WO2022207590A1 - Washing or cleaning agents - Google Patents
Washing or cleaning agents Download PDFInfo
- Publication number
- WO2022207590A1 WO2022207590A1 PCT/EP2022/058190 EP2022058190W WO2022207590A1 WO 2022207590 A1 WO2022207590 A1 WO 2022207590A1 EP 2022058190 W EP2022058190 W EP 2022058190W WO 2022207590 A1 WO2022207590 A1 WO 2022207590A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gel
- weight
- detergent
- cleaning agent
- phase
- Prior art date
Links
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 120
- 238000005406 washing Methods 0.000 title abstract description 47
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- 150000002696 manganese Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LOTBYPQQWICYBB-UHFFFAOYSA-N methyl n-hexyl-n-[2-(hexylamino)ethyl]carbamate Chemical compound CCCCCCNCCN(C(=O)OC)CCCCCC LOTBYPQQWICYBB-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JLCNIMCQBVMUIN-UHFFFAOYSA-N n-docosylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCNC(=O)C=C JLCNIMCQBVMUIN-UHFFFAOYSA-N 0.000 description 1
- DFPMSGMNTNDNHN-ZPHOTFPESA-N naringin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](OC=2C=C3O[C@@H](CC(=O)C3=C(O)C=2)C=2C=CC(O)=CC=2)O[C@H](CO)[C@@H](O)[C@@H]1O DFPMSGMNTNDNHN-ZPHOTFPESA-N 0.000 description 1
- 229940052490 naringin Drugs 0.000 description 1
- 229930019673 naringin Natural products 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000023837 negative regulation of proteolysis Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 108010087558 pectate lyase Proteins 0.000 description 1
- 108020004410 pectinesterase Proteins 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000006337 proteolytic cleavage Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 229960001811 quinine hydrochloride Drugs 0.000 description 1
- 229960003110 quinine sulfate Drugs 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940013883 sucrose octaacetate Drugs 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 108010031354 thermitase Proteins 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 108010068608 xanthan lyase Proteins 0.000 description 1
- 108010083879 xyloglucan endo(1-4)-beta-D-glucanase Proteins 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- 229940006174 zinc valerate Drugs 0.000 description 1
- MXODCLTZTIFYDV-JHZYRPMRSA-L zinc;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O MXODCLTZTIFYDV-JHZYRPMRSA-L 0.000 description 1
- OWVLYQRCCIEOPF-QHTZZOMLSA-L zinc;(2s)-5-oxopyrrolidine-2-carboxylate Chemical compound [Zn+2].[O-]C(=O)[C@@H]1CCC(=O)N1.[O-]C(=O)[C@@H]1CCC(=O)N1 OWVLYQRCCIEOPF-QHTZZOMLSA-L 0.000 description 1
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 description 1
- OWVLYQRCCIEOPF-UHFFFAOYSA-L zinc;5-oxopyrrolidine-2-carboxylate Chemical compound [Zn+2].[O-]C(=O)C1CCC(=O)N1.[O-]C(=O)C1CCC(=O)N1 OWVLYQRCCIEOPF-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- BUDAIZWUWHWZPQ-UHFFFAOYSA-L zinc;pentanoate Chemical compound [Zn+2].CCCCC([O-])=O.CCCCC([O-])=O BUDAIZWUWHWZPQ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- At least one further active ingredient preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20° C., and with the proviso that the following applies to the mixture of the components (number n) according to a) and b) or a), b) and c). : With and
- Detergents or cleaning agents preferably dishwashing agents, in particular machine dishwashing agents, are usually in solid form (for example as tablets) or in liquid form (or else as a flowing gel).
- Liquid cleaning agents in particular are enjoying increasing popularity with consumers.
- Pre-portioned forms of presentation are popular with consumers because they are easier to dose.
- pre-portioned flowing gels are often problematic because they tend to leak, for example when packaged in single-chamber or multi-chamber bags. At the same time, it is necessary for such gels to have good cleaning and rinsing performance.
- the object of the present invention is to provide a system that provides particularly suitable gel formulations comprising PVOH and / or its derivatives, as well as the provision of cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, which can be produced easily and cost-effectively, a good Have storage stability and also have good cleaning and / or rinsing performance.
- cleaning agents preferably dishwashing detergents, in particular automatic dishwashing detergents, which can be produced easily and cost-effectively, a good Have storage stability and also have good cleaning and / or rinsing performance.
- At least one further active ingredient preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20° C., and with the proviso that for the mixture of the components (number n) according to a) and b) or a), b) and c) the following is applicable: and
- Polyvinyl alcohol can thicken various solvents, thereby forming gels.
- the PVOH is stabilized by non-covalent intermolecular interactions.
- the Hansen solubility parameters are based on a semi-empirical concept developed by Charles M. Hansen. Each substance can be analyzed using the three Hansen parameters, disperse/van der Waals forces (dD); Dipolar interactions (dP) and the ability to form hydrogen bonds (dH) can be characterized.
- Hansen parameters for specific substances can be determined by testing their solubility in reference solvents with known Hansen parameters. Based on such data it is then possible to determine the location of this substance in the Hansen space (Hansen Parameters Users Handbook, 2nd Edition, June 15, 2007)
- the Hansen parameters for the mixture of different substances result from the linear combination of the Hansen parameters of the components in the mixture according to Equation 1 below. PVOH is not taken into account in this equation. The sum of all substances adds up to 1 (equation 2).
- Equation 3 The appropriate section of the Hansen space (three-dimensional space spanned by dD, dP and dH), in which gelation and solubility are given, is fitted by a spherical function with radius r, for which Equation 3 applies.
- gels comprising PVOH and/or its derivatives in an amount, based in each case on the total weight of the gel, from 3 to 40% by weight, preferably from 4 to 20% by weight, in particular from 5 up to 18% by weight, have particularly advantageous properties if they also meet the following parameters.
