according to formula (la) are described, for example, in the European patent application with the disclosure number EP 0 164 514 A1 described.
• Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 1.9 to 3.5.
• both delta- and beta-disodium disilicates (Na 2 Si 2 O 5 ⁇ y H 2 O) are preferred, whereby beta-disodium disilicate can be obtained, for example, by the process described in WO 91/08171 A1
• Beta-disodium silicates with a molar ratio of SiO 2 /Na 2 O between 1.9 and 3.2 can be obtained according to Japanese patent applications with the disclosure numbers JP 04/238 809 A or JP 04/260 610 A
• practically anhydrous crystalline alkali silicates produced from amorphous silicates of the above general formula (1), in which x is a number from 1.9 to 2.1, can be used.
• the crystalline layered disodium disilicate of the builder a) is composed of varying percentages of the polymorphic phases alpha, beta and delta.
• amorphous components may also be present. Due to the latter, x in commercial products can also be an odd number. 1.9 ⁇ x ⁇ 2.2 is preferred.
• alpha, beta and delta disodium disilicate are known and can be used, for example, in EP 0 164 514 A1 be taken.
• the disodium disilicate is layered crystalline disodium disilicate which consists of at least one of the polymorphic phases of the disodium disilicate and of sodium silicates of a non-layered silicate nature.
• crystalline sodium layer silicates containing 80 to 100% by weight of delta-disodium disilicate.
• crystalline sodium layer silicates with a content of 70 to 100 wt.% beta-disodium disilicate can also be used.
• Particularly preferably used crystalline sodium layer silicates contain 1 to 40 wt.% of alpha-disodium disilicate, 0 to 50 wt.%, in particular 0 to 45 wt.% of beta-disodium disilicate, 50 to 98 wt.% of delta-disodium disilicate and 0 to 40 wt.% of non-layer silicate sodium silicates (amorphous fractions).
• the dishwashing detergents according to the invention contain crystalline sodium layer silicate of the formula (Ia) in granulated form, as well as cogranulates containing crystalline sodium layer silicate and sparingly soluble metal carbonate, as for example in WO2007/101622 A1 described.
• the dishwashing detergents according to the invention contain crystalline sodium disilicates Na 2 Si 2 O 5 ⁇ y H 2 O with y being 0 to 2.
• the dishwashing detergents according to the invention can contain, in addition to crystalline sodium layer silicate according to formula (la), further water-soluble organic and/or inorganic builders.
• Alkali silicates and polymeric alkali phosphates which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts, are particularly suitable as water-soluble inorganic builder materials.
• examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate as well as the corresponding potassium salts or mixtures of sodium and potassium salts.
• the water-soluble organic builder substances include polycarboxylic acids or their salts, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid or its salt (MGDA), glutamediacetic acid or its salt (GLDA), iminodisuccinic acid (IDS) and ethylenediaminedisuccinic acid or its salt (EDDS), nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid.
• Polyphosphonic acids in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, can also be used.
• Preferred builders or co-builders are also polycarboxylic acids, in particular the polycarboxylates accessible by oxidation of polysaccharides or dextrins, as in WO 93/16110 A1 , WO 92/18542 A1 or EP 0 232 202 A2 described, as well as polymeric acrylic acids, methacrylic acids, AMPS, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality.
• the average molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 2000 and 200 000, that of the copolymers between 2000 and 200 000, preferably between 50 000 and 120 000, in each case based on the free acid.
• a particularly preferred homopolymer is Sokalan ® PA 30 from BASF.
• a particularly preferred acrylic acid-maleic acid copolymer has an average molecular weight of 50,000 to 100,000.
• Commercially available products include Sokalan ® CP 5 and Sokalan ® CP 10 from BASF.
• copolymers of acrylic acid or methacrylic acid with AMPS vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene in which the proportion of acid is at least 50% by weight.
• vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene in which the proportion of acid is at least 50% by weight.
• Terpolymers containing two unsaturated acids and/or their salts as monomers and vinyl alcohol as the third monomer can also be used as water-soluble organic builders. and/or an esterified vinyl alcohol or a carbohydrate.
