EP3802767A1 - Formulations, leur préparation et leur utilisation et constituants appropriés - Google Patents

Formulations, leur préparation et leur utilisation et constituants appropriés

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Publication number
EP3802767A1
EP3802767A1 EP19727667.8A EP19727667A EP3802767A1 EP 3802767 A1 EP3802767 A1 EP 3802767A1 EP 19727667 A EP19727667 A EP 19727667A EP 3802767 A1 EP3802767 A1 EP 3802767A1
Authority
EP
European Patent Office
Prior art keywords
acid
alkali metal
sulfite
formulations
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19727667.8A
Other languages
German (de)
English (en)
Inventor
Frank-Peter Lang
Holger Tuerk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3802767A1 publication Critical patent/EP3802767A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/39—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
    • 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
    • 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
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

  • the present application relates to solid, liquid or gel formulations containing
  • R 1 is selected from methyl and hydrogen
  • a 1 is selected from C 2 -C 4 -alkylene
  • R 2 are identical or different and selected from C 1 -C 4 -alkyl
  • X- is selected from halide, mono-C 1 -C 4 alkyl sulfate and sulfate, with ammonium (bi) sulfite (A) or alkali metal (bi) sulfite (A) and graft copolymer (B) in a weight ratio in the range of 1: 100 to 10: 1.
  • Dishwashing detergents have many requirements to fulfill. They should be thoroughly cleaned, they should not contain any harmful or potentially harmful substances in the wastewater, they should allow the water to run off and be dried from the dishes, and the removed dirt particles must be so well dispersed or emulsified that they can be used do not settle on the surface of the dishes. Dishwashing liquids should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned. In particular, no whitish spots or deposits are to occur which arise due to the presence of lime or other inorganic and organic salts when drying water droplets or precipitate on the items to be washed by depositing dirt constituents or inorganic salts already during the rinsing process.
  • EP 2 138 560 A1 discloses graft copolymers and their use in hard surface cleaning agents, including as dishwashing detergents.
  • WO 2015/197379 and WO 2017/186524 disclose formulations containing a graft copolymer and also a builder selected from MGDA and GLDA and their salts. Although the disclosed formulations show good coating inhibition - especially in phosphate-free compositions and especially on glass. However, some of the disclosed formulations may become discolored upon prolonged storage.
  • formulations defined above were found, and in the context of the present invention also called formulations of the invention.
  • Formulations according to the invention can be liquid or solid at room temperature, ie at 20 ° C.
  • formulations according to the invention are liquid or gel at room temperature.
  • liquid formulations of the invention may contain 30 to 90 wt .-% water, preferably 40 to 80 wt .-%.
  • the water content can be determined by determining the dry residue at 80 ° C under reduced pressure.
  • Liquid formulations according to the invention which are liquid at room temperature can be present, for example, in gel form or as a paste.
  • Formulations of the invention which are solid at room temperature may be anhydrous or contain water, for example up to 20% by weight, preferably 0.1 to 10% by weight of water, for example by Karl Fischer titration or by determination of the dry residue at 80 ° C under reduced pressure.
  • solid formulations of the invention may be present for example in the form of powder, granules or tablets. Contain formulations according to the invention
  • Preferred (bi) sulfite (A) is selected from alkali metal (bi) sulfite (A). It is particularly preferable to choose alkali metal (bi) sulfite (A) from the sodium and potassium salts. Examples are Na 2 S0 3 , NaHSOs, K 2 SO 3 and KHSO 3 . Preference is given to the respective sodium salts.
  • Formulations according to the invention also contain
  • Graft copolymer (B) is called and which is composed of
  • graft base (a) at least one graft base, called graft base (a) for short, which is selected from nonionic monosaccharides, disaccharides, oligosaccharides and polysaccharides,
  • R 1 is selected from methyl and hydrogen
  • a 1 is selected from C 2 -C 4 -alkylene
  • R 2 are identical or different and selected from C 1 -C 4 -alkyl
  • X- is selected from halide, mono-C 1 -C 4 -alkylsulfate and sulfate.
  • aldopentoses pentuloses (ketopentoses), aldohexoses and hexuloses (ketohexoses) can be selected as the graft base (a) suitable nonionic monosaccharides.
  • Suitable aldopentoses are, for example, D-ribose, D-xylose and L-arabinose.
  • aldohexoses D-glucose, D-mannose and D-galactose may be mentioned;
  • Examples of hexuloses (cocoahexoses) are above all D-fructose and D-sorbose.
  • deoxy sugars such as, for example, L-fucose and L-rhamnose should also be counted as nonionic monosaccharides.
  • nonionic disaccharides cellobiose, lactose, maltose and sucrose are mentioned, for example.
  • Non-ionic oligosaccharides in the context of the present invention are nonionic carbohydrates having from three to ten nonionic monosaccharide units per molecule, for example glycans.
  • Nonionic polysaccharides in the context of the present invention are nonionic carbohydrates having more than ten nonionic monosaccharide units per molecule.
  • Nonionic oligosaccharides and polysaccharides can be, for example, linear, cyclic or branched.