- the gel shows unfavorable syneresis, i.e. leakage of solvent, on storage, while at r ⁇ 14.0 the gel becomes too soft and no longer has the desired properties in terms of strength and dimensional stability.
- Hansen parameters (dD, dP, dH) for the individual components can be determined experimentally by testing their solubility in reference solvents with known Hansen parameters.
- At least one of the components according to a) or b) is liquid at 20.degree.
- the mixture preferably has no separation of the mixture of the individual components at 80° C. in a period of 10 minutes, preferably 20 minutes, after the components have been mixed.
- a gel or a gel-like phase means a composition (or phase) which has an internally structuring network.
- This internal structuring (spatial) network is formed by the dispersion of a solid but distributed substance with long or highly branched particles and/or gelling agent, here polyvinyl alcohol and/or its derivatives, in at least one liquid (the at least one liquid is liquid at 20° C) formed.
- the washing or cleaning agent preferably dishwashing detergent, in particular machine dishwashing detergent, can have one, two, three, four or more gels or gel phases.
- the gels/gel phases can be the same or different. In the case of several gels or gel phases, these can preferably be distinguished spatially, optically or on the basis of their ingredients. If the gels/gel phases are different, they can have different dyes and different additions of active ingredients.
- the gel is dimensionally stable.
- the polyvinyl alcohol and/or its derivatives are brought into contact with glycerol. This gives a flowable mixture which can be brought into a desired shape.
- a gel/a gel phase is obtained which remains in the specified form, i.e. is dimensionally stable.
- the setting time is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes or less.
- the gel gives way under pressure, but does not deform as a result, but returns to its original state after the pressure is removed.
- the gel is preferably elastic, in particular linear-elastic.
- the gel is preferably a shaped body.
- a molded body is a single body that stabilizes itself in its imposed shape.
- This dimensionally stable body is formed from a molding compound (e.g. a composition) by deliberately bringing this molding compound into a predetermined shape, e.g. by pouring a liquid composition into a mold and then curing the liquid composition, e.g. as part of a sol-gel process.
- a molding compound e.g. a composition
- the setting time means the period of time during which the gel changes from a flowable to a non-flowable, dimensionally stable state at room temperature during production.
- Room temperature is understood to mean a temperature of 20°C. Where temperatures are mentioned herein, unless otherwise noted, they are to be understood as measured at a pressure of 1013 mbar.
- the gel is a solid gel phase. It is preferably cut-resistant. It can, for example, be cut with a knife after it has solidified without being destroyed further, except at the point where the cut was made.
- a phase within the meaning of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous.
- a phase differs from another phase by various characteristics, such as ingredients, physical properties, external appearance, etc. Different phases can preferably be distinguished visually.
- the at least one gel phase can be clearly distinguished from other phases (solid, preferably granular, liquid or gel-like) for the consumer.
- the washing or cleaning agent according to the invention preferably dishwashing detergent, in particular machine dishwashing detergent
- these can also be distinguished from one another with the naked eye because they differ from one another, for example in terms of color.
- an optical differentiation of the phases is possible, for example on the basis of a difference in color or transparency.
- Phases within the meaning of the present invention are therefore self-contained areas which the consumer can visually distinguish from one another with the naked eye.
- the individual phases can have different properties when used, such as the speed with which the phase dissolves in water and thus the speed and sequence of release of the ingredients contained in the respective phase.
- the gel is preferably translucent (translucent) or transparent, which results in a good optical impression.
- the transmittance of the gel phase (without dye) is preferably in a range between 100% and 20%, between 100% and 30%, in particular between 100% and 40%.
- the permeability was determined in % at 600 nm against water as a reference at 20 °C. For this purpose, the mass was poured into the 11 mm round cuvettes provided and, after a storage time of 12 h at room temperature, measured in a LICO 300 color measuring system according to Lange.
- the detergents or cleaning agents according to the invention preferably dishwashing detergents, in particular machine dishwashing detergents, contain polyvinyl alcohol and/or its derivatives in an amount of 3 to 40% by weight, in particular 4 to 30% by weight, particularly preferably in an amount of 5 to 18% by weight %, in each case based on the total weight of the gel.
- Polyvinyl alcohols are thermoplastics that are usually produced as a white to yellowish powder by the hydrolysis of polyvinyl acetate. Partially hydrolyzed polyvinyl alcohol which still has amounts of up to 30 mol % of non-hydrolyzed acetyl groups is to be understood as polyvinyl alcohol in the context of the invention.
- Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molar mass of 30,000 to 60,000 g/mol are preferred.
- polyvinyl alcohols which are available as yellowish-white powders or granules with degrees of polymerization in the range from about 100 to 2500 (molecular weights from about 4000 to 100,000 g/mol) and degrees of hydrolysis from 80 to 99 mol%, preferably from 85 to 90 mol%, in particular from 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.
- the gel comprises PVOH (polyvinyl alcohol).
- the gels or gel phases produced in this way have a particularly high melting point, are dimensionally stable (even at 40° C.) and do not change their shape, if at all, only insignificantly, even during storage. In particular, they are also not very reactive with regard to a direct negative interaction with components of a granular mixture, in particular an additional powder phase.
- PVOH can produce both water-containing and water-poor or water-free gel phases.
- low-viscosity melts result at 80-90 °C or 110-120 °C, which are particularly easy to process.
