EP3712236A1 - Improvement to the solubility of different surfactant systems by use of phosphonates - Google Patents
Improvement to the solubility of different surfactant systems by use of phosphonates Download PDFInfo
- Publication number
- EP3712236A1 EP3712236A1 EP19164067.1A EP19164067A EP3712236A1 EP 3712236 A1 EP3712236 A1 EP 3712236A1 EP 19164067 A EP19164067 A EP 19164067A EP 3712236 A1 EP3712236 A1 EP 3712236A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- dishwashing detergent
- surfactant
- complexing agent
- detergent according
- 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.)
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Links
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 23
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 230000006872 improvement Effects 0.000 title description 2
- 239000003599 detergent Substances 0.000 claims abstract description 62
- 238000004851 dishwashing Methods 0.000 claims abstract description 61
- 239000008139 complexing agent Substances 0.000 claims abstract description 17
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 17
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- -1 ether sulfates Chemical class 0.000 claims description 34
- 102000004190 Enzymes Human genes 0.000 claims description 32
- 108090000790 Enzymes Proteins 0.000 claims description 32
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- 150000001298 alcohols Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
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- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 claims description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- OSCJHTSDLYVCQC-UHFFFAOYSA-N 2-ethylhexyl 4-[[4-[4-(tert-butylcarbamoyl)anilino]-6-[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)NC(C)(C)C)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 OSCJHTSDLYVCQC-UHFFFAOYSA-N 0.000 description 4
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- YBYRMVIVWMBXKQ-UHFFFAOYSA-N phenylmethanesulfonyl fluoride Chemical compound FS(=O)(=O)CC1=CC=CC=C1 YBYRMVIVWMBXKQ-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 150000003871 sulfonates Chemical class 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
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- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 3
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- 239000000872 buffer Substances 0.000 description 3
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- 239000002738 chelating agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 3
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- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
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- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
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- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/75—Amino oxides
-
- 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 is directed to a dishwashing detergent containing a complexing agent and at least one surfactant.
- the present invention also relates to the use of the dishwashing detergent according to the invention for the manual cleaning of dishes.
- Dishwashing detergents in particular liquid dishwashing detergents for manual cleaning of dishes, are known.
- Organic solvents are added to such dishwashing detergents in order to improve the flow behavior and in particular the solubility of surfactants in the dishwashing detergents.
- This object was surprisingly achieved by the inventors of the present invention by providing a dishwashing detergent which contains a surfactant system which, in addition to an anionic or nonionic surfactant, has a complexing agent with a phosphonate group as a structural element. It was surprisingly found that the addition of such a complexing agent achieved an improvement in the solubility of the surfactant system and consequently organic solvents could be saved. By reducing organic solvents, the manufacturing process for the dishwashing detergents of the present invention can also be shortened.
- the present invention is therefore directed to a dishwashing detergent, preferably hand dishwashing detergent, comprising (A) a complexing agent; and (B) optionally at least one anionic surfactant; and (C) optionally at least one nonionic surfactant; with the proviso that at least one surfactant (B) or (C) is present, and that the complex former (A) has a phosphonate group as a structural element.
- the present invention is also directed to the use of the dishwasher detergent according to the invention for the manual cleaning of dishes.
- At least one refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with constituents of the compounds described herein, this indication does not refer to the absolute amount of molecules, but to the type of constituent. “At least one surfactant” therefore means, for example, that only one type of surfactant compound or several different types of surfactant compounds can be included without specifying the amount of the individual compounds.
- the expression “essentially free from” means that the respective compound can in principle be included, but is then present in an amount that does not impair the function of the other components.
- the property “essentially free of” a certain compound is therefore preferably a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of dishwashing detergent.
- molecular weight relates to the weight average molecular weight in g / mol, unless the number average molecular weight is explicitly mentioned.
- Molecular weights are preferably determined by means of GPC using polystyrene standards.
- fatty acids or fatty alcohols or their derivatives - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms.
- oxo-alcohols or derivatives thereof obtainable, for example, by ROELEN's oxo synthesis, can also be used accordingly.
- components of the present agents are salts, they are preferably alkali metal or alkaline earth metal salts of the respective compounds, more preferably the alkali metal salts, in particular the sodium or potassium salts, most preferably sodium salts thereof.
- alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient to balance the charge - as the anion.
- the expression that the "complexing agent has a phosphonate group as a structural element" is to be understood in connection with the present invention to the effect that the complexing agent is structurally derived from phosphonic acid or phosphonate, i.e. that the complexing agent has phosphonic acid or phosphonate itself as structural elements or structures derived therefrom (derivatives) which are formally represented by substitution of residues and / or addition of residues to phosphonic acid or phosphonate.
- the complexing agent is preferably an amine methylene phosphonic acid, ie a phosphonic acid bound to an amine nitrogen via a C1 unit.
- the complexing agent is more preferably diethylenetriaminepentakis (methylenephosphonic acid):
- diethylenetriaminepentakis (methylenephosphonic acid) does not exclude that one or more or even all of the acid functions are present as salts, alkaline earths and Alkali metal salts are preferred, with alkali metal salts being most preferred, especially sodium and potassium salts, especially sodium salts.
- the complexing agent is preferably present in an amount of 0.1 to 10% by weight, more preferably in an amount of 0.5 to 3% by weight and even more preferably in an amount of 0.5 to 2% by weight. % based on the total amount of dishwashing detergent.
- the dishwashing detergent according to the invention comprises a surfactant system.
- the totality of the surfactants contained in the dishwashing detergent is referred to as the surfactant system, the surfactant system according to the invention comprising or consisting of at least one anionic surfactant or at least one nonionic surfactant.
- the dishwashing detergent according to the invention is essentially free of cationic surfactants.
- anionic surfactants known for dishwashing detergents are suitable as anionic surfactants. This is preferably contained in 1 to 50% by weight, preferably 2 to 40% by weight, more preferably 5 to 35% by weight, based on the total weight of the dishwashing detergent; and or
- the anionic surfactant can be an alpha-olefin sulfonate.
- This can be selected from known alpha-olefin sulfonates.
- it is selected from C 10-20 alpha olefin sulfonates, more preferably from linear C 10-20 alpha olefin sulfonates.
- it is selected from C 12-14 alpha olefin sulfonates; most preferably it is a linear C 12-14 alpha olefin sulfonate.
- a suitable alpha-olefin sulfonate is commercially available, for example, under the trade name Bio-Terge® AS-40 from Stephan.
- the at least one anionic surfactant is selected from ether sulfates, alkylbenzenesulfonates, alkyl sulfates and mixtures thereof.
- Preferred ether sulfates are those of the formula (I) R 1 -O- (AO) n -SO 3 - X + (I).
- R 1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly 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, the representatives with an even number of C- Atoms are preferred.
- Especially preferred radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
- X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na + or K + , Na + being extremely preferred. Further cations X + can be selected from NH 4 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ , and mixtures thereof.
- AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group.
- the index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
- the further anionic surfactant is selected from linear or branched alkylbenzenesulfonates of the formula A-1
- R 'and R represent, independently of one another, H or a linear C 2-18 alkyl radical, at least one radical not being H. It is particularly preferred cumene sulfonate.
- anionic surfactants are the alkyl sulfates of the formula R 2 -O-SO 3 - X + (II).
- R 2 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
- Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and their Mixtures, the representatives with an even number of carbon atoms being preferred.
- radicals R 2 are derived from C 12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10-20 oxo alcohols.
- X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na + or K +, Na + being extremely preferred. Further cations X + can be selected from NH 4 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ , and mixtures thereof.
- the at least one nonionic surfactant is contained in 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, based on the total weight of the dishwashing detergent .
- nonionic surfactants known for dishwashing detergents are suitable as nonionic surfactants.
- the at least one nonionic surfactant is selected from amine oxides, alkoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, alkyl glycosides and alkoxylated alcohols and mixtures thereof.
- the at least one nonionic surfactant is selected from amine oxides, i.e. compounds which have the formula R 1 R 2 R 3 NO, in which each R 1 , R 2 and R 3 independently of the others is an optionally substituted, for example hydroxy-substituted, C 1 -C 30 hydrocarbon chain can be used.
- amine oxides are those in which R 1 is C 12 -C 18 alkyl and R 2 and R 3 are each independently C 1 -C 4 alkyl, in particular C 12 -C 18 alkyldimethylamine oxides.
- amine oxides are N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide.
- C 12 -C 18 alkyldimethylamine oxides or mixtures which also contain C 16 and C 18 alkyldimethylamine oxides are preferred over C 12 -C 14 alkyldimethylamine oxides.
- amine oxides in which R 1 also comprises C 16 and C 18 radicals are generally preferred over those in which R 1 only comprises C 12-14 radicals.