  • non-ionic polysaccharides examples include biopolymers such as starch and glycogen, as well as cellulose and dextran. Also to be mentioned are inulin as a polycondensate of D-fructose (fructans) and chitin. Further examples of non-ionic polysaccharides are non-ionic starch degradation products, for example products which can be obtained by enzymatic or so-called chemical degradation of starch. An example of the so-called chemical degradation of starch is the acid-catalyzed hydrolysis.
  • non-ionic starch degradation products are maltodextrins.
  • mixtures of monomers, dimers, oligomers and polymers of glucose are taken to mean maltodextrin.
  • the percentage composition differs. This is described by the dextrose equivalent, which is between 3 and 40 for maltodextrin.
  • graft base (a) from nonionic polysaccharides, in particular from starch, which is preferably not chemically modified, for example whose hydroxyl groups are preferably neither esterified nor etherified.
  • starch is selected from those non-ionic polysaccharides having in the range of 20 to 30% by weight of amylose and in the range of 70 to 80% of amylopectin. Examples are corn starch, rice starch, potato starch and wheat starch.
  • side chains are grafted.
  • One to ten side chains may preferably be grafted on average per molecule of graft copolymer (B).
  • a side chain is preferably linked to the anomeric C atom of a monosaccharide or to an anomeric C atom of the chain end of an oligosaccharide or polysaccharide.
  • the number of side chains is limited by the number of C atoms with hydroxyl groups of the relevant grafting base (a).
  • monocarboxylic acids (b) are ethylenically unsaturated C 3 -C 10 monocarboxylic acids and their alkali metal or ammonium salts, in particular the potassium and sodium salts.
  • Preferred monocarboxylic acids (b) are acrylic acid and methacrylic acid and also sodium (meth) acrylate. Mixtures of ethylenically unsaturated C 3 -C 10 monocarboxylic acids and in particular mixtures of acrylic and methacrylic acid are preferred components
  • dicarboxylic acids (b) are ethylenically unsaturated C 4 -C 10 -dicarboxylic acids and their mono- and especially dialkali metal or ammonium salts, in particular the dipotassium and disodium salts, and also anhydrides of ethylenically unsaturated C 4 -C 10 -dicarboxylic acids.
  • Preferred dicarboxylic acids (b) are maleic acid, fumaric acid, itaconic acid and maleic anhydride and itaconic anhydride.
  • graft copolymer (B) contains in at least one side chain in addition to monomer (c) at least one monocarboxylic acid (b) and at least one dicarboxylic acid (b).
  • graft copolymer (B) in the side chains in addition to monomer (c) exclusively monocarboxylic acid (b), but no dicarboxylic acid (b) copolymerized.
  • Monomers (c) are ethylenically unsaturated N-containing compounds with a permanent cationic charge.
  • R 1 is selected from methyl and hydrogen
  • a 1 is selected from C 2 -C 4 -alkylene, for example -CH 2 -CH 2 -, CH 2 -CH (CH 3) -, - (CH 2) 3, - (CH 2) 4 -, -CH 2 -CH 2 - are preferred and - (CH2) 3-,
  • R 2 are different or preferably identical and selected from C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, preferably at least two R 2 are the same and each is methyl, and the third group R 2 is ethyl, n-propyl or n-butyl, or two R 2 are the same and each is ethyl, and the third group R 2 is methyl, n Propyl or n-butyl. More preferably, all three R 2 are the same and are selected from methyl.
  • X- is selected from halide, for example iodide, bromide and in particular chloride, furthermore from mono-C 1 -C 4 -alkyl sulfate and sulfate.
  • mono-C 1 -C 4 -alkylsulfate are methylsulfate, ethylsulfate, iso-propylsulfate and n-butylsulfate, preferred are methylsulfate and ethylsulfate. If one chooses X- as sulfate, then X- stands for half an equivalent of sulfate.
  • variables in monomer (c) are selected as follows:
  • R 1 is hydrogen or methyl
  • R 2 are the same and each is methyl
  • a 1 is CH 2 CH 2 and X- is chloride.
  • monomer (c) is selected from
  • Graft copolymer (B) may contain in one or more side chains at least one further comonomer (d) in copolymerized form, for example hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate, or esters of alkoxylated fatty alcohols, or sulfonic acid-containing comonomers, such as 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and their alkali metal salts.
  • hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate
  • esters of alkoxylated fatty alcohols or sulfonic acid-containing comonomers, such as 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and their alkali metal salts.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • graft copolymer (B) preferably contains no further comonomers (d) in one or more side chains.
  • the proportion of graft base (a) in graft copolymer (B) is in the range of 40 to 95 wt .-%, preferably from 50 to 90 wt .-%, each based on the total graft copolymer (B).
  • the proportion of monocarboxylic acid (b) or dicarboxylic acid (b) is in the range from 2 to 40% by weight, preferably from 5 to 30% by weight and in particular from 5 to 25% by weight. , in each case based on the total graft copolymer (B).
  • Monomer or monomers (c) is or are incorporated in amounts of from 5 to 50% by weight, preferably from 5 to 40% by weight and more preferably from 5 to 30% by weight, in each case based on the total amount Graft copolymer (B).