• the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid, preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth)acrylic acid, whereby the second acidic monomer or its salt can be a derivative of a C 2 -C 6 dicarboxylic acid, whereby maleic acid and AMPS are particularly preferred, and/or a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl or aryl radical.
• Such polymers can be produced in particular by processes which are described in the German patent documents DE 42 21 381 and DE 43 00 772 and generally have a relative molecular weight of between 1000 and 200,000.
• Other preferred copolymers are those described in the German patent applications with the disclosure number DE 43 03 320 A1 and DE 44 17 734 A1 and preferably contain acrolein and acrylic acid/acrylic acid salts or vinyl acetate as mono
• the organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali salts.
• water-soluble builder components include, for example, organic polymers of native or synthetic origin of the polycarboxylate type listed above, which act as co-builders particularly in hard water regions, and naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid.
• the salts of citric acid especially sodium citrate, both anhydrous trisodium citrate and trisodium citrate dihydrate can be used.
• the dishwashing detergents according to the invention exhibit a pronounced cleaning power when they contain, in addition to crystalline layered silicate of formula (la), Builder selected from methylglycinediacetic acid or its salts, sodium gluconate, IDS, sodium tripolyphosphate (STTP) and/or sodium citrate.
• La crystalline layered silicate of formula (la)
• Builder selected from methylglycinediacetic acid or its salts, sodium gluconate, IDS, sodium tripolyphosphate (STTP) and/or sodium citrate.
• the dishwashing detergents according to the invention contain one or more builders in an amount of 10 to 90% by weight, preferably 15 to 70% by weight, particularly preferably 20 to 60% by weight, and very particularly preferably 30 to 55% by weight, in each case based on the total weight of the dishwashing detergents according to the invention.
• the dishwashing detergents according to the invention contain bleach activators b). These are compounds that release peroxocarboxylic acids under perhydrolysis conditions.
• Suitable bleach activators contain O- and/or N-acyl groups.
• the dishwashing detergents according to the invention preferably contain acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives - in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates, in particular nonanoyl, isononanoyl or lauroyloxybenzenesulfonate (NOBS, ISONOBS or LOBS) or their amido derivatives (e.g.
• TAED tetraacetylethylenediamine
• TAGU acylated glycolurils
• TAGU tetraacetylglycoluril
• DADHT acylated triazine derivatives - in particular
• NACAOBS acylated hydroxycarboxylic acids such as acetylsalicylic acid or nonanoyloxybenzoic acid (NOBA) and decanoyloxybenzoic acid (DOBA), acetyltriethylcitrate, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, as well as N-acetylcaprolactam, N-benzoylcaprolactam and
• open-chain or cyclic nitrile quats as well as those from DE-A 44 43 177 known combinations of bleach activators.
• the dishwashing detergents contain acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates, in particular nonanoyl, isononanoyl or lauroyloxybenzenesulfonate (NOBS, ISONOBS or LOBS) or their amido derivatives (e.g. NACAOBS), acylated hydroxycarboxylic acids such as acetylsalicylic acid or nonanoyloxybenzoic acid (NOBA) and decanoyloxybenzoic acid (DOBA).
• TAED tetraacetylethylenedi
• the dishwashing detergents contain acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED).
• TAED tetraacetylethylenediamine
• the dishwashing detergents according to the invention contain one or more bleach activators in an amount of 0.1 to 20 wt. %, preferably 0.5 to 10 wt. %, particularly preferably 0.5 to 8 wt. %, and very particularly preferably 1 to 6 wt. %, in each case based on the total weight of the dishwashing detergents according to the invention.
• the dishwashing detergents according to the invention contain non-ionic surfactants c).
• alcohol ethoxylates with linear radicals are made from alcohols of native origin with 12 to 18 C atoms, e.g. B.
• the degrees of ethoxylation and propoxylation given above represent statistical averages which may be a whole or a fractional number for a specific product.
• the dishwashing detergents according to the invention can also contain alkyl glycosides of the general formula RO(G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 C atoms, and G 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, which as a quantity to be determined analytically can also assume fractional values, between 1 and 10; x is preferably 1.2 to 1.4.