- the amine oxides used therefore contain at least 20% by weight, preferably at least 30% by weight, even more preferably at least 40% by weight, most preferably at least 50% by weight, 60% by weight, 70% by weight. -% or 80% by weight of C 16-18 amine oxides based on the total weight of the amine oxides.
- the remainder of the amine oxides can consist of C 12-14 amine oxides. It has been shown that such long-chain amine oxides are superior to the shorter-chain amine oxides in terms of cleaning performance, in particular in the surfactant combination described.
- the nonionic surfactant is preferably selected from C 12-18 amine oxides, in particular from C 12-18 alkyldimethylamine oxides.
- nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
- surfactants are the polyhydroxy fatty acid amides known as PHFA.
- alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- the nonionic surfactants are selected from the group of alkoxylated alcohols.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) or propylene oxide (PO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2 -Position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
- EO ethylene oxide
- PO propylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
- the total amount of surfactants i. of the surfactant system, based on the weight of the agent, 2.5 to 70% by weight, preferably 5 to 50% by weight, more preferably 6 to 40% by weight.
- the dishwashing detergent according to the present invention can also contain at least one additional ingredient selected from the group consisting of water, organic solvents, enzymes, additives to improve the drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, Pearlescent agents, dyes, corrosion inhibitors, preservatives, bitter substances, organic salts, Contain disinfectants, structure-giving polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for the skin.
- at least one additional ingredient selected from the group consisting of water, organic solvents, enzymes, additives to improve the drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, Pearlescent agents, dyes, corrosion inhibitors, preservatives, bitter substances, organic salts, Contain disinfectants, structure-giving polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for the skin.
- the dishwashing detergents according to the present invention are liquid and contain water as the main solvent, i. they are aqueous dishwashing detergents.
- the water content of the aqueous agent according to the invention is usually 15 to 90% by weight, preferably 20 to 50% by weight. In various embodiments, the water content is more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 25% by weight, based in each case on the total amount of dishwashing detergent.
- Organic solvents can also be added to the dishwashing detergent.
- Suitable organic solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range.
- the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ether, butyl glycol propyl ether, ethylene glycol ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl
- the dishwashing detergents described herein can also contain at least one enzyme, preferably a protease.
- the proteases used are preferably alkaline serine proteases. They act as unspecific endopeptidases, that is, they hydrolyze any acid amide bonds that are inside peptides or proteins and thereby break down protein-containing soiling on the items to be cleaned. Their pH optimum is usually in the clearly alkaline range.
- subtilisin 309 examples of the proteases that can be used in the agents described herein are subtilisin 309 or functional fragments / variants thereof and variants of the alkaline protease from Bacillus lentus or variants thereof.
- Subtilisin 309 is sold under the trade name Savinase® by Novozymes A / S, Bagsvaerd, Denmark.
- Optimized enzyme variants of the subtilisin 309 from Bacillus lentus are available from the Novozymes company under the trade names Blaze® and Ovozyme®, which represent a preferred embodiment of the invention.
- the protease variants sold under the name BLAP® are derived from the alkaline protease from Bacillus lentus DSM 5483.
- Protease variants are particularly preferred here which have at least one mutation at R99 compared to the BLAP wt (wild type) enzyme, in the count according to BLAP wt, in particular R99E or R99D, particularly preferred is R99E, and optionally additionally at least one or two , preferably all three of the amino acid substitutions S3T, V4I and V199I, particularly preferred are the BLAP variants as they are in SeqID No 4 or 5 of the WO 2014/177430 are described.
- the enzymes to be used can also be packaged together with accompanying substances, for example from fermentation.
- the enzymes are preferably used as liquid enzyme formulation (s).
- the proteases are not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
- These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.
- the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
- Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be used in superimposed layers 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 are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.
- Dishwashing detergents according to the invention can alternatively or in addition to the at least one protease contain one or more further enzymes, in particular from the following group: amylases, hemicellulases, cellulases, lipases and oxidoreductases.
- the dishwashing detergent according to the invention particularly preferably also contains at least one amylase.
- the amylase (s) is preferably an ⁇ -amylase.
- the hemicellulase is preferably a ⁇ -glucanase, a pectinase, a pullulanase and / or a mannanase.
- the cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase.
- the oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
- the enzymes mentioned can all be packaged as described above for the proteases.
- the at least one enzyme preferably the at least one protease and / or at least one amylase, is in an amount of 0.01-1.6% by weight, preferably 0.05-1.2% by weight based on the total weight of the dishwashing detergent.
- the enzyme (s) can be pre-formulated with enzyme stabilizers in an enzyme composition.
- the enzyme protein usually only forms a fraction of the total weight of the enzyme preparation.
- Preferably used enzyme 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 wt .-% % of the enzyme protein.
- an enzyme stabilizer can be included in the enzyme composition in an amount of 0.05-35% by weight, preferably 0.05-10% by weight, based on the total weight.
- This enzyme composition can then be used in dishwashing detergents according to the invention, specifically in amounts which lead to the final concentrations specified above in the dishwashing detergent.
- Suitable enzyme stabilizers are known in the art.
- the agent according to the invention can accordingly additionally have one or more enzyme stabilizers.
- the protein concentration can be determined with the aid of known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method.
- the active protein concentration is determined in this regard by titrating the active centers using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).
- a suitable irreversible inhibitor for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)
- the agent according to the invention can contain one or more additives from the group of polymers and builders, usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4 % By weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2% by weight, extremely preferably 0.5 to 1.5% by weight, for example 1% by weight.
- Polymeric thickeners for the purposes of the present invention are the polycarboxylates that act as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, especially heteropolysaccharides, and other conventional thickening polymers.
- Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar and their mixtures.
- Other polysaccharide thickeners such as starches or cellulose derivatives, can be used as an alternative, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g.
- Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI Carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
- a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
- Particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C 1-4 alkanols (INCI Acrylates Copolymer) which include copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, including the copolymers of C 10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C 14 alkanols formed, esters (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) belong.
- the content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, particularly preferably between 0.5 and 6% by weight, in particular between 1 and 5% by weight and extremely preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight, based on the total weight of the dishwashing detergent.
- one or more dicarboxylic acids and / or their salts can be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as e.g. is available under the trade name Sokalan® DSC. They are advantageously used in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1.3 to 6% by weight and particularly preferably 2 to 4% by weight, based on the total weight of the dishwashing detergent.
- the agent according to the invention is preferably free from dicarboxylic acid (salts).
- auxiliaries and additives customary in hand dishwashing detergents in particular UV stabilizers, perfume, pearlescent agents (INCI Opacifying Agents; for example glycol distearate, e.g. Cutina® AGS from Cognis, or mixtures containing this, e.g.
- the pH of the agent according to the invention can be adjusted by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, with a range from 4 to 9, preferably 5 to 8.5, in particular 5.5 to 8, is preferred.
- acids such as mineral acids or citric acid
- alkalis such as sodium or potassium hydroxide
- the dishwashing detergent according to the invention also contains potassium acetate.
- the agent according to the invention can contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, in particular 0 0.1 to 2% by weight, particularly preferably 0.05 to 1% by weight, extremely preferably 0.1 to 0.5% by weight, for example 0.2% by weight.
- buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents).
- Particularly preferred buffer substances are 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.
- the agent according to the invention can be used for the manual cleaning of dishes.
- the dishwashing detergent is produced using customary and known methods and processes.
- DTPMP i.e. Diethylenetriaminepentakis (methylenephosphonic acid, used (Dequest 2066; Italmatch Chemicals).
- a dishwashing detergent was produced by mixing the components listed in Table 1.
- the dishwashing detergent of Example 1 showed good solubility, prevented undesired skin formation and showed a clear appearance.
- the pH was 7.9 with the pH adjustment being made using citric acid.
- a dishwashing detergent was produced by mixing the components listed in Table 2. The composition skinned and had poor solubility. The pH was 7.9 with the pH adjustment being made using citric acid.
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Abstract
Handgeschirrspülmittel, enthaltend(A) ein Komplexbildner; und(B) gegebenenfalls mindestens ein anionisches Tensid; und(C) gegebenenfalls mindestens ein nichtionisches Tensid;mit der Maßgabe, dass mindestens ein Tensid (B) oder (C) vorliegt, und dass der Komplexbildner eine Phosphonat Gruppe als Strukturelement aufweist.Verwendung des Geschirrspülmittels zum manuellen Reinigen von Geschirr.Hand dishwashing detergents containing (A) a complexing agent; and (B) optionally at least one anionic surfactant; and (C) optionally at least one nonionic surfactant; with the proviso that at least one surfactant (B) or (C) is present and that the complexing agent has a phosphonate group as a structural element. Use of the dishwashing detergent for manual cleaning of dishes.
