EP3194552B1 - Reinigungsmittel - Google Patents

Reinigungsmittel Download PDF

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Publication number
EP3194552B1
EP3194552B1 EP15767448.2A EP15767448A EP3194552B1 EP 3194552 B1 EP3194552 B1 EP 3194552B1 EP 15767448 A EP15767448 A EP 15767448A EP 3194552 B1 EP3194552 B1 EP 3194552B1
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EP
European Patent Office
Prior art keywords
acid
weight
water
cleaning agent
salts
Prior art date
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EP15767448.2A
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German (de)
English (en)
French (fr)
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EP3194552A1 (de
Inventor
Noelle Wrubbel
David MATULLA
Britta Strauss
Inga Kerstin Vockenroth
Thomas Weber
Johannes Zipfel
Volker Blank
von den Karl-Josef DRIESCH
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL15767448T priority Critical patent/PL3194552T3/pl
Publication of EP3194552A1 publication Critical patent/EP3194552A1/de
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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
    • C11D3/16—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
    • 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
    • C11D3/22—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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/268—Carbohydrates or derivatives 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids

Definitions

  • the present invention relates to a cleaning agent, in particular dishwashing detergent, preferably pre-portioned automatic dishwashing detergent.
  • Hard surface cleaners such as dishwashing detergents
  • dishwashing detergents are available to the consumer in a variety of forms.
  • traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance.
  • the consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.
  • the EP 1 846 482 discloses, for example, the coating of the polyvinyl alcohol-containing film with a salt layer containing carboxymethyl cellulose as a binder.
  • the US 7,259,134 discloses a multi-chamber bag (Mehrschpouch), in which a chamber is a liquid A composition comprising a moisture control system comprising a mixture of C 2 -C 6 monoalkylpolyol and C 2 -C 3 monoalkylpolyol.
  • a moisture control system comprising a mixture of C 2 -C 6 monoalkylpolyol and C 2 -C 3 monoalkylpolyol.
  • systems containing 40% by weight of dipropylene glycol and 4 to 15% by weight of glycerol, which contain 10% by weight of H 2 O are disclosed as the liquid detergent component.
  • a waiver of larger amounts of organic solvents would be desirable.
  • aqueous cleaning formulations containing enzymes in particular protease (s) and / or amylase (s)
  • enzymes in particular protease (s) and / or amylase (s)
  • the storage stability of the enzymes by a high water content is not possible without stabilizers.
  • Boric acid or borates which are known to stabilize the enzyme, can even lead to compatibility problems in polyvinyl alcohol-containing films even at lower concentrations.
  • divalent cations in particular from the group of alkaline earth metals, preferably calcium and / or magnesium salts, are also proposed for enzyme stabilization.
  • the presence of such divalent salts in dishwashing detergents has the disadvantage that the effectiveness of the added builders is reduced depending on the amount of added salts.
  • crosslinking of the polyvinyl alcohol used for the film may occur, thereby worsening the dissolution behavior of the disposable portion in the dishwasher.
  • the object of the present invention was therefore to provide a cleaning agent which has improved stability, in particular with regard to the stability of the enzyme activities during storage and, if the detergents are present as pre-portioned cleaners, good stability of the pre-portioned detergent units, especially with regard to leakage of the package (especially in packages comprising polyvinyl-containing films).
  • detergents in particular liquid detergents, can also be formulated storage-stable with relatively large amounts of water, preferably 40% by weight and more, in combination with at least one aminocarboxylic acid as nonphosphate builders, in particular GLDA or MGDA.
  • pre-portioned cleaners in particular automatic dishwashing detergents (especially in disposable portions).
  • disposable portions show no leaks even during prolonged storage, especially in packaging comprising polyvinyl alcohol-containing films.
  • cleaning formulations without the addition of larger amounts of divalent cations, a good and stable performance of the enzymes contained.
  • wt .-% refers to the amount of active substance based on the total amount of the cleaning agent.
  • the cleaning agents according to the invention in particular the pre-portioned automatic dishwashing agents, contain between 40 and 60% by weight of water.