- the gel phase can be filled into the water-soluble coating quickly and precisely , without sticking or the amount being dosed imprecisely. Furthermore, these gel phases adhere particularly well to the water-soluble coating, in particular if this is also made from PVOH. This is also a visual advantage. Due to the rapid solidification of the at least one gel phase with PVOH, the further processing of the gel phases can take place particularly quickly. Furthermore, the good solubility of the gel phases produced is particularly favorable for the overall solubility of the washing or cleaning agent. In addition, gel phases with such short setting times are advantageous in the event that a solid, preferably granular phase dosed thereon, comprising granular mixtures, in particular powder, does not sink into the gel that is not yet completely solidified or is too soft. This leads to visually unappealing washing or cleaning agent portions.
- polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range from about 100 to 2500 (molar masses from about 4000 to 100,000 g/mol) and degrees of hydrolysis from 80 to 99 mol%, preferably from 85 to 90 mol %, in particular from 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.
- PVOH powders with the properties mentioned above, which are suitable for use in the at least one gel phase, are marketed, for example, by Kuraray under the name Mowiol® or Poval®.
- Exceval® AQ4104 from Kuraray, for example, is also suitable.
- Particularly suitable are Mowiol C30, the Poval® qualities, in particular the qualities 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, very particularly preferably Poval 4-88 S2 and Mowiol® 4- 88 by Kuraray.
- preferred derivatives of PVOH are copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers.
- anionic Monomers are preferably suitable vinylacetic acid, alkyl acrylates, maleic acid and their derivatives, in particular monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, fumaric acid and their derivatives, especially monoalkyl fumarate (especially monomethyl fumarate), dialkyl fumarate (especially dimethyl fumarate), fumaric anhydride, itaconic acid and derivatives thereof, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and derivatives thereof, monoalkyl citraconic acid (especially methyl citraconic acid), dialkyl citraconic acid (dimethyl citraconic acid), citraconic acid anhydride, mesaconic acid (methyl fuma
- Particularly preferred derivatives of PVOH are those selected from copolymers of polyvinyl alcohol with a monomer selected in particular from the group of monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, and combinations thereof, and the alkali metal salts or esters of the above mentioned monomers.
- the values given for the polyvinyl alcohols themselves apply to the suitable molar masses.
- the gel comprises a polyvinyl alcohol and/or derivatives thereof, preferably polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol %, in particular 80 to 90 mol %, particularly preferably 81 to 89 mol %. % and especially 82 to 88 mol%.
- the water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). These are also to be understood as derivatives of polyvinyl alcohol.
- Polyvinyl alcohols which are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous due to their extremely good solubility in cold water.
- the reaction products of polyvinyl alcohol and starch can be used extremely advantageously.
- the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to desired values.
- At least one further active ingredient preferably selected from dyes, perfumes, pH adjusters and other processing auxiliaries, can be used.
- the gel according to the invention preferably comprises less than 1% by weight, in particular less than 0.5% by weight, particularly preferably less than 0.1% by weight, of at least one benzylidene alditol compound of the formula (I), wherein
- *- stands for a covalent single bond between an oxygen atom of the alditol backbone and the intended residue
- n stands for 0 or 1, preferably for 1
- m stands for 0 or 1, preferably for 1, stands,
- the gel according to the invention comprises less than 1% by weight, in particular less than 0.5% by weight, particularly preferably less than 0.1% by weight, of the compounds selected from 1,3:2,4-Di-O -benzylidene-D-sorbitol; 1,3:2,4-di-0-(p-methyl-benzylidene)-D-sorbitol; 1,3:2,4-di-O-(p-chlorobenzylidene)-D-sorbitol; 1,3:2,4-di-0-(2,4-dimethylbenzylidene)-D-sorbitol; 1,3:2,4-Di-Q-(p- ethylbenzylidene)-D-sorbitol; 1,3:2,4-di-0-(3,4-dimethylbenzylidene)-D-sorbitol or mixtures thereof.
- the gel according to the invention comprises polyvinyl alcohol as the only gel former, as described above.
- Gel formers other than PVOH are preferably not contained in the gel.
- the gel contains at least one component according to a), which is liquid at 20° C., i.e. a component with a parameter ra less than or equal to 15.3 MPa 05 , preferably less than 15.3 MPa 05 , particularly preferably less than 15 2 MPa 05 , very particularly preferably less than 15.0 MPa 05 .
- a component with a parameter ra less than or equal to 15.3 MPa 05 preferably less than 15.3 MPa 05 , particularly preferably less than 15 2 MPa 05 , very particularly preferably less than 15.0 MPa 05 .
- the gel contains at least one component according to a) which is liquid at 20° C., ie a component with a parameter rb greater than or equal to 16.3, and at least one component according to b) which is liquid at 20° C.
- the gel contains at least one component according to a), preferably one component according to a) which is liquid at 20° C. and at least two components according to b), preferably two components according to b) which are liquid at 20° C. This makes it much easier to set and control the particularly important gelation parameters with regard to storage stability and setting time.
- component a) is selected from the group consisting of water, glycerol and the oligomeric or polymeric carboxylates, preferably polycarboxylates as described in detail below, particularly preferably polyacrylates, very particularly preferably polyacrylates containing sulfonic acid groups.
- At least one of the components according to a), preferably two or more, in particular three or more, of the components according to a) is present in the gels according to the invention.
- components a) which are liquid at 20° C. are glycerol or water and mixtures thereof.
- the gel preferably comprises oligomers or polymeric carboxylates, such as citrates, amino carboxylates and/or polycarboxylates, as described in detail below.
- oligomers or polymeric carboxylates such as citrates, amino carboxylates and/or polycarboxylates, as described in detail below.
- acrylate homopolymers or acrylate copolymers e.g Maleic acid-acrylic acid copolymer sodium salt or sulfopolymers. These can act either as builders and/or as a thickening polymer.
- copolymers can have two, three, four or more different monomer units.
- preferred copolymers polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.
- the gel-like phase contains as one of the components according to a), ie a component with a Hansen parameter r less than or equal to 15.3, a polymer comprising at least one sulfonic acid-containing monomer.