Description
In einem ersten Aspekt richtet sich die vorliegende Erfindung auf ein Geschirrspülmittel enthaltend einen Komplexbildner und wenigstens ein Tensid. Ferner betrifft die vorliegende Erfindung die Verwendung des erfindungsgemäßen Geschirrspülmittels zum manuellen Reinigen von Geschirr.In a first aspect, the present invention is directed to a dishwashing detergent containing a complexing agent and at least one surfactant. The present invention also relates to the use of the dishwashing detergent according to the invention for the manual cleaning of dishes.
Geschirrspülmittel, insbesondere flüssige Geschirrspülmittel für die manuelle Reinigung von Geschirr sind bekannt. Organischen Lösungsmittel werden solchen Geschirrspülmitteln zugesetzt, um das Fließverhalten und insbesondere die Löslichkeit von Tensiden in den Geschirrspülmitteln zu verbessern. Im Hinblick auf die Nachhaltigkeit, Verträglichkeit mit der Haut und einen einfacheren Herstellungsprozess wäre es wünschenswert, Geschirrspülmittel mit einem möglichst geringen Anteil an organischen Lösungsmitteln herzustellen.Dishwashing detergents, in particular liquid dishwashing detergents for manual cleaning of dishes, are known. Organic solvents are added to such dishwashing detergents in order to improve the flow behavior and in particular the solubility of surfactants in the dishwashing detergents. With a view to sustainability, compatibility with the skin and a simpler manufacturing process, it would be desirable to manufacture dishwashing detergents with the lowest possible proportion of organic solvents.
Diese Aufgabe wurde von den Erfindern der vorliegenden Erfindung überraschend durch das Bereitstellen eines Geschirrspülmittels, welches ein Tensidsystem enthält, welches neben einem anionischen oder nichtionischen Tensid einen Komplexbildner mit einer Phosphonat Gruppe als Strukturelement aufweist, gelöst. Es wurde überraschend gefunden, dass durch die Zugabe eines solchen Komplexbildners eine Verbesserung der Löslichkeit des Tensidsystems erreicht wurde und folglich organische Lösungsmittel eingespart werden konnten. Durch die Verminderung von organischen Lösungsmitteln kann zudem der Herstellungsprozess für die Geschirrspülmittel der vorliegenden Erfindung verkürzt werden.This object was surprisingly achieved by the inventors of the present invention by providing a dishwashing detergent which contains a surfactant system which, in addition to an anionic or nonionic surfactant, has a complexing agent with a phosphonate group as a structural element. It was surprisingly found that the addition of such a complexing agent achieved an improvement in the solubility of the surfactant system and consequently organic solvents could be saved. By reducing organic solvents, the manufacturing process for the dishwashing detergents of the present invention can also be shortened.
In einem ersten Aspekt richtet sich die vorliegende Erfindung daher auf ein Geschirrspülmittel, bevorzugt Handgeschirrspülmittel, enthaltend (A) ein Komplexbildner; und (B) gegebenenfalls mindestens ein anionisches Tensid; und (C) gegebenenfalls mindestens ein nichtionisches Tensid; mit der Maßgabe, dass mindestens ein Tensid (B) oder (C) vorliegt, und dass der Komplexbilder (A) eine Phosphonat Gruppe als ein Strukturelement aufweist.In a first aspect, the present invention is therefore directed to a dishwashing detergent, preferably hand dishwashing detergent, comprising (A) a complexing agent; and (B) optionally at least one anionic surfactant; and (C) optionally at least one nonionic surfactant; with the proviso that at least one surfactant (B) or (C) is present, and that the complex former (A) has a phosphonate group as a structural element.
In einem weiteren Aspekt richtet sich die vorliegende Erfindung ferner auf die Verwendung des erfindungsgemäßen Geschirrspülmittels zur manuellen Reinigung von Geschirr.In a further aspect, the present invention is also directed to the use of the dishwasher detergent according to the invention for the manual cleaning of dishes.
"Mindestens ein", wie hierin verwendet, bezieht sich auf 1 oder mehr, beispielsweise 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Im Zusammenhang mit Bestandteilen der hierin beschriebenen Verbindungen bezieht sich diese Angabe nicht auf die absolute Menge an Molekülen, sondern auf die Art des Bestandteils. "Mindestens ein Tensid" bedeutet daher beispielsweise, dass nur eine Art von Tensidverbindung oder mehrere verschiedene Arten von Tensidverbindungen, ohne Angaben über die Menge der einzelnen Verbindungen zu machen, enthalten sein können."At least one" as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with constituents of the compounds described herein, this indication does not refer to the absolute amount of molecules, but to the type of constituent. “At least one surfactant” therefore means, for example, that only one type of surfactant compound or several different types of surfactant compounds can be included without specifying the amount of the individual compounds.
Alle im Zusammenhang mit den hierin beschriebenen Geschirrspülmitteln angegeben Mengenangaben beziehen sich, sofern nichts anderes angegeben ist, auf Gew.-% jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels. Des Weiteren beziehen sich derartige Mengenangaben, die sich auf mindestens einen Bestandteil beziehen, immer auf die Gesamtmenge dieser Art von Bestandteil, die in dem Geschirrspülmittel enthalten ist, sofern nicht explizit etwas anderes angegeben ist. Das heißt, dass sich derartige Mengenangaben, beispielsweise im Zusammenhang mit "mindestens einem Tensid", auf die Gesamtmenge von Tensiden, welche in dem Geschirrspülmittel enthalten sind, bezieht, wenn nicht explizit etwas anderes angegeben ist.Unless stated otherwise, all of the quantities given in connection with the dishwashing detergents described herein relate to% by weight in each case based on the total weight of the dishwashing detergent. Furthermore, quantities of this type which relate to at least one constituent always relate to the total quantity of this type of constituent contained in the dishwashing detergent, unless explicitly stated otherwise. This means that such quantities, for example in connection with “at least one surfactant”, refer to the total amount of surfactants contained in the dishwashing detergent, unless explicitly stated otherwise.
Zahlenwerte, die hierin ohne Dezimalstellen angegeben sind, beziehen sich jeweils auf den vollen angegebenen Wert mit einer Dezimalstelle. So steht beispielsweise "99%" für "99,0%".Numerical values given herein without decimal places refer to the full value given with one decimal place. For example, "99%" stands for "99.0%".
Der Ausdrücke "ungefähr" "ca." oder "etwa", in Zusammenhang mit einem Zahlenwert, bezieht sich auf eine Varianz von ±10% bezogen auf den angegebenen Zahlenwert, bevorzugt ±5%, besonders bevorzugt ±1%.The terms "about" "about" or “about”, in connection with a numerical value, relates to a variance of ± 10% based on the specified numerical value, preferably ± 5%, particularly preferably ± 1%.
Der Ausdruck "im Wesentlichen frei von" bedeutet, dass die jeweilige Verbindung grundsätzlich enthalten sein kann, dann allerdings in einer Menge vorliegt, die eine Funktion der anderen Komponenten nicht beeinträchtigt. Im Rahmen der vorliegenden Erfindung wird daher unter der Eigenschaft "im Wesentlichen frei von" einer bestimmten Verbindung bevorzugt ein Gesamtgewicht von unter 0,1 Gew.-%, stärker bevorzugt unter 0,001 Gew.-%, insbesondere frei von dieser, bezogen auf das Gesamtgewicht des Geschirrspülmittels, angesehen.The expression “essentially free from” means that the respective compound can in principle be included, but is then present in an amount that does not impair the function of the other components. In the context of the present invention, the property “essentially free of” a certain compound is therefore preferably a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of dishwashing detergent.
Numerische Bereiche, die in dem Format "in/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.Numeric ranges given in the format "in / from x to y" include the stated values. If several preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also recorded.
Angaben über das Molekulargewicht beziehen sich auf das gewichtsmittlere Molekulargewicht in g/mol, falls nicht explizit das zahlenmittlere Molekulargewicht genannt ist. Molekulargewichte werden bevorzugt mittels GPC unter Verwendung von Polystyrol-Standards ermittelt.Information on the molecular weight relates to the weight average molecular weight in g / mol, unless the number average molecular weight is explicitly mentioned. Molecular weights are preferably determined by means of GPC using polystyrene standards.
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, fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms. In particular, the oxo-alcohols or derivatives thereof obtainable, for example, by ROELEN's oxo synthesis, can also be used accordingly.