  • the proportion of water is mathematically calculated on the one hand from the explicitly added amount of water and on the other hand from the amount of water, which are introduced by aqueous raw materials, etc. in the formulation.
  • the cleaning agents according to the invention contain between 50 and 60% by weight of water.
  • the water content is between 51 and 55 wt .-% water, each based on the total weight of the detergent formulation.
  • Liquid as used herein with respect to the cleaning agent of the present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian fluids having a yield point. Because of the relatively high water content, the cleaning agents according to the invention, in particular pre-portioned automatic dishwashing agents, are liquid or, depending on the amount of thickening substances used, also gelatinous to pasty, non-solid cleaning formulations.
  • the detergents according to the invention in particular dishwashing detergents, preferably pre-portioned automatic dishwashing detergents, contain at least one aminocarboxylic acid selected from GLDA and / or MGDA and / or their salts.
  • At least one means 1 or more, for example, 1 or 2 or more. If a plurality of aminocarboxylic acids and / or their salts are used, the amounts stated below are based on the total amount of all aminocarboxylic acids. According to the invention, 15 to 30% by weight of at least one aminocarboxylic acid is selected from methylglycinediacetic acid (MGDA) or its salts and also glutamine-N, N- diacetic acid (GLDA) or its salts.
  • MGDA methylglycinediacetic acid
  • GLDA glutamine-N, N- diacetic acid
  • the cleaning agents according to the invention contain the selected aminocarboxylic acid (s) in amounts, based in each case on the total weight of the cleaning agent, of from 15 to 25% by weight, preferably from 15 to 20% by weight, of at least one aminocarboxylic acid selected from MGDA and / or salts thereof, and It is particularly preferred to use either 15 to 25% by weight of MGDA and / or its salts or 15 to 25% by weight of GLDA and / or their salts. It is very particularly preferred to use 15 to 20% by weight of MGDA and / or its salts or 15 to 20% by weight of GLDA and / or its salts. 15 to 20 wt .-% GLDA and / or their salts, in particular to use the partially or fully neutralized sodium or potassium salts of GLDA, is particularly preferred.
  • the present invention contains 0.20 to 2.5% by weight of xanthan, preferably 0.25 to 2.0% by weight, in particular 0.25 to 1.5% by weight, for example 1% by weight of xanthan.
  • Xanthan gum is a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular mass of 2 to 15 million daltons.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
  • xanthan gum as a thickener leads to stable cleaning agents even on prolonged storage, especially when packaged in water-soluble films, in particular polyvinyl alcohol-containing films, in particular water-soluble ones Disposable portions, not the surrounding packaging, in particular attack the polyvinyl alcohol-containing film and thus do not lead to leaks.
  • the cleaning agents according to the invention contain less than 10% by weight of polyol (one or more polyhydric alcohols).
  • polyol is understood to mean liquid polyols at room temperature (20 ° C. and normal pressure), in particular glycerol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol and mixtures thereof.
  • the cleaning agents in particular the pre-portioned automatic dishwashing agents, particularly preferably contain less than 7% by weight, preferably less than 6% by weight, of polyol.
  • a polyol used particularly preferably according to the invention is glycerol.
  • Glycerol is used in inventive compositions preferably in an amount of 0 to 5 wt .-%.
  • the total amount of polyol is, as described above, a total of less than 10 wt .-%, in particular less than 7 wt .-%, in particular less than 6 wt .-% polyol.
  • the ratio of water to polyol is at least 4: 1, particularly preferably at least 5: 1, for example 6: 1.
  • the cleaning agents according to the invention contain less than 0.02% by weight (in each case based on the total weight of the cleaning formulation) of calcium ions.
  • Reference cleaning agents contain the following combinations of components a) to d) according to Table 1 or Table 2 (in% by weight of active substance):
  • further active and auxiliary substances in particular those as described below may be present
  • Combinations mentioned herein are particularly suitable for detergent in disposable portions, in particular disposable portions in bags of polyvinyl alcohol-containing film.