  • graft copolymer (B) contains more monocarboxylic acid (b) than monomer (c) in copolymerized form, based on the molar fractions, for example in the range from 1.1: 1 to 5: 1, preferably 2: 1 to 4: 1.
  • the average molecular weight (M w ) of graft copolymer (B) is in the range of 1,500 to 200,000 g / mol, preferably 2,000 to 150,000, and more preferably in the range of 3,000 to 100,000 g / mol.
  • the average molecular weight M w is preferably measured by gel permeation chromatography (GPC) in aqueous KCl / formic acid solution.
  • sulfite (A) and graft copolymer (B) are present in a weight ratio in the range from 1: 100 to 10: 1, preferably in the range from 1:50 to 2: 1 and more preferably in the range from 1:20 to 1 :1.
  • (bi) sulfite (A) is selected from alkali metal (bi) sulfite, and alkali metal (bi) sulfite (A) and graft copolymer (B) are in a weight ratio in the range of 1: 100 to 10: 1 above, preferably in the range from 1:50 to 2: 1 and particularly preferably in the range from 1:20 to 1: 1.
  • graft copolymer (B) or dried graft copolymer (B) to prepare the formulations of this invention. It is preferred to stabilize graft copolymer (B) by at least one biocide.
  • suitable biocides are isothiazolinones, for example 1,2-benzisothiazolin-3-one ("BIT"), octylisothiazolinone ("OIT”), dichloroctylisothiazolinone (“DCOIT”), 2-methyl-2A / isothiazolin-3 on (“MIT”) and 5-chloro-2-methyl-2A / -isothiazolin-3-one (“CIT”), phenoxyethanol, alkylparabens such as methylparaben, ethylparaben, propylparaben, benzoic acid and their salts such as sodium benzoate, benzyl alcohol Alkali metal sorbates such as sodium sorbate, and optionally substituted
  • Further examples are 1, 2-dibromo-2, 4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine and iodophores.
  • Further examples are quaternary ammonium salts such as, for example, dialkyldimethylammonium salts, for example di-decyldimethylammonium chloride or benzyldimethylalkylammonium chloride, and cationic polyelectrolytes such as polydimethyldiallylammonium chloride.
  • the formulation according to the invention is free of phosphates and polyphosphates, with hydrogen phosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexadecyl metaphosphate.
  • the term "free of" in connection with phosphates and polyphosphates in the context of the present invention is understood to mean that the total content of phosphate and polyphosphate is in the range from 10 ppm to 0.2% by weight, determined by gravimetry.
  • formulation according to the invention is free of those heavy metal compounds which do not function as bleach catalysts, in particular of compounds of iron.
  • free from is to be understood in connection with heavy metal compounds as meaning that the content of
  • Heavy metal compounds which do not act as bleach catalysts in total in the range of 0 to 100 ppm, preferably 1 to 30 ppm, determined by the Leach method.
  • heavy metals are all metals having a specific density of at least 6 g / cm 3 , with the exception of manganese, zinc and bismuth.
  • heavy metals include precious metals as well as iron, copper, lead, tin, nickel, cadmium and chromium.
  • formulation according to the invention contains in total in the range from 0.005 to 2.0% by weight of (bi) sulfite (A), preferably alkali metal (bi) sulfite (A), preferably from 0.01 to 1.0% by weight %, more preferably 0.02 to 0.5% by weight;
  • formulations according to the invention may contain one or more enzymes, for example 0.1 to 5% by weight of enzyme, based on solids content.
  • enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
  • formulations according to the invention are free of enzymes, i. less than 0.01 wt .-% enzyme and preferably no measurable levels of enzyme, based in each case on solids content.
  • enzyme-free formulations according to the invention are also free of enzyme stabilizers such as protease inhibitors, for example benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters.
  • enzyme stabilizers such as protease inhibitors, for example benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters.
  • At least one complexing agent selected from alkali metal salts of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and citric acid and combinations of at least two of the foregoing.
  • MGDA and GLDA may be present as a racemate or as an enantiomerically pure compound.
  • GLDA is preferably selected from L-GLDA or enantiomerically enriched mixtures of L-GLDA in which at least 80 mol%, preferably at least 90 mol%, of L-GLDA is present.
  • complexing agent (C) is selected from racemic MGDA.
  • complexing agents (C) are selected from L-MGDA or from mixtures of L- and D-MGDA in which L-MGDA predominates and in which the molar ratio L / D is in the range of 55:45 to 95 : 5 is, preferably 60:40 to 85:15.
  • the molar ratio L / D can be determined, for example, by polarimetry or chromatographically, preferably by HPLC with a chiral column, for example with cyclodextrin as the stationary phase or with an optically active ammonium salt immobilized on the column.
  • an immobilized D-penicillamine salt can be used, for example, one can use an immobilized D-penicillamine salt.
  • MGDA or GLDA is preferably used as a salt.