Sind Bestandteile der vorliegenden Mittel Salze, so handelt es sich dabei bevorzugt um Alkalimetall- oder Erdalkalimetallsalze der jeweiligen Verbindungen, stärker bevorzugt um die Alkalimetallsalze, insbesondere um die Natrium- oder Kaliumsalze, am stärksten bevorzugt Natriumsalze, davon. 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.If components of the present agents are salts, they are preferably alkali metal or alkaline earth metal salts of the respective compounds, more preferably the alkali metal salts, in particular the sodium or potassium salts, most preferably sodium salts thereof. Whenever alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient to balance the charge - as the anion.
In der vorliegenden Erfindung sind substituierte Reste bevorzugt solche Reste, in welchen der Substituent ausgewählt ist aus -F, -Cl, -Br, -OH, -OC1-4Alkyl, =O, -NH2, oder -N(C1-4Alkyl)2, bevorzugt ersetzt dabei der Substituent ein oder mehrere H Atome.In the present invention, substituted radicals are preferably those radicals in which the substituent is selected from -F, -Cl, -Br, -OH, -OC 1-4 alkyl, = O, -NH 2 , or -N (C 1 -4 alkyl) 2 , the substituent preferably replacing one or more H atoms.
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 oder jede Ausführungsform aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Beispielweise können beschriebene Merkmale oder Ausführungsformen der Geschirrspülmittel auch auf die beanspruchten Verwendungen angewendet werden, und umgekehrt. 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.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. Each feature or each embodiment from one aspect of the invention can be used in any other aspect of the invention. For example, described features or embodiments of the dishwashing detergents can also be applied to the claimed uses, and vice versa. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to restrict it, and in particular the invention is not limited to these examples.
Der Ausdruck, dass der "Komplexbildner eine Phosphonat Gruppe als Strukturelement aufweist" ist im Zusammenhang mit der vorliegenden Erfindung dahingehend zu verstehen, dass sich der Komplexbildner strukturell von Phosphonsäure oder Phosphonat ableitet, d.h. dass der Komplexbildner Phosphonsäure oder Phosphonat selbst als Strukturelemente aufweist oder aber hiervon abgeleitete Strukturen (Derivate), die sich formal durch Substitution von Resten und/oder Hinzufügung von Resten zu Phosphonsäure bzw. Phosphonat darstellen.The expression that the "complexing agent has a phosphonate group as a structural element" is to be understood in connection with the present invention to the effect that the complexing agent is structurally derived from phosphonic acid or phosphonate, i.e. that the complexing agent has phosphonic acid or phosphonate itself as structural elements or structures derived therefrom (derivatives) which are formally represented by substitution of residues and / or addition of residues to phosphonic acid or phosphonate.
Der Komplexbildner ist bevorzugt eine Aminmethylenphosphonsäure, also eine über eine C1 Einheit an einen Aminstickstoff angebundene Phosphonsäure. Der Komplexbildner ist weiter bevorzugt Diethylentriaminpentakis(methylenphosphonsäure):
Der Begriff Diethylentriaminpentakis(methylenphosphonsäure) schließt nicht aus, dass ein oder mehrere oder gar alle der Säurefunktionen als Salze vorliegen, wobei Erdalkali und Alkalimetallsalze bevorzugt sind, wobei am meisten Alkalimetallsalze bevorzugt sind, insbesondere Natrium- und Kaliumsalze, insbesondere Natriumsalze.The term diethylenetriaminepentakis (methylenephosphonic acid) does not exclude that one or more or even all of the acid functions are present as salts, alkaline earths and Alkali metal salts are preferred, with alkali metal salts being most preferred, especially sodium and potassium salts, especially sodium salts.
Der Komplexbildner ist bevorzugt in einer Menge von 0,1 bis 10 Gew.-% vorhanden, weiter bevorzugt in einer Menge von 0,5 bis 3 Gew.-% und noch weiter bevorzugt in einer Menge von 0,5 bis 2 Gew.-% bezogen auf Gesamtmenge an Geschirrspülmittel.The complexing agent is preferably present in an amount of 0.1 to 10% by weight, more preferably in an amount of 0.5 to 3% by weight and even more preferably in an amount of 0.5 to 2% by weight. % based on the total amount of dishwashing detergent.
Das erfindungsgemäße Geschirrspülmittel umfasst ein Tensidsystem. Als Tesidsystem wird die Gesamtheit der in dem Geschirrspülmittel enthaltenen Tenside bezeichnet, wobei das Tensidsystem erfindungsgemäß mindestens ein anionisches Tensid oder mindestens ein nichtionisches Tensid umfasst oder daraus besteht.The dishwashing detergent according to the invention comprises a surfactant system. The totality of the surfactants contained in the dishwashing detergent is referred to as the surfactant system, the surfactant system according to the invention comprising or consisting of at least one anionic surfactant or at least one nonionic surfactant.
Das erfindungsgemäße Geschirrspülmittel ist in einer bevorzugten Ausführungsform im Wesentlichen frei von kationischen Tensiden.In a preferred embodiment, the dishwashing detergent according to the invention is essentially free of cationic surfactants.
Als anionische Tenside sind alle für Geschirrspülmittel bekannten anionischen Tenside geeignet. Dieses ist bevorzugt in 1 bis 50 Gew.-%, bevorzugt 2 bis 40 Gew.-%, stärker bevorzugt in 5 bis 35 Gew.-%, basierend auf dem Gesamtgewicht des Geschirrspülmittels enthalten ist; und/oderAll anionic surfactants known for dishwashing detergents are suitable as anionic surfactants. This is preferably contained in 1 to 50% by weight, preferably 2 to 40% by weight, more preferably 5 to 35% by weight, based on the total weight of the dishwashing detergent; and or
Das anioinische Tensid kann ein alpha-Olefinsulfonat sein. Dieses kann dabei aus bekannten alpha-Olefinsulfonaten ausgewählt werden. Bevorzugt ist es ausgewählt aus C10-20 alpha-Olefinsulfonaten, stärker bevorzugt aus linearen C10-20 alpha-Olefinsulfonaten. Insbesondere ist es ausgewählt aus C12-14 alpha-Olefinsulfonaten; am stärksten bevorzugt ist es ein lineares C12-14 alpha-Olefinsulfonat. Ein geeignetes alpha-Olefinsulfonat ist beispielsweise unter dem Handelsnahmen Bio-Terge® AS-40 der Firma Stephan kommerziell erhältlich.The anionic surfactant can be an alpha-olefin sulfonate. This can be selected from known alpha-olefin sulfonates. Preferably it is selected from C 10-20 alpha olefin sulfonates, more preferably from linear C 10-20 alpha olefin sulfonates. In particular, it is selected from C 12-14 alpha olefin sulfonates; most preferably it is a linear C 12-14 alpha olefin sulfonate. A suitable alpha-olefin sulfonate is commercially available, for example, under the trade name Bio-Terge® AS-40 from Stephan.
In einer Ausführungsform ist das mindestens eine anionische Tensid ausgewählt aus Ethersulfaten, Alkylbenzolsulfonaten, Alkylsulfaten und Mischungen davon.In one embodiment, the at least one anionic surfactant is selected from ether sulfates, alkylbenzenesulfonates, alkyl sulfates and mixtures thereof.
Bevorzugte Ethersulfate sind solche der Formel (I)
R1-O-(AO)n-SO3 -X+ (I).
Preferred ether sulfates are those of the formula (I)
R 1 -O- (AO) n -SO 3 - X + (I).
In dieser Formel (I) steht R1 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest, 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 (I), R 1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly 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, the representatives with an even number of C- Atoms are preferred. Especially preferred radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
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.X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na + or K + , Na + being extremely preferred. Further cations X + can be selected from NH 4 + , ½Zn 2+ , ½Mg 2+ , ½Ca 2+ , ½Mn 2+ , and mixtures thereof.
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.AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
Bevorzugt sind Fettalkoholethersulfate der Formel I-1
In einer bevorzugten Ausführungsform ist das weitere anionische Tensid ausgewählt aus linearen oder verzweigten Alkylbenzolsulfonaten der Formel A-1
In der R' und R" unabhängig voneinander H oder einen linearen C2-18 Alkylrest darstellen, wobei mindesten ein Rest nicht H ist. Besonders bevorzugt ist es Cumolsulfonat.In which R 'and R "represent, independently of one another, H or a linear C 2-18 alkyl radical, at least one radical not being H. It is particularly preferred cumene sulfonate.
Weitere geeignete anionischen Tenside sind die Alkylsulfate der Formel
R2-O-SO3 -X+ (II).
Further suitable anionic surfactants are the alkyl sulfates of the formula
R 2 -O-SO 3 - X + (II).