  • Table 1 1 2 3 4 5 a) GLDA or GLDA salt 15-30 15-25 15-20 15-20 15-20 15-20 b) water 50-60 50-60 51-55 51-55 51-55 c) polyol ⁇ 7 ⁇ 7 ⁇ 6 ⁇ 6 d) xanthan 0.2-2 0.2-2 0.2-2 0.2-1.5 0.2-1.5 calcium ions ⁇ 0.1 ⁇ 0.05 ⁇ 0.05 ⁇ 0.05 ⁇ 0.02 1 2 3 4 5 a) MGDA or MGDA salt 15-30 15-25 15-20 15-20 15-20 b) water 50-60 50-60 51-55 51-55 51-55 c) polyol ⁇ 7 ⁇ 7 ⁇ 6 ⁇ 6 ⁇ 6 d) xanthan 0.2-2 0.2-2 0.2-2 0.2-1.5 0.2-1.5 calcium ions ⁇ 0.05 ⁇ 0.05 ⁇ 0.05 ⁇ 0.02
  • the cleaning agents according to the invention contain, in a preferred embodiment, at least one rinse aid surfactant.
  • the rinse aid surfactant is a nonionic surfactant.
  • all nonionic surfactants known to the person skilled in the art can be used, weakly foaming nonionic surfactants, in particular alkoxylated, in particular ethoxylated, low-foaming nonionic surfactants, are preferably used.
  • the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.
  • nonionic surfactants can be used which have a melting point above room temperature.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants used are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • nonionic surfactants of the general formula in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
  • nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
  • the cleaning performance of the preparations according to the invention can be significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • 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 are 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 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.
  • the liquid detergents of the invention preferably contain 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 0.1 to 3.5, preferably 0.5 to 2.5, more preferably 1.0 to 2.0 wt .-% is.
  • the at least one rinse aid surfactant is a surfactant selected from the group consisting of polyalkoxylated fatty alcohols, especially hydroxy mixed ethers, preferably end-capped hydroxy mixed ethers, and the at least one hydrophobically modified acrylate polymer or copolymer is an alkyl-modified polyacrylate or alkyl-modified one Acrylate / vinyl ester copolymer, in particular a partially C 10 -C 30 alkyl-modified crosslinked polyacrylate or a partially C 10 -C 30 alkyl modified acrylate / vinyl ester copolymer.
  • the weight proportion of the polyalkoxylated fatty alcohol, especially the hydroxy mixed ethers, preferably the end-capped hydroxy mixed ethers may be 0.1 to 3.5, preferably 0.5 to 2.5, more preferably 1.0 to 2.0, weight.
  • the alkyl-modified polyacrylate or alkyl-modified acrylate / vinyl ester copolymer in particular a partially C 10 -C 30 -alkyl-modified crosslinked polyacrylate or a partially C 10 -C 30 -alkyl-modified acrylate / vinyl ester copolymer, 0, 02 to 0.9, preferably 0.05 to 0.5, more preferably 0.07 to 0.2, most preferably 0.1 wt .-%, each based on the total weight of the cleaning agent, amount.
  • the cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.
  • the cleaning agents according to the invention may contain, in addition to 15 to 30% by weight, preferably 15 to 25% by weight, in particular 15-20% by weight of MGDA and / or its salt, and / or GLDA and / or its salt, also other builders , Be used in particular with the phosphate-free builders.
  • EDDS ethylenediamine disuccinic acid or its salts
  • IDS iminodisuccinic acid
  • IDA iminodiacetic acid
  • HEIDA 2-hydroxyethylimino-diacetic acid
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
  • further 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 being understood as meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents.
  • an acidifying component typically be mentioned here.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Particularly preferred is 15 to 25 wt .-%, in particular 15-20 wt .-% of MGDA and / or its salt, and / or 15 to 25 wt .-%, in particular 15-20 wt .-% of GLDA and / or their salt, with 0.1 to 10 wt .-%, in particular 1 to 7 wt .-%, for example, between 3 and 6 wt .-% citrate, to use in the detergents according to the invention.
  • the citrate ions can be used as citric acid or its salts, in particular sodium or potassium salts, and the quantities of these substances to be employed are based on the amount of citrate according to the invention to calculate.
  • Particularly preferred is the combination of 15 to 20 wt .-% GLDA and / or their salts with 3 to 6 wt .-% citrate ions.