• the dishwashing detergents according to the invention can also contain polyhydroxy fatty acid amides of the formula (VIII) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and Z is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (IX) in which R 3 is a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 6 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1 -C 4 alkyl or phenyl radicals being preferred, and Z is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
• R 3 is a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms
• R 4 is a linear, branched or cyclic alkylene radical or an ary
• Z is preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-alyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
• nonionic surfactants preferably used in the context of the present invention which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and/or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamide type may also be suitable according to the invention.
• the proportion of the one or more nonionic surfactants in the total weight of the dishwashing detergents according to the invention is 0.1 to 20 wt.%, preferably 0.1 to 10 wt.%, particularly preferably 0.5 to 8 wt.%, and very particularly preferably 1 to 6 wt.%.
• the dishwashing detergents according to the invention contain oxygen-containing bleaching agents d).
• Bleaching agents are, on the one hand, oxygen-containing compounds that react with bleach activators to form peroxyacids that bleach much more effectively at low temperatures (e.g. ⁇ 70 °C) than the bleaching agents alone.
• Suitable bleaching agents of this type are hydrogen peroxide and inorganic persalts, preferably percarbonates, perborates, persulfates and persilicates, in particular in the form of alkali metal salts.
• Particularly preferred bleaching agents of this type are hydrogen peroxide, sodium perborate (monohydrate and tetrahydrate) and/or sodium percarbonate, particularly preferably sodium perborate (monohydrate and tetrahydrate) and/or sodium percarbonate.
• the one or more bleaching agents d) are therefore selected from the group consisting of sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.
• Oxygen-containing bleaching agents are also compounds that work without a bleach activator. Suitable bleaching agents of this type are peracids or their salts.
• peracids or peracid salts are peroxycarboxylic acids and their salts according to the formula where R is an alkyl group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyl group, particularly preferably an alkyl group having 6 to 9 carbon atoms, and X + is a suitable counterion, preferably an H + , potassium or sodium ion. Preference is given to peroxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid and salts thereof.
• peracids or peracid salts are peroxysulfonic acids and their salts according to the formula wherein R represents an alkyl group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyl group, particularly preferably an alkyl group having 6 to 9 carbon atoms, and X + represents a suitable counterion, preferably H + , a potassium or sodium ion.
• peracids or peracid salts are peroxophthalic acids and their salts, phthalimino peracids and their salts, diperoxycarboxylic acids and their salts or peroxysulfuric acids and their salts.
• the peracids or their salts are particularly preferred, which are selected from the group consisting of Monoperoxyphthalic acid and its salts, N,N-phthaloylaminoperoxycaproic acid (PAP) and its salts, diperazelaic acid and its salts, diperdodecanedioic acid and its salts and monoperoxysulfuric acid and its salts, the salts preferably being selected from the sodium and/or potassium salts.
• PAP N,N-phthaloylaminoperoxycaproic acid
• diperazelaic acid and its salts diperdodecanedioic acid and its salts and monoperoxysulfuric acid and its salts
• the salts preferably being selected from the sodium and/or potassium salts.
• potassium peroxymonosulfate available under the trade name Caroat is particularly preferred.
• the amounts of bleach used are generally chosen so that the solutions of the compositions used as automatic dishwashing detergents contain between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, during the washing process.
• the proportion of the one or more oxygen-containing bleaching agents in the total weight of the dishwashing detergents according to the invention is 5 to 40 wt.%, preferably 5 to 30 wt.%, particularly preferably 10 to 25 wt.%, and most preferably 10 to 20 wt.%.
• the dishwashing detergents according to the invention contain pH regulators e). These are required to adjust the application pH of the dishwashing detergents according to the invention to a value between 9 and 11.
• the dishwashing detergents according to the invention preferably contain alkali carbonates, in particular sodium carbonate, alkali hydrogen carbonates, alkali hydroxides, in particular potassium hydroxide and sodium hydroxide, disilicates and amino acids.
• Inorganic acids such as mineral acids, e.g. hydrochloric acid
• organic acids such as saturated or unsaturated mono-, di- and tricarboxylic acids and hydroxycarboxylic acids with one or more hydroxy groups, e.g. citric acid, glycolic acid, lactic acid, maleic acid, formic acid and acetic acid, amidosulfuric acid, C 6 -C 22 fatty acids and anionic sulfonic acids, as well as mixtures thereof, are also used.
