Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2065—Polyhydric alcohols
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • C11D17/0091—Dishwashing tablets
• • 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
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
  • C11D17/043—Liquid or thixotropic (gel) 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
• • 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
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
  • C11D3/2048—Dihydric alcohols branched
• • 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
• • 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
  • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

• the present invention relates to liquid detergents in a water-soluble packaging containing at least one sulfopolymer and at least one polyhydric alcohol as defined herein, a process for its preparation and a process for the use of automatic dishwashing detergents.
• EP 2 399 979 A1 discloses a product in unit dosage form containing a nonaqueous composition comprising a cationic polymer and a fatty acid or salt trapped in stable and rapidly dissolving capsules.
• a so-called "3 in 1" product is disclosed WO 03/006593 A2 .
• the non-aqueous machine dishwashing detergent contains a composition of a) 1-60% by weight of non-aqueous solvents, b) 0.1-70% by weight of copolymers of (i) unsaturated carboxylic acids, ii) monomers containing sulfonic acid groups and iv) optionally further ionic or nonionic monomers and c) 5 to 30 wt .-% of nonionic surfactants.
• a first subject of the present application is therefore a liquid detergent in a water-soluble packaging, comprising at least one sulfopolymer, which was used in the preparation of the agent in solid form, and at least one polyhydric alcohol, wherein a mixture of 1-10 wt .-% Glycerol and 15-35 wt .-% 1,2-propylene glycol is used and the total amount of glycerol and 1,2-propylene glycol 25 to 45 wt .-%. is, and at most 25 wt .-% water, based on the total weight of the composition;
• the cleaning agent according to the invention is preferably a dishwasher detergent, in particular a machine dishwashing detergent.
• Another object of the present invention is also a machine dishwashing process in which a detergent according to the invention is used.
• the amount of polyhydric alcohol or polyhydric alcohols used in detergents according to the invention is preferably at least 20% by weight, in particular at least 25% by weight, more preferably at least 28% by weight, especially at least 30% by weight.
• Preferred Quilth Kunststoffe here are 20 to 50 wt .-%, in particular 25 to 45 wt .-%, especially 28 to 40 wt .-%.
• the polyhydric alcohols are preferably selected from glycerol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and mixtures thereof.
• a mixture of at least two polyhydric alcohols is used.
• An inventively used polyhydric alcohol is 1,2-propylene glycol.
• 1,2-Propylene glycol is used in inventive "means in an amount of 15 to 35 wt .-%, preferably in an amount of 20 to 30 wt .-%.
• Glycerol is used in inventive compositions in an amount of 1 to 10 wt .-%, preferably in an amount of 3 to 7 wt .-%.
• a mixture of glycerol and 1,2-propylene glycol is used as a polyhydric alcohol in the detergent.
• the glycerol is in this case in an amount of 1 to 10 Wt .-%, preferably in an amount of 3 to 7 wt .-%, used.
• the 1,2-propylene glycol is used here in an amount of 15 to 35 wt .-%, preferably in an amount of 20 to 30 wt .-%, each based on the total amount of the cleaning agent, wherein the total amount of glycerol and 1, 2-propylene glycol 25 to 45 wt .-%, in particular 28 to 40 wt .-%, especially 28.5 to 32.0 wt .-%, is.
• the liquid cleaning agent is preferably a hydrous composition.
• the water content of the composition according to the invention is at most 25 wt .-%, preferably below 20 wt .-%. Preferred amount ranges here are 5 to 20 wt .-%, in particular 15 to 20 wt .-%, especially 18 to 19.8 wt .-%.
• the proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%.
• the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
• the copolymers may have two, three, four or more different monomer units.
• Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
• unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, Cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
• Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
• the sulfonic acid groups may be wholly or partially in neutralized form, that is, the acidic acid of the sulfonic acid group in some or all of them Sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular against sodium ions.
• metal ions preferably alkali metal ions and in particular against sodium ions.
• the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
• the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
• Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
• the copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
• the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
• the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, particularly preferably the proportion of the sulfonic acid group-containing monomer and of the monomer each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid-group-containing monomer 60 to 80 wt .-%, the monomers are hereby preferably selected from the aforementioned.
