EP3502220A1 - Machine dishwashing detergent with improved rinsing and cleaning power, method using said agent as well as its utilization - Google Patents
Machine dishwashing detergent with improved rinsing and cleaning power, method using said agent as well as its utilization Download PDFInfo
- Publication number
- EP3502220A1 EP3502220A1 EP18206516.9A EP18206516A EP3502220A1 EP 3502220 A1 EP3502220 A1 EP 3502220A1 EP 18206516 A EP18206516 A EP 18206516A EP 3502220 A1 EP3502220 A1 EP 3502220A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- dishwashing
- sorbitan ester
- group
- dishwashing detergent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 22
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- 238000004140 cleaning Methods 0.000 title claims description 16
- -1 sorbitan ester Chemical class 0.000 claims abstract description 97
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 10
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-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to a non-phosphate machine dishwashing detergent which exhibits improved cleaning performance and rinse performance, the use of this dishwashing detergent and a machine dishwashing method using this dishwashing detergent.
- Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be free from food debris, but also, for example, have no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. Such staining and streaking is in principle observable on surfaces of all kinds (porcelain, glass, plastic, stainless steel). This harness is the consumer - often by hand - post-treated, which is not very user-friendly. Therefore, there is a need for automatic dishwashing agents that reduce the formation of so-called spotting and / or filming stains and / or deposits.
- rinse aids are used in dishwashing formulations. Through a mediated by these agents film formation on the dishes, the water should run as completely as possible from the dishes, so that the surfaces are residue-free and flawless gloss at the end of the wash program. Although the use of such rinse aids is known in the art, there continues to be a need for dishwashing detergents which exhibit improved rinse performance.
- the object of the present application was to provide a dishwasher detergent, which shows both in terms of its cleaning performance and with respect to its rinse results improved performance over conventional detergents.
- a phosphate-free dishwashing detergent in particular a machine dishwashing detergent containing at least one nonionic surfactant and at least one builder, wherein the at least one nonionic surfactant is a sorbitan ester.
- a first subject of the present application is therefore a phosphate-free dishwashing detergent, in particular automatic dishwashing detergent, comprising at least one nonionic surfactant and at least one builder, wherein the at least one nonionic surfactant is a sorbitan ester.
- the present application also relates to a machine dishwashing method for cleaning dishes, wherein a dishwasher detergent according to the invention is used.
- a further subject of the invention is the use of at least one sorbitan ester as enzyme-enhancing and bleach-enhancing agent and / or for improving the rinse aid performance, preferably in automatic dishwashing compositions according to the invention and / or in automatic dishwashing processes according to the invention.
- At least one means 1 or more, i. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the type of ingredient, not the absolute number of molecules.
- at least one surfactant means, for example, at least one type of surfactant, i. that is, one type of surfactant or a mixture of several different surfactants may be meant.
- the term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.
- fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
- oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.
- alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
- the agent is phosphate-free; this means that the dishwashing agents according to the invention are essentially phosphate-free, i. Phosphate in amounts less than 1 wt .-%, preferably less 0.1 wt .-%, and / or contain no deliberately added phosphate.
- the agent according to the invention contains at least one sorbitan ester.
- this sorbitan ester is a mono-, di- or triester or a mixture of those mentioned, preferably a monoester.
- the sorbitan ester is formal esterification products with carboxylic acids wherein the carboxylic acids have a chain length of 6 to 22 carbon atoms, are linear or branched, and are saturated or unsaturated. They are preferably linear alkyl chains of carboxylic acids which are saturated or mono- or polyunsaturated. Preferably, these carboxylic acids have a chain length of 10 to 20 carbon atoms, more preferably 12 to 18 carbon atoms.
- the carboxylic acid is selected from the group comprising lauric acid, palmitic acid, stearic acid and oleic acid and mixtures thereof. Most preferably, the carboxylic acid is palmitic acid.
- the sorbitan ester is a polysorbate.
- Polysorbates are alkoxylated sorbitan esters. They contain two or more alkoxy groups between sorbitan unit and carboxylic acid unit and / or on the non-esterified hydroxy functions of sorbitan. The alkoxy groups may be ethoxy, propoxy and / or butoxy units.
- the sorbitan ester is an alkoxylated sorbitan ester, preferably an ethoxylated sorbitan ester.
- the alkoxylated sorbitan ester may have one or more polyalkoxy moieties, preferably more than one hydroxy function of sorbitan and between sorbitan moiety and carboxylic acid moiety, most preferably all hydroxy functions of sorbitan and sorbitan moiety and carboxylic acid moiety.
- Each polyalkoxy unit is independently composed of two or more alkoxy groups.
- a polyalkoxy moiety preferably consists of 2 to 30 alkoxy groups, particularly preferably 2 to 20 or 3 to 10 alkoxy groups.
- the alkoxy groups may be ethoxy, propoxy and / or butoxy units.
- each mole of the sorbitan ester is alkoxylated with from about 4 to 60 moles of alkylene oxide, preferably ethylene oxide. Particularly preferred are embodiments in which each mole of sorbitan ester is alkoxylated with about 8 to 40 moles of ethylene oxide. Therefore, in a preferred embodiment, the sorbitan ester is an ethoxylated sorbitan ester having a total of 4 to 60 ethoxy units. Particularly preferred ethoxylated sorbitan esters have a total of 8 to 40 ethoxy units.
- the alkoxylated sorbitan ester is an alkoxylated sorbitan esterified simply with palmitic acid, which has a total of 8 to 40 ethoxy units, more preferably 15 to 25 ethoxy units.
- Tween 40LQ from Croda can be used.
- the dishwashing agent contains the sorbitan ester in an amount of 0.1 to 25 wt .-%, preferably in an amount of 0.2 to 10 wt .-%, particularly preferably in an amount of 0.5 to 7 Wt .-% and most preferably in an amount of 0.7 to 4 wt .-%, based on the total weight of the dishwashing detergent.
- the agent according to the invention also contains at least one builder.
- Builders which may be present in the dishwashing detergent are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, phosphonates, organic (co) builders, for example salts of organic di- and polycarboxylic acids, and mixtures of these substances.
- crystalline layer-form silicates of the general formula NaMSi x O 2x + 1 .yH 2 O in which M represents sodium or hydrogen, x a number from 1.9 to 22, preferably from 1.9 to 4, where especially preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
- the crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS.
- silicates Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 ⁇ x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ xH 2 O, makatite).
- Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi x O 2x + 1 ⁇ yH 2 O, in which x is 2 stands.
- both ⁇ - and ⁇ -sodium disilicates are Na 2 Si 2 O 5 .yH 2 O and furthermore especially Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 ⁇ H 2 O), Na-SKS-10 (NaHSi 2 O 5 ⁇ 3H 2 O, kanemite), Na-SKS-11 (t- Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ).
- the dishwashing detergents in various embodiments contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 .yH 2 O of from 0.1 to 45% by weight, preferably from 1 to 40% by weight and in particular from 5 to 35 Wt .-%, each based on the total weight of these agents.
- the agents are free of such silicates.
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- amorphous is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.
- the agents are free of these silicates.
- alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, it being possible to use the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention.
- the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 Wt .-% and in particular below 2 wt .-%, each based on the total weight of Dishwashing agent, used.
- Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
- the dishwashing detergents can contain as further builders in particular also phosphonates, which according to the invention are not subsumed under the phosphates.
- 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 contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.3 to 8 wt .-%, each based on the total weight of the dishwashing detergent.
- organic (co) builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders. These classes of substances are described below.
- Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
- these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
- NTA nitrilotriacetic acid
- the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of the dishwashing detergent.
- citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
- dishwashing detergents according to the invention are preferred in that the dishwashing detergent contains citric acid or a salt of citric acid, and that the weight fraction of citric acid or of the salt of citric acid or of the salt of citric acid Citric acid preferably 1 to 40 wt .-%, preferably 10 to 25 wt .-% and in particular between 15 and 22 wt .-% is.
- aminocarboxylic acids and / or their salts are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid (EDDS) or its salts. Very particular preference is GLDA or its salts.
- MGDA methylglycinediacetic acid
- GLDA glutamic diacetic acid
- EDDS ethylenediaminediacetic acid
- the content of these aminocarboxylic acids or their salts, in particular GLDA sodium salt may for example be between 0.1 and 25% by weight, preferably between 5 and 25% by weight and in particular between 15 and 25% by weight.
- Aminocarboxylic acids and their salts can be used, for example, together with the abovementioned builders, in particular together with citrate and the abovementioned phosphonates.
- the at least one builder of the dishwashing detergent according to the invention is preferably selected from the group consisting of silicates, aluminum silicates, carbonates, phosphonates, organic di- and polycarboxylic acids or salts thereof and mixtures thereof.
- composition according to the invention preferably comprises at least one further surfactant selected from the group of anionic, nonionic, amphoteric and cationic surfactants, more preferably from the group of nonionic surfactants.
- anionic, cationic, amphoteric or nonionic surfactants it is possible to use all surfactants of these types known to the person skilled in the art.
- Suitable further nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
- surfactants are the polyhydroxy fatty acid amides known as PHFA.
- Aminalkoxylate can be included in the inventive compositions.
- low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
- the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
- a class of useful nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
- surfactants come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
- structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
- Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.
- nonionic surfactants are those 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.
- 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.
- nonionic surfactants include, for example, the C 2-26 fatty alcohol (PO) i (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.
- 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.
- compositions described herein which preferably comprise at least one further nonionic surfactant, more preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the further nonionic surfactant in various embodiments in an amount based on the total weight of the composition of at least 1% by weight. , preferably at least 2.5 wt .-%.
- Suitable anionic surfactants in dishwashing detergents are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. Example, a carboxylate, sulfate or sulfonate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group.
- Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
- the dishwashing detergents can therefore, in various embodiments, contain at least one surfactant of the formula R 4 -O- (AO) n -SO 3 - X + .
- R 4 is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
- Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with an even number of carbon atoms atoms are preferred.
- radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols.
- AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
- the index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
- X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + including Na, with Na + being extremely preferred.
- Other cations X + may be selected from NH 4 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ , and mixtures thereof.
- the agents may additionally or alternatively contain at least one surfactant of the formula R 5 -A-SO 3 - Y + .
- R 5 is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the grouping -A- for -O- or a chemical bond.
- certain radicals R 5 are preferred.
- R 5 preferably represents a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
- Preferred radicals R 5 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with an even number of carbon atoms Atoms are preferred.
- Particularly preferred radicals R 5 are derived from C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols.
- Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred.
- Other cations Y + may be selected from NH 4 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ , and mixtures thereof.
- R 5 preferably represents a linear or branched unsubstituted alkylaryl radical.
- X is a monovalent cation or the nth part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred.
- Other cations X + may be selected from NH 4 +, 1 ⁇ 2 Zn 2+, 1 ⁇ 2Mg 2+, 1 ⁇ 2Ca 2+, 1 ⁇ 2Mn 2+, and mixtures thereof.
- Such surfactants may be selected from linear or branched alkyl benzene sulfonates.
- sulfated and / or sulfonated triglycerides may also be present as anionic surfactants in the compositions according to the invention.
- the content of anionic surfactants is preferably less than 4 wt .-%, more preferably less than 2 wt .-% and in particular less than 1 wt .-%.
- Dishwashing detergents which do not contain anionic surfactants are particularly preferred.
- No surfactant means less than 0.5% by weight of said surfactant, preferably less than 0.2% by weight of said surfactant, more preferably no surfactant has been added to said group.
- 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 -alkyl-dimethylcarboxymethylbetain 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 content of cationic and / or amphoteric surfactants is preferably less than 4% by weight, more preferably less than 2% by weight and in particular less than 1% by weight. Dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.
- silicone surfactants can also be present in the compositions according to the invention, which, depending on their structure, can be assigned to different classes of surfactants.
- amphiphilic carboxyalkylated polyamines can also be present in the agents according to the invention.
- the agents of the present invention contain one or more enzymes in preferred embodiments.
- the enzyme or enzymes used may be present in an enzyme preparation or enzyme composition.
- Suitable enzymes include, but are not limited to, proteases, amylases, lipases, hemicellulases, cellulases, ⁇ -glucanases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are preferably used accordingly.
- the agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein.
- the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
- proteases are among the most technically important enzymes of all. They cause the degradation of protein-containing stains on the items to be cleaned.
- proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range.
- Subtilases are naturally produced by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
- subtilisin type proteases preferably used in washing and dishwashing detergents are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the the subtilases, but not the subtilisins in the narrower sense attributable enzyme thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of said proteases, which have a relation to the parent protease modified amino acid sequence.
- Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.
- amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in dishwashing detergents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
- lipases or cutinases in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors.
- lipases 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 for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect.
- peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
- phenol oxidases, polyphenol oxidases can be used to increase the bleaching effect.
- organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
- the agent according to the invention preferably contains at least one enzyme selected from the group comprising proteases, amylases, lipases, hemicellulases, cellulases, ⁇ -glucanases, perhydrolases and oxidoreductases.
- An enzyme can be particularly protected during storage against damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage.
- damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage.
- inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
- Dishwashing agents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
- Cleaning-active proteases and amylases are generally not provided in the form of the pure protein, but rather in the form of stabilized, storage and transportable preparations.
- Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
- the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
- 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.
- preferred protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 10% by weight of the enzyme protein.
- dishwashing detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
- compositions described herein may also include enzyme stabilizers.
- stabilizers are reversible protease inhibitors.
- Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned.
- peptide aldehydes that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose.
- peptidic reversible protease inhibitors include ovomucoid and leupeptin.
- specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.
- enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art.
- the dishwashing detergent according to the invention preferably contains at least one further constituent, preferably from the group comprising further builders, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaches, bleach catalysts, bleach activators, foam inhibitors, dyes, fragrances , Bitter substances, antimicrobial agents and disintegration aids.
- further builders thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaches, bleach catalysts, bleach activators, foam inhibitors, dyes, fragrances , Bitter substances, antimicrobial agents and disintegration aids.
- the dishwashing agents according to the invention may further comprise a sulfopolymer as further builder.
- the proportion by weight of the sulfopolymer in the total weight of the dishwashing 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 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 .-% sulfopolymers.
- the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
- the copolymers may be two, three, four or three have 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-sulfo propyl 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 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 the proportion of the sulfonic acid group-containing monomer is from 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
- the molecular weight of the sulfo copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired end use.
- Preferred dishwashing detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
- other polymers can be used in the compositions of the invention.
- the group of suitable polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
- cationic, anionic and amphoteric polymers can be used in automatic dishwashing detergents in addition to nonionic polymers.
- the sulfo (co) polymers described above are, for example, anionic polymers.
- amphoteric polymers furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be e.g. to act carboxylic acids, sulfonic acids or phosphonic acids.
- Preferred polymers which can be used are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic mono
- acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts come 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 Methacroylethylbetain / methacrylate copolymers.
- “Cationic polymers” 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.
- Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred.
- a bleaching agent as further constituent, with oxygen bleaches being preferred.
- sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- bleaching agents from the group of organic bleaching agents can also be used.
- Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
- Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.
- the percarbonates and in particular sodium percarbonate are particularly preferred.
- Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate.
- the proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, in preferred embodiments is between 1 and 35% by weight, preferably between 2.5 and 30% by weight, more preferably between 5 and 20% by weight in particular between 10 and 15 wt .-%.
- the automatic dishwashing agents additionally contain at least one bleach activator.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used.
- TAED especially in combination with a percarbonate bleach, preferably sodium percarbonate, is most preferred.
- bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight or 2 to 3 % By weight, based in each case on the total weight of the agent.
- the automatic dishwasher detergents according to the invention preferably contain at least one bleach catalyst.
- bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
- complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
- ligands are used which have nitrogen donor functions.
- bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
- Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononan
- TACN 1,4,7-triazacyclononane
- TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
- Me-TACD 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane
- 2-methyl-1,4,7-triazacyclononane
- Machine dishwashing detergent characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.
- a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned
- the aforementioned bleach-enhancing transition metal complexes are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0 , 01 wt .-% to 0.30 wt .-% or 0.02 wt .-% to 0.5 wt .-%, each based on the total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.
- the pH of the dishwashing detergent can be adjusted by means of customary pH regulators, the pH value being chosen as a function of the desired intended use.
- the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, particularly preferably greater than 7, very particularly preferably greater than 7.5 and in particular greater than 8, 5.
- a dishwasher detergent for example a tablet
- a pH greater than 10 and in a preferred embodiment, the rinse liquor, when using the dishwashing agent, has a pH of between 9 and 10, for example 9.5.
- the pH adjusting agents are acids and / or alkalis, preferably 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 amidosulfonic acid.
- mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof.
- 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.
- particularly preferred is 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 composition according to the invention may also contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%. 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.
- Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
- Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
- the content of zinc salt in dishwashing detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt.
- the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.
- fragrance compounds for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention.
- mixtures of different fragrances are used, which together produce an attractive fragrance.
- perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
- preservatives may be included in the compositions. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides.
- Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2 Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13
- particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.
- Solvents which are suitable for the compositions used according to the invention are, in addition to water as the preferred solvent, generally water-miscible organic solvents, such as, without limitation, ethanol, propanol, 1,2-propanediol and glycerol.
- the dishwashing detergent may be a low-water, liquid dishwashing detergent containing water in amounts up to a maximum of 25% by weight, preferably up to 20% by weight, based on the total weight of the composition.
- low in water means that the composition thus characterized contains less than 25% by weight of water, preferably less than 20% by weight of water. In particular, this term covers compositions which contain from 1 to 20% by weight of water.
- the water content as defined herein refers to the water content determined by Karl Fischer titration.
- the formulation of automatic dishwashing agents described herein can be carried out in different ways.
- the agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, in particular tablets, are particularly suitable as firm supply forms.
- the liquid ones Supply forms based on water and / or organic solvents may be thickened, in the form of gels.
- the agents can be formulated in the form of single-phase or multi-phase products. The individual phases of multiphase agents may have the same or different states of matter.
- Liquid as used herein with respect to the agent of the invention therefore includes all flowable compositions and, in particular, also encompasses gels and pasty compositions.
- the dishwashing agents described herein are preferably automatic dishwashing agents, which may be in solid or liquid form.
- the solid moldings described below are particularly preferably also liquid agents, in particular in the form of gels.
- the dishwashing detergents can be present as shaped bodies.
- disintegration aids so-called tablet disintegrants
- tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.
- Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
- the dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.
- the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
- the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.
- the dishwashing agents in particular the prefabricated metering units, may have a water-soluble coating.
- 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 Foils that can be glued and / or sealed to packages such as tubing or cushions, for example, after being filled with an agent.
- the water soluble package may have one or more chambers.
- the agent may be contained in one or more chambers, if any, of the water soluble envelope.
- the amount of agent preferably corresponds to the full or half dose needed for a rinse.
- the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
- Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
- polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
- polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
- a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above may be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers.
- a preferred additional polymer is polylactic acids.
- Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
- Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
- polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
- Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
- the film material contains further additives.
- the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
- Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
- Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
- Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
- a further subject of this application is a machine dishwashing process for the cleaning of dishes, wherein a dishwasher detergent according to the invention is used.
- the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the start of the main wash cycle or during the main wash cycle.
- the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.
- Another object of the invention is the use of at least one sorbitan ester as an enzyme-enhancing and bleach-enhancing agent and / or to improve the rinsing performance, preferably in automatic dishwashing detergents according to the invention and / or automatic dishwashing processes according to the invention.
- a solid detergent having the following composition was prepared: raw material Amount (wt%) Na citrate 15.00 to 20.00 Phosphonate (HEDP) 2.50 to 7.50 MGDA 0.00 to 25.00 Na disilicate 5.00 to 35.00 soda 12.50 to 25.00 Na Percarbonate 10.00 to 15.00 Bleach catalyst (Mn-based) 0.02-0.50 TAED 2.00-3.00 Nonionic surfactant 20-40 EO end-cap mgl.
- the dishwashing process was carried out in a dishwasher Bosch® SMS68m62 (program: 40 ° C, 8 min holding time, program duration 57 min) with a water hardness of 21 ° German hardness according to the IKW method.
- the detergent 1 corresponded to the above-mentioned composition.
- Experiment V1 thus represents the comparative example.
- Tween 40LQ results in improved cleaning of stubborn tea and mince stains as compared to the commercially available dishwashing detergent.
- Rinse rinses based on the visual appearance of the dry items to be washed (porcelain, glasses, plastic parts and stainless steel) are assigned as parameters. Per rinse 100 g of dirt are dosed to simulate a normally dirty load.
- a standard household dishwashing machine (Miele® GSL) was used in the 50 ° C program (50 ° C, 8 min holding time, 65 ° C rinse temperature) with a water hardness of 21 ° German hardness.
- the machine After completion of the rinse cycle, the machine is fully opened for 30 minutes and then the clear rinse effect is visually determined in the black box (black-painted room, D6500 daylight lamp). On the crockery and cutlery remaining dried water drops, streaks, coverings and films are scored on a scale of 1 to 5. 5 means no drops / films, 1 means heavy drops / filming.
- V1 Composition according to Example 1
- V2 V1 - 1% by weight of nonionic surfactant (based on the total weight of the cleaning agent)
- E1 V2 + 1% by weight Tween 40LQ (based on the total weight of the cleaning agent)
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Abstract
Die vorliegende Erfindung betrifft ein phosphatfreies Geschirrspülmittel, insbesondere maschinelles Geschirrspülmittel, enthaltend wenigstens ein nichtionisches Tensid und wenigstens einen Gerüststoff, dadurch gekennzeichnet, dass es sich bei dem nichtionischen Tensid um einen Sorbitanester handelt. Weiterhin ist ein maschinelles Geschirrspülverfahren, bei dem dieses Geschirrspülmittel zum Einsatz kommt, Gegenstand der Erfindung. Ebenfalls Gegenstand der Erfindung ist die Verwendung von mindestens einem Sorbitanester als enzymverstärkendes und bleicheverstärkendes Mittel und/oder zur Verbesserung der Klarspülleistung.The present invention relates to a phosphate-free dishwashing agent, in particular a machine dishwashing agent, containing at least one nonionic surfactant and at least one builder, characterized in that the nonionic surfactant is a sorbitan ester. The invention also relates to an automatic dishwashing process in which this dishwashing agent is used. The invention also relates to the use of at least one sorbitan ester as an enzyme-strengthening and bleach-strengthening agent and / or to improve the rinsing performance.
Description
Die vorliegende Erfindung betrifft ein phosphatfreies, maschinelles Geschirrspülmittel, das eine verbesserte Reinigungsleistung und Klarspülleistung zeigt, die Verwendung dieses Geschirrspülmittels sowie ein Verfahren zum maschinellen Geschirrspülen unter Verwendung dieses Geschirrspülmittels.The present invention relates to a non-phosphate machine dishwashing detergent which exhibits improved cleaning performance and rinse performance, the use of this dishwashing detergent and a machine dishwashing method using this dishwashing detergent.
An maschinell gespültes Geschirr werden heute häufig höhere Anforderungen gestellt als an manuell gespültes Geschirr. So soll das Geschirr nach der maschinellen Reinigung nicht nur frei von Speiseresten sein, sondern beispielsweise auch keine weißlichen, auf Wasserhärte oder anderen mineralischen Salzen beruhenden Flecken aufweisen, die mangels Netzmittel aus eingetrockneten Wassertropfen stammen. Derartige Flecken-und Schlierenbildung ist prinzipiell auf Oberflächen aller Art (Porzellan, Glas, Kunststoff, Edelstahl) beobachtbar. Dieses Geschirr wird vom Verbraucher - oftmals per Hand - nachbehandelt, was wenig anwenderfreundlich ist. Deshalb besteht ein Bedarf an maschinellen Geschirrspülmitteln, die die Bildung von sogenannten spotting- und/oder filming- Flecken und/oder Belägen mindern.Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be free from food debris, but also, for example, have no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. Such staining and streaking is in principle observable on surfaces of all kinds (porcelain, glass, plastic, stainless steel). This harness is the consumer - often by hand - post-treated, which is not very user-friendly. Therefore, there is a need for automatic dishwashing agents that reduce the formation of so-called spotting and / or filming stains and / or deposits.
Um glanzklares und fleckenloses Geschirr zu erhalten, werden in Geschirrspülrezepturen Klarspülreagenzien verwendet. Durch eine durch diese Agenzien vermittelte Filmbildung auf dem Geschirr soll das Wasser möglichst vollständig vom Spülgut ablaufen, so dass die Oberflächen am Ende des Spülprogramms rückstandsfrei und makellos glänzend sind. Obwohl die Verwendung derartiger Klarspüler im Stand der Technik bekannt ist, besteht weiterhin Bedarf an Geschirrspülmitteln, die eine verbesserte Klarspülleistung zeigen.To obtain glossy and spotless dishes, rinse aids are used in dishwashing formulations. Through a mediated by these agents film formation on the dishes, the water should run as completely as possible from the dishes, so that the surfaces are residue-free and flawless gloss at the end of the wash program. Although the use of such rinse aids is known in the art, there continues to be a need for dishwashing detergents which exhibit improved rinse performance.
In Anbetracht dieser Ausgangssituation bestand demnach die Aufgabe der vorliegenden Anmeldung in der Bereitstellung eines maschinellen Geschirrspülmittels, welches sowohl in Bezug auf seine Reinigungsleistung als auch in Bezug auf seine Klarspülergebnisse eine verbesserte Leistung gegenüber herkömmlichen Reinigungsmitteln zeigt.In view of this initial situation, therefore, the object of the present application was to provide a dishwasher detergent, which shows both in terms of its cleaning performance and with respect to its rinse results improved performance over conventional detergents.
Es wurde überraschend festgestellt, dass der Einsatz von Sorbitanestern sowohl zu einer Steigerung der Reinigungsleistung an hartnäckigen enzymsensitiven und bleichesensitiven Anschmutzungen als auch zu einer Steigerung der Klarspülleistung führt.It has surprisingly been found that the use of sorbitan esters leads both to an increase in the cleaning performance of persistent enzyme-sensitive and bleach-sensitive soiling and to an increase in the final rinse performance.
Die der vorliegenden Erfindung zu Grunde liegenden Aufgabe wurde daher gelöst durch ein phosphatfreies Geschirrspülmittel, insbesondere maschinelles Geschirrspülmittel, enthaltend wenigstens ein nichtionisches Tensid und wenigstens einen Gerüststoff, wobei es sich bei dem wenigstens einen nichtionischen Tensid um einen Sorbitanester handelt.The object on which the present invention is based has therefore been solved by a phosphate-free dishwashing detergent, in particular a machine dishwashing detergent containing at least one nonionic surfactant and at least one builder, wherein the at least one nonionic surfactant is a sorbitan ester.
Ein erster Gegenstand der vorliegenden Anmeldung ist daher ein phosphatfreies Geschirrspülmittel, insbesondere maschinelles Geschirrspülmittel, enthaltend wenigstens ein nichtionisches Tensid und wenigstens einen Gerüststoff, wobei es sich bei dem wenigstens einen nichtionischen Tensid um einen Sorbitanester handelt.A first subject of the present application is therefore a phosphate-free dishwashing detergent, in particular automatic dishwashing detergent, comprising at least one nonionic surfactant and at least one builder, wherein the at least one nonionic surfactant is a sorbitan ester.
Ebenfalls Gegenstand der vorliegenden Anmeldung ist ein maschinelles Geschirrspülverfahren zur Reinigung von Geschirr, wobei ein erfindungsgemäßes Geschirrspülmittel zum Einsatz kommt.The present application also relates to a machine dishwashing method for cleaning dishes, wherein a dishwasher detergent according to the invention is used.
Noch ein weiterer Gegenstand der Erfindung ist die Verwendung von mindestens einem Sorbitanester als enzymverstärkendes und bleicheverstärkendes Mittel und/oder zur Verbesserung der Klarspülleistung, bevorzugt in erfindungsgemäßen maschinellen Geschirrspülmitteln und/oder in erfindungsgemäßen maschinellen Geschirrspülverfahren.A further subject of the invention is the use of at least one sorbitan ester as enzyme-enhancing and bleach-enhancing agent and / or for improving the rinse aid performance, preferably in automatic dishwashing compositions according to the invention and / or in automatic dishwashing processes according to the invention.
Diese und weitere Aspekte, Merkmale und Vorteile der Erfindung werden für den Fachmann aus dem Studium der folgenden detaillierten Beschreibung und Ansprüche ersichtlich. Dabei kann jedes Merkmal aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Ferner ist es selbstverständlich, dass die hierin enthaltenen Beispiele die Erfindung beschreiben und veranschaulichen sollen, diese aber nicht einschränken und insbesondere die Erfindung nicht auf diese Beispiele beschränkt ist. Alle Prozentangaben sind, sofern nicht anders angegeben, Gewichts-%. Numerische Bereiche, die in dem Format "von x bis y" angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden.These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. All percentages are by weight unless otherwise specified. Numeric ranges indicated in the format "from x to y" include the above values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints are also captured.
"Mindestens ein", wie hierin verwendet, bedeutet 1 oder mehr, d.h. 1, 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Bezogen auf einen Inhaltsstoff bezieht sich die Angabe auf die Art des Inhaltsstoffs und nicht auf die absolute Zahl der Moleküle. "Mindestens ein Tensid" bedeutet somit beispielsweise mindestens eine Art von Tensid, d.h. dass eine Art von Tensid oder eine Mischung mehrerer verschiedener Tenside gemeint sein kann. Zusammen mit Gewichtsangaben bezieht sich die Angabe auf alle Verbindungen der angegebenen Art, die in der Zusammensetzung/Mischung enthalten sind, d.h. dass die Zusammensetzung über die angegebene Menge der entsprechenden Verbindungen hinaus keine weiteren Verbindungen dieser Art enthält."At least one" as used herein means 1 or more, i. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the type of ingredient, not the absolute number of molecules. Thus, "at least one surfactant" means, for example, at least one type of surfactant, i. that is, one type of surfactant or a mixture of several different surfactants may be meant. The term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.