• the proportion of the one or more pH regulators e) in the total weight of the dishwashing detergents according to the invention is 0.1 to 80 wt.%, preferably 3 to 70 wt.%, particularly preferably 5 to 60 wt.%, and very particularly preferably 5 to 50 wt.%.
• the dishwashing detergents according to the invention contain sulfonimines f).
• R 1 is hydrogen, alkyl, cycloalkyl, aryl, aralkyl, or heterocyclyl, where the alkyl, cycloalkyl, aryl, aralkyl, or heterocyclyl radicals are unsubstituted or have one to three substituents selected from the group alkyl, alkoxy, aryl, heterocyclyl, amino, carboxyl, carboxylic acid ester, carboxamide, sulfonyl, cyano, hydroxy, or halogen, or where an alkyl group is interrupted by one or more oxygen atoms which are not directly adjacent to one another or by one or more keto groups which are not directly adjacent to one another, R 2 is hydrogen, alkyl, alkoxy, cycloalkyl, aryl, aralkyl, heterocyclyl, nitro, cyano, halogen, carboxyl, carboxylic acid ester or carboxamide, where the alkyl, alkoxy, cycloalkyl,
• Preferably used sulfonimines are compounds of formula (I) in which R 1 is hydrogen, R 2 is unsubstituted phenyl or phenyl substituted in the 4-position by carboxyl, chlorine, cyano, hydroxy or methoxy, and R 3 is unsubstituted phenyl or phenyl substituted in the 4-position by carboxyl, chlorine or nitro.
• Particularly preferred sulfonimines are compounds of formula II wherein R 4 and R 5 are independently unsubstituted phenyl or phenyl substituted in the 4-position with carboxyl, chlorine, cyano, hydroxy or methoxy.
• sulfonimines are compounds of the formula III wherein R 7 is hydrogen, C 1 -C 6 alkyl or phenyl, and R 6 is unsubstituted phenyl or phenyl substituted in the 4-position with carboxyl, chlorine, cyano, hydroxy or methoxy.
• Particularly preferred sulfonimines are compounds of the formula IV wherein R 8 and R 9 are independently hydrogen, C 1 -C 6 alkyl or phenyl.
• R 9 is hydrogen and R 8 is C 1 -C 6 alkyl, in particular methyl or ethyl, or phenyl are very particularly preferred.
• the most preferred sulfonimine of formula IV is 3-methyl-1,2-benzisothiazole-1,1-dioxide.
• sulfonimines are compounds of the formula V wherein R 9 is hydrogen, C 1 -C 6 alkyl or phenyl, especially hydrogen.
• the proportion of the one or more sulfonimines f) in the total weight of the dishwashing detergents according to the invention is 0.1 to 5 wt.%, preferably 0.2 to 5 wt.%, and very particularly preferably 0.5 to 3 wt.%.
• alkyl group can be either branched or unbranched.
• An alkyl group typically contains one to twenty carbon atoms, preferably one to ten carbon atoms.
• alkyl groups are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecy
• Alkyl radicals may optionally be substituted, for example with alkyl, alkoxy, aryl, heterocyclyl, amino, hydroxy, carboxy, carboxylic acid ester, carboxamide, sulfonyl, cyano, hydroxy or halogen.
• Alkyl radicals can optionally be interrupted by one or more divalent oxygen atoms that are not directly adjacent to one another. Examples of this are monovalent radicals derived from polyethylene glycols or polypropylene glycols.
• Alkyl residues can also be interrupted by one or more keto groups that are not directly adjacent to each other.
• An example of this is the acetonyl residue.
• the cycloalkyl group is typically a cyclic group containing five to eight, preferably five, six or seven ring carbon atoms, each of which can be independently substituted. Examples of substituents are listed above in the description of the alkyl groups. Examples of cycloalkyl groups are cyclopentyl or cyclohexyl.
• the aryl group is typically a cyclic aromatic group containing five to fourteen carbon atoms, each of which can be independently substituted. Examples of substituents are listed above in the description of the alkyl groups. Examples of aryl groups are phenyl, biphenyl or anthryl.