In dieser Formel (II) steht R2 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest, vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R2 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 R2 sind abgeleitet von C12-18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von C10-20-Oxoalkoholen.In this formula (II), R 2 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and their Mixtures, the representatives with an even number of carbon atoms being preferred. Particularly preferred radicals R 2 are derived from C 12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10-20 oxo alcohols.
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.X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na + or K +, Na + being extremely preferred. Further cations X + can be selected from NH 4 + , ½Zn 2+ , ½Mg 2+ , ½Ca 2+ , ½Mn 2+ , and mixtures thereof.
Falls vorhanden, so ist das mindestens eine nichtionische Tensid in 0,1 bis 20 Gew.-%, bevorzugt 0,5 bis 10 Gew.-%, stärker bevorzugt in 1 bis 8 Gew.-%, basierend auf dem Gesamtgewicht des Geschirrspülmittels enthalten.If present, the at least one nonionic surfactant is contained in 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, based on the total weight of the dishwashing detergent .
Als nichtionische Tenside sind alle für Geschirrspülmittel bekannten nichtionischen Tenside geeignet.All nonionic surfactants known for dishwashing detergents are suitable as nonionic surfactants.
In einer Ausführungsform ist das mindestens eine nichtionische Tensid ausgewählt aus Aminoxiden, alkoxylierten Fettsäurealkylestern, Polyhydroxyfettsäureamiden, Alkylglykosiden und alkoxylierten Alkoholen und Mischungen davon.In one embodiment, the at least one nonionic surfactant is selected from amine oxides, alkoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, alkyl glycosides and alkoxylated alcohols and mixtures thereof.
In einer bevorzugten Ausführungsform ist das mindestens eine nichtionische Tensid ausgewählt aus Aminoxiden, also Verbindungen, die die Formel R1R2R3NO aufweisen, worin jedes R1, R2 und R3 unabhängig von den anderen eine gegebenenfalls substituierte, beispielsweise Hydroxysubstituierte, C1-C30 Kohlenwasserstoffkette ist, einsetzbar. Besonders bevorzugt eingesetzte Aminoxide sind solche in denen R1 C12-C18 Alkyl und R2 und R3 jeweils unabhängig C1-C4 Alkyl sind, insbesondere C12-C18 Alkyldimethylaminoxide. Beispielhafte Vertreter geeigneter Aminoxide sind N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid. C12-C18 Alkyldimethylaminoxide bzw. Mischungen, die auch C16 und C18-Alkyldimethylaminoxide enthalten, sind gegenüber C12-C14 Alkyldimethylaminoxiden bevorzugt. In gleicher Art und Weise sind generell Aminoxide in denen R1 auch C16- und C18-Reste umfasst gegenüber solchen, in denen R1 nur C12-14 Reste umfasst, bevorzugt. In verschiedenen Ausführungsformen enthalten die eingesetzten Aminoxide daher mindestens 20 Gew.-%, vorzugsweise mindestens 30 Gew.-%, noch bevorzugter mindestens 40 Gew.-%, am bevorzugtesten mindestens 50 Gew.-%, 60 Gew.-%, 70 Gew.-% oder 80 Gew.-% C16-18 Aminoxide bezogen auf das Gesamtgewicht der Aminoxide. In solchen Ausführungsformen kann der Rest der Aminoxide aus C12-14 Aminoxiden bestehen. Es hat sich gezeigt, dass solche langkettigen Aminoxide den kürzerkettigen im Hinblick auf die Reinigungsleistung, insbesondere in der beschriebenen Tensidkombination, überlegen sind.In a preferred embodiment, the at least one nonionic surfactant is selected from amine oxides, i.e. compounds which have the formula R 1 R 2 R 3 NO, in which each R 1 , R 2 and R 3 independently of the others is an optionally substituted, for example hydroxy-substituted, C 1 -C 30 hydrocarbon chain can be used. Particularly preferably used amine oxides are those in which R 1 is C 12 -C 18 alkyl and R 2 and R 3 are each independently C 1 -C 4 alkyl, in particular C 12 -C 18 alkyldimethylamine oxides. Exemplary representatives of suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide. C 12 -C 18 alkyldimethylamine oxides or mixtures which also contain C 16 and C 18 alkyldimethylamine oxides are preferred over C 12 -C 14 alkyldimethylamine oxides. In the same way, amine oxides in which R 1 also comprises C 16 and C 18 radicals are generally preferred over those in which R 1 only comprises C 12-14 radicals. In various embodiments, the amine oxides used therefore contain at least 20% by weight, preferably at least 30% by weight, even more preferably at least 40% by weight, most preferably at least 50% by weight, 60% by weight, 70% by weight. -% or 80% by weight of C 16-18 amine oxides based on the total weight of the amine oxides. In such embodiments, the remainder of the amine oxides can consist of C 12-14 amine oxides. It has been shown that such long-chain amine oxides are superior to the shorter-chain amine oxides in terms of cleaning performance, in particular in the surfactant combination described.
Bevorzugt ist das nichtionische Tensid ausgewählt aus C12-18 Aminoxiden, insbesondere aus C12-18 Alkyldimethylaminoxiden.The nonionic surfactant is preferably selected from C 12-18 amine oxides, in particular from C 12-18 alkyldimethylamine oxides.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette.Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
Weitere geeignete Tenside sind die als PHFA bekannten Polyhydroxyfettsäureamide.Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
Ebenfalls geeignet sind 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.Also suitable are alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
In einer Ausführungsform sind die nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole ausgewählt. Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C- Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) oder Propylenoxid (PO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum Beispielaus Kokos-, Palm-, Talgfett oder Oleylalkohol, und durchschnittlich 2 bis 8 Mol EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO oder 4 EO, C8-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 5 EO.In one embodiment, the nonionic surfactants are selected from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) or propylene oxide (PO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2 -Position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
In verschiedenen Ausführungsformen beträgt die Gesamtmenge der Tenside, d.h. des Tensidsystems, bezogen auf das Gewicht des Mittels 2,5 bis 70 Gew.-%, vorzugsweise 5 bis 50 Gew.-%, noch bevorzugter 6 bis 40 Gew.-%.In various embodiments, the total amount of surfactants, i. of the surfactant system, based on the weight of the agent, 2.5 to 70% by weight, preferably 5 to 50% by weight, more preferably 6 to 40% by weight.
Das Geschirrspülmittel gemäß der vorliegenden Erfindung kann ferner mindestens einen zusätzlichen Inhaltsstoff ausgewählt aus der Gruppe bestehend aus Wasser, organischen Lösungsmitteln, Enzymen, Additiven zur Verbesserung des Ablauf- und Trocknungsverhaltens, zur Einstellung der Viskosität und/oder zur Stabilisierung, UV-Stabilisatoren, Parfüm, Perlglanzmitteln, Farbstoffen, Korrosionsinhibitoren, Konservierungsmitteln, Bitterstoffen, organischen Salzen, Desinfektionsmitteln, strukturgebenden Polymeren, Entschäumern, verkapselten Inhaltsstoffen, pH-Stellmitteln sowie Hautgefühl-verbessernden oder pflegenden Additiven enthalten.The dishwashing detergent according to the present invention can also contain at least one additional ingredient selected from the group consisting of water, organic solvents, enzymes, additives to improve the drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, Pearlescent agents, dyes, corrosion inhibitors, preservatives, bitter substances, organic salts, Contain disinfectants, structure-giving polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for the skin.
In einer Ausführungsform sind die Geschirrspülmittel gemäß der vorliegenden Erfindung flüssig und enthalten Wasser als Hauptlösungsmittel, d.h. es handelt sich um wässrige Geschirrspülmittelmittel. Der Wassergehalt des erfindungsgemäßen wässrigen Mittels beträgt üblicherweise 15 bis 90 Gew.-%, vorzugsweise 20 bis 50 Gew.-%. In verschiedenen Ausführungsformen beträgt der Wassergehalt mehr als 5 Gew.-%, bevorzugt mehr als 15 Gew.-% und insbesondere bevorzugt mehr als 25 Gew.-%, jeweils bezogen auf die Gesamtmenge an Geschirrspülmittel.In one embodiment, the dishwashing detergents according to the present invention are liquid and contain water as the main solvent, i. they are aqueous dishwashing detergents. The water content of the aqueous agent according to the invention is usually 15 to 90% by weight, preferably 20 to 50% by weight. In various embodiments, the water content is more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 25% by weight, based in each case on the total amount of dishwashing detergent.