  • Preferred salts are ammonium salts and alkali metal salts, particularly preferred are the potassium and in particular the sodium salts. These may, for example, have the general formula (II) or (III):
  • Complexing agent (C) may contain in small amounts cations which are different from alkali metal ions, for example Mg 2+ , Ca 2+ or iron ions, for example Fe 2+ or Fe 3+ . In many cases, such ions are contained in complexing agent (C) as a result of the preparation. In one embodiment of the present invention, cations other than alkali metal ions are contained in the range from 0.01 to 5 mol%, based on the total MGDA or the total GLDA.
  • complexing agent (C) contains small amounts of one or more impurities which may or may be due to production.
  • impurities for example, be propionic acid, alanine or lactic acid.
  • small amounts are proportions, for example, in the range from 0.01 to 1% by weight, based on complexing agent (C).
  • impurities are neglected in the context of the present invention, unless expressly stated otherwise.
  • the formulation according to the invention contains a complexing agent (C), for example only trisodium salt of MGDA or only tetra sodium salt of GLDA.
  • a complexing agent for example only trisodium salt of MGDA or only tetra sodium salt of GLDA.
  • compounds of the formula (II) or (III) should also be denoted by x or y, equal to zero, in each case as a compound.
  • formulation according to the invention contains two complexing agents (C), for example a mixture of trisodium salt of MGDA and tetrasodium salt of GLDA, for example in a molar ratio in the range from 1: 1 to 1:10.
  • C complexing agents
  • formulations according to the invention comprise from 20 to 95% by weight of complexing agent (C),%, preferably from 30 to 90% by weight, particularly preferably from 40 to 80% by weight, of complexing agent (C) , It is not significant in the context of the present invention whether complexing agents (C) such as MGDA or GLDA or the corresponding the salts in enantiomerically pure or racemic form or as an enantiomer- enriched mixture.
  • complexing agents (C) such as MGDA or GLDA or the corresponding the salts in enantiomerically pure or racemic form or as an enantiomer- enriched mixture.
  • Citrates, GLDA and MGDA, as well as their alkali metal salts can be present as hydrates. Unless expressly stated otherwise, quantities in the context of the present invention always refer to the active ingredient in connection with MGDA or GLDA or their alkali metal salts, ie without consideration of hydrate.
  • Liquid and in particular gel formulations according to the invention are free of bleaching agents (D), for example free from inorganic peroxide compounds such as H 2 O 2 or chlorine bleaches such as sodium hypochlorite.
  • the term "free of bleaching agents (D)” is understood to mean that such formulations according to the invention contain no detectable fractions of inorganic peroxide compounds and chlorine bleaches. Any existing bleaching agents (D) would react directly with (bi) sulfite (A) such as alkali metal (bi) sulfite (A).
  • Solid formulations of the invention at room temperature may contain one or more bleaches (D) selected from inorganic peroxide compounds and chlorine bleaches.
  • solid formulations according to the invention contain
  • Peroxide (D) at least one inorganic peroxide compound, in the context of the present inven tion briefly as peroxide (D) is called.
  • Peroxide (D) is selected from sodium peroxodisulfate, sodium perborate and sodium percarbonate, sodium percarbonate being preferred.
  • Peroxide (D) may be anhydrous or preferably hydrous.
  • water-containing sodium is Na 2 [B (0H) 2 (0 2)] 2) is also sometimes written as NaB0 2 -0 2 -3H 2 0th
  • hydrous sodium percarbonate is 2 Na 2 C0 3 -3H 2 O 2 . Particular preference is given to choosing peroxide (D) from hydrous percarbonates.
  • Percarbonates and especially sodium percarbonate are preferably used in coated form.
  • the coating may be inorganic or organic in nature.
  • coating agents are sodium sulfate, silica gel, sodium silicate, sodium carbonate and combination of at least two of the preceding coating agents, for example sodium carbonate and sodium sulfate.
  • Further suitable coating agents are waxy substances such as, for example, fatty alcohols or fatty acids or their salts.
  • the formulation according to the invention preferably contains from 1 to 20% by weight of peroxide (D), preferably from 2 to 12% by weight, particularly preferably from 3 to 12% by weight, based on the solids content of the relevant formulation.
  • peroxide D
  • solid formulation according to the invention preferably contains from 1 to 20% by weight of peroxide (D), preferably from 2 to 12% by weight, particularly preferably from 3 to 12% by weight, based on the solids content of the relevant formulation.
  • Chlorine bleach (D) is preferably sodium hypochlorite.
  • Chlorine bleach- (D) -containing formulations according to the invention are preferably liquid at room temperature.
  • the formulation according to the invention preferably contains in the range from 0.1 to 20% by weight of chlorine bleach (D), preferably 0.5 to 12% by weight, particularly preferably 1 to 12% by weight, based on the solids content of the relevant liquid formulation
  • Ingredients (E) are different from complexing agent (C), graft copolymer (B) and bleaching agents (D) and can be selected from one or more surfactants, one or more More builders, in particular phosphate-free builders, one or more cobuilders, one or more alkali carriers, one or more acids, one or more defoamers, one or more corrosion inhibitors, one or more buffers, dyes, color pigments, fragrances, thickeners, a or more organic solvents, one or more biocides, or one or more solubilizing agents.