- the unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R 1 (R 2 )C ⁇ C(R 3 )COOH, in which R 1 to R 3 independently represent —H, —CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -OH or -COOH as defined above or for -COOH or- COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
- unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
- unsaturated dicarboxylic acids can also be used.
- H 2 C CH-X-S0 3 H
- H 2 C C(CH 3 )-X-S0 3 H or H0 3
- SX-(R 6 )C C(R 7 ) -X-S0 3 H
- R 6 and R 7 are independently selected from -H, -Chh, -CH2CH3, -CH2CH2CH3 and -CH(CH 3 )2
- the gel/gel phase contains a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as the monomer containing sulfonic acid groups.
- Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propenesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water
- some or all of the sulfonic acid groups can be present in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular sodium ions.
- metal ions preferably alkali metal ions and in particular sodium ions.
- the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which only contain carboxylic acid group-containing monomers and sulfonic acid group-containing monomers is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight; the monomers are preferably selected from those mentioned above.
- the molar mass of the sulfo-copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired application.
- Preferred detergents or cleaning agents are characterized in that the copolymers have molecular weights of 2000 to 200,000 g mol -1 , preferably 4000 to 25,000 g mol -1 and in particular 5000 to 15,000 g mol -1 .
- the copolymers also comprise at least one nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups.
- the gel particularly preferably also comprises an anionic copolymer, a copolymer comprising i) carboxylic acid group-containing monomers ii) sulfonic acid group-containing monomers iii) nonionic monomers, in particular hydrophobic monomers, being used as anionic copolymer.
- the nonionic monomers used are preferably monomers of the general formula R 1 (R 2 )C ⁇ C(R 3 )—XR 4 , in which R 1 to R 3 independently represent —H, —Ch or —C2H5, X represents one optionally present spacer group, which is selected from -CH2-, -C(0)0- and -C(0)-NH-, and R 4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
- nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, 1-hexene, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 ,4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1 , 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22
- AMPS 2-acrylamido-2-methylpropanesulfonic acid
- the polymers containing sulfonic acid groups are present in the gel in an amount of 0 to 30% by weight, in particular 0 to 20% by weight.
- the washing or cleaning agent according to one of the preceding claims characterized in that component b) in the gel is selected from the group formed by polyalkylene glycols (especially polyethylene glycols, polypropylene glycols), carbonate esters (especially glycerol carbonates, propylene carbonates, Ethylene carbonates, diethyl carbonates, dimethyl carbonates), 3-methyl-1,3-butanediol, fatty alcohol alkoxylates (possibly end-capped), acetates and zinc salts, in particular zinc acetates, in particular zinc acetate.
- polyalkylene glycols especially polyethylene glycols, polypropylene glycols
- carbonate esters especially glycerol carbonates, propylene carbonates, Ethylene carbonates, diethyl carbonates, dimethyl carbonates
- 3-methyl-1,3-butanediol fatty alcohol alkoxylates (possibly end-capped)
- acetates and zinc salts in particular zinc
- the gel preferably contains polypropylene glycol, preferably in an amount of 0.1 to 30% by weight.
- polypropylene glycol preferably in an amount of 0.1 to 30% by weight.
- Mixtures of different polypropylene glycols can of course be used. These are commercially available, for example, under the trade name Pluriol® (BASF).
- the average molecular weight of the propylene glycol is from 500 to 10,000 g/mol, in particular from 1000 to 6000 g/mol.
- polypropylene glycol is contained in an amount of 0.6 to 25% by weight, preferably in an amount of 1 to 15% by weight, based in each case on the total weight of the gel.
- Preferred components according to b) are carbonate esters (in particular glycerol carbonate (glycerol carbonate, 4-hydroxymethyl-1,3-dioxolan-2-one), propylene carbonate (4-methyl-1,3-dioxolan-2-one), ethylene carbonate ( 1,3-dioxolan-2-one), diethyl carbonate, dimethyl carbonate).
- carbonate esters in particular glycerol carbonate (glycerol carbonate, 4-hydroxymethyl-1,3-dioxolan-2-one), propylene carbonate (4-methyl-1,3-dioxolan-2-one), ethylene carbonate ( 1,3-dioxolan-2-one), diethyl carbonate, dimethyl carbonate).
- Glycerol carbonate, propylene carbonate and/or ethylene carbonate are particularly preferred.
- the gel phase preferably contains at least one polyethylene glycol.
- Polyethylene glycols with an average molar mass of between about 100 and 8000 are particularly suitable. Mixtures thereof can also be used.
- the abovementioned polyethylene glycols are particularly preferred in amounts of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 12 to 25% by weight, preferably based on the total weight of the gel phase or .of the gel used; 12 to 18.5% by weight of polyethylene glycol, in particular 13.5 to 16.5% by weight of polyethylene glycol, preferably polyethylene glycol, are very particularly preferably present in the gel.
- the polyethylene glycols used are preferably liquid at 20° C. and 1 bar.
- polyethylene glycol(s) with an average molar mass of 200 to 600 g/mol in the at least one gel phase or the gel phases.
- Washing or cleaning agents according to the invention preferably dishwashing detergents, in particular machine dishwashing detergents, are thus characterized in that they contain polyethylene glycol(s) with an average molar mass of 300 to 500 g/mol, in particular 350 to 450 g/mol.
- the amount of polyethylene glycol(s) with an average molar mass of 350 to 450 g/mol, for example around 400 g/mol is 10 to 22% by weight, based on the total weight of the gel.
- polyethylene glycols mentioned with an average molecular weight of 200 to 600 g/mol in addition to the polyethylene glycols mentioned with an average molecular weight of 200 to 600 g/mol, further polyethylene glycols, in particular further polyethylene glycols, with an average molecular weight between about 800 and 8000 can be contained in the at least one gel phase.