  • Reference cleaning agents contain the following combinations of components a) to d) and citrate ion and calcium ion according to Table 3 or Table 4 (in% by weight of active substance): In addition, further active ingredients and auxiliaries (in particular those as described below) may be used.
  • the combinations mentioned herein are particularly suitable for detergents in disposable portions, in particular disposable portions in bags made of polyvinyl alcohol-containing film.
  • the cleaning agents may contain as further constituent preferably one or more builders (builders / cobuilders) in addition to the at least one aminocarboxylic acid selected according to the invention (and optionally in combinations with the abovementioned citrations).
  • the proportion by weight of these additional builder components in the total weight of the compositions according to the invention is (with the exception of the amounts of the citrates already mentioned above), preferably 0.1 to 15 wt .-% and in particular 2 to 10 wt .-%.
  • Such builders other than the selected aminocarboxylic acids include those described above, preferably carbonates, phosphonates, iminodisuccinic acid, iminodiacetic acid, EDDS (ethylenediamine-N, N'-disuccinic acid), HEIDA (2-hydroxyethylimino-diacetic acid) or the salts of said acids, others organic cobuilders and silicates.
  • the cleaning agents may additionally or alternatively, preferably as further builder, more preferably also contain phosphonates.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are preferably present in the compositions in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.3 to 8% by weight, very particularly preferably from 0.5 to 3% by weight, based in each case on the total weight of the cleaning agent.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 1000 to 10 000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the polyacrylates and acrylate copolymers likewise to be used according to the invention are characterized in that they are at least partially C 10 -C 30 -alkyl-modified crosslinked polyacrylates or at least partially hydrophobic, in particular C 10 -C 30 -alkyl, modified acrylate / vinyl ester copolymers is.
  • Partially modified in this context means that at least one part, preferably at least 20, more preferably at least 40, particularly preferably at least 50% of the monomer units each having at least one C 10 -C 30 -alkyl radical is substituted.
  • the polymers are therefore such as acrylate / C 10 -C 30 alkyl acrylate copolymers or acrylate / C 10 -C 30 alkyl acrylate / C 10 -C 30 alkyl Vinylester copolymers.
  • polymers are commercially available as thickeners and emulsifiers.
  • polygels DR 3V Sigma, Italy
  • Pemulen® TR1 Librizol, USA
  • the amount of the at least one hydrophobically modified acrylate polymer or copolymer in the detergent is from 0.02 to 0.8, preferably from 0.03 to 0.5, more preferably from 0.05 to 0.15 most preferably 0.1 wt .-% based on the cleaning agent.
  • the silicates used are in particular crystalline layer-form 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 x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into account. 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.
  • 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 are silicate-free.
  • the cleaning agents of the invention may further contain a sulfopolymer.
  • 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 15 wt .-%, particularly preferably 1.0 to 10 wt .-%, in particular from 3 to 9 wt .-%, especially from 4 to 8 wt .-%.
  • the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymer (s).
  • the sulfopolymer used is preferably a 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 monomers containing sulfonic acid groups 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, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • 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.
  • Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • 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, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
  • the pH of the cleaning agent (10% by weight in distilled water) at 22 ° C. is particularly preferably between 6.8 and 8.3, in particular between 7.0 and 8.2, for example 8.0.
  • the pH of the cleaning agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application.
  • the pH-adjusting agents are acids and / or alkalis. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or else sulfamic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. If citric acid is used as a pH adjuster, this is taken into account in the total amount of citrate ions as indicated above.
  • Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred.
  • alkali metal hydroxides of which potassium hydroxide and especially sodium hydroxide is preferred.
  • hydroxides which have only the smallest amounts of calcium or magnesium ions, if hydroxides should be used, in particular alkali metal hydroxides, in particular potassium hydroxide and sodium hydroxide are preferred.
  • volatile alkali for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule.
  • the alkanolamine here is 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 0.1 to 10% by weight, in particular in an amount of 0.5 to 5% by weight.
  • the cleaning agent according to the invention contains 0.5 to 5 wt .-% monoethanolamine.
  • the detergents may contain alkali metal hydroxides.
  • 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.
  • the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents).
  • buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H 2 O and tripotassium citrate H 2 O or else the corresponding anhydrates.