Daneben können dem Geschirrspülmittel organische Lösungsmittel zugesetzt werden. Geeignete organische Lösungsmittel umfassen ein- oder mehrwertige Alkohole, Alkanolamine oder Glykolether, sofern sie im angegebenen Konzentrationsbereich mit Wasser mischbar sind. Vorzugsweise werden die Lösungsmittel ausgewählt aus Ethanol, n-Propanol, i-Propanol, Butanolen, Glykol, Propandiol, Butandiol, Methylpropandiol, Glycerin, Diglykol, Propyldiglycol, Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykolmethylether, Diethylenglykolethylether, Propylenglykolmethylether, Propylenglykolethylether, Propylenglykolpropylether, Dipropylenglykolmonomethylether, Dipropylenglykolmonoethylether, Methoxytriglykol, Ethoxytriglykol, Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen-glykol-t-butylether, Di-n-octylether sowie Mischungen dieser Lösungsmittel.Organic solvents can also be added to the dishwashing detergent. Suitable organic solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ether, butyl glycol propyl ether, ethylene glycol ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, 1-butoxyethoxy-2-propanol, propylene-butoxyethoxy-2-propanol, propylene-butoxy-3-butyl ether, and mixtures of these n-butoxyethoxy-2-propanol, 3-butyl-3-butylether, propylene-propylene, propylene-octanol, propylene-octanol, 3-butyl ether, di-propylene-butyl-3-ether, propylene-octanolether, propylene-octanolether, di-propylene-butyl-3-ether, propylene glycol monomethyl ether, Solvent.
Die hierin beschriebenen Geschirrspülmittel können in verschiedenen Ausführungsformen ferner mindestens ein Enzym, vorzugsweise eine Protease enthalten. Die eingesetzten Proteasen sind vorzugsweise alkalische Serin-Proteasen. Sie wirken als unspezifische Endopeptidasen, das heißt, sie hydrolysieren beliebige Säureamidbindungen, die im Inneren von Peptiden oder Proteinen liegen und bewirken dadurch den Abbau proteinhaltiger Anschmutzungen auf dem Reinigungsgut. Ihr pH-Optimum liegt meist im deutlich alkalischen Bereich.In various embodiments, the dishwashing detergents described herein can also contain at least one enzyme, preferably a protease. The proteases used are preferably alkaline serine proteases. They act as unspecific endopeptidases, that is, they hydrolyze any acid amide bonds that are inside peptides or proteins and thereby break down protein-containing soiling on the items to be cleaned. Their pH optimum is usually in the clearly alkaline range.
Bei den erfindungsgemäß bevorzugt eingesetzten Proteasen handelt es sich vorzugsweise um eine Serin-Protease, insbesondere um eine Subtilase, besonders bevorzugt um ein Subtilisin. Das Subtilisin kann dabei ein Wildtypenzym oder eine Subtilisin-Variante sein, wobei das Wildtypenzym bzw. das Ausgangsenzym der Variante vorzugsweise aus einer der folgenden ausgewählt ist:
- der Alkalischen Protease aus Bacillus amyloliquefaciens (BPN'),
- der Alkalischen Protease aus Bacillus licheniformis (Subtilisin Carlsberg),
- der Alkalischen Protease PB92,
- Subtilisin 147 und/oder 309 (Savinase)
- der Alkalischen Protease aus Bacillus lentus, vorzugsweise aus Bacillus lentus (DSM 5483),
- der Alkalischen Protease aus Bacillus alcalophilus (DSM 11233),
- der Alkalischen Protease aus Bacillus gibsonii (DSM 14391) oder einer hierzu mindestens zu 70% identischen Alkalischen Protease,
- der Alkalischen Protease aus Bacillus sp. (DSM 14390) oder einer hierzu mindestens zu 98,5% identischen Alkalischen Protease, und
- der Alkalischen Protease aus Bacillus sp. (DSM 14392) oder einer hierzu mindestens zu 98,1 % identischen Alkalischen Protease.
- the alkaline protease from Bacillus amyloliquefaciens (BPN '),
- the alkaline protease from Bacillus licheniformis (subtilisin Carlsberg),
- the alkaline protease PB92,
- Subtilisin 147 and / or 309 (Savinase)
- the alkaline protease from Bacillus lentus, preferably from Bacillus lentus (DSM 5483),
- the alkaline protease from Bacillus alcalophilus (DSM 11233),
- the alkaline protease from Bacillus gibsonii (DSM 14391) or an alkaline protease that is at least 70% identical to this,
- the alkaline protease from Bacillus sp. (DSM 14390) or an alkaline protease that is at least 98.5% identical to this, and
- the alkaline protease from Bacillus sp. (DSM 14392) or an alkaline protease that is at least 98.1% identical to this.
Beispiele für die in den hierin beschriebenen Mitteln einsetzbaren Proteasen sind Subtilisin 309 oder funktionale Fragmente/Varianten davon und Varianten der Alkalischen Protease aus Bacillus lentus oder Varianten davon. Subtilisin 309 wird unter dem Handelsnamen Savinase® von der Firma Novozymes A/S, Bagsvaerd, Dänemark vertrieben. Von dem Subtilisin 309 aus Bacillus lentus sind unter den Handelsnamen Blaze® und Ovozyme® von der Firma Novozymes optimierte Enzymvarianten erhältlich, die eine bevorzugte Ausführungsform der Erfindung darstellen. Von der Alkalischen Protease aus Bacillus lentus DSM 5483 leiten sich beispielsweise die unter der Bezeichnung BLAP® geführten Protease-Varianten ab. Bevorzugt sind hier insbesondere solche Protease-Varianten, die gegenüber dem BLAP wt (Wildtyp) Enzym, in der Zählung gemäß BLAP wt, mindestens eine Mutation an R99 aufweisen, insbesondere R99E oder R99D, insbesondere bevorzugt ist R99E, sowie optional zusätzlich mindestens eine oder zwei, vorzugsweise alle drei der Aminosäuresubstitutionen S3T, V4I und V199I aufweist, insbesondere bevorzugt sind die BLAP-Varianten, wie sie in SeqID No 4 oder 5 der
In den hierin beschriebenen Geschirrspülmitteln können die einzusetzenden Enzyme ferner zusammen mit Begleitstoffen, etwa aus der Fermentation, konfektioniert sein. In flüssigen Mitteln werden die Enzyme bevorzugt als Enzymflüssigformulierung(en) eingesetzt.In the dishwashing detergents described herein, the enzymes to be used can also be packaged together with accompanying substances, for example from fermentation. In liquid agents, the enzymes are preferably used as liquid enzyme formulation (s).
Die Proteasen 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.As a rule, the proteases are not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other 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 Chemikalienundurchlässigen 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 can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be used in superimposed layers 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 are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.
Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.Furthermore, it is possible to pack two or more enzymes together so that a single granulate has several enzyme activities.
Erfindungsgemäße Geschirrspülmittel können alternativ oder neben der mindestens einen Protease ein oder mehrere weitere Enzyme enthalten, insbesondere aus folgender Gruppe: Amylasen, Hemicellulasen, Cellulasen, Lipasen und Oxidoreduktasen.Dishwashing detergents according to the invention can alternatively or in addition to the at least one protease contain one or more further enzymes, in particular from the following group: amylases, hemicellulases, cellulases, lipases and oxidoreductases.
Das erfindungsgemäße Geschirrspülmittel enthält besonders bevorzugt ferner mindestens eine Amylase.The dishwashing detergent according to the invention particularly preferably also contains at least one amylase.
Bei der/den Amylase(n) handelt es sich vorzugsweise um eine α-Amylase. Bei der Hemicellulase handelt es sich vorzugsweise um eine β- Glucanase, eine Pektinase, eine Pullulanase und/oder eine Mannanase. Bei der Cellulase handelt es sich vorzugsweise um ein Cellulase-Gemisch oder eine Einkomponenten-Cellulase, vorzugsweise bzw. überwiegend um eine Endoglucanase und/oder eine Cellobiohydrolase. Bei der Oxidoreduktase handelt es sich vorzugsweise um eine Oxidase, insbesondere eine Cholin-Oxidase, oder um eine Perhydrolase. Die genannten Enzyme können alle wie oben für die Proteasen beschrieben konfektioniert sein.The amylase (s) is preferably an α-amylase. The hemicellulase is preferably a β-glucanase, a pectinase, a pullulanase and / or a mannanase. The cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase. The oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase. The enzymes mentioned can all be packaged as described above for the proteases.
In erfindungsgemäßen Geschirrspülmitteln, die in einer Ausführungsform in überwiegend flüssiger, pastöser oder Gelform vorliegen, ist das mindestens eine Enzym, vorzugsweise die mindestens eine Protease und/oder mindestens eine Amylase in einer Menge von 0,01 - 1,6 Gew.-%, vorzugsweise 0,05 - 1,2 Gew.-% bezogen auf das Gesamtgewicht des Geschirrspülmittels, in diesem enthalten.In dishwashing detergents according to the invention, which in one embodiment are predominantly liquid, pasty or gel form, the at least one enzyme, preferably the at least one protease and / or at least one amylase, is in an amount of 0.01-1.6% by weight, preferably 0.05-1.2% by weight based on the total weight of the dishwashing detergent.