Alle Prozentangaben, die im Zusammenhang mit den hierin beschriebenen Zusammensetzungen gemacht werden, beziehen sich, sofern nicht explizit anders angegeben auf Gew.-%, jeweils bezogen auf die betreffende Mischung.All percentages given in connection with the compositions described herein, unless explicitly stated otherwise, relate to% by weight, in each case based on the mixture in question.
Im Rahmen der vorliegenden Erfindung stehen Fettsäuren bzw. Fettalkohole bzw. deren Derivate - soweit nicht anders angegeben - stellvertretend für verzweigte oder unverzweigte Carbonsäuren bzw. Alkohole bzw. deren Derivate mit vorzugsweise 6 bis 22 Kohlenstoffatomen. Insbesondere sind auch die beispielsweise nach der ROELENschen Oxo-Synthese erhältlichen Oxo-Alkohole bzw. deren Derivate entsprechend einsetzbar.In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.
Wann immer im Folgenden Erdalkalimetalle als Gegenionen für einwertige Anionen genannt sind, so bedeutet das, dass das Erdalkalimetall natürlich nur in der halben - zum Ladungsausgleich ausreichenden - Stoffmenge wie das Anion vorliegt.Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
Das Mittel ist phosphatfrei; dies bedeutet, dass die erfindungsgemäßen Geschirrspülmittel im Wesentlichen phosphatfrei sind, d.h. Phosphat in Mengen weniger 1 Gew.-%, vorzugsweise weniger 0,1 Gew.-% enthalten, und/oder kein bewusst zugesetztes Phosphat enthalten.The agent is phosphate-free; this means that the dishwashing agents according to the invention are essentially phosphate-free, i. Phosphate in amounts less than 1 wt .-%, preferably less 0.1 wt .-%, and / or contain no deliberately added phosphate.
Das erfindungsgemäße Mittel enthält mindestens einen Sorbitanester. In einer bevorzugten Ausführungsform handelt es sich diesem Sorbitanester um einen Mono-, Di- oder Triester oder eine Mischung aus den genannten, bevorzugt um einen Monoester.The agent according to the invention contains at least one sorbitan ester. In a preferred embodiment, this sorbitan ester is a mono-, di- or triester or a mixture of those mentioned, preferably a monoester.
In einer weiteren bevorzugten Ausführungsform handelt es sich bei dem Sorbitanester um formale Veresterungsprodukte mit Carbonsäuren, wobei die Carbonsäuren eine Kettenlänge von 6 bis 22 Kohlenstoffatomen besitzen, linear oder verzweigt sowie gesättigt oder ungesättigt sind. Bevorzugt handelt es sich um lineare Alkylketten von Carbonsäuren, welche gesättigt oder einfach oder mehrfach ungesättigt sind. Bevorzugt besitzen diese Carbonsäuren eine Kettenlänge von 10 bis 20 Kohlenstoffatomen, besonders bevorzugt von 12 bis 18 Kohlenstoffatomen.In a further preferred embodiment, the sorbitan ester is formal esterification products with carboxylic acids wherein the carboxylic acids have a chain length of 6 to 22 carbon atoms, are linear or branched, and are saturated or unsaturated. They are preferably linear alkyl chains of carboxylic acids which are saturated or mono- or polyunsaturated. Preferably, these carboxylic acids have a chain length of 10 to 20 carbon atoms, more preferably 12 to 18 carbon atoms.
In einer bevorzugten Ausführungsform ist die Carbonsäure ausgewählt aus der Gruppe umfassend Laurinsäure, Palmitinsäure, Stearinsäure und Ölsäure sowie Mischungen aus diesen. Besonders bevorzugt handelt es sich bei der Carbonsäure um Palmitinsäure.In a preferred embodiment, the carboxylic acid is selected from the group comprising lauric acid, palmitic acid, stearic acid and oleic acid and mixtures thereof. Most preferably, the carboxylic acid is palmitic acid.
In einer bevorzugten Ausführungsform handelt es sich bei dem Sorbitanester um ein Polysorbat. Polysorbate sind alkoxylierte Sorbitanester. Sie enthalten zwei oder mehrere Alkoxygruppen zwischen Sorbitaneinheit und Carbonsäureeinheit und/oder an den nicht veresterten Hydroxyfunktionen des Sorbitans. Es kann sich bei den Alkoxygruppen um Ethoxy-, Propoxy- und/oder Butoxy-Einheiten handeln. In einer weiteren bevorzugten Ausführungsform handelt es sich bei dem Sorbitanester um einen alkoxylierten Sorbitanester, bevorzugt um einen ethoxylierten Sorbitanester.In a preferred embodiment, the sorbitan ester is a polysorbate. Polysorbates are alkoxylated sorbitan esters. They contain two or more alkoxy groups between sorbitan unit and carboxylic acid unit and / or on the non-esterified hydroxy functions of sorbitan. The alkoxy groups may be ethoxy, propoxy and / or butoxy units. In a further preferred embodiment, the sorbitan ester is an alkoxylated sorbitan ester, preferably an ethoxylated sorbitan ester.
Der alkoxylierte Sorbitanester kann ein oder mehrere Polyalkoxyeinheiten aufweisen, bevorzugt an mehr als einer Hydroxyfunktion des Sorbitans und zwischen Sorbitaneinheit und Carbonsäureeinheit, besonders bevorzugt an allen Hydroxyfunktionen des Sorbitans und zwischen Sorbitaneinheit und Carbonsäureeinheit. Jede Polyalkoxyeinheit ist unabhängig voneinander aus zwei oder mehr Alkoxygruppen aufgebaut. Bevorzugt besteht eine Polyalkoxyeinheit aus 2 bis 30 Alkoxygruppen, besonders bevorzugt aus 2 bis 20 oder 3 bis 10 Alkoxygruppen. Es kann sich bei den Alkoxygruppen um Ethoxy-, Propoxy- und/oder Butoxy-Einheiten handeln.The alkoxylated sorbitan ester may have one or more polyalkoxy moieties, preferably more than one hydroxy function of sorbitan and between sorbitan moiety and carboxylic acid moiety, most preferably all hydroxy functions of sorbitan and sorbitan moiety and carboxylic acid moiety. Each polyalkoxy unit is independently composed of two or more alkoxy groups. A polyalkoxy moiety preferably consists of 2 to 30 alkoxy groups, particularly preferably 2 to 20 or 3 to 10 alkoxy groups. The alkoxy groups may be ethoxy, propoxy and / or butoxy units.
In einer bevorzugten Ausführungsform ist jedes Mol des Sorbitanesters mit etwa 4 bis 60 Mol Alkylenoxid, bevorzugt Ethylenoxid, alkoxyliert. Besonders bevorzugt werden Ausführungsformen, in denen jedes Mol des Sorbitanesters mit etwa 8 bis 40 Mol Ethylenoxid alkoxyliert ist. Daher handelt es sich in einer bevorzugten Ausführungsform bei dem Sorbitanester um einen ethoxylierten Sorbitanester mit insgesamt 4 bis 60 Ethoxyeinheiten. Besonders bevorzugte ethoxylierte Sorbitanester weisen insgesamt 8 bis 40 Ethoxyeinheiten auf.In a preferred embodiment, each mole of the sorbitan ester is alkoxylated with from about 4 to 60 moles of alkylene oxide, preferably ethylene oxide. Particularly preferred are embodiments in which each mole of sorbitan ester is alkoxylated with about 8 to 40 moles of ethylene oxide. Therefore, in a preferred embodiment, the sorbitan ester is an ethoxylated sorbitan ester having a total of 4 to 60 ethoxy units. Particularly preferred ethoxylated sorbitan esters have a total of 8 to 40 ethoxy units.
In einer bevorzugten Ausführungsform handelt es sich bei dem alkoxylierten Sorbitanester um ein einfach mit Palmitinsäure verestertes alkoxyliertes Sorbitan, welches insgesamt 8 bis 40 Ethoxyeinheiten, besonders bevorzugt 15 bis 25 Ethoxyeinheiten, aufweist. Es kann zum Beispiel Tween 40LQ der Firma Croda verwendet werden.In a preferred embodiment, the alkoxylated sorbitan ester is an alkoxylated sorbitan esterified simply with palmitic acid, which has a total of 8 to 40 ethoxy units, more preferably 15 to 25 ethoxy units. For example, Tween 40LQ from Croda can be used.
In einer weiteren bevorzugten Ausführungsform enthält das Geschirrspülmittel den Sorbitanester in einer Menge von 0,1 bis 25 Gew.-%, bevorzugt in einer Menge von 0,2 bis 10 Gew.-%, besonders bevorzugt in einer Menge von 0,5 bis 7 Gew.-% und ganz besonders bevorzugt in einer Menge von 0,7 bis 4 Gew.-%, bezogen auf das Gesamtgewicht des Geschirrspülmittels.In a further preferred embodiment, the dishwashing agent contains the sorbitan ester in an amount of 0.1 to 25 wt .-%, preferably in an amount of 0.2 to 10 wt .-%, particularly preferably in an amount of 0.5 to 7 Wt .-% and most preferably in an amount of 0.7 to 4 wt .-%, based on the total weight of the dishwashing detergent.
Das erfindungsgemäße Mittel enthält weiterhin mindestens einen Gerüststoff. Als Gerüststoffe, die in dem Geschirrspülmittel enthalten sein können, sind insbesondere Silikate, Aluminiumsilikate (insbesondere Zeolithe), Carbonate, Phosphonate, organische (Co)builder, wie beispielsweise Salze organischer Di- und Polycarbonsäuren, sowie Mischungen dieser Stoffe zu nennen.The agent according to the invention also contains at least one builder. Builders which may be present in the dishwashing detergent are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, phosphonates, organic (co) builders, for example salts of organic di- and polycarboxylic acids, and mixtures of these substances.
Es können beispielsweise kristalline schichtförmige Silikate der allgemeinen Formel NaMSixO2x+1 · y H2O eingesetzt werden, worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, wobei besonders bevorzugte Werte für x 2, 3 oder 4 sind, und y für eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20 steht. Die kristallinen schichtförmigen Silikate der Formel NaMSixO2x+1 · yH2O werden beispielsweise von der Firma Clariant GmbH (Deutschland) unter dem Handelsnamen Na-SKS vertrieben. Beispiele für diese Silikate sind Na-SKS-1 (Na2Si22O45 · xH2O, Kenyait), Na-SKS-2 (Na2Si14O29 · xH2O, Magadiit), Na-SKS-3 (Na2Si8O17 · x H2O) oder Na-SKS-4 (Na2Si4O9 · xH2O, Makatit). Für die Zwecke der vorliegenden Erfindung besonders geeignet sind kristalline Schichtsilikate der Formel NaMSixO2x+1 · yH2O, in denen x für 2 steht. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5 · yH2O sowie weiterhin vor allem Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (β-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5 · H2O), Na-SKS-10 (NaHSi2O5 · 3H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (δ-Na2Si2O5) bevorzugt.It is possible, for example, to use crystalline layer-form silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, in which M represents sodium or hydrogen, x a number from 1.9 to 22, preferably from 1.9 to 4, where especially preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 · x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 · xH 2 O, makatite). Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi x O 2x + 1 · yH 2 O, in which x is 2 stands. In particular, both β- and δ-sodium disilicates are Na 2 Si 2 O 5 .yH 2 O and furthermore especially Na-SKS-5 (α-Na 2 Si 2 O 5 ), Na-SKS-7 (β-Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 · H 2 O), Na-SKS-10 (NaHSi 2 O 5 · 3H 2 O, kanemite), Na-SKS-11 (t- Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 (δ-Na 2 Si 2 O 5 ).
Die Geschirrspülmittel enthalten in verschiedenen Ausführungsformen einen Gewichtsanteil des kristallinen schichtförmigen Silikats der Formel NaMSixO2x+1 · yH2O von 0,1 bis 45 Gew.-%, bevorzugt von 1 bis 40 Gew.-% und insbesondere von 5 bis 35 Gew.-%, jeweils bezogen auf das Gesamtgewicht dieser Mittel. In verschiedenen Ausführungsformen sind die Mittel frei von derartigen Silikaten.The dishwashing detergents in various embodiments contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 .yH 2 O of from 0.1 to 45% by weight, preferably from 1 to 40% by weight and in particular from 5 to 35 Wt .-%, each based on the total weight of these agents. In various embodiments, the agents are free of such silicates.
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O:SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche vorzugsweise löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" verstanden, dass die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen, hervorrufen.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 dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.
In verschiedenen Ausführungsformen können diese(s) Silikat(e), vorzugsweise Alkalisilikate, besonders bevorzugt kristalline oder amorphe Alkalidisilikate, in den Mitteln in Mengen von 3 bis 60 Gew.-%, vorzugsweise von 8 bis 50 Gew.-% und insbesondere von 20 bis 40 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels, enthalten sein. In anderen Ausführungsformen sind die Mittel frei von diesen Silikaten.In various embodiments, these silicate (s), preferably alkali metal silicates, more preferably crystalline or amorphous Alkalidisilikate, in the compositions in amounts of from 3 to 60 wt .-%, preferably from 8 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the dishwashing detergent to be included. In other embodiments, the agents are free of these silicates.
Weitere Gerüststoffe sind die Alkaliträger. Als Alkaliträger gelten beispielsweise Alkalimetallhydroxide, Alkalimetallcarbonate, Alkalimetallhydrogencarbonate, Alkalimetallsesquicarbonate, die genannten Alkalisilikate, Alkalimetasilikate, und Mischungen der vorgenannten Stoffe, wobei im Sinne dieser Erfindung bevorzugt die Alkalicarbonate, insbesondere Natriumcarbonat, Natriumhydrogencarbonat oder Natriumsesquicarbonat eingesetzt werden können. Aufgrund ihrer im Vergleich mit anderen Buildersubstanzen geringen chemischen Kompatibilität mit den übrigen Inhaltsstoffen von maschinellen Geschirrspülmitteln, werden die optionalen Alkalimetallhydroxide bevorzugt nur in geringen Mengen, vorzugsweise in Mengen unterhalb 10 Gew.-%, bevorzugt unterhalb 6 Gew.-%, besonders bevorzugt unterhalb 4 Gew.-% und insbesondere unterhalb 2 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels, eingesetzt. Besonders bevorzugt werden Mittel, welche bezogen auf ihr Gesamtgewicht weniger als 0,5 Gew.-% und insbesondere keine Alkalimetallhydroxide enthalten.Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, it being possible to use the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention. Because of their low chemical compatibility with the other ingredients of dishwasher detergents in comparison with other builders, the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 Wt .-% and in particular below 2 wt .-%, each based on the total weight of Dishwashing agent, used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
In verschiedenen Ausführungsformen können Carbonat(e) und/oder Hydrogencarbonat(e), vorzugsweise Alkalicarbonat(e), besonders bevorzugt Natriumcarbonat, in Mengen von 2 bis 50 Gew.-%, vorzugsweise von 5 bis 40 Gew.-% und insbesondere von 7,5 bis 30 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels eingesetzt werden.In various embodiments, carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7 , 5 to 30 wt .-%, each based on the weight of the dishwashing detergent are used.