  • surfactants one or more More builders, in particular phosphate-free builders, one or more cobuilders, one or more alkali carriers, one or more acids, one or more defoamers, one or more corrosion inhibitors, one or more buffers, dyes, color pigments, fragrances, thickeners, a or more organic solvents, one or more biocides, or one or more solubilizing agents.
  • More builders in particular phosphate-free builders, one
  • surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants.
  • Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
  • alkoxylated alcohols and alkoxylated fatty alcohols are compounds of the general formula (IV)
  • R 3 is selected, identically or differently, from linear C 1 -C 10 -alkyl, preferably ethyl and more preferably methyl
  • R 4 is selected from C 8 -C 22 -alkyl, for example n-CsH, nC-ioFh-i, n-C 12 H 25, nCi 4 H 29, n-C 16 H 33 or n-CieH 37, or mixtures of at least two of the abovementioned alkyl radicals,
  • R 5 is selected from hydrogen and C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- Decyl or iso-decyl, m and n are in the range of zero to 300, the sum of n and m being at least one.
  • m is in the range of 1 to 100 and n is in the range of 0 to 30.
  • these may be block copolymers or random copolymers, preference being given to block copolymers.
  • alkoxylated alcohols and alkoxylated fatty alcohols are compounds of the general formula (V)
  • R 6 is selected from C6-C2o-alkyl, in particular n-CSH ⁇ nC ioFh-i, n-Ci2H25, n-C 4 H29, n-Ci6H33, n-C18H37,
  • R 7 is identical or different and selected from linear C 1 -C 4 -alkyl, preferably in each case the same and ethyl and particularly preferably methyl.
  • a is a number in the range of 1 to 6
  • b is a number in the range of 4 to 20
  • d is a number in the range of 4 to 25.
  • Compounds of the general formula (V) may be block copolymers or random copolymers, preference being given to block copolymers.
  • alkoxylated alcohols and alkoxylated fatty alcohols are hydroxy mixed ethers of the general formula (VI) R 8 -CH (OH) -CH 2 -O- (A0) k -R 9 (VI) where the variables are chosen as follows:
  • R 8 is C 4 -C 30 -alkyl, branched or unbranched, or
  • R 8 is selected from C 4 C 3 -alkyl, branched or unbranched, more preferably unbranched C4-C 3 -alkyl, and most preferably n-Cio-Ci2 alkyl.
  • R 9 is C 1 -C 30 -alkyl, branched or unbranched, or C 2 -C 30 -alkenyl, branched or unbranched, having at least one C-C double bond.
  • R 9 is selected from C 4 -C 3 O-alkyl, branched or unbranched, more preferably unbranched C 6 -C 2 o-alkyl and most preferably n-Cs-Cn-alkyl.
  • k is a number in the range from 1 to 100, preferably from 5 to 60, particularly preferably 10 to 50 and very particularly preferably 15 to 40,
  • AO is selected from alkylene oxide, different or the same and selected from CH 2 -CH 2 -O,
  • (AO) k is selected from (CFhCFhO ⁇ -i, where k1 is selected from numbers in the range of 1 to 50.
  • (AO) k is selected
  • k2 and k3 may be the same or different and be selected from numbers in the range of 1 to 30.
  • (AO) k is selected from - (CFhCFhO ⁇ wherein k4 is in the range of 10 to 50, AO is EO, and R 8 and R 9 are independently selected from C 8 -C 14 alkyl.
  • k or k1, k2, k3 and k4 are in each case mean values, the number average being preferred. Therefore, each of the variables k or k1, k2, k3 or k4 - if present - can mean a fraction. Of course, a given molecule can only carry a whole number of AO units.
  • nonionic surfactants are compounds of the general formula (VII) and in particular of the formula (VII a) in which
  • R 4 and AO are as defined above and EO is ethylene oxide, ie CH 2 CH 2 O, where the AO in formula (VII) and (VII a) may each be identical or different,
  • R 8 selected from Cs-C-is-alkyl, linear or branched
  • a 3 0 is selected from propylene oxide and butylene oxide
  • w is a number in the range of 15 to 70, preferably 30 to 50,
  • w1 and w3 are numbers in the range of 1 to 5 and
  • w2 is a number in the range of 13 to 35.
  • suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide.
  • suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters.
  • amine oxides or alkyl glycosides are also suitable. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187.
  • anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.
  • formulation of the invention may contain in the range of from 3 to 20% by weight of surfactant.
  • Formulations according to the invention may contain one or more builders (F), in particular phosphate-free builders (F).
  • complexing agent (C) does not count as builder (F).
  • suitable builders (F) are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, in particular those of the formula a-Na 2 Si 2 O 5, ⁇ -Na 2 ShO 5, and ⁇ -Na 2 ShO5, succinic acid and their alkali metal salts, fatty acids.
  • acid sulfonates ⁇ -hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl- and alkenyl disuccinates, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriamine pentaacetic acid, hydroxyethylethylenediaminetriacetic acid, iminodisuccinic acid, hydroxymininodisuccinic acid, ethylenediamine disuccinic acid, aspartic acid diacetic acid and salts thereof, furthermore carboxymethylinulin, tartaric diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders (F), for example polycarboxylates and polyaspartic acid.