In verschiedenen Ausführungsformen können das Enzym/die Enzyme mit Enzymstabilisatoren in einer Enzymzusammensetzung vorformuliert vorliegen. Das Enzym-Protein bildet dabei üblicherweise nur einen Bruchteil des Gesamtgewichts der Enzym-Zubereitung. Bevorzugt eingesetzte Enzymzubereitungen 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. In solchen Zusammensetzungen kann ein Enzymstabilisator in einer Menge von 0,05-35 Gew.-%, vorzugsweise 0,05-10 Gew.-%, bezogen auf das Gesamtgewicht, in der Enzymzusammensetzung enthalten sein. Diese Enzymzusammensetzung kann dann in erfindungsgemäßen Geschirrspülmitteln eingesetzt werden und zwar in Mengen, die zu den oben angegeben Endkonzentrationen im Geschirrspülmittel führen. Geeignete Enzymstabilisatoren sind im Stand der Technik bekannt. In verschiedenen Ausführungsformen kann das erfindungsgemäße Mittel dementsprechend zusätzlich einen oder mehrere Enzymstabilisatoren aufweisen.In various embodiments, the enzyme (s) can be pre-formulated with enzyme stabilizers in an enzyme composition. The enzyme protein usually only forms a fraction of the total weight of the enzyme preparation. Preferably used enzyme 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 wt .-% % of the enzyme protein. In such compositions, an enzyme stabilizer can be included in the enzyme composition in an amount of 0.05-35% by weight, preferably 0.05-10% by weight, based on the total weight. This enzyme composition can then be used in dishwashing detergents according to the invention, specifically in amounts which lead to the final concentrations specified above in the dishwashing detergent. Suitable enzyme stabilizers are known in the art. In various embodiments, the agent according to the invention can accordingly additionally have one or more enzyme stabilizers.
Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren (Bicinchoninsäure; 2,2'-Bichinolyl-4,4'-dicarbonsäure) oder dem Biuret-Verfahren bestimmt werden. Die Bestimmung der Aktivproteinkonzentration erfolgt diesbezüglich über eine Titration der aktiven Zentren unter Verwendung eines geeigneten irreversiblen Inhibitors (für Proteasen beispielsweise Phenylmethylsulfonylfluorid (PMSF)) und Bestimmung der Restaktivität (vgl.
Zur weiteren Verbesserung des Ablauf- und/oder Trocknungsverhaltens kann das erfindungsgemäße Mittel ein oder mehrere Additive aus der Gruppe der Polymere und der Buildersubstanzen (Builder) enthalten, üblicherweise in einer Menge von 0,001 bis 5 Gew.-%, vorzugsweise 0,01 bis 4 Gew.-%, insbesondere 0,1 bis 3 Gew.-%, besonders bevorzugt 0,2 bis 2 Gew.-%, äußerst bevorzugt 0,5 bis 1,5 Gew.-%, beispielsweise 1 Gew.-%.To further improve the drainage and / or drying behavior, the agent according to the invention can contain one or more additives from the group of polymers and builders, usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4 % By weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2% by weight, extremely preferably 0.5 to 1.5% by weight, for example 1% by weight.
Polymere Verdickungsmittel im Sinne der vorliegenden Erfindung sind die als Polyelektrolyte verdickend wirkenden Polycarboxylate, vorzugsweise Homo- und Copolymerisate der Acrylsäure, insbesondere Acrylsäure-Copolymere wie Acrylsäure-Methacrylsäure-Copolymere, und die Polysaccharide, insbesondere Heteropolysaccharide, sowie andere übliche verdickende Polymere.Polymeric thickeners for the purposes of the present invention are the polycarboxylates that act as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, especially heteropolysaccharides, and other conventional thickening polymers.
Geeignete Polysaccharide bzw. Heteropolysaccharide sind die Polysaccharidgummen, beispielsweise Gummi arabicum, Agar, Alginate, Carrageene und ihre Salze, Guar, Guaran, Tragacant, Gellan, Ramsan, Dextran oder Xanthan und ihre Derivate, z.B. propoxyliertes Guar, sowie ihre Mischungen. Andere Polysaccharidverdicker, wie Stärken oder Cellulosederivate, können alternativ, vorzugsweise aber zusätzlich zu einem Polysaccharidgummi eingesetzt werden, beispielsweise Stärken verschiedensten Ursprungs und Stärkederivate, z.B. Hydroxyethylstärke, Stärkephosphatester oder Stärkeacetate, oder Carboxymethylcellulose bzw. ihr Natriumsalz, Methyl-, Ethyl-, Hydroxyethyl-, Hydroxypropyl-, Hydroxypropyl-methyl- oder Hydroxyethyl-methyl-cellulose oder Celluloseacetat.Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used as an alternative, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g. Hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
Als polymere Verdickungsmittel geeignete Acrylsäure-Polymere sind beispielsweise hochmolekulare mit einem Polyalkenylpolyether, insbesondere einem Allylether von Saccharose, Pentaerythrit oder Propylen, vernetzte Homopolymere der Acrylsäure (INCI Carbomer), die auch als Carboxyvinylpolymere bezeichnet werden.Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI Carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
Besonders geeignete polymere Verdickungsmittel sind aber folgende Acrylsäure-Copolymere: (i) Copolymere von zwei oder mehr Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C1-4-Alkanolen gebildeten, Ester (INCI Acrylates Copolymer), zu denen etwa die Copolymere von Methacrylsäure, Butylacrylat und Methylmethacrylat (CAS 25035-69-2) oder von Butylacrylat und Methylmethacrylat (CAS 25852-37-3) gehören; (ii) vernetzte hochmolekulare Acrylsäurecopolymere, zu denen etwa die mit einem Allylether der Saccharose oder des Pentaerythrits vernetzten Copolymere von C10-30-Alkylacrylaten mit einem oder mehreren Monomeren aus der Gruppe der Acrylsäure, Methacrylsäure und ihrer einfachen, vorzugsweise mit C14-Alkanolen gebildeten, Ester (INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer) gehören.Particularly suitable polymeric thickeners, however, are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C 1-4 alkanols (INCI Acrylates Copolymer) which include copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, including the copolymers of C 10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C 14 alkanols formed, esters (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) belong.
Der Gehalt an polymerem Verdickungsmittel beträgt üblicherweise nicht mehr als 8 Gew.-%, vorzugsweise zwischen 0,1 und 7 Gew.-%, besonders bevorzugt zwischen 0,5 und 6 Gew.-%, insbesondere zwischen 1 und 5 Gew.-% und äußerst bevorzugt zwischen 1,5 und 4 Gew.-%, beispielsweise zwischen 2 und 2,5 Gew.-%, bezogen auf das Gesamtgewicht des Geschirrspülmittels.The content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, particularly preferably between 0.5 and 6% by weight, in particular between 1 and 5% by weight and extremely preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight, based on the total weight of the dishwashing detergent.
Zur Stabilisierung des erfindungsgemäßen Mittels, insbesondere bei hohem Tensidgehalt, können ein oder mehrere Dicarbonsäuren und/oder deren Salze zugesetzt werden, insbesondere eine Zusammensetzung aus Na-Salzen der Adipin-, Bernstein- und Glutarsäure, wie sie z.B. unter dem Handelsnamen Sokalan® DSC erhältlich ist. Der Einsatz erfolgt hierbei vorteilhafterweise in Mengen von 0,1 bis 8 Gew.-%, vorzugsweise 0,5 bis 7 Gew.-%, insbesondere 1,3 bis 6 Gew.-% und besonders bevorzugt 2 bis 4 Gew.-%, bezogen auf das Gesamtgewicht des Geschirrspülmittels.To stabilize the agent according to the invention, especially with a high surfactant content, one or more dicarboxylic acids and / or their salts can be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as e.g. is available under the trade name Sokalan® DSC. They are advantageously used in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1.3 to 6% by weight and particularly preferably 2 to 4% by weight, based on the total weight of the dishwashing detergent.
Kann jedoch auf deren Einsatz verzichtet werden, so ist das erfindungsgemäße Mittel vorzugsweise frei von Dicarbonsäure(salze)n.However, if their use can be dispensed with, the agent according to the invention is preferably free from dicarboxylic acid (salts).