  • compositions according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, phase mediators (for example cumene sulfonate), enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors , Foam inhibitors, dyes, fragrances, bittering agents, and antimicrobial agents and other auxiliaries.
  • phase mediators for example cumene sulfonate
  • enzymes for example cumene sulfonate
  • thickeners for example cumene sulfonate
  • sequestering agents for example cumene sulfonate
  • electrolytes corrosion inhibitors
  • corrosion inhibitors in particular silver protectants, glass corrosion inhibitors , Foam inhibitors, dyes, fragrances, bittering agents, and antimicrobial agents and other auxiliaries.
  • Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • fatty acid cyanamides sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • sulfosuccinates sulfosuccinic esters
  • sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters sulfosuccinamates
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -Alkyldimethylcarboxymethylbetain and C 11 -C 17 -Alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix are four identical or different, in particular two long and two short-chain, alkyl radicals and X - are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • quaternary surface-active compounds in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • the agents according to the invention may contain from 0.01 to 10% by weight of at least one polymer having a molecular weight of 2000 gmol -1 or more, which has at least one positive charge.
  • the above positive charge polymers may in principle be cationic or amphoteric polymers.
  • Preferred cleaners according to the invention in particular automatic dishwasher detergents, are characterized in that the polymer which has cationic monomer units is a cationic polymer and / or an amphoteric polymer.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • Cationic or amphoteric polymers which are particularly preferred for the purposes of the present invention comprise as monomer unit a compound of the general formula (I) in which R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3.
  • R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms
  • R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group
  • x and y independently represent integers between 1 and 3.
  • X - represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • Preferred radicals R 1 and R 4 in the above formula (VII) are selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH ) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • polymers which have a cationic monomer unit of the general formula (I) in which R 1 and R 4 are H, R 2 and R 3 are methyl and x and y are each 1.
  • R 1 and R 4 are H
  • R 2 and R 3 are methyl
  • x and y are each 1.
  • R 1 HC CR 2 -C (O) -NH- (CH 2 ) x -N + R 3 R 4 R 5 X - (II) in which R 1 , R 2 , R 3 , R 4 and R 5 independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 ,
  • X - chloride also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).
  • Automated dishwashing agents which are preferred according to the invention are characterized in that the polymer a) contains, as monomer units, diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts.
  • amphoteric polymers have not only cationic groups but also anionic groups.
  • anionic Monomereinhajien originate for example from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acids, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or non
  • Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) -ammonium chloride.
  • amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl - (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.
  • All of these products contain, as a first essential ingredient, one or more polymer (s) having a molecular weight of 2000 gmol -1 or above, which has at least one positive charge.
  • the compositions of the invention have a weight fraction of these polymers between 0.01 and 10 wt .-%, each based on the total weight of the cleaning agent.
  • the weight fraction of the polymer a) is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight .-%, more preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the cleaning agent is.
  • the enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
  • 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, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents.
  • the ⁇ -amylase from Bacillus sp. A 7-7 DSM 12368
  • CTTase cyclodextrin glucanotransferase
  • DSM 9948 commercially available alpha-amylases such as Duramyl®, Termamyl® Stainzyme®, Stainzyme Plus® from Novozymes are suitable.
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from, or further developed, Humicola lanuginosa (Thermomyces lanuginosus), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, most preferably all of the exchanges D96L, T213R and N233R.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • 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.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzyme preparations used contain stabilizers (for example reversible inhibitors) in their concentrated form, no further stabilizers are additionally added to the cleaning agent.
  • stabilizers for example reversible inhibitors
  • the enzyme preparations such as calcium or magnesium salts or organic solvents, in particular at room temperature and normal pressure liquid polyols, introduced amounts are already included in the above limits for the respective active ingredients.
  • 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 by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • 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, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • novel cleaning compositions contain, based on their total weight, 0.1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% enzyme preparations.
  • Zinc and / or bismuth salts, or polyethyleneimines, for example those obtainable under the name Lupasol® from BASF, in particular zinc acetate, 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 to 5% by weight, in particular in an amount of from 0 to 2% by weight.