  • F polymeric builders
  • polymeric builders are understood as meaning organic polymers, in particular polycarboxylates and polyaspartic acid. Polymer builders (F) have no or only a negligible effect as a surfactant.
  • polymeric builders (F) are selected from polycarboxylates, for example alkali metal salts of (meth) acrylic acid homo- or
  • Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
  • a suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 1,000 to 40,000 g / mol, preferably from 1,000 to 10,000 g / mol, in particular from 1,000 to 4,000 g / mol.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
  • polymeric builders (F) are selected from one or more copolymers prepared from at least one monomer selected from the group consisting of monoethylenically unsaturated C 3 -C 10 -mono- or dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, Acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid and at least one hydrophilic or hydrophobic comonomer, as enumerated below.
  • monomers selected from the group consisting of monoethylenically unsaturated C 3 -C 10 -mono- or dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, Acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid and at least one hydrophilic or hydrophobic comonomer, as enumerated below.
  • Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22- ⁇ -olefin, a mixture of C2o-C24- ⁇ -olefins and polyisobutene having on average 12 to 100 carbon atoms.
  • Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol col (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate.
  • the polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.
  • Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2- hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide
  • Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.
  • graft polymer (B) different amphoteric polymers can be used as a polymeric builder (F).
  • amphoteric polymers are copolymers of at least one ethylenically unsaturated carboxylic acid selected from acrylic acid and methacrylic acid, at least one amide selected from N-C 1 -C 10 -alkyl (meth) acrylamide, acrylamide and methacrylamide, and at least one comonomer, selected from DADMAC, MAPTAC and APTAC.
  • Formulations according to the invention may contain, for example, in the range of a total of 10 to 75% by weight, preferably up to 50% by weight of builder (F), based on the solids content of the relevant formulation according to the invention.
  • Formulations according to the invention may contain, for example, in the range from 2 to 15% by weight, preferably up to 10% by weight, of polymeric builder (F), based on the solids content of the relevant formulation according to the invention.
  • the formulation according to the invention contains, in addition to graft polymer (B), a polymeric builder (F).
  • the weight ratio of polymeric builder (F) to graft copolymer (B) is then preferably from 30: 1 to 3: 1.
  • formulations according to the invention may contain one or more co-builders.
  • cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as a natural used, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
  • Formulations of the invention may contain one or more alkali carriers.
  • Alkaline carriers for example, provide the pH of at least 9 if an alkaline pH is desired.
  • Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates.
  • Preferred alkali metal is in each case potassium, particularly preferred is sodium.
  • Formulations of the invention may contain one or more acids.
  • Acids provide the pH of less than 7 when an acidic pH is desired.
  • Suitable acids are, for example, citric acid, tartaric acid and methanesulfonic acid.
  • Solid formulations of the invention may contain one or more bleach catalysts.
  • Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.
  • Solid formulations of the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1, 5-diacetyl-2, 2-dioxo-hexahydro-1,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.
  • Formulations according to the invention may contain one or more corrosion inhibitors.
  • these are understood as meaning compounds which inhibit the corrosion of metal or glass.
  • suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin or pyrogallol, furthermore polyethyleneimine and salts of bismuth or zinc.
  • formulations according to the invention contain a total of in the range from 0.1 to 1, 5 wt .-% corrosion inhibitor, based on the solids content of the relevant inventive formulation.
  • Solid formulations of the invention may contain one or more builders, for example, sodium sulfate.
  • Formulations according to the invention may contain one or more defoamers, selected for example from silicone oils and paraffin oils.
  • formulations according to the invention contain in total from 0.05 to 0.5% by weight of defoamer, based on the solids content of the relevant formulation according to the invention.
  • formulations according to the invention contain one or more thickeners.
  • one or more thickeners are preferably added to gel-like formulations according to the invention, it being particularly advantageous if the formulation according to the invention comprises thickeners in the range from 0.1 to 8% by weight. %, preferably from 0.2 to 6 wt .-% and particularly preferably from 0.2 to 4 wt .-%, based on the solids content of the relevant inventive formulation.
  • the thickening agent may be selected from natural polymers or modified natural or synthetic thickening agents.
  • Naturally-derived polymers useful as thickening agents in the present invention include: agar-agar, carrageenan, gum tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starch, dextri - ne, xanthan, gelatin and casein.
  • thickeners from the group of modified natural substances can be selected, for example, from the group of modified starches and celluloses. Examples which may be mentioned are carboxymethylcellulose and other cellulose ethers, hydroxyethylcellulose and hydroxypropylcellulose, and gum ethers.
  • Synthetic thickeners are selected from partially crosslinked poly (meth) acrylic acids, hydrophobically modified polyurethanes (HEUR thickener) and esterified with fatty alcohol ethoxylates poly (meth) acrylic acid copolymers (HASE thickener).
  • a particularly preferred thickener used is xanthan gum.
  • Formulations of the invention may contain one or more biocides.
  • Biocides can be generated indirectly by the raw materials used, for example by adding the graft poly- mere (B), but also added separately or in addition.