Die Geschirrspülmittel können als weiteren Gerüststoff insbesondere auch Phosphonate enthalten, die erfindungsgemäß nicht unter die Phosphate subsummiert werden. Als Phosphonat-Verbindung wird vorzugsweise ein Hydroxyalkan- und/oder Aminoalkanphosphonat eingesetzt. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Phosphonate sind in den Mitteln vorzugsweise in Mengen von 0,1 bis 10 Gew.-%, insbesondere in Mengen von 0,3 bis 8 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels, enthalten.The dishwashing detergents can contain as further builders in particular also phosphonates, which according to the invention are not subsumed under the phosphates. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the 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 contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.3 to 8 wt .-%, each based on the total weight of the dishwashing detergent.
Als organische (Co)builder sind insbesondere Polycarboxylate / Polycarbonsäuren, polymere Polycarboxylate, Asparaginsäure, Polyacetale, Dextrine, weitere organische Cobuilder sowie die bereits oben als Gerüststoffe genannten Phosphonate zu nennen. Diese Stoffklassen werden nachfolgend beschrieben.Particularly suitable organic (co) builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders. These classes of substances are described below.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form der freien Säure und/oder ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes der Geschirrspülmittel. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.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. For example, 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. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of the dishwashing detergent. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
Als besonders vorteilhaft für die Reinigungs- und Klarspülleistung hat sich der Einsatz von Citronensäure und/oder Citraten erwiesen. Erfindungsgemäß bevorzugt werden daher maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass das Geschirrspülmittel Citronensäure oder ein Salz der Citronensäure enthält und dass der Gewichtsanteil der Citronensäure oder des Salzes der Citronensäure vorzugsweise 1 bis 40 Gew.-%, vorzugsweise 10 bis 25 Gew.-% und insbesondere zwischen 15 und 22 Gew.-% beträgt.The use of citric acid and / or citrates has proved to be particularly advantageous for the cleaning and rinsing performance. Therefore, dishwashing detergents according to the invention are preferred in that the dishwashing detergent contains citric acid or a salt of citric acid, and that the weight fraction of citric acid or of the salt of citric acid or of the salt of citric acid Citric acid preferably 1 to 40 wt .-%, preferably 10 to 25 wt .-% and in particular between 15 and 22 wt .-% is.
Eine weitere bedeutende Klasse der phosphatfreien Gerüststoffe stellen Aminocarbonsäuren und/oder ihre Salze dar. Besonders bevorzugte Vertreter dieser Klasse sind Methylglycindiessigsäure (MGDA) oder ihre Salze sowie Glutamindiessigsäure (GLDA) oder ihre Salze oder Ethylendiamindiessigsäure (EDDS) oder ihre Salze. Ganz besonders bevorzugt ist GLDA bzw. dessen Salze. Der Gehalt an diesen Aminocarbonsäuren bzw. ihren Salzen, insbesondere GLDA-Natriumsalz, kann beispielsweise zwischen 0,1 und 25 Gew.-% bevorzugt zwischen 5 und 25 Gew.-% und insbesondere zwischen 15 und 25 Gew.-% betragen. Aminocarbonsäuren und ihre Salze können beispielsweise zusammen mit den vorgenannten Gerüststoffen eingesetzt werden, insbesondere zusammen mit Citrat und den vorgenannten Phosphonaten.Another important class of phosphate-free builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid (EDDS) or its salts. Very particular preference is GLDA or its salts. The content of these aminocarboxylic acids or their salts, in particular GLDA sodium salt, may for example be between 0.1 and 25% by weight, preferably between 5 and 25% by weight and in particular between 15 and 25% by weight. Aminocarboxylic acids and their salts can be used, for example, together with the abovementioned builders, in particular together with citrate and the abovementioned phosphonates.
Bevorzugt ist der wenigstens eine Gerüststoff des erfindungsgemäße Geschirrspülmittels ausgewählt aus der Gruppe umfassend Silikate, Aluminiumsilikate, Carbonate, Phosphonate, organische Di- und Polycarbonsäuren bzw. deren Salze sowie Mischungen davon.The at least one builder of the dishwashing detergent according to the invention is preferably selected from the group consisting of silicates, aluminum silicates, carbonates, phosphonates, organic di- and polycarboxylic acids or salts thereof and mixtures thereof.
Das erfindungsgemäße Mittel enthält bevorzugt wenigstens ein weiteres Tensid ausgewählt aus der Gruppe der anionischen, nichtionischen, amphoteren und kationischen Tenside, besonders bevorzugt aus der Gruppe der nichtionischen Tenside.The composition according to the invention preferably comprises at least one further surfactant selected from the group of anionic, nonionic, amphoteric and cationic surfactants, more preferably from the group of nonionic surfactants.
Als anionische, kationische, amphotere oder nichtionische Tenside können alle dem Fachmann bekannten Tenside dieser Arten eingesetzt werden.As anionic, cationic, amphoteric or nonionic surfactants it is possible to use all surfactants of these types known to the person skilled in the art.
Als weitere nichtionische Tenside eignen sich beispielsweise Alkylglykoside der allgemeinen Formel RO(G)x, in der R einem primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen entspricht und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.Suitable further nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
Weitere geeignete Tenside sind die als PHFA bekannten Polyhydroxyfettsäureamide.Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
In verschiedenen Ausführungsformen können auch Aminalkoxylate in den erfindungsgemäßen Mitteln enthalten sein.In various embodiments, also Aminalkoxylate can be included in the inventive compositions.
Bevorzugt werden allerdings schwachschäumende nichtionische Tenside eingesetzt, insbesondere alkoxylierte, vor allem ethoxylierte, schwachschäumende nichtionische Tenside. Mit besonderem Vorzug enthalten die maschinellen Geschirrspülmittel nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole.However, low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. With particular preference, the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
Eine Klasse einsetzbarer nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden können, sind demnach alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette.A class of useful nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
Bevorzugt einzusetzende Tenside stammen aus den Gruppen der ethoxylierten primären Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen ((PO/EO/PO)-Tenside). Solche (PO/EO/PO)-Niotenside zeichnen sich durch gute Schaumkontrolle aus.Preferably used surfactants come from the groups of 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 characterized by good foam control.
Besonders bevorzugte Niotenside sind solche, welche alternierende Ethylenoxid- und Alkylenoxideinheiten aufweisen. Unter diesen sind wiederum Tenside mit EO-AO-EO-AO-Blöcken bevorzugt, wobei jeweils eine bis zehn EO- bzw. AO-Gruppen aneinander gebunden sind, bevor ein Block aus den jeweils anderen Gruppen folgt. Hier sind nichtionische Tenside der allgemeinen Formel
Somit sind insbesondere nichtionische Tenside bevorzugt, die einen C9-15-Alkylrest mit 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten, gefolgt von 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten aufweisen.Thus, particularly preferred are 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.
Bevorzugte nichtionische Tenside sind hierbei solche der allgemeinen Formel
R1-CH(OH)CH2O-(AO)w-(A'O)x-(A"O)y-(A"'O)z-R2,
in der
- R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder -Alkenylrest steht;
- R2 für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-,-CH2-CH(CH2-CH3) stehen,
- w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.
R 1 is -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 ,
in the
- R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
- R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- A, A ', A "and A'" independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, - CH 2 -CH (CH 2 -CH 3 ),
- w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
Bevorzugt werden insbesondere solche endgruppenverschlossene, poly(oxyalkylierten) Niotenside, die, gemäß der Formel R1O[CH2CH2O]xCH2CH(OH)R2, neben einem Rest R1, welcher für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen steht, weiterhin einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest R2 mit 1 bis 30 Kohlenstoffatomen aufweisen, wobei x für Werte zwischen 1 und 90, vorzugsweise für Werte zwischen 30 und 80 und insbesondere für Werte zwischen 30 und 60 steht.Preference is given in particular to those 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 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
Besonders bevorzugt sind Tenside der Formel R1O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R2, in der R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 18 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x für Werte zwischen 0,5 und 1,5 sowie y für einen Wert von mindestens 15 steht.Particularly preferred are 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.
Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C2-26 Fettalkohol-(PO)i-(EO)15-40-2-hydroxyalkylether, insbesondere auch die C8-10 Fettalkohol-(PO)1-(EO)22-2-hydroxydecylether.
Besonders bevorzugt werden weiterhin solche endgruppenverschlossene poly(oxyalkylierten) Niotenside der Formel R1O[CH2CH2O]x[CH2CH(R3)O]yCH2CH(OH)R2, in der R1 und R2 unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht, R3 unabhängig voneinander ausgewählt ist aus -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2, vorzugsweise jedoch für -CH3 steht, und x und y unabhängig voneinander für Werte zwischen 1 und 32 stehen, wobei Niotenside mit R3 = -CH3 und Werten für x von 15 bis 32 und y von 0,5 und 1,5 ganz besonders bevorzugt sind.The group of these nonionic surfactants include, for example, the C 2-26 fatty alcohol (PO) i (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2 -hydroxydecylether.
Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH 2 O] x [ CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2 , in which R 1 and R 2 independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 , but preferably -CH 3 , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R 3 = -CH 3 and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.
Weitere bevorzugt einsetzbare Niotenside sind die endgruppenverschlossenen poly(oxyalkylierten) Niotenside der Formel R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2, in der R1 und R2 für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R3 für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x für Werte zwischen 1 und 30, k und j für Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen. Wenn der Wert x ≥ 2 ist, kann jedes R3 in der oben stehenden Formel R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2 unterschiedlich sein. R1 und R2 sind vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. Für den Rest R3 sind H, -CH3 oder -CH2CH3 besonders bevorzugt. Besonders bevorzugte Werte für x liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15.Other preferred 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. When the value x ≥ 2, 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. For the radical 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.
Wie vorstehend beschrieben, kann jedes R3 in der oben stehenden Formel unterschiedlich sein, falls x ≥ 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht x beispielsweise für 3, kann der Rest R3 ausgewählt werden, um Ethylenoxid- (R3 = H) oder Propylenoxid- (R3 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefügt sein können, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 für x ist hierbei beispielhaft gewählt worden und kann durchaus größer sein, wobei die Variationsbreite mit steigenden x-Werten zunimmt und beispielsweise eine große Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)-Gruppen einschließt, oder umgekehrt.As described above, each R 3 in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R 3 can be selected to form ethylene oxide (R 3 = H) or propylene oxide (R 3 = CH 3 ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). 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 ,
Besonders bevorzugte endgruppenverschlossene poly(oxyalkylierte) Alkohole der oben stehenden Formel weisen Werte von k = 1 und j = 1 auf, so dass sich die vorstehende Formel zu R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2 vereinfacht. In der letztgenannten Formel sind R1, R2 und R3 wie oben definiert und x steht für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R1 und R2 9 bis 14 C-Atome aufweisen, R3 für H steht und x Werte von 6 bis 15 annimmt.Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH ) CH 2 OR 2 simplified. In the latter formula, 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.
Als besonders wirkungsvoll haben sich schließlich die nichtionischen Tenside der allgemeinen Formel R1-CH(OH)CH2O-(AO)w-R2 erwiesen, in der
- R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder -Alkenylrest steht;
- R2 für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- A für einen Rest aus der Gruppe CH2CH2, CH2CH2CH2, CH2CH(CH3), vorzugsweise für CH2CH2 steht, und
- w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht
- R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
- R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3 ), preferably CH 2 CH 2 , and
- w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40
Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C4-22 Fettalkohol-(EO)10-80-2-hydroxyalkylether, insbesondere auch die C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4-22 Fettalkohol-(EO)40-80-2-hydroxyalkylether.The group of these 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.
In verschiedenen Ausführungsformen der Erfindung können anstelle der oben definierten endgruppenverschlossenen Hydroxymischether auch die entsprechenden nicht endgruppenverschlossenen Hydroxymischether eingesetzt werden. Diese können den obigen Formeln genügen, wobei R2 aber Wasserstoff ist und R1, R3, A, A', A", A"', w, x, y und z wie oben definiert sind.In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R 2 is hydrogen and R 1 , R 3 , A, A ', A ", A"', w, x, y and z are as defined above.
Die hierin beschriebenen Mittel, die bevorzugt mindestens ein weiteres nichtionisches Tensid, besonders bevorzugt ein nichtionisches Tensid aus der Gruppe der Hydroxymischether, umfassen, enthalten das weitere nichtionische Tensid in verschiedenen Ausführungsformen in einer Menge bezogen auf das Gesamtgewicht des Mittels von mindestens 1 Gew.-%, vorzugsweise mindestens 2,5 Gew.-%.The compositions described herein, which preferably comprise at least one further nonionic surfactant, more preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the further nonionic surfactant in various embodiments in an amount based on the total weight of the composition of at least 1% by weight. , preferably at least 2.5 wt .-%.
Als anionische Tenside eignen sich in den Geschirrspülmitteln alle anionischen oberflächenaktiven Stoffe. Diese sind gekennzeichnet durch eine wasserlöslich machende, anionische Gruppe wie z. B. eine Carboxylat-, Sulfat- oder Sulfonat-Gruppe und eine lipophile Alkylgruppe mit etwa 8 bis 30 C-Atomen. Zusätzlich können im Molekül Glykol- oder Polyglykolether-Gruppen, Ester-, Ether- und Amidgruppen sowie Hydroxylgruppen enthalten sein. Geeignete anionische Tenside liegen vorzugsweise in Form der Natrium-, Kalium- und Ammonium- sowie der Mono-, Di- und Trialkanolammoniumsalze mit 2 bis 4 C-Atomen in der Alkanolgruppe vor.Suitable anionic surfactants in dishwashing detergents are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. Example, a carboxylate, sulfate or sulfonate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group.
Bevorzugte anionische Tenside sind Alkylsulfate, Alkylpolyglykolethersulfate und Ethercarbonsäuren mit 10 bis 18 C-Atomen in der Alkylgruppe und bis zu 12 Glykolethergruppen im Molekül.Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
Die Geschirrspülmittel können daher in verschiedenen Ausführungsformen mindestens ein Tensid der Formel R4-O-(AO)n-SO3 -X+ enthalten.The dishwashing detergents can therefore, in various embodiments, contain at least one surfactant of the formula R 4 -O- (AO) n -SO 3 - X + .
In dieser Formel steht R4 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkyl-, Aryl- oder Alkylarylrest, vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R1 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R1 sind abgeleitet von C12-C18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von C10-C20-Oxoalkoholen.In this formula, R 4 is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with an even number of carbon atoms atoms are preferred. Particularly preferred radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols.