  • less than 0.1% by weight, in particular 0.05% by weight, particularly preferably less than 0.01% by weight, of zinc salt (s) is added.
  • no zinc salt is used (beyond the usual amount of zinc salt introduced by contamination of raw materials), since, surprisingly, the cleaning formulation is very gentle on the items to be washed, in particular the glasses, and so additional glass corrosion protection can be dispensed with.
  • Particularly preferred embodiments of the cleaning agent according to the invention comprise the following combinations of components a) to d) and of calcium ions and zinc salts according to Table 5 or Table 6 (details in% by weight of active compound.)
  • the formulations 1-6 in Table 5 and the formulations 1- 7 in Table 6 are reference formulations
  • further active ingredients and auxiliaries in particular those as described below
  • the combinations mentioned herein are particularly suitable for detergents in single-use portions, in particular disposable portions in bags made from polyvinyl alcohol-containing film.
  • alternative glass corrosion inhibitors in particular at least one Amine polymer, wherein the amine polymer has an amino group in at least 50% of the constitutional repeat units of the polymer, and wherein one or more nonionic surfactants are contained in an amount of at least 1 wt.% Based on the total weight of the dishwashing detergent.
  • the at least one aminopolymer is present in an amount in the range of 0.001 to 10 weight percent, more preferably in the range of 0.005 to 1 weight percent, most preferably in the range of 0 , 01 to 0.2 wt.% Based on the total weight of the composition.
  • the amino-polymer is a polyethylenimine which also has primary amino groups.
  • the amino-polymer is a polyethylenimine or polyvinylamine which is not an alkoxylate.
  • the amino polymer has a molecular weight Mw in a range of 3,000 to 10,000 g / mol.
  • the detergent has a viscosity above 700 mPas directly after preparation (Brookfield Viscometer DV-II + Pro, Spindle 25, set to achieve 40-60% torque, ie, 30 rpm, 20 ° in the low range C), in particular between 1000 and 10000 mPas (Brookfield Viscometer DV-II + Pro, spindle 31, rotation adjusted so that 40-60% torque is achieved, usually 30 rpm, 20 ° C).
  • the viscosity may be higher, for example, greater than 1500 mPas, such as in the range 1500-50000 mPas, (Brookfield Viscometer DV-II + Pro, Spindle 31, rotation adjusted to achieve 40-60% torque, 20 ° C). It is preferred that the agent is flowable at room temperature.
  • the invention relates to such cleaning agents which may be present in a water-insoluble, water-soluble or water-dispersible packaging, for example a film containing a disposable portion.
  • the cleaning agent can be in a water-insoluble, water-soluble or water-dispersible packaging.
  • the invention therefore also relates to kits containing the cleaning agent together with such a package.
  • the cleaning agent can be made up so that disposable portions are each packed separately.
  • 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 13.5 to 25 g.
  • the water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath (Meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
  • the film material contains further additives.
  • the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
  • Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwasher detergents.
  • the corresponding use is also the subject of the invention.
  • the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used.
  • the cleaning agents according to the invention are characterized by the fact that they are stable in storage and even after a prolonged period no leaks occur. In addition, they continue to have a good enzyme activity even after prolonged storage.
  • detergents prepared according to the following frame formulation (Tables 7-10): The combinations mentioned herein are especially for Detergent in disposable portions, in particular disposable portions in bags made of polyvinyl alcohol-containing film suitable.
  • Table 7 glycerin 0-5.0 0-5.0 0-5.0 0-5.0 xanthan 0.2-2.5 0.50 0.50 0.40 polyacrylate 0.1-5.0 2.0-4.0 0.0 3.0 sulfopolymer 4-10.00 5.00 to 9.00 7.00-8.00 4.00 to 8.00 GLDA 15 to 30.00 16.00 to 25.00 16.00 to 25.00 16.00 to 25.00 citric acid 0.0 to 10.00 0.1 to 7.00 5.00 5.00 phosphonate 0.0-10.0 0.5-8 0.4-0.8 0.4-0.8 Nonionic surfactant 1.00 to 5.00 2.00 to 4.00 3.00 3.00 3.00 Monoethanolamine 0.0 to 7.00 3.00 to 7.00 3.00-5.00 3.00-5.00 Cationic rinse aid polymer 0.01 to 1.00 0.05-0.50 0.1-0.3 0.1-0.3 Amylase (wt%
  • a further subject of the present application is a machine dishwashing process in which a cleaning agent according to the invention is used.