- the abovementioned polyethylene glycols are particularly preferably used in amounts of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 15 to 25% by weight, based on the total weight of the gel .
- Nonionic surfactants as described in detail below, can also be used as preferred components according to b). All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. To be favoured low-foaming nonionic surfactants used, in particular alkoxylated fatty acid alkyl ethers (fatty acid polyalkylene glycols). Particularly preferred nonionic surfactants are specified in more detail below as being particularly preferred.
- At least one water-soluble zinc salt is preferably present as a further component according to b).
- detergents or cleaning agents preferably dishwashing agents, in particular automatic dishwashing agents, which are packaged as washing or cleaning agent portions, preferably dishwashing agent portions, in particular automatic dishwashing agent portions, which preferably contain the active ingredients necessary for a cleaning cycle, are packaged as the total amount of the water-soluble zinc salts , in particular zinc sulphate and/or zinc acetate, in particular zinc acetate, in the washing or cleaning agent portion, preferably dishwashing agent portion, in particular automatic dishwashing agent portion, preferably 0.0004 to 0.5 g, preferably 0.001 to 0.2 g, in particular 0.02 to 0.06 g .
- the individual detergent or cleaning agent portion preferably dishwashing agent portion, in particular machine dishwashing agent portion, which is used to carry out a single cleaning cycle, in particular in a cleaning cycle of a machine dishwasher, is 0.0005 to 1 g, preferably 0.01 to 0 5 g, in particular 0.02 to 0.06 g of water-soluble zinc salts, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate.
- an individual detergent or cleaning agent portion according to the invention preferably a dishwashing detergent portion, in particular an automatic dishwashing detergent portion, which is added in particular to a cleaning cycle of an automatic dishwasher, contains 0.001 to 0.5 g, in particular 0.02 to 0.05 g, of water-soluble zinc salts, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, based on the total amount of the detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent.
- the zinc salt to be used with preference according to the invention is water-soluble, which means that it has a solubility in water of more than 100 mg/l, preferably more than 500 mg/l, particularly preferably more than 1 g/l and in particular more than 5 g/l (all solubilities at 20° C water temperature).
- the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
- the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc PCA (zinc 5-oxopyrrolidine-2-carboxylate), zinc benzoate, zinc chloride, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate , zinc abietate, zinc valerate and zinc p-toluenesulfonate.
- the water-soluble zinc salt used is zinc chloride, zinc acetate or zinc sulfate, in particular anhydrous zinc salt (anhydrate), particularly preferably zinc acetate (anhydrate).
- Another component according to b) is preferably at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, in an amount of from 0.05 to 5% by weight, in particular from 0.1 to 2.0% by weight. , very particularly preferably from 0.2 to 1.0% by weight, based on the total weight of the gel.
- the zinc salt is present in the gel phase preferably in an amount of from 0.05% to 3% by weight, more preferably in an amount of from 0.1% to 2.4% by weight, especially in a Amount of 0.2% by weight to 1.0% by weight, based on the total weight of the gel phase.
- Zinc salts can also be contained in a solid phase that may be present.
- the zinc salt in agents according to the invention is preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1% by weight to 2% by weight, based on the total weight of the detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent.
- the gel comprises at least one other ingredient according to component c), which is selected from dyes, glass corrosion inhibitors, and other processing aids, in particular perfume, pH adjusters.
- the water content of the gel is from 0 to 55% by weight, preferably from 1 to 50% by weight, based on the total weight of the gel.
- the gel comprises less than 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight, of a component with 15.3 ⁇ r ⁇ 16.3.
- the gel comprises less than 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight, of 1,3-propanediol.
- 1,3-propanediol The absence of 1,3-propanediol makes it possible to set the critical gel parameters, such as hardness of the gel, setting time, syneresis and/or storage stability, by combining the components according to a) and the components according to b).
- Propanediols in particular 1,3-propanediol, also lead to interactions with water-soluble coatings and/or other components, in particular coated components, with unsightly discolorations being able to form on the coated components, the discolored appearance of which is then perceived by the end user as unattractive or even harmful Part is considered to be no longer perfectly usable.
- the coating can also be softened in the presence of propanediols, so that the protective effect of the coating for the encapsulated active ingredient may no longer be available.
- 1,3 propanediol has clear disadvantages in large-scale production, since some of it evaporates when the gel is dosed and quickly condenses again in the environment. This makes it difficult to suck off this solvent. Contamination of other surfaces of plants or other product components (e.g. a water-soluble film) with 1,3-propanediol as a result of evaporation should be avoided as far as possible in order to prevent negative interactions.
- product components e.g. a water-soluble film
- the proportion of 1,3-propanediol and 1,2-propanediol, based on the total weight of the gel is preferably ⁇ 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight based on the total weight of the gel.
- the information refers to the type of ingredient and not to the absolute number of molecules.
- “At least one bleach catalyst” thus means, for example, at least one type of bleach catalyst, ie it can mean one type of bleach catalyst or a mixture of several different bleach catalysts.
- the information relates to all compounds of the specified type that are contained in the composition/mixture, ie the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.
- the number average molar mass can be determined, for example, by means of gel permeation chromatography (GPC) in accordance with DIN 55672-1:2007-08 with THF as the eluent.
- GPC gel permeation chromatography
- the mass-average molar mass M can also be determined by means of GPC , as described for Mn.
- the gel phase according to the invention is a component of a washing or cleaning agent, preferably a dishwashing detergent, in particular a machine dishwashing detergent.
- a dishwashing detergent in particular a machine dishwashing detergent.
- Such detergents or cleaning agents are usually stored in a household for a certain period of time. They are usually stored near the washing machine or dishwasher.