• the liquid and water-containing cleaning agent according to the invention contains water to a maximum of 20 wt .-% in combination with sulfopolymer, which was used in the preparation of the agent in solid form. It has been found that the homogeneous and stable incorporation of solid sulfopolymer succeeds when a mixture of 1-10 wt .-% glycerol and 15-35 wt .-% 1,2-propylene glycol is used.
• the cleaning agent according to the invention is preferably contained in a water-soluble packaging.
• the water-soluble packaging allows a portioning of the cleaning agent.
• the amount of detergent in the sachet is preferably -5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.
• the water-soluble packaging preferably comprises a water-soluble polymer.
• Some preferred water-soluble polymers which are preferably used as water-soluble packaging are polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones, Polyethylene oxides, celluloses and gelatin, wherein polyvinyl alcohols and acetalated polyvinyl alcohols are particularly preferably used.
• Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural types of the type contain.
• Commercially available polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 87-99 mol%, that is, contain one more Residual content of acetyl groups.
• the water-soluble packaging at least partially comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mole%.
• the water-soluble packaging consists of at least 20 wt .-%, more preferably at least 40 wt .-%, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol, the Hydrolysis degree 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%, is.
• Polyvinyl alcohols of a specific molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention that the packaging material comprises a polyvinyl alcohol whose molecular weight is in the range from 5,000 to 100,000 gmol-1, preferably from 10,000 to 90,000 gmol-1, particularly preferably 12,000 to 80,000 gmol-1 and in particular from 15,000 to 70,000 gmol-1.
• the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and more particularly between about 260 to about 1500.
• the water solubility of polyvinyl alcohol can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
• aldehydes acetalization
• ketones ketalization
• polyvinyl alcohols have been found to be acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof.
• reaction products of polyvinyl alcohol and starch are also be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
• the water-soluble packaging preferably has a thickness of 10 .mu.m to 500 .mu.m, in particular from 20 .mu.m to 400 .mu.m, more preferably from 30 .mu.m to 300 .mu.m, especially from 40 .mu.m to 200 .mu.m, in particular from 50 .mu.m to 150 .mu.m.
• polyvinyl alcohol is available, for example, under the trade name M8630 (Monosol).
• the viscosity of cleaning agents according to the invention is preferably above 4000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C.), in particular between 4000 and 7000 mPas, more preferably between 4500 and 6500 mPas, especially between 5000 and 6000 mPas.
• the pH of cleaning agents according to the invention is preferably between 6 and 10, more preferably between 7 and 9, especially between 7 and 8.
• Detergents according to the invention preferably also contain at least one hichtionic surfactant.
• nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
• Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
• nonionic surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A" O) z -R 2 , Also referred to below as "hydroxy mixed ethers", surprisingly, the cleaning performance of inventive preparations can be significantly improved, both compared to surfactant-free system and compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
• nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals can markedly improve the stability of the enzymes contained in the cleaning detergent preparations according to the invention.
• end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
• surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
• the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 - 2-hydroxydecylether.
• nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 X is butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
• each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
• R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
• R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
• Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
• each R 3 in the above formula may be different if x ⁇ 2.
• the alkylene oxide unit in the square bracket can be varied.
• the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
• R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
• Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
• nonionic surfactants include, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
• Preferred liquid cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the cleaning agent preferably 0.5 to 10 wt .-%, preferably 1 , 0 to 8.0 wt .-% and in particular 2.0 to 6.0 wt .-% is.
• compositions according to the invention preferably contain one or more builder (s).
• the proportion by weight of these builders in the total weight of compositions according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.
• These builders include in particular carbonates, phosphates, citrates, phosphonates, MGDA, GLDA, EDDS, organic cobuilders and silicates.
• phosphate Preference is also the use of phosphate.
• alkali metal phosphates have, with particular preference of pentasodium or.
• Pentakaliumtriphosphat sodium or potassium tripolyphosphate
• the detergents and cleaning agents industry the greatest importance.
• Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one
• the phosphates combine several advantages. They act as alkali carriers, prevent calf deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
• Particularly preferred phosphates according to the invention are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
• the sodium-potassium tripolyphosphates are also preferably used according to the invention.