  • the dishwashing detergent is preferably metered into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle.
  • the dispensing or the entry of the dishwashing detergent into the interior of the dishwasher can be done manually, but preferably the dishwashing detergent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher.
  • no additional water softener and no additional rinse aid is metered into the interior of the dishwasher.
  • the dishwashing process is preferably carried out at a liquor temperature below 60 ° C., preferably not above 50 ° C., preferably at 35 to 45 ° C.
  • the dishwashing process takes 5 to 90 minutes, in particular 10 to 75 minutes, particularly preferably 20 to 60 minutes.
  • the dishwashing process takes a maximum of 50, 40 or 30 minutes.
  • Another object of the present invention is the use of a detergent according to the invention in a dishwasher machine, in particular for the cleaning of dishes, cooking utensils and cutlery. Incidentally, the inside of the dishwasher is also cleaned during use.
  • a liquid detergent according to the invention is prepared according to the recipe given in Table 11.
  • the detergent according to the invention according to Table 11 has (at a dilution of 10 wt .-% detergent in distilled water, measured at 22 ° C) to a pH of 8.0.
  • Table 11 (data: amount of active substance in% by weight, based on the total cleaning agent): glycerin 2.50 xanthan 0.50 sulfopolymer 7.5 GLDA, tetrasodium salt 18,00 citric acid 5.00 phosphonate 0.6
  • Monoethanolamine 4.00 Cationic rinse aid polymer 0.2
  • Dye bitrex, perfume, preservatives 0.5 Resulting water content of the formulation 55,00
  • the single-chamber bags thus prepared were stored at temperatures of 0, room temperature (20 ° -25 ° C), 30, 40 and 50 ° C for 4 weeks.
  • the single-chamber bags were packed in a sealed bag consisting of PE, coated with PET.
  • the disposable portions showed no leaks after storage (without air exchange) of 4 weeks at all temperatures.
  • the liquid detergents also showed no phase separation.
  • the stability of the enzymes was determined by the cleaning performance of the predosed detergent in a dishwasher (type Miele GSL) at 45 ° C (8 min hold time) fresh and after storage times of 4, 8 and 12 weeks at 0 ° C (Table 12), room temperature ( Table 13) and 30 ° C and 80% relative humidity (Table 14). The determination was carried out gravimetrically according to IKW. Changes of 1.0 units are considered significant.
  • Table 12 Storage at 0 ° C product Egg yolk, 1g Strength Fresh 3.0 8.4 Storage time 4 weeks, 0 ° C 3.0 8.2 Storage time 8 weeks, 0 ° C 2.5 8.2 Storage time 12 weeks, 0 ° C 2.7 8.2 product Egg yolk, 1g Strength Fresh 3.0 8.4 Storage time 4 weeks, room temperature 2.4 8.5 Storage time 8 weeks, room temperature 2.9 7.8 Storage time 12 weeks, room temperature 2.6 7.9 product Egg yolk, 1g Strength Fresh 3.0 8.4 4 weeks, 30 ° C / 80% relative humidity 2.4 8.2 8 weeks, 30 ° C / 80% relative humidity 2.5 6.8 12 weeks, 30 ° C / 80% relative humidity 2.2 6.9

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  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
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CA2527316C (en) 2003-06-03 2011-08-16 The Procter & Gamble Company Detergent pouch
US8728449B2 (en) 2005-01-22 2014-05-20 Monosol Llc Water-soluble film article having salt layer, and method of making the same
GB0611206D0 (en) * 2006-06-07 2006-07-19 Reckitt Benckiser Nv Detergent composition
ES2532289T3 (es) * 2008-03-31 2015-03-25 The Procter & Gamble Company Composición para lavavajillas que contiene un copolímero sulfonado
US20090258810A1 (en) * 2008-04-01 2009-10-15 Brian Xiaoqing Song Gel automatic dishwashing detergent composition

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