  • suitable biocides are isothiazolinones, for example 1, 2-benzisothiazolin-3-one ("BIT”), octylisothiazolinone ("OIT”), dichloroctylisothiazolinone (“DCOIT”), 2-methyl-2A / isothiazolin-3 on (“MIT”) and 5-chloro-2-methyl-2A-isothiazolin-3-one (“CIT”), phenoxyethanol, alkylparabens such as methylparaben, ethylparaben, propylparaben, benzoic acid and their salts such as sodium benzoate, benzyl alcohol, Alkali metal sorbates such as sodium sorbate, and optionally substituted hydantoins such as 1, 3-bis (
  • Further examples are 1, 2-dibromo-2, 4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine and iodophores.
  • Further examples are quaternary ammonium salts such as dialkyldimethylammonium salts, for example di-decyl-dimethyl-ammonium chloride or benzyl-dimethyl-alkylammonium chloride, and cationic polyelectrolytes such as poly-dimethyl-diallyl-ammonium chloride.
  • formulations according to the invention may contain one or more organic solvents.
  • organic solvents from the groups of mono-alcohols, diols, triols or polyols, ethers, esters and / or amides.
  • Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents in the sense of the present application being solvents which are completely miscible with water at room temperature, that is to say without a mixture gap.
  • Organic solvents which are suitable for formulations according to the invention are preferably selected from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers which are miscible with water in the given concentration range.
  • organic solvents are selected from ethanol, n- or i-propanol, butanols, glycol, 1,2-propanediol, or butanediol, glycerol, diglycol, propyl- or n-butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono n-butyl ether, diethylene glycol methyl ether, di-ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or
  • solid formulations according to the invention contain one or more disintegrating agents, also called tablet disintegrating agents.
  • disintegrating agents also called tablet disintegrating agents.
  • examples are starch, polysaccharides, for example dextranes, furthermore crosslinked polyvinylpyrrolidone and polyethylene glycol borate fatty acid esters.
  • formulations according to the invention have a pH in the range from 5 to 14, preferably 6 to 10.
  • the pH value of a 1 wt .-% aqueous solution or the liquid phase of a 1 wt .-% aqueous suspension are well suited for or for the production of cleaners for hard surfaces, for example of ceramics, in particular porcelain and earthenware, furthermore glass, stone, metal and plastic, in the home, private or public, for example toilets, bathrooms, showers or kitchens.
  • Formulations of the invention are very suitable as or for the preparation of dishwashing detergents, in particular for machine dishwashing (English "Automatic
  • formulations according to the invention are also effective against stubborn stains.
  • dishes of metal are cutlery, pots, pans and garlic presses, in particular cutlery items such as knives, cake servers and serving cutlery.
  • plastic ware dishes cups, cups and bowls made of melamine, polystyrene, polypropylene and polyethylene called.
  • Another object of the present invention is therefore the use of formulations according to the invention for rinsing dishes and kitchen utensils, in particular for machine dishwashing, that is, for rinsing with a dishwasher.
  • Another object of the present invention is a method for machine dishwashing using at least one formulation according to the invention, also referred to in the present invention dishwashing process according to the invention.
  • dishwashing process it is possible to bring dishes or kitchen utensils into contact with an aqueous solution or suspension containing at least one formulation according to the invention. After contacting it can be allowed to act. Subsequently, the so available liquor is removed, rinsed one or more times with preferably clear water and allowed to dry.
  • Another object of the present invention is a process for the preparation of formulations according to the invention, in the context of the present invention also erfindungsconcees manufacturing process mentioned.
  • the preparation process according to the invention is characterized in that an alkali metal (hydro) sulft (A), graft copolymer (B) and optionally at least one complexing agent (C) and optionally at least one or more further ingredients (E) in one or more If appropriate, mixed steps in the presence of water, and then optionally water completely or partially removed.
  • Chelating agent (C), graft copolymer (B) and other ingredients (E) are described above.
  • complexing agent (C), one or more further ingredients (E) are mixed in dry form and then an aqueous solution of graft copolymer (B) and (bi) sulfite (A), in particular alkali metal (bi) sulfite (A) to, either outside or inside a dishwasher.
  • complexing agent (C), graft copolymer (B) and (bi) sulfite (A), in particular alkali metal (bi) sulfite (A) and one or more further ingredients (E) and bleaching agent (D) are mixed. in dry form and compresses the resulting mixture into tablets.
  • complexing agent (C), graft copolymer (B), at least one thickener and one or more further ingredients (E) are mixed in dry form and produce a gelatinous formulation by addition of water.
  • one or more further ingredients (E) for the formulation according to the invention for example with one or more surfactants or more enzymes, one or more enzyme stabilizers, one or more builders (F), preferably one or more phosphate-free builders (F), in particular one or more polymer builders (F), one or more cobuilders, one or more alkali carriers or acids , one or more defoamers, one or more corrosion inhibitors, one or more builders, with buffer or dye.
  • one or more surfactants or more enzymes for the formulation according to the invention, for example with one or more surfactants or more enzymes, one or more enzyme stabilizers, one or more builders (F), preferably one or more phosphate-free builders (F), in particular one or more polymer builders (F), one or more cobuilders, one or more alkali carriers or acids , one or more defoamers, one or more corrosion inhibitors, one or more builders, with buffer or dye.