• phosphates are used as cleaning-active substances in the cleaning agents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 5 to 60 Wt .-%, preferably from 15 to 45% by weight and in particular from 20 to 40 wt .-%, each based on the weight of the cleaning agent.
• phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
• the use of phosphates is largely or completely omitted.
• the agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s).
• the agent is completely phosphate-free in this embodiment.
• organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
• Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
• the free acids typically also have the property of an acidifying component and thus also serve for setting a lower and milder pH of cleaning agents.
• citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
• Particularly preferred cleaning agents according to the invention contain citrate as one of their essential builders.
• Detergents characterized in that they contain 2 to 40 wt .-%, preferably 5 to 30 wt .-% and in particular 5 to 20 wt .-% citrate, are inventively preferred.
• Particularly preferred cleaning agents according to the invention are characterized in that the cleaning agent contains at least two builders from the group of phosphates, carbonates and citrates, wherein the proportion by weight of these builders, based on the total weight of the cleaning agent according to the invention, preferably 5 to 60 wt .-%, preferably 15 to 50 wt .-% and in particular 25 to 40 wt .-% is.
• the combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
• a mixture of phosphate and citrate or a mixture of GLDA and citrate is used, the amount of phosphate or GLDA preferably being from 10 to 35% by weight and the amount of citrate preferably from 2 to 10% by weight .-%, in each case based on the total amount of the cleaning agent, is, wherein the total amount of these builders is preferably 20 to 35 wt .-%, in particular 25 to 35 wt .-%, is.
• polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
• Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
• the content of (homo) polymeric polycarboxylates according to the invention is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
• the cleaning agents according to the invention may contain in particular phosphonates as further builder.
• the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
• hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.
• Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
• Phosphonates are in agents according to the invention preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
• At least one compound selected from MGDA, GLDA and EDDS is preferably used, in particular in phosphate-reduced and phosphate-free compositions.
• MGDA methylglycinediacetic acid
• GLDA glutamic acid-N, N-diacetic acid
• EDDS ethylenediamine-N, N'-disuccinic acid
• Compositions according to the invention can furthermore comprise, as builder, crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
• amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
• the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
• Particularly preferred cleaning agents according to the invention are silicate-free.
• the agents according to the invention may contain alkali metal hydroxides.
• These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
• Alternative cleaning agents according to the invention are free of alkali metal hydroxides.
• cleaning agents preferably contain enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are correspondingly preferred be used.
• Detergents according to the invention preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
• subtilisin type those of the subtilisin type are preferable.
• these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
• amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. orizae, as well as the further developments of the abovementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
• DSM 12368 Bacillus sp. A 7-7
• CTTase cyclodextrin glucanotransferase
• lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
• lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.
• oxidoreductases such as oxidases, oxygenases, catalases, Peroxidäsen, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (Phenöloxidasen, Polyphenoloxidasen) can be used.
• organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
• a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
• damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
• inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
• Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
• Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
• These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form, solutions of the enzymes, advantageously as concentrated as possible, sparing with water and / or mixed with stabilizers or further auxiliaries.
• the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
• further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
• Such capsules are applied according to methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
• such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
• the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
• Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
• detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
• Compositions according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and ampholytic surfactants, bleaching agents, bleach activators, bleach catalysts, further solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances and antimicrobial agents.
• at least one further constituent preferably selected from the group consisting of anionic, cationic and ampholytic surfactants, bleaching agents, bleach activators, bleach catalysts, further solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances and antimicrobial agents.
• solvent agents according to the invention preferably contain at least one alkanolamine.
• the alkanolamine is here, preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
• the alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.
• Zinc salts are preferably used as glass corrosion inhibitors.
• Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.

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• 2012
  • 2012-02-14 DE DE102012202176A patent/DE102012202176A1/de not_active Withdrawn
  • 2012-11-02 PL PL12781091T patent/PL2814932T3/pl unknown
  • 2012-11-02 WO PCT/EP2012/071716 patent/WO2013120550A1/de not_active Ceased
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• 2014
  • 2014-08-13 US US14/458,379 patent/US20140349905A1/en not_active Abandoned

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