AO steht für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung, vorzugsweise für eine Ethylenoxidgruppierung. Der Index n steht für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und insbesondere von 2 bis 10. Ganz besonders bevorzugt steht n für die Zahlen 2, 3, 4, 5, 6, 7 oder 8. X steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen X+ können ausgewählt sein aus NH4 +, ½Zn2+, ½Mg2+, ½Ca2+, ½Mn2+, und deren Mischungen.AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + including Na, with Na + being extremely preferred. Other cations X + may be selected from NH 4 + , ½Zn 2+ , ½Mg 2+ , ½Ca 2+ , ½Mn 2+ , and mixtures thereof.
Besonders bevorzugte anionische Tenside werden ausgewählt aus Fettalkoholethersulfaten der Formel
Die Mittel können ferner zusätzlich oder alternativ mindestens ein Tensid der Formel R5-A-SO3 -Y+ enthalten.The agents may additionally or alternatively contain at least one surfactant of the formula R 5 -A-SO 3 - Y + .
In dieser Formel steht R5 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkyl-, Aryl- oder Alkylarylrest und die Gruppierung -A- für -O- oder eine chemische Bindung. In anderen Worten lassen sich durch die vorstehende Formel Sulfat- (A = O) oder Sulfonat- (A = chemische Bindung) -tenside beschreiben. In Abhängigkeit von der Wahl der Gruppierung A sind bestimmte Reste R5 bevorzugt. Bei den Sulfattensiden (A = O) steht R5 vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R5 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R5 sind abgeleitet von C12-C18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von C10-C20-Oxoalkoholen. Y steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen Y+ können ausgewählt sein aus NH4 +, ½Zn 2+, ½Mg2+, ½Ca2+, ½Mn2+, und deren Mischungen.In this formula, R 5 is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the grouping -A- for -O- or a chemical bond. In other words, sulfate (A = O) or sulfonate (A = chemical bond) surfactants can be described by the above formula. Depending on the choice of the group A, certain radicals R 5 are preferred. In the case of the sulfate surfactants (A = O), R 5 preferably represents a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R 5 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with an even number of carbon atoms Atoms are preferred. Particularly preferred radicals R 5 are derived from C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols. Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred. Other cations Y + may be selected from NH 4 + , ½Zn 2+ , ½Mg 2+ , ½Ca 2+ , ½Mn 2+ , and mixtures thereof.
Solche besonders bevorzugten Tenside sind ausgewählt aus Fettalkoholsulfaten der Formel
Bei den Sulfonattensiden (A = chemische Bindung) steht R5 vorzugsweise für einen linearen oder verzweigten unsubstituierten Alkylarylrest. Auch hier steht X für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen X+ können ausgewählt sein aus NH4 +, ½ Zn2+, ½Mg2+, ½Ca2+, ½Mn2+, und deren Mischungen. Solche Tenside können ausgewählt sein aus linearen oder verzweigten Alkylbenzolsulfonaten.In the case of the sulfonate surfactants (A = chemical bond) R 5 preferably represents a linear or branched unsubstituted alkylaryl radical. Here, too, X is a monovalent cation or the nth part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred. Other cations X + may be selected from NH 4 +, ½ Zn 2+, ½Mg 2+, ½Ca 2+, ½Mn 2+, and mixtures thereof. Such surfactants may be selected from linear or branched alkyl benzene sulfonates.
In verschiedenen Ausführungsformen können auch sulfatierte und/oder sulfonierte Triglyceride als anionische Tenside in den erfindungsgemäßen Mitteln enthalten sein.In various embodiments, sulfated and / or sulfonated triglycerides may also be present as anionic surfactants in the compositions according to the invention.
In den erfindungsgemäßen Mitteln, beträgt der Gehalt an anionischen Tensiden vorzugsweise weniger als 4 Gew.-%, besonders bevorzugt weniger als 2 Gew.-% und insbesondere weniger als 1 Gew.-%. Geschirrspülmittel, welche keine anionischen Tenside enthalten, werden besonders bevorzugt. Kein Tensid bedeutet, dass weniger als 0,5 Gew.-% des genannten Tensids, bevorzugt weniger als 0,2 Gew.-% des genannten Tensids, enthalten sind, besonders bevorzugt wurde kein Tensid dieser Gruppe zugesetzt.In the compositions of the invention, the content of anionic surfactants is preferably less than 4 wt .-%, more preferably less than 2 wt .-% and in particular less than 1 wt .-%. Dishwashing detergents which do not contain anionic surfactants are particularly preferred. No surfactant means less than 0.5% by weight of said surfactant, preferably less than 0.2% by weight of said surfactant, more preferably no surfactant has been added to said group.
Geeignete Amphotenside sind beispielsweise Betaine der Formel (Riii)(Riv)(Rv)N+CH2COO-, in der Riii einen gegebenenfalls durch Heteroatome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 25, vorzugsweise 10 bis 21 Kohlenstoffatomen und Riv sowie Rv gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten, insbesondere C10-C18-Alkyl-dimethylcarboxymethylbetain und C11-C17-Alkylamidopropyl-dimethylcarboxymethylbetain.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 -alkyl-dimethylcarboxymethylbetain and C 11 -C 17 -alkylamidopropyl-dimethylcarboxymethylbetain.
Geeignete Kationtenside sind u.a. die quartären Ammoniumverbindungen der Formel (Rvi)(Rvii)(Rviii)(Rix)N+X-, in der Rvi bis Rix für vier gleich- oder verschiedenartige, insbesondere zwei lang- und zwei kurzkettige, Alkylreste und X- für ein Anion, insbesondere ein Halogenidion, stehen, beispielsweise Didecyl-dimethyl-ammoniumchlorid, Alkyl-benzyl-didecyl-ammoniumchlorid und deren Mischungen. Weitere geeignete kationische Tenside sind die quaternären oberflächenaktiven Verbindungen, insbesondere mit einer Sulfonium-, Phosphonium-, Jodonium- oder Arsoniumgruppe, die auch als antimikrobielle Wirkstoffe bekannt sind. Durch den Einsatz von quaternären oberflächenaktiven Verbindungen mit antimikrobieller Wirkung kann das Mittel mit einer antimikrobiellen Wirkung ausgestaltet werden bzw. dessen gegebenenfalls aufgrund anderer Inhaltsstoffe bereits vorhandene antimikrobielle Wirkung verbessert werden.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. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial effect, the agent with an antimicrobial effect be designed or its possibly due to other ingredients already existing antimicrobial effect can be improved.
In Geschirrspülmitteln, beträgt der Gehalt an kationischen und/oder amphoteren Tensiden vorzugsweise weniger als 4 Gew.-%, besonders bevorzugt weniger als 2 Gew.-% und insbesondere weniger als 1 Gew.-%. Geschirrspülmittel, welche keine kationischen oder amphoteren Tenside enthalten, werden besonders bevorzugt.In dishwashing detergents, the content of cationic and / or amphoteric surfactants is preferably less than 4% by weight, more preferably less than 2% by weight and in particular less than 1% by weight. Dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.
In verschiedenen Ausführungsformen können auch Silikontenside in den erfindungsgemäßen Mitteln enthalten sein, welche abhängig von ihrem Aufbau verschiedenen Klassen an Tensiden zuzuordnen sind.In various embodiments, silicone surfactants can also be present in the compositions according to the invention, which, depending on their structure, can be assigned to different classes of surfactants.
In verschiedenen Ausführungsformen können auch amphiphile carboxyalkylierte Polyamine in den erfindungsgemäßen Mitteln enthalten sein.In various embodiments, amphiphilic carboxyalkylated polyamines can also be present in the agents according to the invention.
Die Mittel der vorliegenden Erfindung enthalten in bevorzugten Ausführungsformen ein oder mehrere Enzyme. Das eingesetzte Enzym oder die eingesetzten Enzyme können in einer Enzymzubereitung oder Enzymzusammensetzung vorliegen.The agents of the present invention contain one or more enzymes in preferred embodiments. The enzyme or enzymes used may be present in an enzyme preparation or enzyme composition.
Geeignete Enzyme umfassen, ohne darauf beschränkt zu sein, Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, β-Glucanasen, Perhydrolasen oder Oxidoreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Geschirrspülmitteln verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Die Mittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10-6 bis 5 Gew.-% bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren oder dem Biuret-Verfahren bestimmt werden.Suitable enzymes include, but are not limited to, proteases, amylases, lipases, hemicellulases, cellulases, β-glucanases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are preferably used accordingly. The agents contain enzymes preferably in total amounts of 1 × 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
Proteasen gehören zu den technisch bedeutendsten Enzymen überhaupt. Sie bewirken den Abbau proteinhaltiger Anschmutzungen auf dem Reinigungsgut. Hierunter sind wiederum Proteasen vom Subtilisin-Typ (Subtilasen, Subtilopeptidasen, EC 3.4.21.62) besonders wichtig, welche aufgrund der katalytisch wirksamen Aminosäuren Serin-Proteasen sind. Sie wirken als unspezifische Endopeptidasen und hydrolysieren beliebige Säureamidbindungen, die im Inneren von Peptiden oder Proteinen liegen. Ihr pH-Optimum liegt meist im deutlich alkalischen Bereich. Subtilasen werden natürlicherweise von Mikroorganismen gebildet. Hierunter sind insbesondere die von Bacillus-Spezies gebildeten und sezernierten Subtilisine als bedeutendste Gruppe innerhalb der Subtilasen zu erwähnen.Proteases are among the most technically important enzymes of all. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. Subtilases are naturally produced by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
Beispiele für die in Wasch- und Geschirrspülmitteln bevorzugt eingesetzten Proteasen vom Subtilisin-Typ sind die Subtilisine BPN' und Carlsberg, die Protease PB92, die Subtilisine 147 und 309, die Protease aus Bacillus lentus, insbesondere aus Bacillus lentus DSM 5483, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7, sowie Varianten der genannten Proteasen, die eine gegenüber der Ausgangsprotease veränderte Aminosäuresequenz aufweisen. Proteasen werden durch aus dem Stand der Technik bekannte Verfahren gezielt oder zufallsbasiert verändert und so beispielsweise für den Einsatz in Wasch- und Geschirrspülmitteln optimiert. Dazu gehören Punktmutagenese, Deletions- oder Insertionsmutagenese oder Fusion mit anderen Proteinen oder Proteinteilen. So sind für die meisten aus dem Stand der Technik bekannten Proteasen entsprechend optimierte Varianten bekannt.Examples of the subtilisin type proteases preferably used in washing and dishwashing detergents are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the the subtilases, but not the subtilisins in the narrower sense attributable enzyme thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of said proteases, which have a relation to the parent protease modified amino acid sequence. Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.
Beispiele für einsetzbare Amylasen sind die α-Amylasen aus Bacillus licheniformis, aus B. amyloliquefaciens, aus B. stearothermophilus, aus Aspergillus niger und A. oryzae sowie die für den Einsatz in Geschirrspülmitteln verbesserten Weiterentwicklungen der vorgenannten Amylasen. Des Weiteren sind für diesen Zweck die α-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus B. agaradherens (DSM 9948) hervorzuheben.Examples of usable amylases are the α-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 dishwashing detergents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
Einsetzbar sind weiterhin Lipasen oder Cutinasen, insbesondere wegen ihrer Triglyceridspaltenden Aktivitäten, aber auch, um aus geeigneten Vorstufen in situ Persäuren zu erzeugen. Hierzu gehören beispielsweise die ursprünglich aus Humicola lanuginosa (Thermomyces lanuginosus) erhältlichen, beziehungsweise weiterentwickelten Lipasen, insbesondere solche mit dem Aminosäureaustausch D96L.It is also possible to use lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
Weiterhin können Enzyme eingesetzt werden, die unter dem Begriff Hemicellulasen zusammengefasst werden. Hierzu gehören beispielsweise Mannanasen, Xanthanlyasen, Pektinlyasen (=Pektinasen), Pektinesterasen, Pektatlyasen, Xyloglucanasen (=Xylanasen), Pullulanasen und β-Glucanasen. Unter den letzteren sind insbesondere die Licheninasen zu nennen.Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Among the latter, the licheninases in particular should be mentioned.
Zur Erhöhung der bleichenden Wirkung können Oxidoreduktasen, beispielsweise Oxidasen, Oxygenasen, Katalasen, Peroxidasen, wie Halo-, Chloro-, Bromo-, Lignin-, Glucose- oder Mangan-Peroxidasen, Dioxygenasen oder Laccasen (Phenoloxidasen, Polyphenoloxidasen) eingesetzt werden. Vorteilhafterweise werden zusätzlich vorzugsweise organische, besonders bevorzugt aromatische, mit den Enzymen wechselwirkende Verbindungen zugegeben, um die Aktivität der betreffenden Oxidoreduktasen zu verstärken (Enhancer) oder um bei stark unterschiedlichen Redoxpotentialen zwischen den oxidierenden Enzymen und den Anschmutzungen den Elektronenfluss zu gewährleisten (Mediatoren).Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect. Advantageously, it is additionally preferred to add 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.
Bevorzugt enthält das erfindungsgemäße Mittel mindestens ein Enzym ausgewählt aus der Gruppe umfassend Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, β-Glucanasen, Perhydrolasen und Oxidoreduktasen.The agent according to the invention preferably contains at least one enzyme selected from the group comprising proteases, amylases, lipases, hemicellulases, cellulases, β-glucanases, perhydrolases and oxidoreductases.
Ein Enzym kann besonders während der Lagerung gegen Schädigungen wie beispielsweise Inaktivierung, Denaturierung oder Zerfall etwa durch physikalische Einflüsse, Oxidation oder proteolytische Spaltung geschützt werden. Bei mikrobieller Gewinnung der Proteine und/oder Enzyme ist eine Inhibierung der Proteolyse besonders bevorzugt, insbesondere wenn auch die Mittel Proteasen enthalten. Geschirrspülmittel können zu diesem Zweck Stabilisatoren enthalten; die Bereitstellung derartiger Mittel stellt eine bevorzugte Ausführungsform der vorliegenden Erfindung dar.An enzyme can be particularly protected during storage against damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Dishwashing agents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
Reinigungsaktive Proteasen und Amylasen werden in der Regel nicht in Form des reinen Proteins, sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt.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.
Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil.Alternatively, 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. In deposited layers, 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. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.
Wie aus der vorherigen Ausführungen ersichtlich, bildet das Enzym-Protein nur einen Bruchteil des Gesamtgewichts üblicher Enzym-Zubereitungen. Bevorzugt eingesetzte Protease- und Amylase-Zubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, besonders bevorzugt zwischen 0,4 und 20 Gew.-% und insbesondere zwischen 0,8 und 10 Gew.-% des Enzymproteins.As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Preferably used protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 10% by weight of the enzyme protein.