  • one or more surfactants or more enzymes for example with one or more surfactants or more
  • the water is removed completely or partially, for example, to a residual moisture in the range from zero to 15% by weight, preferably from 0.1 to 10% by weight, of the solid formulation according to the invention, by evaporating it, in particular by spray drying, spray granulation or compaction.
  • water is removed at a pressure in the range of 0.3 to 2 bar.
  • water is removed at temperatures in the range of 60 to 220 ° C.
  • the water is not removed. Instead, you can add more water. It is also particularly preferable to add a thickener. In this way one can obtain gel-like formulations according to the invention.
  • the formulations of the invention may be liquid, for example gelatinous or pasty, or solid, single- or multiphase, as tablets or in the form of other dosing units, for example as so-called pouches, packaged or unpackaged.
  • Graft copolymer (B.1) corresponds to graft copolymers (B.4) from WO 2015/197379. It was made as follows:
  • graft copolymer (B.1) 220 g (c.1) in 618 g of water were introduced into a stirred reactor and heated to 80 ° C. with stirring. At 80 ° C., the following solutions were metered in simultaneously and via separate feeds as follows: a) an aqueous solution of 40.6 g (a.1) in 149 g of water, within 4 hours.
  • the biocide used was a 9% by weight solution of 1,2-benzisothiazolin-3-one in a water-propylene glycol mixture, commercially available as Proxel TM XL2 antimicrobial. Quantitative data for biocide are partly qu'elle.
  • liquid base detergent formulation was prepared, the weighings each referring to the solids content.
  • additive was added according to Table 2 and made up to one liter with demineralized water. As needed, enough citric acid was added to adjust the pH to 6, 7 or 8. Pale yellow cleaner formulations were obtained.
  • formulations thus obtainable were stored at + 40 ° C. over a period of 10 weeks. Then the color was determined. Although formulations without polymer (B.1) showed comparatively good color values, unsatisfactory rinsing results.
  • Table 2 formulations according to the invention and comparative formulations as well as storage tests
  • Percentages are wt .-% and refer to the solids content, ie without water and without glycerol.

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Abstract

La présente invention concerne une formulation sous forme de gel, contenant (A) un sulfite de métal alcalin ou un bisulfite de métal alcalin, (B) au moins un copolymère greffé, constitué par (a) au moins une base de greffage, choisie parmi les monosaccharides, les disaccharides, les oligosaccharides et les polysaccharides non ioniques, et des chaînes latérales, pouvant être obtenues par greffage de (b) au moins un acide monocarboxylique ou dicarboxylique éthyléniquement insaturé et (c) au moins un composé de formule générale (I), les variables étant définies comme suit : R1 est choisi parmi un groupe méthyle et l'hydrogène, A est choisi parmi un groupe alkylène en C2-C4, les radicaux R2 sont identiques ou différents et choisis parmi un groupe alkyle en C1-C4, X- est choisi parmi un halogénure, un sulfate d'alkyle en C1-C4 et un sulfate, le (bi)sulfite de métal alcalin (A) et le copolymère greffé (B) présentant un rapport pondéral dans la plage de 1/100 à 10/1.
EP19727667.8A 2018-06-06 2019-05-29 Formulations, leur préparation et leur utilisation et constituants appropriés Withdrawn EP3802767A1 (fr)

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US3701735A (en) * 1971-04-12 1972-10-31 Colgate Palmolive Co Automatic dishwashing compositions
DE4316743A1 (de) * 1993-05-19 1994-11-24 Huels Chemische Werke Ag Klarspülmittel mit biologisch abbaubaren Polymeren
US5837663A (en) 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
CA2617144A1 (fr) * 2005-07-29 2007-02-01 Flexitral, Inc. Stabilisation de couleur de composants chimiques aromatiques
EP2138560B2 (fr) 2008-06-24 2015-04-01 Cognis IP Management GmbH Produit de nettoyage contenant des copolymères greffés
EP2886634B1 (fr) * 2013-12-20 2016-08-24 Rohm and Haas Company Détergent pour lave-vaisselle automatique
MX2016017276A (es) * 2014-06-23 2017-04-25 Basf Se Formulaciones, produccion y uso de las mismas y componentes adecuados.
US10294444B2 (en) * 2014-06-23 2019-05-21 Basf Se Formulations, use thereof as or for the production of dishwashing detergents, and production thereof
JP2019515082A (ja) 2016-04-27 2019-06-06 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 配合物、その製造及び使用、並びに適切な構成成分
PL3556834T3 (pl) * 2016-05-09 2021-02-08 The Procter & Gamble Company Kompozycja detergentowa zawierająca dekarboksylazę kwasu tłuszczowego
PL3243898T3 (pl) * 2016-05-09 2019-08-30 The Procter & Gamble Company Kompozycja detergentowa zawierająca enzym przekształcający kwas oleinowy
EP3284805B1 (fr) * 2016-08-17 2020-02-19 The Procter & Gamble Company Composition de nettoyage

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