• the heterocyclyl group can typically be a cyclic group with four to ten ring carbon atoms and with at least one ring heteroatom, each of which can be independently substituted.
• substituents are listed above in the description of the alkyl groups.
• heteroatoms are oxygen, nitrogen, phosphorus, boron, selenium or sulfur.
• heterocyclyl groups are furyl, thienyl, pyrrolyl or imidazolyl.
• Heterocyclyl groups can be aromatic or non-aromatic.
• the aralkyl group is typically an aryl group, where aryl has already been defined, to which an alkyl group is covalently bonded.
• the aralkyl group can be substituted on the aromatic ring. Examples of substituents are listed above in the description of the alkyl groups.
• An example of an aralkyl group is benzyl.
• one of the substituents in this description is halogen, this is to be understood as a fluorine, chlorine, bromine or iodine atom. Fluorine, chlorine or bromine are preferred, especially chlorine.
• the dishwashing detergents according to the invention contain one or more enzymes selected from proteases, amylases, mannases, lipases, endolases, pectinases, cellulases, pullinases, cutinases or peroxidases.
• proteases are Blaze Evity 150T, Liquanase ® Ultra 2.0 XL, BLAP ® , Opticlean ® , Maxacal ® , Maxapem ® , Esperase ® , Savinase ® , Purafect ® , OxP and/or Duraxym ® .
• amylases are Stainzyme Plus Evity 24T, Stainzyme ® Plus 12L, Termamyl ® , Amylase ® LT, Maxamyl ® , Duramyl ® and/or Purafect ® Ox.
• mannase An example of a mannase is Mannaway 4.0 L.
• lipases examples include Lipex ® 100 L, Lipolase ® , Lipomax ® , Lumafast ® and/or Lipozym ® .
• Endolase ® 5000L An example of an endolase is Endolase ® 5000L.
• pectinases examples include Pectinex 3X L and/or Pectinex Ultra SPL.
• cellulases are Carezyme 1000 L and/or Celluclast 1.5 L.
• the weight proportion of the one or more enzymes in the total weight of the dishwashing detergents according to the invention is preferably from 0.001 to 8 wt.%, particularly preferably from 0.001 to 4.5 wt.% and extremely preferably from 0.01 to 3.5 wt.%.
• the dishwashing detergents according to the invention contain crystalline sodium layer silicate of the formula (Ia) in the form of a compound containing crystalline sodium layer silicate of the formula (Ia) and an acidic component.
• the acidic component is preferably a polycarboxylate, in particular a non-neutralized or only partially neutralized homopolymer and/or copolymer of acrylic acid, AMPS, methacrylic acid, maleic acid, polyaspartic acid, sugar carboxylic acid and/or other monomers.
• the molecular weight of the homopolymers and copolymers is preferably in the range from 1000 to 100,000 g/mol, particularly preferably 2,000 to 50,000 g/mol.
• acrylic acid/maleic acid copolymers with a molecular weight of 4,000 to 50,000 g/mol.
• copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinyl methyl ether, vinyl ester, ethylene, propylene and styrene.
• the dishwashing detergents according to the invention can contain further components such as electrolytes, silver corrosion inhibitors, foam regulators, compounds for increasing the drying performance of the dishes, compounds for preventing the formation of sieve residues during dishwashing, silicones, disintegrants, dyes and/or fragrances.
• Dishwashing detergents containing compounds to increase the drying performance of dishes and to prevent the formation of sieve residues when washing dishes are known, for example, from EP 3 320 068 B1 known.
• the dishwashing detergents according to the invention can contain phosphate or be phosphate-free.
• the dishwashing detergents according to the invention are phosphate-free.
• oxygen-containing bleaching agents such as persalts
• the dishwashing detergents according to the invention also contain bleach activators b) and sulfonimines as bleach catalysts f).
• Bleach activators and/or bleach catalysts are preferably added to the dishwashing detergents according to the invention in the form of granules. This is done on the one hand to increase the storage stability of these ingredients, but on the other hand also to ensure homogeneous incorporation of tiny amounts of bleach activator and bleach catalyst into the formulations.