- the gel should be stable.
- the gel should be stable even after a storage time of, for example, 4 to 12 weeks, especially 10 to 12 weeks or longer at a temperature of up to 40°C, especially at 30°C, especially at 25°C or at 20°C be and do not deform during this time or otherwise change in consistency.
- the gel and a solid, in particular a powder phase are in direct contact with one another, the gel penetrates into the interstices of the immediately underlying powder phase by a maximum of 1 mm during the storage period of 4 weeks at 25°C.
- a change in volume or shrinkage during storage would be disadvantageous, since this would result in poor acceptance of the product by consumers. Escape of liquid or exudation of components from the gel phase is also undesirable. On the one hand, the visual impression is also relevant here.
- the stability of the gel phase can be affected by the escape of liquid, such as solvents, so that the components cannot are contained more stably and thereby the washing or cleaning effect can be influenced.
- the detergents or cleaning agents are in particular not films. Rather, they represent moldings that have a non-film-like thickness. They therefore have a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular at least 1.0 mm, very particularly preferably at least 1.2 mm. The layer thickness is measured in the plane with the smallest expansion.
- Another subject of the present invention relates to a detergent or cleaning agent portion, comprising at least one gel as described above, in a water-soluble casing.
- the washing or cleaning agents are a washing or cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing agent portion, in a water-soluble casing.
- This can have one or more chambers/compartments.
- the washing or cleaning agent preferably dishwashing agent, in particular machine dishwashing agent, is preferably packaged as a single portion washing or cleaning agent, so that it is used to carry out a dishwasher cycle and is (largely) essentially or completely consumed.
- the water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures.
- the cover can be formed from one or from two or more layers of the water-soluble film material.
- the water-soluble film material of the first layer and the further layers, if any, can be the same or different.
- the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
- Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility.
- Suitable water-soluble films for producing the water-soluble envelope are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in Range from 10,000 to 1,000,000 gmol 1 , preferably from 20,000 to 500,000 gmol 1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
- Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.
- the water-soluble packaging consists of at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight of a polyvinyl alcohol whose Degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
- a polyvinyl alcohol-containing film material suitable for producing the water-soluble casing can also have a polymer selected from the group consisting of (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added.
- a preferred additional polymer are polylactic acids.
- preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
- Polyvinyl alcohol copolymers which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
- the film material contains further additives.
- the film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
- Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof.
- Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packaging according to the invention are films available from MonoSol LLC, for example under the designation M8720, M8630, M8312, M8440, M7062, C8400 or M8900 to be expelled. Films sold by Nippon Gohsei under the name SH2601, SH2504, SH2707 or SH2701 are also suitable. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or films VF-HP from Kuraray.
- the outer surface of the water-soluble casing is at least partially coated with a bitter substance with a bitterness between 1,000 and 200,000.
- the water-soluble coating is coated to an extent of at least 50%, preferably at least 75% and very particularly preferably at least 90% with the bitter substance with a bitterness value between 1,000 and 200,000.
- the application of the bitter substance with a bitter value between 1,000 and 200,000 can be done, for example, by printing, spraying or brushing.
- the water-soluble casing preferably has at least one continuous circumferential sealing seam, which essentially lies in one plane.
- This is favorable in terms of process technology, since only a single sealing step, possibly using only a single sealing tool, is necessary for a circumferential sealing seam which lies essentially in one plane.
- the continuously circumferential sealing seam leads to a better closure compared to such casings with several sealing seams and an excellent tightness of the sealing seam and thus of the casing itself. Leaking of product from the casing, e.g. on the surface of the portion would be disadvantageous, since the consumer would then be exposed to the product came into contact. However, this is precisely what should be avoided as far as possible in the case of a detergent or cleaning agent portion, preferably a dishwashing agent portion, in particular a machine dishwashing agent portion, with a water-soluble coating.
- the water-soluble casing can preferably be made from at least 2 packaging parts.
- the at least two packaging parts are preferably water-soluble, so that no packaging parts remain in the dishwasher, which could then lead to problems in the dishwasher. It is not necessary for the at least two packaging parts to be different. They can preferably be made from the same material and in the same way. In a preferred embodiment, these are two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.
- the at least two packaging parts made of different materials, for example different films or material with two different properties (e.g. hot and cold water soluble film).
- a water-soluble film and another packaging member made by injection molding are combined.
- the water-soluble cover comprises at least one at least partially plastically deformed film.
- this plastic deformation of the film can be produced by methods known to those skilled in the art, such as deep drawing (with and without applying a vacuum), blow molding or stamping.
- the water-soluble covering comprises at least one at least partially plastically deformed film that was produced by deep-drawing.
- the water-soluble coating has a layer thickness of from 30 to 100 ⁇ m, in particular from 40 to 800 ⁇ m.
- the at least one solid, preferably granular phase and the gel can be arranged within the water-soluble envelope in any combination with one another.
- a solid, preferably granular phase can be arranged on or next to a gel phase.
- the washing or cleaning agent according to the invention preferably dishwashing detergent, in particular machine dishwashing detergent, has a solid, preferably granular phase and a gel phase or gel. It is also conceivable that a solid, preferably granular phase is surrounded by gel phases. Embedding one phase in another is also included according to the invention.
- the gel is in cast form, for example in the form of a gel core surrounded by a solid phase. There can also be 2 or more separate cavities that are filled with at least one gel phase.
- the washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent comprises two gel phases, it being possible for the two gel phases to have different compositions.
- Such detergents or cleaning agents preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprise 3, 4, 5 or 6 or more gel phases, it being possible for these gel phases to have the same or also different compositions.
- a preferred subject of the present invention is a detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent, which, in addition to the at least one gel phase, at least one solid, in particular particulate phase and optionally at least one other liquid / gel-like or solid, preferably granular phase includes.