Bevorzugt werden insbesondere solche Geschirrspülmittel, die, jeweils bezogen auf ihr Gesamtgewicht, 0,1 bis 12 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-% und insbesondere 0,5 bis 8 Gew.-% Enzym-Zubereitungen enthalten.Preference is given in particular to dishwashing detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
Die hierin beschriebenen Zusammensetzungen können auch Enzymstabilisatoren beinhalten. Eine Gruppe von Stabilisatoren sind reversible Proteaseinhibitoren. Häufig werden hierfür Benzamidin-Hydrochlorid, Borax, Borsäuren, Boronsäuren oder deren Salze oder Ester eingesetzt, darunter vor allem Derivate mit aromatischen Gruppen, etwa ortho-, meta- oder para-substituierte Phenylboronsäuren, insbesondere 4-Formylphenyl-Boronsäure, beziehungsweise die Salze oder Ester der genannten Verbindungen. Auch Peptidaldehyde, das heißt Oligopeptide mit reduziertem C-Terminus, insbesondere solche aus 2 bis 50 Monomeren werden zu diesem Zweck eingesetzt. Zu den peptidischen reversiblen Proteaseinhibitoren gehören unter anderem Ovomucoid und Leupeptin. Auch spezifische, reversible Peptid-Inhibitoren für die Protease Subtilisin sowie Fusionsproteine aus Proteasen und spezifischen Peptid-Inhibitoren sind hierfür geeignet.The compositions described herein may also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.
Weitere Enzymstabilisatoren sind Aminoalkohole wie Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen, aliphatische Carbonsäuren bis zu C12, wie beispielsweise Bernsteinsäure, andere Dicarbonsäuren oder Salze der genannten Säuren. Auch endgruppenverschlossene Fettsäureamidalkoxylate sind für diesen Zweck geeignet. Weitere Enzymstabilisatoren sind dem Fachmann aus dem Stand der Technik bekannt.Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art.
Bevorzugt enthält das erfindungsgemäße Geschirrspülmittel mindestens einen weiteren Bestandteil, vorzugsweise mindestens zwei weitere Bestandteile, ausgewählt aus der Gruppe umfassend weitere Gerüststoffe, Verdicker, Sequestrierungsmittel, Elektrolyte, Korrosionsinhibitoren, insbesondere Silberschutzmittel, Glaskorrosionsinhibitoren, Polymere, Bleichmittel, Bleichkatalysatoren, Bleichaktivatoren, Schauminhibitoren, Farbstoffe, Duftstoffe, Bitterstoffe, antimikrobielle Wirkstoffe und Desintegrationshilfsmittel.The dishwashing detergent according to the invention preferably contains at least one further constituent, preferably from the group comprising further builders, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaches, bleach catalysts, bleach activators, foam inhibitors, dyes, fragrances , Bitter substances, antimicrobial agents and disintegration aids.
Die erfindungsgemäßen Geschirrspülmittel können ferner ein Sulfopolymer als weiteren Gerüststoff enthalten. Der Gewichtsanteil des Sulfopolymers am Gesamtgewicht des erfindungsgemäßen Geschirrspülmittels beträgt vorzugsweise von 0,1 bis 20 Gew.-%, insbesondere von 0,5 bis 18 Gew.-%, besonders bevorzugt 1,0 bis 15 Gew.-%, insbesondere von 4 bis 14 Gew.-%, vor allem von 6 bis 12 Gew.-%. Das Sulfopolymer wird üblicherweise in Form einer wässrigen Lösung eingesetzt, wobei die wässrigen Lösungen typischerweise 20 bis 70 Gew.-%, insbesondere 30 bis 50 Gew.-%, vorzugsweise etwa 35 bis 40 Gew.-% Sulfopolymere enthalten.The dishwashing agents according to the invention may further comprise a sulfopolymer as further builder. The proportion by weight of the sulfopolymer in the total weight of the dishwashing 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 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 .-% sulfopolymers.
Als Sulfopolymer wird vorzugsweise ein copolymeres Polysulfonat, vorzugsweise ein hydrophob modifiziertes copolymeres Polysulfonat, eingesetzt. Die Copolymere können zwei, drei, vier oder mehr unterschiedliche Monomereinheiten aufweisen. Bevorzugte copolymere Polysulfonate enthalten neben Sulfonsäuregruppen-haltigem(n) Monomer(en) wenigstens ein Monomer aus der Gruppe der ungesättigten Carbonsäuren.The sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate. The copolymers may be two, three, four or three have 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.
Als ungesättigte Carbonsäure(n) wird/werden mit besonderem Vorzug ungesättigte Carbonsäuren der Formel R1(R2)C=C(R3)COOH eingesetzt, in der R1 bis R3 unabhängig voneinander für-H, - CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettiger oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.As unsaturated carboxylic acid (s) is / are used with particular preference unsaturated carboxylic acids of the formula R 1 (R 2 ) C = C (R 3 ) COOH, in which R 1 to R 3 are independently -H, - CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH 2 , -OH or -COOH as defined above or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
Besonders bevorzugte ungesättigte Carbonsäuren sind Acrylsäure, Methacrylsäure, Ethacrylsäure, α-Chloroacrylsäure, α-Cyanoacrylsäure, Crotonsäure, α-Phenyl-Acrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Citraconsäure, Methylenmalonsäure, Sorbinsäure, Zimtsäure oder deren Mischungen. Einsetzbar sind selbstverständlich auch die ungesättigten Dicarbonsäuren.Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-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.
Bei den Sulfonsäuregruppen-haltigen Monomeren sind solche der Formel
R5(R6)C=C(R7)-X-SO3H
bevorzugt, in der R5 bis R7 unabhängig voneinander für-H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit-NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für -COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.In the sulfonic acid-containing monomers are those of the formula
R 5 (R 6 ) C = C (R 7 ) -X-SO 3 H
in which R 5 to R 7 independently of one another are H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 - , -C (O) -NH-C (CH 3 ) 2 -CH 2 - and -C (O) -NH-CH (CH 3 ) -CH 2 -.
Unter diesen Monomeren bevorzugt sind solche der Formeln
H2C=CH-X-SO3H
H2C=C(CH3)-X-SO3H
HO3S-X-(R6)C=C(R7)-X-SO3H,
in denen R6 und R7 unabhängig voneinander ausgewählt sind aus -H, -CH3, -CH2CH3, - CH2CH2CH3 und -CH(CH3)2 und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.Preferred among these monomers are those of the formulas
H 2 C = CH-X-SO 3 H
H 2 C = C (CH 3 ) -X-SO 3 H
HO 3 SX- (R 6 ) C = C (R 7 ) -X-SO 3 H,
in which R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , - CH 2 CH 2 CH 3 and -CH (CH 3 ) 2 and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 -, - C (O) -NH-C (CH 3 ) 2 -CH 2 - and -C (O) -NH-CH (CH 3 ) -CH 2 -.
Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acrylamido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methyl-1-propansulfonsäure, 2-Methacrylamido-2-methyl-1-propansulfonsäure, 3-Methacrylamido-2-hydroxy-propansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propen1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 3-Sulfo-propylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Mischungen der genannten Säuren oder deren wasserlösliche Salze.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-sulfo propyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.
In den Polymeren können die Sulfonsäuregruppen ganz oder teilweise in neutralisierter Form vorliegen, d.h. dass das acide Wasserstoffatom der Sulfonsäuregruppe in einigen oder allen Sulfonsäuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Der Einsatz von teil- oder vollneutralisierten sulfonsäuregruppenhaltigen Copolymeren ist erfindungsgemäß bevorzugt.In the polymers, 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. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
Die Monomerenverteilung der bevorzugt eingesetzten Copolymere beträgt bei Copolymeren, die nur Carbonsäuregruppen-haltige Monomere und Sulfonsäuregruppen-haltige Monomere enthalten, vorzugsweise jeweils 5 bis 95 Gew.-%, besonders bevorzugt beträgt der Anteil des Sulfonsäuregruppen-haltigen Monomers 50 bis 90 Gew.-% und der Anteil des Carbonsäuregruppen-haltigen Monomers 10 bis 50 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewählt aus den zuvor genannten.The monomer distribution of the copolymers preferably used 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 the proportion of the sulfonic acid group-containing monomer is from 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
Die Molmasse der bevorzugt eingesetzten Sulfo-Copolymere kann variiert werden, um die Eigenschaften der Polymere dem gewünschten Verwendungszweck anzupassen. Bevorzugte Geschirrspülmittel sind dadurch gekennzeichnet, dass die Copolymere Molmassen von 2000 bis 200.000 gmol-1, vorzugsweise von 4000 bis 25.000 gmol-1 und insbesondere von 5000 bis 15.000 gmol-1 aufweisen.The molecular weight of the sulfo copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired end use. Preferred dishwashing detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
In verschiedenen Ausführungsformen können in den Mitteln der Erfindung weitere Polymere eingesetzt werden. Zur Gruppe der geeigneten Polymere zählen insbesondere die wasch- oder reinigungsaktiven Polymere, beispielsweise die Klarspülpolymere und/oder als Enthärter wirksame Polymere. Generell sind in maschinellen Geschirrspülmitteln neben nichtionischen Polymeren auch kationische, anionische und amphotere Polymere einsetzbar. Bei den vorstehend beschriebenen Sulfo(co)polymeren handelt es sich beispielsweise um anionische Polymere.In various embodiments, other polymers can be used in the compositions of the invention. The group of suitable polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in automatic dishwashing detergents in addition to nonionic polymers. The sulfo (co) polymers described above are, for example, anionic polymers.
"Amphotere Polymere" im Sinne der vorliegenden Erfindung weisen neben einer positiv geladenen Gruppe in der Polymerkette weiterhin auch negativ geladenen Gruppen bzw. Monomereinheiten auf. Bei diesen Gruppen kann es sich z.B. um Carbonsäuren, Sulfonsäuren oder Phosphonsäuren handeln.For the purposes of the present invention, "amphoteric polymers" furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be e.g. to act carboxylic acids, sulfonic acids or phosphonic acids.
Bevorzugte einsetzbare Polymere stammen aus der Gruppe der Alkylacrylamid/Acrylsäure-Copolymere, der Alkylacrylamid/Methacrylsäure-Copolymere, der Alkylacrylamid/Methylmethacrylsäure-Copolymere, der Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere, der Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)-acrylsäure-Copolymere, der Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere, der Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere sowie der Copolymere aus ungesättigten Carbonsäuren, kationisch derivatisierten ungesättigten Carbonsäuren und gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.Preferred polymers which can be used are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.
Weitere einsetzbare Polymere stammen aus der Gruppe der Acrylamidoalkyltrialkylammonium-chlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze, der Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze und der Methacroylethylbetain/Methacrylat-Copolymere.Other usable polymers come 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 Methacroylethylbetain / methacrylate copolymers.
"Kationische Polymere" sind Polymere, welche eine positive Ladung im Polymermolekül tragen. Diese kann beispielsweise durch in der Polymerkette vorliegende (Alkyl-)Ammoniumgruppierungen oder andere positiv geladene Gruppen realisiert werden. Besonders bevorzugte kationische Polymere stammen aus den Gruppen der quaternierten Cellulose-Derivate, der Polysiloxane mit quaternären Gruppen, der kationischen Guar-Derivate, der polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure, der Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, der Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, der quaternierter Polyvinylalkohole oder der unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere."Cationic polymers" 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.
Die vorstehend für die beschriebenen Tenside und Gerüststoffe angegebenen Mengen beziehen sich üblicherweise auf die Mengen, die eingesetzt werden, wenn das jeweilige Tensid oder der jeweilige Gerüststoff allein eingesetzt wird, sofern nicht explizit anders angegeben. Es ist daher selbstverständlich, dass beim Einsatz mehrerer Tenside oder Gerüststoffe, die Mengenangaben entsprechend anzupassen sind.The amounts given above for the described surfactants and builders usually refer to the amounts that are used when the particular surfactant or the respective builder is used alone, unless explicitly stated otherwise. It is therefore natural that when using multiple surfactants or builders, the quantities are adjusted accordingly.
Erfindungsgemäße maschinelle Geschirrspülmittel können als weiteren Bestandteil ein Bleichmittel enthalten, wobei Sauerstoffbleichmittel bevorzugt werden. Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumpercarbonat, das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure.
Weiterhin können auch Bleichmittel aus der Gruppe der organischen Bleichmittel eingesetzt werden. Typische organische Bleichmittel sind die Diacylperoxide, wie z.B. Dibenzoylperoxid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden. Einsetzbar sind außerdem alle weiteren dem Fachmann aus dem Stand der Technik bekannten anorganischen oder organischen Peroxybleichmittel. Als Bleichmittel werden die Percarbonate und hier insbesondere Natriumpercarbonat besonders bevorzugt.Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred. Among the compounds serving as bleaches in water H 2 O 2 , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art. As a bleaching agent, the percarbonates and in particular sodium percarbonate are particularly preferred.
Bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel sind dadurch gekennzeichnet, dass sie ein Sauerstoffbleichmittel, vorzugsweise Natriumpercarbonat, besonders bevorzugt ein beschichtetes Natriumpercarbonat enthalten. Der Gewichtsanteil des Bleichmittels, bezogen auf das Gesamtgewicht des Wasch- oder Reinigungsmittels, beträgt in bevorzugten Ausführungsformen zwischen 1 und 35 Gew.-%, vorzugsweise zwischen 2,5 bis 30 Gew.-%, besonders bevorzugt 5 bis 20 Gew.-% und insbesondere zwischen 10 und 15 Gew.-%.Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate. The proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, in preferred embodiments is between 1 and 35% by weight, preferably between 2.5 and 30% by weight, more preferably between 5 and 20% by weight in particular between 10 and 15 wt .-%.
In verschiedenen Ausführungsformen der Erfindung enthalten die maschinellen Geschirrspülmittel zusätzlich mindestens einen Bleichaktivator. Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Von allen dem Fachmann aus dem Stand der Technik bekannten Bleichaktivatoren werden mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS) besonders bevorzugt eingesetzt. Auch Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Als Bleichaktivator wird TAED, insbesondere in Kombination mit einem Percarbonat-Bleichmittel, vorzugsweise Natriumpercarbonat, ganz besonders bevorzugt.In various embodiments of the invention, the automatic dishwashing agents additionally contain at least one bleach activator. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. As a bleach activator, TAED, especially in combination with a percarbonate bleach, preferably sodium percarbonate, is most preferred.
Diese Bleichaktivatoren werden vorzugsweise in Mengen bis 10 Gew.-%, insbesondere 0,1 Gew.-% bis 8 Gew.-%, besonders 2 bis 8 Gew.-% und besonders bevorzugt 2 bis 6 Gew.-% oder 2 bis 3 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Mittel, eingesetzt.These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight or 2 to 3 % By weight, based in each case on the total weight of the agent.