• the bleach activators b) and bleach catalysts f) are preferably contained in the dishwashing detergent according to the invention in the form of co-granules.
• the sulfonimine f) is particularly preferably a cyclic sulfonimine.
• the bleach activator b) is particularly preferably tetraacetylethylenediamine and/or decanoyloxybenzoic acid.
• Such co-granules are from the EP 3 874 949 A1 known.
• the co-granulate preferably contains a carboxymethylcellulose as binder iii).
• the co-granulate is coated with methylcellulose.
• the dishwashing detergents according to the invention demonstrate very good cleaning performance when used, particularly in removing red and/or yellow stains on household items, especially on plastic parts.
• the dishwashing detergents according to the invention can be in the form of powdered, granular or tablet-shaped preparations, which can be produced in a conventional manner, for example by mixing, granulating, roller compacting and/or by spray drying.
• the dishwashing detergents according to the invention can also be in the form of liquid or gel-like formulations, which can be prepared in a conventional manner, for example by mixing the individual components.
• individual ingredients or combinations of ingredients can be placed in multi-chamber containers that can be used directly in the dishwasher.
• the dishwashing detergents according to the invention can be used for hand washing, but in particular as machine dishwashing detergents.
• the dishwashing detergents according to the invention can be used in processes for cleaning bathroom or kitchen articles, such as pots, bowls, dishes, glasses, or baby articles.
• the process comprises bringing the dishwashing detergents according to the invention into contact with water and with the items to be cleaned, in particular with kitchen or baby articles, and allowing the aqueous cleaning liquid formed to act on the items to be cleaned.
• the invention also relates to the use of the dishwashing detergents according to the invention for removing red and/or yellow stains from household articles, in particular bathroom or kitchen articles.
• Household articles include those found in private households; but also those used in trade and industry, for example articles used in canteens or restaurants.
• the dishwashing detergents according to the invention are preferably used for removing red and/or yellow stains in industrial processes. This preferably involves cleaning plastic bottles, in particular polyethylene terephthalate bottles, for recycling.
• composition of the dishwashing detergents used is shown in the following table.
• formulation 1 formulation 2 g/wash cycle g/wash cycle sodium citrate 7.2 7.2 sodium carbonate 5.0 5.0 sodium percarbonate 3.0 3.0 Peractive ® AC white 1) 1.0 1.0 Pluriol ® E 1500 2) 0.6 0.6 Pluriol ® E 6000 3) 0.4 0.4 Sokalan ® PA25 Cl 4) 1.0 1.0 Lutensol ® TO 7 5) 0.2 0.2 Protease Blaze Evity 150T 0.3 0.3 Amylase Stainzyme Plus Evity 24T 0.1 0.1 WeylClean ® SKS-6 WB 6) 1.0 1.0 WeylClean ® CC 30 7) - 0.3 1) TAED bleach activator, WeylChem Wiesbaden, Wiesbaden 2) Polyethylene glycol, MW 1500 g/mol, BASF, Ludwigshafen 3) Polyethylene glycol, MW 6000 g/mol,
• the plastic parts used in the test were placed in a standard household
• the ion exchanger installed in the machine at the factory was deactivated and the water, set to a defined total water hardness, was supplied via an external tank.
• ballast dirt was placed in the upper basket for each wash cycle. The test was carried out at 45 °C. Between each wash cycle, the machine was opened for 45 minutes to allow it to cool completely. After 1, 3 and 5 wash cycles, the load items were visually assessed for discoloration using a 4-point scale. In addition, the color shift (dE) of the cutting board was measured using Mach 5+.
• machine loading result of the visual evaluation material type plastic can, transparent 2.0 plastic (PE) cutting board, white 2.0 plastic (PP) funnel, white 1.0 plastic (PP/silicone) baby pacifier 1.5 plastic (PP) baby pacifier lid 2.0
• machine loading result of the visual evaluation material type plastic can, transparent 2.0 plastic (PE) cutting board, white 2.5 plastic (PP) funnel, white 2.0 plastic (PP/silicone) baby pacifier 1.5 plastic (PP) baby pacifier lid 2.0
• Example 3 Measuring the color shift dE of the cutting boards using Mach5+

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