- Solid in this context means that the composition is in solid form under standard conditions (temperature 25°C, pressure 1013 mbar).
- Suitable solid, preferably granular phases are, on the one hand, granular mixtures of a solid composition, such as, for example, powder and/or granules, in particular pulverulent phases.
- solid compositions/phases which have greater dimensional stability than the loose powder, for example powder or granulate preparations which have been compacted by compression before or after being enclosed in the film, e.g. by restoring forces of the film after deep-drawing or directly compressed compositions such as compresses or tablets.
- This at least one solid, preferably granular phase can be in direct contact with the gel-like phase.
- detergent or cleaning agent portions preferably dishwashing detergent portions, in particular machine dishwashing detergent portions, in particular multi-chamber bags, in which the solid and the gel/the gel phase are present in close proximity but separate from one another.
- the two chambers can be separated, for example, by a film, in particular a water-soluble film, or by a sealed seam (preferably a sealed seam of 3 mm or less).
- a film in particular a water-soluble film
- a sealed seam preferably a sealed seam of 3 mm or less.
- chambers of a multi-chamber pouch are arranged one above the other or next to one another.
- mixtures of single or multi-chamber bags, which comprise a gel-like phase according to the invention and separately from it at least one solid, preferably granular phase, which can be arranged, for example by folding and fixing a pouch, or by storage at a distance of less than 3 mm come into contact, for example in a packaging bag or a device for portioned dosing, according to the invention.
- a granular mixture is to be understood as a powdery phase within the meaning of the present invention, which is formed from a large number of loose, solid particles, which in turn comprise so-called grains.
- powdery phase includes powders and/or granules according to the following definition.
- a grain is a designation for the particulate components of powders (grains are the loose, solid particles), dusts (grains are the loose, solid particles), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures.
- a preferred embodiment of the granular mixture of the composition of the solid phase is the powder and/or the granulate, if “powder” or “granulate” is mentioned here, it also includes mixtures of different powders or different granulates .
- powder and granules also mean mixtures of different powders with different granules.
- Said solid particles of the granular mixture in turn preferably have a particle diameter X (volume average) of 10 to 1500 ⁇ m, more preferably of 200 ⁇ m to 1200 ⁇ m, particularly preferably of 600 ⁇ m to 1100 ⁇ m. These particle sizes can by sieving or by means a particle size analyzer Camsizer from Retsch.
- the granular mixture of the solid composition of the present invention which serves as the solid, preferably granular phase, is preferably in a free-flowing form (particularly preferably as a free-flowing powder and/or free-flowing granules).
- the agent of the portion according to the invention thus comprises at least one solid, preferably granular phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one gel phase, as defined above.
- a particularly preferred subject of the present invention are detergents or cleaning agents, preferably dishwashing agents, in particular automatic dishwashing agents, in particular a portion of washing or cleaning agent, preferably dishwashing agent portion, in particular automatic dishwashing agent portion, in which the gel/the gel phase is in direct contact, for example in a chamber, is included with the at least one solid phase.
- the at least one solid, preferably granular phase and the gel are in direct contact with one another.
- No negative interaction means here, for example, that no ingredients or solvents pass from one phase to the other or that the stability, in particular storage stability, preferably at 4 weeks and 30 °C storage temperature, and / or the aesthetics of the product in any form, for example by Color change, the formation of edges that appear moist, the boundary between the two phases becoming blurred, or the like.
- a gel phase preferably dimensionally stable gel phase, comprising at least one polypropylene glycol, preferably having an average molecular weight of 1000 to 6000 g/mol, preferably in an amount of 1 to 15% by weight, which with a granular mixture of a solid composition, in particular a powdered phase is combined, this goal can be achieved. It is particularly suitable if the granular mixture of a solid composition, in particular the powdery phase, is free-flowing, since a more targeted filling of the water-soluble covering can be achieved as a result of the process, in particular when filling a cavity produced by deep drawing.
- the visual appearance of the granular mixture of a solid composition in particular the powder
- the visual appearance of the granular mixture of a solid composition can be changed better compared to a compressed tablet, in particular differences in texture, such as coarse and fine particles as well as particles or areas with different colors, overall or as colored speckles, can thus be Improving a visually appealing appearance are used.
- the granular mixture of the solid in particular the powder, also offers improved solubility compared to compressed tablets, even without the addition of disintegrants.
- the gel is dimensionally stable so that as few interactions as possible can take place between the solid and the gel phase.
- the at least one solid, preferably granular phase of the present invention comprises a granular mixture of a solid composition, in particular it is in powdered and free-flowing form.
- the washing or cleaning agent according to the invention preferably dishwashing detergents, in particular machine dishwashing detergents, thus comprises at least one solid powdery and free-flowing phase, and at least one gel phase, the at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, and at least one polyvinyl alcohol, at least PVOH and/or derivatives thereof, particularly preferably at least PVOH, and glycerol as gel formers.
- the pourability of a granular mixture, in particular of a powdery solid, of the powdery phase, preferably of the powder and/or granulate relates to its ability to pour freely under its own weight.
- the pourability is determined by measuring the flow time of 1000 ml of detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing powder, from a standardized flow test funnel that is initially closed in its outlet direction and has an outlet diameter of 16.5 mm by measuring the time it takes for it to flow out completely of the granular mixture, in particular the powdery phase, preferably the powder and/or granules, e.g.
- the powder is measured after opening the outlet and compared with the outlet speed (in seconds) of a standard test sand, the outlet speed of which is defined as 100%.
- the defined sand mixture for calibrating the trickle apparatus is dry sea sand. Sea sand with a particle diameter of 0.4 to 0.8 mm is used, available for example from Carl Roth, Germany CAS no. [14808- 60-7] Before the measurement, the sea sand is dried for 24 h at 60 °C in a drying cabinet on a plate with a maximum layer height of 2 cm.