Zusätzlich oder alternativ zu den konventionellen Bleichaktivatoren enthalten die erfindungsgemäßen maschinellen Geschirrspülmittel vorzugsweise mindestens einen Bleichkatalysator. Bei diesen Stoffen handelt es sich um bleichverstärkende Übergangsmetallsalze bzw. Übergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo-Salenkomplexe oder -carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe-, Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar.In addition or as an alternative to the conventional bleach activators, the automatic dishwasher detergents according to the invention preferably contain at least one bleach catalyst. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
Mit besonderem Vorzug werden Komplexe des Mangans in der Oxidationsstufe II, III, IV oder IV eingesetzt, die vorzugsweise einen oder mehrere makrocyclische(n) Ligand(en) mit den Donorfunktionen N, NR, PR, O und/oder S enthalten. Vorzugsweise werden Liganden eingesetzt, die Stickstoff-Donorfunktionen aufweisen. Dabei ist es besonders bevorzugt, Bleichkatalysator(en) in den erfindungsgemäßen Mitteln einzusetzen, welche als makromolekularen Liganden 1,4,7-Trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-Triazacyclononan (TACN), 1,5,9-Trimethyl-1,5,9-triazacyclododecan (Me-TACD), 2-Methyl-1,4,7-trimethyl-1,4,7-triazacyclononan (Me/Me-TACN) und/oder 2-Methyl-1,4,7-triazacyclononan (Me/TACN) enthalten. Geeignete Mangankomplexe sind beispielsweise [MnIII 2(µ-O)1(µ-OAc)2(TACN)2](ClO4)2, [MnIIIMnIV(µ-O)2(µ-OAc)1(TACN)2](BPh4)2, [MnIV 4(µ-O)6(TACN)4](ClO4)4, [MnIII 2(µ-O)1(µ-OAc)2(Me-TACN)2](ClO4)2, [MnIIIMnIV(µ-O)1(µ-OAc)2(Me-TACN)2](ClO4)3, [MnIV 2(µ-O)3(Me-TACN)2](PF6)2 und [MnIV 2(µ-O)3(Me/Me-TACN)2](PF6)2 (OAc = OC(O)CH3).It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn III 2 (μ-O) 1 (μ-OAc) 2 (TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV (μ-O) 2 (μ-OAc) 1 (TACN ) 2 ] (BPh 4 ) 2 , [Mn IV 4 (μ-O) 6 (TACN) 4 ] (ClO 4 ) 4 , [Mn III 2 (μ-O) 1 (μ-OAc) 2 (Me-TACN ) 2 ] (ClO 4 ) 2 , [Mn III Mn IV (μ-O) 1 (μ-OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn IV 2 (μ-O) 3 ( Me-TACN) 2 ] (PF 6 ) 2 and [Mn IV 2 (μ-O) 3 (Me / Me-TACN) 2 ] (PF 6 ) 2 (OAc = OC (O) CH 3 ).
Maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass sie weiterhin einen Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe, vorzugsweise aus der Gruppe der Komplexe des Mangans mit 1,4,7-trimethyl-1,4,7-triazacyclononan (Me3-TACN) oder 1,2, 4,7-tetramethyl-1,4,7-triazacyclononan (Me4-TACN) enthalten, werden erfindungsgemäß bevorzugt, da durch die vorgenannten Bleichkatalysatoren insbesondere das Reinigungsergebnis signifikant verbessert werden kann.Machine dishwashing detergent, characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.
Die vorgenannten bleichverstärkenden Übergangsmetallkomplexe, insbesondere mit den Zentralatomen Mn und Co, werden in üblichen Mengen, vorzugsweise in einer Menge bis zu 5 Gew.-%, insbesondere von 0,0025 Gew.-% bis 1 Gew.-% und besonders bevorzugt von 0,01 Gew.-% bis 0,30 Gew.-% oder 0,02 Gew.-% bis 0,5 Gew.-%, jeweils bezogen auf das Gesamtgewicht der bleichkatalysatorhaltigen Mittel, eingesetzt. In speziellen Fällen kann jedoch auch mehr Bleichkatalysator eingesetzt werden.The aforementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0 , 01 wt .-% to 0.30 wt .-% or 0.02 wt .-% to 0.5 wt .-%, each based on the total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.
Generell kann der pH-Wert des Geschirrspülmittels mittels üblicher pH-Regulatoren eingestellt werden, wobei der pH-Wert abhängig von dem gewünschten Einsatzzweck gewählt wird. In verschiedenen Ausführungsformen liegt der pH-Wert in einem Bereich von 5,5 bis 10,5, vorzugsweise 5,5 bis 9,5, besonders bevorzugt größer 7, ganz besonders bevorzugt größer 7,5 und insbesondere größer 8, 5. Üblicherweise weist ein Geschirrspülmittel-Formkörper, beispielsweise eine Tablette, dabei einen pH-Wert größer als 10 auf, und die Spülflotte erhält in einer bevorzugten Ausführungsform bei Anwendung des Geschirrspülmittels einen pH-Wert zwischen 9 und 10, beispielsweise 9,5.
Als pH-Stellmittel dienen Säuren und/oder Alkalien, vorzugsweise Alkalien. Geeignete Säuren sind insbesondere organische Säuren wie die Essigsäure, Zitronensäure, Glycolsäure, Milchsäure, Bernsteinsäure, Adipinsäure, Äpfelsäure, Weinsäure und Gluconsäure oder auch Amidosulfonsäure. Daneben können aber auch die Mineralsäuren Salzsäure, Schwefelsäure und Salpetersäure bzw. deren Mischungen eingesetzt werden. Geeignete Basen stammen aus der Gruppe der Alkali- und Erdalkalimetallhydroxide und -carbonate, insbesondere der Alkalimetallhydroxide, von denen Kaliumhydroxid und vor allem Natriumhydroxid bevorzugt ist. Besonders bevorzugt ist allerdings flüchtiges Alkali, beispielsweise in Form von Ammoniak und/oder Alkanolaminen, die bis zu 9 C-Atome im Molekül enthalten können. Das Alkanolamin ist hierbei vorzugsweise ausgewählt aus der Gruppe bestehend aus Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen.In general, the pH of the dishwashing detergent can be adjusted by means of customary pH regulators, the pH value being chosen as a function of the desired intended use. In various embodiments, the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, particularly preferably greater than 7, very particularly preferably greater than 7.5 and in particular greater than 8, 5. Usually, a dishwasher detergent, for example a tablet, while a pH greater than 10, and in a preferred embodiment, the rinse liquor, when using the dishwashing agent, has a pH of between 9 and 10, for example 9.5.
The pH adjusting agents are acids and / or alkalis, preferably 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 amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. 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. However, particularly preferred is 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.
Zur Einstellung und/oder Stabilisierung des pH-Werts kann das erfindungsgemäße Mittel auch ein oder mehrere Puffersubstanzen (INCI Buffering Agents) enthalten, üblicherweise in Mengen von 0,001 bis 5 Gew.-%. Bevorzugt sind Puffersubstanzen, die zugleich Komplexbildner oder sogar Chelatbildner (Chelatoren, INCI Chelating Agents) sind. Besonders bevorzugte Puffersubstanzen sind die Citronensäure bzw. die Citrate, insbesondere die Natrium- und Kaliumcitrate, beispielsweise Trinatriumcitrat·2H2O und Trikaliumcitrat·H2O.To adjust and / or stabilize the pH, the composition according to the invention may also contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred 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.
Glaskorrosionsinhibitoren verhindern das Auftreten von Trübungen, Schlieren und Kratzern aber auch das Irisieren der Glasoberfläche von maschinell gereinigten Gläsern. Bevorzugte Glaskorrosionsinhibitoren stammen aus der Gruppe der Magnesium- und Zinksalze sowie der Magnesium- und Zinkkomplexe. Im Rahmen der vorliegenden Erfindung beträgt der Gehalt an Zinksalz in Geschirrspülmitteln vorzugsweise zwischen 0,1 bis 5 Gew.-%, bevorzugt zwischen 0,2 bis 4 Gew.-% und insbesondere zwischen 0,4 bis 3 Gew.-%, bzw. der Gehalt an Zink in oxidierter Form (berechnet als Zn2+) zwischen 0,01 bis 1 Gew.-%, vorzugsweise zwischen 0,02 bis 0,5 Gew.-% und insbesondere zwischen 0,04 bis 0,2 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Glaskorrosionsinhibitor-haltigen Mittels.Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in dishwashing detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt. the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.
Als Parfümöle bzw. Duftstoffe können im Rahmen der vorliegenden Erfindung einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen.As perfume oils or fragrances, individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pinien-, Citrus-, Jasmin-, Patchouli-, Rosen- oder Ylang-Ylang-Öl.Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
Weiterhin können Konservierungsmittel in den Mitteln enthalten sein. Geeignet sind beispielsweise Konservierungsmittel aus den Gruppen der Alkohole, Aldehyde, antimikrobiellen Säuren und/oder deren Salze, Carbonsäureester, Säureamide, Phenole, Phenolderivate, Diphenyle, Diphenylalkane, Harnstoffderivate, Sauerstoff-, Stickstoff-Acetale sowie -Formale, Benzamidine, Isothiazole und deren Derivate wie Isothiazoline und Isothiazolinone, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chinoline, 1,2-Dibrom-2,4-dicyanobutan, Iodo-2-propynyl-butyl-carbamat, Iod, lodophore und Peroxide. Bevorzugte antimikrobielle Wirkstoffe werden vorzugsweise ausgewählt aus der Gruppe umfassend Ethanol, n-Propanol, i-Propanol, 1,3-Butandiol, Phenoxyethanol, 1,2-Propylenglykol, Glycerin, Undecylensäure, Zitronensäure, Milchsäure, Benzoesäure, Salicylsäure, Thymol, 2-Benzyl-4-chlorphenol, 2,2'-Methylen-bis-(6-brom-4-chlorphenol), 2,4,4'-Trichlor-2'-hydroxydiphenylether, N-(4-Chlorphenyl)-N-(3,4-dichlorphenyl)-harnstoff, N,N'-(1,10-decandiyldi-1-pyridinyl-4-yliden)-bis-(1-octanamin)-dihydrochlorid, N,N'-Bis-(4-Chlorphenyl)-3,12-diimino-2,4,11,13-tetraazatetradecandiimidamid, antimikrobielle quaternäre oberflächenaktive Verbindungen, Guanidine. Besonders bevorzugte Konservierungsmittel sind jedoch ausgewählt aus der Gruppe umfassend Salicylsäure, quaternäre Tenside, insbesondere Benzalkoniumchlorid und Isothiazole und deren Derivate wie Isothiazoline und Isothiazolinone.Furthermore, preservatives may be included in the compositions. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2 Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.
Lösemittel, die für die erfindungsgemäß eingesetzten Zusammensetzungen geeignet sind, sind neben Wasser als bevorzugtes Lösemittel generell mit Wasser mischbare organische Lösemittel, wie beispielsweise, ohne Einschränkung, Ethanol, Propanol, 1,2-Propandiol und Glycerin. In verschiedenen Ausführungsformen kann das Geschirrspülmittel ein wasserarmes, flüssiges Geschirrspülmittel sein und Wasser in Mengen bis maximal 25 Gew.-%, vorzugsweise bis 20 Gew.-% bezogen auf das Gesamtgewicht der Zusammensetzung enthalten.Solvents which are suitable for the compositions used according to the invention are, in addition to water as the preferred solvent, generally water-miscible organic solvents, such as, without limitation, ethanol, propanol, 1,2-propanediol and glycerol. In various embodiments, the dishwashing detergent may be a low-water, liquid dishwashing detergent containing water in amounts up to a maximum of 25% by weight, preferably up to 20% by weight, based on the total weight of the composition.
Der Ausdruck "wasserarm", wie hierin verwendet, bedeutet, dass die derart charakterisierte Zusammensetzung weniger als 25 Gew.-% Wasser, vorzugsweise weniger als 20 Gew.-% Wasser enthält. Insbesondere fallen unter diesen Begriff Zusammensetzungen, die 1 bis 20 Gew.-% Wasser enthalten. Der Wassergehalt wie hierin definiert bezieht sich auf den mittels der Karl Fischer Titration ermittelten Wassergehalt.The term "low in water" as used herein means that the composition thus characterized contains less than 25% by weight of water, preferably less than 20% by weight of water. In particular, this term covers compositions which contain from 1 to 20% by weight of water. The water content as defined herein refers to the water content determined by Karl Fischer titration.
Generell kann die Konfektionierung hierin beschriebener maschineller Geschirrspülmittel in unterschiedlicher Weise erfolgen. Die Mittel können in fester oder flüssiger sowie als Kombination fester und flüssiger Angebotsformen vorliegen. Als feste Angebotsformen eignen sich insbesondere Pulver, Granulate, Extrudate, Kompaktate, insbesondere Tabletten. Die flüssigen Angebotsformen auf Basis von Wasser und/oder organischen Lösungsmitteln können verdickt, in Form von Gelen vorliegen. Die Mittel können in Form einphasiger oder mehrphasiger Produkte konfektioniert werden. Die einzelnen Phasen mehrphasiger Mittel können gleiche oder unterschiedliche Aggregatzustände aufweisen.In general, the formulation of automatic dishwashing agents described herein can be carried out in different ways. The agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, in particular tablets, are particularly suitable as firm supply forms. The liquid ones Supply forms based on water and / or organic solvents may be thickened, in the form of gels. The agents can be formulated in the form of single-phase or multi-phase products. The individual phases of multiphase agents may have the same or different states of matter.
"Flüssig", wie hierin in Bezug auf das erfindungsgemäße Mittel verwendet, schließt daher alle fließfähigen Zusammensetzungen ein und erfasst insbesondere auch Gele und pastöse Zusammensetzungen."Liquid" as used herein with respect to the agent of the invention therefore includes all flowable compositions and, in particular, also encompasses gels and pasty compositions.
Die hierin beschriebenen Geschirrspülmittel sind vorzugsweise maschinelle Geschirrspülmittel, die in fester oder flüssiger Form vorliegen können. Besonders bevorzugt sind die im Folgenden beschriebenen festen Formkörper aber auch flüssige Mittel, insbesondere in Form von Gelen.The dishwashing agents described herein are preferably automatic dishwashing agents, which may be in solid or liquid form. However, the solid moldings described below are particularly preferably also liquid agents, in particular in the form of gels.
Die Geschirrspülmittel können als Formkörper vorliegen. Um den Zerfall solcher vorgefertigter Formkörper zu erleichtern, ist es möglich, Desintegrationshilfsmittel, so genannte Tablettensprengmittel, in diese Mittel einzuarbeiten, um die Zerfallszeiten zu verkürzen. Unter Tablettensprengmitteln bzw. Zerfallsbeschleunigern werden Hilfsstoffe verstanden, die für den raschen Zerfall von Tabletten in Wasser oder anderen Medien und für die zügige Freisetzung der Wirkstoffe sorgen. Bevorzugt können Desintegrationshilfsmittel in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 3 bis 7 Gew.-% und insbesondere 4 bis 6 Gew.-%, jeweils bezogen auf das Gesamtgewicht des desintegrationshilfsmittelhaltigen Mittels, eingesetzt werden.The dishwashing detergents can be present as shaped bodies. In order to facilitate the disintegration of such prefabricated shaped bodies, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients. Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
Die hierin beschriebenen Geschirrspülmittel werden vorzugsweise zu Dosiereinheiten vorkonfektioniert. Diese Dosiereinheiten umfassen vorzugsweise die für einen Reinigungsgang notwendige Menge an wasch- oder reinigungsaktiven Substanzen. Bevorzugte Dosiereinheiten weisen ein Gewicht zwischen 12 und 30 g, bevorzugt zwischen 14 und 26 g und insbesondere zwischen 16 und 22 g auf. Das Volumen der vorgenannten Dosiereinheiten sowie deren Raumform sind mit besonderem Vorzug so gewählt, dass eine Dosierbarkeit der vorkonfektionierten Einheiten über die Dosierkammer einer Geschirrspülmaschine gewährleistet ist. Das Volumen der Dosiereinheit beträgt daher bevorzugt zwischen 10 und 35 ml, vorzugsweise zwischen 12 und 30 ml.The dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g. The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.