Daneben können noch ein oder mehrere weitere - insbesondere in Handgeschirrspülmitteln - übliche Hilfs- und Zusatzstoffe, insbesondere UV-Stabilisatoren, Parfüm, Perlglanzmittel (INCI Opacifying Agents; beispielsweise Glykoldistearat, z.B. Cutina® AGS der Fa. Cognis, bzw. dieses enthaltende Mischungen, z.B. die Euperlane® der Fa. Cognis), Farbstoffe, Korrosionsinhibitoren, Konservierungsmittel (z.B. das technische auch als Bronopol bezeichnete 2-Brom-2-nitropropan-1 ,3-diol (CAS 52-51-7), das beispielsweise als Myacide® BT oder als Boots Bronopol BT von der Firma Boots gewerblich erhältlich ist) oder Acticide MBR 1, organische Salze, Desinfektionsmittel, pH-Stellmittel sowie Hautgefühl-verbessernde oder hautpflegende Additive (z.B. dermatologisch wirksame Substanzen wie Vitamin A, Vitamin B2, Vitamin B12, Vitamin C, Vitamin E, D-Panthenol, Sericerin, Collagen-Partial-Hydrolysat, verschiedene pflanzliche Protein-Partial-Hydrolysate, Proteinhydrolysat-Fettsäure-Kondensate, Liposome, Cholesterin, pflanzliche und tierische Öle wie z.B. Lecithin, Sojaöl, usw., Pflanzenextrakte wie z.B. Aloe Vera, Azulen, Hamamelisextrakte, Algenextrakte, usw., Allantoin, A.H.A.-Komplexe, Glycerin, Harnstoff, quaternisierte Hydroxyethylcellulose), in Mengen von üblicherweise nicht mehr als 5 Gew.-% enthalten sein, bezogen auf das Gesamtgewicht des Geschirrspülmittels.In addition, one or more other auxiliaries and additives customary in hand dishwashing detergents, in particular UV stabilizers, perfume, pearlescent agents (INCI Opacifying Agents; for example glycol distearate, e.g. Cutina® AGS from Cognis, or mixtures containing this, e.g. the Euperlane® from Cognis), dyes, corrosion inhibitors, preservatives (for example the technical 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), which is also known as bronopol, for example Myacide® BT or as Boots Bronopol BT is commercially available from Boots) or Acticide MBR 1, organic salts, disinfectants, pH adjusters and additives that improve or care for the skin (e.g. dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C. , Vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes, glycerine, urea, quaternized hydroxyethyl cellulose), in amounts usually not more than 5 % By weight, based on the total weight of the dishwashing detergent.
Der pH-Wert des erfindungsgemäßen Mittels kann mittels üblicher pH-Regulatoren, beispielsweise Säuren wie Mineralsäuren oder Citronensäure und/oder Alkalien wie Natrium- oder Kaliumhydroxid, eingestellt werden, wobei - insbesondere bei gewünschter Handverträglichkeit - ein Bereich von 4 bis 9, vorzugsweise 5 bis 8,5, insbesondere 5,5 bis 8, bevorzugt ist.The pH of the agent according to the invention can be adjusted by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, with a range from 4 to 9, preferably 5 to 8.5, in particular 5.5 to 8, is preferred.
In einer Ausführungsform enthält das erfindungsgemäße Geschirrspülmittel ferner Kaliumacetat.In one embodiment, the dishwashing detergent according to the invention also contains potassium acetate.
Zur Einstellung und/oder Stabilisierung des pH-Werts kann das erfindungsgemäße Mittel ein oder mehrere Puffer-Substanzen (INCI Buffering Agents) enthalten, üblicherweise in Mengen von 0,001 bis 5 Gew.-%, vorzugsweise 0,005 bis 3 Gew.-%, insbesondere 0,01 bis 2 Gew.-%, besonders bevorzugt 0,05 bis 1 Gew.-%, äußerst bevorzugt 0,1 bis 0,5 Gew.-%, beispielsweise 0,2 Gew.-%. Bevorzugt sind Puffer-Substanzen, die zugleich Komplexbildner oder sogar Chelatbildner (Chelatoren, INCI Chelating Agents) sind. Besonders bevorzugte Puffer-Substanzen sind die Citronensäure bzw. die Citrate, insbesondere die Natrium- und Kaliumcitrate, beispielsweise Trinatriumcitrat·2 H2O und Trikaliumcitrat·H2O.To adjust and / or stabilize the pH, the agent according to the invention can contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, in particular 0 0.1 to 2% by weight, particularly preferably 0.05 to 1% by weight, extremely preferably 0.1 to 0.5% by weight, for example 0.2% by weight. Preference is given to buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents). Particularly preferred buffer substances are 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.
Das erfindungsgemäße Mittel lässt sich zur manuellen Reinigung von Geschirr verwenden.The agent according to the invention can be used for the manual cleaning of dishes.
Die Herstellung des Geschirrspülmittels erfolgt mittels üblicher und bekannter Methoden und Verfahren.The dishwashing detergent is produced using customary and known methods and processes.
Alle Angaben beziehen sich auf die Aktivstoffmenge. Im vorliegenden Beispiel wurde DTPMP, d.h. Diethylentriaminpentakis(methylenphosphonsäure, verwendet (Dequest 2066; Italmatch Chemicals).All information relates to the amount of active ingredient. In the present example, DTPMP, i.e. Diethylenetriaminepentakis (methylenephosphonic acid, used (Dequest 2066; Italmatch Chemicals).
Es wurde ein Geschirrspülmittel durch Vermischen der in Tabelle 1 genannten Komponenten hergestellt. Das Geschirrspülmittel des Beispiels 1 zeigte eine gute Löslichkeit, verhindert eine unerwünschte Hautbildung und zeigte ein klares Erscheinungsbild. Der pH-Wert betrugt 7,9, wobei die pH-Wert Einstellung durch Verwenden von Citronensäure erfolgte.A dishwashing detergent was produced by mixing the components listed in Table 1. The dishwashing detergent of Example 1 showed good solubility, prevented undesired skin formation and showed a clear appearance. The pH was 7.9 with the pH adjustment being made using citric acid.
Im vorliegenden Vergleichsbeispiel wird kein DTPMP verwendet.In the present comparative example, no DTPMP is used.
Es wurde ein Geschirrspülmittel durch Vermischen der in Tabelle 2 genannten Komponenten hergestellt. Die Zusammensetzung zeigte eine Hautbildung und wies eine schlechte Löslichkeit auf. Der pH-Wert betrugt 7,9, wobei die pH-Wert Einstellung durch Verwenden von Citronensäure erfolgte.A dishwashing detergent was produced by mixing the components listed in Table 2. The composition skinned and had poor solubility. The pH was 7.9 with the pH adjustment being made using citric acid.
Claims (8)
Priority Applications (1)
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| EP19164067.1A EP3712236A1 (en) | 2019-03-20 | 2019-03-20 | Improvement to the solubility of different surfactant systems by use of phosphonates |
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| Application Number | Priority Date | Filing Date | Title |
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| EP19164067.1A EP3712236A1 (en) | 2019-03-20 | 2019-03-20 | Improvement to the solubility of different surfactant systems by use of phosphonates |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1218476A1 (en) * | 1999-09-16 | 2002-07-03 | The Procter & Gamble Company | Dishwashing detergent compositions containing color-stabilizing phosphonates |
| US20020193268A1 (en) * | 2000-02-08 | 2002-12-19 | The Procter & Gamble Company | Dishwashing detergent compositions containing color-stabilizing phosphonates |
| WO2014177430A1 (en) | 2013-04-30 | 2014-11-06 | Henkel Ag & Co. Kgaa | Cleaning agent containing proteases |
| US8901059B2 (en) * | 2009-06-19 | 2014-12-02 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
| US20180340138A1 (en) * | 2015-11-25 | 2018-11-29 | Henkel Ag & Co. Kgaa | Enzyme stabilizers |
-
2019
- 2019-03-20 EP EP19164067.1A patent/EP3712236A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1218476A1 (en) * | 1999-09-16 | 2002-07-03 | The Procter & Gamble Company | Dishwashing detergent compositions containing color-stabilizing phosphonates |
| US20020193268A1 (en) * | 2000-02-08 | 2002-12-19 | The Procter & Gamble Company | Dishwashing detergent compositions containing color-stabilizing phosphonates |
| US8901059B2 (en) * | 2009-06-19 | 2014-12-02 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
| WO2014177430A1 (en) | 2013-04-30 | 2014-11-06 | Henkel Ag & Co. Kgaa | Cleaning agent containing proteases |
| US20180340138A1 (en) * | 2015-11-25 | 2018-11-29 | Henkel Ag & Co. Kgaa | Enzyme stabilizers |
Non-Patent Citations (1)
| Title |
|---|
| M. BENDER ET AL., J. AM. CHEM. SOC., vol. 88, no. 24, 1966, pages 5890 - 5913 |
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