Die Geschirrspülmittel, insbesondere die vorgefertigten Dosiereinheiten, können eine wasserlösliche Umhüllung aufweisen.The dishwashing agents, in particular the prefabricated metering units, may have a water-soluble coating.
Die wasserlösliche Umhüllung wird vorzugsweise aus einem wasserlöslichen Folienmaterial, welches ausgewählt ist aus der Gruppe, bestehend aus Polymeren oder Polymergemischen, gebildet. Die Umhüllung kann aus einer oder aus zwei oder mehr Lagen aus dem wasserlöslichen Folienmaterial gebildet werden. Das wasserlösliche Folienmaterial der ersten Lage und der weiteren Lagen, falls vorhanden, kann gleich oder unterschiedlich sein. Besonders bevorzugt sind Folien, die beispielsweise zu Verpackungen wie Schläuchen oder Kissen verklebt und/oder versiegelt werden können, nachdem sie mit einem Mittel befüllt wurden.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 Foils that can be glued and / or sealed to packages such as tubing or cushions, for example, after being filled with an agent.
Die wasserlösliche Verpackung kann eine oder mehr Kammern aufweisen. Das Mittel kann in einer oder mehreren Kammern, falls vorhanden, der wasserlöslichen Umhüllung enthalten sein. Die Menge an Mittel entspricht vorzugsweise der vollen oder halben Dosis, die für einen Spülgang benötigt wird.
Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält. Wasserlösliche Umhüllungen, die Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthalten, weisen eine gute Stabilität bei einer ausreichend hohen Wasserlöslichkeit, insbesondere Kaltwasserlöslichkeit, auf.The water soluble package may have one or more chambers. The agent may be contained in one or more chambers, if any, of the water soluble envelope. The amount of agent preferably corresponds to the full or half dose needed for a rinse.
It is preferable that 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.
Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 10.000 bis 1.000.000 gmol-1, vorzugsweise von 20.000 bis 500.000 gmol-1, besonders bevorzugt von 30.000 bis 100.000 gmol-1 und insbesondere von 40.000 bis 80.000 gmol-1 liegt.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 .
Die Herstellung von Polyvinylalkohol geschieht üblicherweise durch Hydrolyse von Polyvinylacetat, da der direkte Syntheseweg nicht möglich ist. Ähnliches gilt für Polyvinylalkoholcopolymere, die aus entsprechend aus Polyvinylacetatcopolymeren hergestellt werden. Bevorzugt ist, wenn wenigstens eine Lage der wasserlöslichen Umhüllung einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht.The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to 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%.
Einem zur Herstellung der wasserlöslichen Umhüllung geeignetem Polyvinylalkohol-enthaltendem Folienmaterial kann zusätzlich ein Polymer ausgewählt aus der Gruppe umfassend (Meth)Acrylsäure-haltige (Co)Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether, Polymilchsäure oder Mischungen der vorstehenden Polymere zugesetzt sein. Ein bevorzugtes zusätzliches Polymer sind Polymilchsäuren.In addition, a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above may be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers. A preferred additional polymer is polylactic acids.
Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol Dicarbonsäuren als weitere Monomere. Geeignete Dicarbonsäuren sind Itaconsäure, Malonsäure, Bernsteinsäure und Mischungen daraus, wobei Itaconsäure bevorzugt ist.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.
Ebenfalls bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesättigte Carbonsäure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Polyvinylalkoholcopolymere neben Vinylalkohol Acrylsäure, Methacrylsäure, Acrylsäureester, Methacrylsäureester oder Mischungen daraus.Also 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.
Es kann bevorzugt sein, dass das Folienmaterial weitere Zusatzstoffe enthält. Das Folienmaterial kann beispielsweise Weichmacher wie Dipropylenglycol, Ethylenglycol, Diethylenglycol, Propylenglycol, Glycerin, Sorbitol, Mannitol oder Mischungen daraus enthalten. Weitere Zusatzstoffe umfassen beispielsweise Freisetzungshilfen, Füllmittel, Vernetzungsmittel, Tenside, Antioxidationsmittel, UV-Absorber, Antiblockmittel, Antiklebemittel oder Mischungen daraus.It may be preferred that 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.
Geeignete wasserlösliche Folien zum Einsatz in den wasserlöslichen Umhüllungen der wasserlöslichen Verpackungen gemäß der Erfindung sind Folien, die von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8630, C8400 oder M8900 vertrieben werden. Andere geeignete Folien umfassen Folien mit der Bezeichnung Solublon® PT, Solublon® GA, Solublon® KC oder Solublon® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray.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.
Ein weiterer Gegenstand dieser Anmeldung ist ein maschinelles Geschirrspülverfahren zur Reinigung von Geschirr, wobei ein erfindungsgemäßes Geschirrspülmittel zum Einsatz kommt.A further subject of this application is a machine dishwashing process for the cleaning of dishes, wherein a dishwasher detergent according to the invention is used.
Bei diesem Verfahren wird das erfindungsgemäße Mittel während des Durchlaufens eines Geschirrspülprogramms vor Beginn des Hauptspülgangs oder im Verlaufe des Hauptspülgangs in den Innenraum einer Geschirrspülmaschine eindosiert. Die Eindosierung bzw. der Eintrag des erfindungsgemäßen Mittels in den Innenraum der Geschirrspülmaschine kann manuell erfolgen, vorzugsweise wird das Mittel jedoch mittels der Dosierkammer in den Innenraum der Geschirrspülmaschine dosiert.In this method, the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the start of the main wash cycle or during the main wash cycle. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.
Bevorzugt sind maschinelle Geschirrspülverfahren, bei welchen die Reinigung bei einer Temperatur im Bereich von 30 °C bis 70 °C, bevorzugt von 35 °C bis 60 °C, besonders bevorzugt von 35 °C bis 50 °C, insbesondere bevorzugt bei 40 bis 45 °C erfolgt.Preference is given to automatic dishwashing processes in which the cleaning takes place at a temperature in the range from 30 ° C to 70 ° C, preferably from 35 ° C to 60 ° C, more preferably from 35 ° C to 50 ° C, particularly preferably from 40 to 45 ° C takes place.
Ein weiterer Gegenstand der Erfindung ist die Verwendung von mindestens einem Sorbitanester als enzymverstärkendes und bleicheverstärkendes Mittel und/oder zur Verbesserung der Klarspülleistung, bevorzugt in erfindungsgemäßen maschinellen Geschirrspülmitteln und/oder in erfindungsgemäßen maschinellen Geschirrspülverfahren.Another object of the invention is the use of at least one sorbitan ester as an enzyme-enhancing and bleach-enhancing agent and / or to improve the rinsing performance, preferably in automatic dishwashing detergents according to the invention and / or automatic dishwashing processes according to the invention.
Die im Kontext mit den erfindungsgemäßen Mitteln beschriebenen Ausführungsformen sind ohne Weiteres auch auf die erfindungsgemäßen Verfahren und Verwendungen übertragbar und umgekehrt.The embodiments described in context with the agents according to the invention are readily transferable to the methods and uses of the invention and vice versa.
Es wurde ein festes Reinigungsmittel mit der folgenden Zusammensetzung hergestellt:
Das Geschirrspülverfahren wurde in einer Geschirrspülmaschine Bosch® SMS68m62 (Programm: 40 °C, 8 min Haltezeit, Programmdauer 57 min) bei einer Wasserhärte von 21° deutscher Härte nach der IKW Methode durchgeführt.The dishwashing process was carried out in a dishwasher Bosch® SMS68m62 (program: 40 ° C, 8 min holding time, program duration 57 min) with a water hardness of 21 ° German hardness according to the IKW method.
Diese
Die Auswertung der Reinigungsleistung erfolgte visuell gemäß einer Skala von 1 bis 10, wobei der Wert 10 die beste Note ist (kein erkennbarer Rückstand). Es erfolgten Wiederholungen mit jeweils 6 internen Replikaten pro Maschine. Die angegebenen Ergebnisse sind die Mittelwerte der MehrfachbestimmungenThe evaluation of the cleaning performance was carried out visually according to a scale of 1 to 10, with the value 10 being the best grade (no discernible residue). There were repetitions with 6 internal replicates per machine. The results given are the means of multiple determinations
Das Reinigungsmittel 1 entsprach der oben genannten Zusammensetzung. Versuch V1 stellt somit das Vergleichsbeispiel dar.The detergent 1 corresponded to the above-mentioned composition. Experiment V1 thus represents the comparative example.
Im Versuch E2 wurde 1 Gew.-% Tween 40LQ der Firma Croda bezogen auf das Gesamtgewicht des Reinigungsmittels in das Reinigungsmittel aus V1 eingearbeitet.
E2: V1 + 1 Gew.-% Tween 40LQ (bezogen auf das Gesamtgewicht des Reinigungsmittels)
E2: V1 + 1% by weight Tween 40LQ (based on the total weight of the cleaning agent)
Wie aus der beigefügten Tabelle zu erkennen ist, führt die Verwendung von Tween 40LQ zu einer verbesserten Reinigung von hartnäckigen Tee- und Hackfleischanschmutzungen gegenüber dem kommerziell erhältlichen Geschirrspülmittel.As can be seen from the attached table, the use of Tween 40LQ results in improved cleaning of stubborn tea and mince stains as compared to the commercially available dishwashing detergent.
Zur Bestimmung des Klarspüleffekts werden ausgewählte und definierte Geschirrteile 4-mal gespült und nach dem 2., 3. und 4. Spülzyklus visuell abgemustert. Der erste Spülgang dient zur Konditionierung der Geschirrteile. Als Kenngrößen werden Klarspülnoten auf Basis des optischen Erscheinungsbildes des trockenen Spülguts (Porzellan, Gläser, Kunststoffteile und Edelstahl) vergeben. Pro Spülgang werden 100 g Schmutz dosiert, um eine normal verschmutzte Beladung zu simulieren.To determine the rinse effect, selected and defined dishes are rinsed 4 times and visually scrapped after the 2nd, 3rd and 4th rinse cycles. The first rinse is used to condition the dishes. Rinse rinses based on the visual appearance of the dry items to be washed (porcelain, glasses, plastic parts and stainless steel) are assigned as parameters. Per rinse 100 g of dirt are dosed to simulate a normally dirty load.
Es wurde eine haushaltsübliche Geschirrspülmaschine (Miele® GSL) im 50 °C-Programm (50 °C, 8 min Haltezeit, 65 °C Klarspültemperatur) bei einer Wasserhärte von 21° deutscher Härte verwendet.A standard household dishwashing machine (Miele® GSL) was used in the 50 ° C program (50 ° C, 8 min holding time, 65 ° C rinse temperature) with a water hardness of 21 ° German hardness.
Nach Beendigung des Spülzyklus wird die Maschine 30 min vollständig geöffnet und anschließend im schwarzen Kasten (schwarz gestrichener Raum, D6500 Tageslichtlampe) der Klarspüleffekt visuell bestimmt. Auf dem Geschirr und Besteck werden verbliebene eingetrocknete Wassertropfen, Schlieren, Beläge und Filme auf einer Skala von 1 bis 5 bewertet. 5 bedeutet keine Tropfen/Filme, 1 bedeutet starke Tropfen/Filmbildung.
V2: V1 - 1 Gew.-% Niotensid (bezogen auf das Gesamtgewicht des Reinigungsmittels)
E1: V2 + 1 Gew.-% Tween 40LQ (bezogen auf das Gesamtgewicht des Reinigungsmittels)
V2: V1 - 1% by weight of nonionic surfactant (based on the total weight of the cleaning agent)
E1: V2 + 1% by weight Tween 40LQ (based on the total weight of the cleaning agent)
Es ist klar zu sehen, dass die erfindungsgemäße Kombination im Vergleich zu den Vergleichsversuchen zu einer Verbesserung beim Filming (Schlieren) auf Kunststoff führt.It can be clearly seen that the combination according to the invention leads to an improvement in the filming (striae) on plastic in comparison with the comparative experiments.
Claims (14)
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DE102017223123.8A DE102017223123A1 (en) | 2017-12-18 | 2017-12-18 | Machine dishwashing detergent with improved rinsing and cleaning performance, method using this agent and use of the agent |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5154850A (en) * | 1989-07-18 | 1992-10-13 | Kao Corporation | Neutral liquid detergent composition |
EP0736594A1 (en) * | 1995-04-03 | 1996-10-09 | The Procter & Gamble Company | Soaker compositions |
EP0861885A1 (en) * | 1997-02-27 | 1998-09-02 | The Procter & Gamble Company | Soaker compositions |
US20060019864A1 (en) * | 2004-07-24 | 2006-01-26 | Goldschmidt Gmbh | Aqueous detergent concentrates for rough, especially profiled tiles and flags |
US20100234271A1 (en) * | 2008-08-26 | 2010-09-16 | Scheuing David R | Natural cleaners |
WO2013139842A1 (en) * | 2012-03-20 | 2013-09-26 | Bernd Schwegmann Gmbh & Co. Kg | Microemulsion-based cleaning agent |
US20160160158A1 (en) * | 2013-07-04 | 2016-06-09 | Basf Se | Process for cleaning dishware |
-
2017
- 2017-12-18 DE DE102017223123.8A patent/DE102017223123A1/en not_active Withdrawn
-
2018
- 2018-11-15 EP EP18206516.9A patent/EP3502220A1/en not_active Withdrawn
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US5154850A (en) * | 1989-07-18 | 1992-10-13 | Kao Corporation | Neutral liquid detergent composition |
EP0736594A1 (en) * | 1995-04-03 | 1996-10-09 | The Procter & Gamble Company | Soaker compositions |
EP0861885A1 (en) * | 1997-02-27 | 1998-09-02 | The Procter & Gamble Company | Soaker compositions |
US20060019864A1 (en) * | 2004-07-24 | 2006-01-26 | Goldschmidt Gmbh | Aqueous detergent concentrates for rough, especially profiled tiles and flags |
US20100234271A1 (en) * | 2008-08-26 | 2010-09-16 | Scheuing David R | Natural cleaners |
WO2013139842A1 (en) * | 2012-03-20 | 2013-09-26 | Bernd Schwegmann Gmbh & Co. Kg | Microemulsion-based cleaning agent |
US20160160158A1 (en) * | 2013-07-04 | 2016-06-09 | Basf Se | Process for cleaning dishware |
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