- Preferred embodiments of the solid phases according to the invention have an angle of repose/repose of 26 to 35, 27 to 34, 28 to 33, the angle of repose according to the method mentioned below after 24 hours after the preparation of the granular mixture of the solid composition, in particular the powdery solid phase, preferably the powder and/or granules and storage at 20° C., is determined.
- Such angles of repose have the advantage that the cavities can be filled with the at least one solid phase comparatively quickly and precisely.
- a powder funnel with a capacity of 400 ml and an outlet with a diameter of 25 mm is hung straight on a tripod.
- the hopper is moved upwards at a speed of 80 mm/min using a manually operated knurled wheel, so that the granular mixture, in particular the powdered phase, preferably the powder and/or granules, eg the powder, trickles out.
- the height of the cone of repose and the diameter of the cone of repose are determined for the individual solid phases.
- the angle of repose is calculated from the quotient of the heap of repose and the diameter of the cone of repose * 100.
- Such granular mixtures of a solid composition in particular such powdery phases, preferably the powders and/or granules, e.g. the powders which have a flowability in % of the standard test material specified above of greater than 40%, preferably greater than 50, in particular greater than 55 %, particularly preferably greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75%.
- the granular mixture, in particular the pulverulent phase, preferably the powder and/or granulate, eg the powder can be easily dosed, so that the dosing process runs more quickly. Furthermore, such a good flowability better prevents the granular mixture, in particular the powdery phase, preferably the powder and/or granules, e.g. the powder, from getting onto the part of the water-soluble cover that is intended for the production of the sealed seam and is therefore possible should remain granule-free, in particular powder-free.
- the granular mixture of the solid composition of the present invention which serves as the solid, preferably granular phase, is preferably in a free-flowing form (particularly preferably as a free-flowing powder and/or free-flowing granules).
- the means of the portion according to the invention thus comprises at least one solid, preferably granular phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one previously defined gel phase.
- the washing or cleaning agent according to the invention preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprises at least one surfactant.
- This surfactant is selected from the group of anionic, nonionic and cationic surfactants.
- the washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents can also contain mixtures of two or more surfactants selected from the same group.
- the at least one solid, preferably granular phase and/or the gel comprise at least one surfactant. It is possible for only the at least one solid, preferably granular phase or only the gel to comprise at least one surfactant. If both phases comprise a surfactant, they are preferably different surfactants. However, it is also possible for the solid and gel phases to have the same surfactant or surfactants. At least one solid and/or gel phase according to the invention preferably contains at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants.
- Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants, such as, for example, alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides or amine oxides. Particularly preferred nonionic surfactants are specified in more detail below.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- ethoxylated nonionic surfactants obtained from C6-20 monohydroxyalkanols or C6-20 alkylphenols or C16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol, deployed.
- a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (Ci6-20 alcohol), preferably a cis alcohol, and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
- the so-called “narrow range ethoxylates” are particularly preferred.
- Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants).
- Such (PO/EO/PO) nonionic surfactants are also distinguished by good foam control.
- nonionic surfactants have been found for the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
- preference is in turn given to surfactants with EO-AO-EO-AO blocks, in which case one to ten EO or AO groups are bonded to one another before a block of the other groups follows.
- nonionic surfactants of the general formula preferably in which R 1 is a straight-chain or branched, saturated or one or more times unsaturated C6-24 -alkyl or - alkenyl radical; each group R 2 or R 3 is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH 3 ) 2 and the indices w, x, y, z are independently integers from 1 to 6 .
- Preferred nonionic surfactants of the above formula can be prepared from the corresponding alcohols R 1 —OH and ethylene or alkylene oxide by known methods.
- the radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, with the linear radicals from alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred.
- Alcohols obtainable from synthetic sources are, for example, the Guerbet alcohols or a mixture of methyl-branched or linear and methyl-branched radicals in the 2-position, such as are usually present in oxo alcohol radicals.
- nonionic surfactants are preferred in which R 1 in the above formula is an alkyl radical with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
- a suitable alkylene oxide unit which is present in the preferred nonionic surfactants alternating with the ethylene oxide unit, is, in addition to propylene oxide, in particular butylene oxide.
- R 2 or R 3 are independently selected from -CH2CH2-CH3 or -CH(CH3)2 are also suitable.
- nonionic surfactants preferably used in the solid phase are nonionic surfactants of the general formula R 1 0(Alk0) x M(0Alk) y 0R 2 , where
- R 1 and R 2 independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
- Alk represents a branched or unbranched alkyl group having 2 to 4 carbon atoms;
- x and y independently represent values between 1 and 70; and
- M is an alkyl radical from the group CH 2 , CHR 3 , CR 3 R 4 , CH2CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 are independently branched or unbranched, saturated or unsaturated alkyl radicals having 1 to 18 carbon atoms.
- Nonionic surfactants of the general formula are preferred here.
- R, R 1 and R 2 are independently an alkyl radical or alkenyl radical with 6 to 22
- carbon atoms independently represent values between 1 and 40.
- R 1 -CH(0H)CH 2 -0(CH 2 CH 2 0)xCH 2 CHR(0CH 2 CH 2 )y0-CH 2 CH(0H)-R 2 in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently have values of 20 to 30.
- Corresponding compounds can be obtained, for example, by reacting alkyl diols HO-CHR-CH2-OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close the free OH functions with formation of a dihydroxy ether.
- Preferred nonionic surfactants here are those of the general formula R 1 -CH(OH)CH 2 0-(A0)w-(A0)x-(A"0) y- (A'"0)zR 2 , in which
- R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical
- R 2 represents hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
- - A, A', A" and A'" independently represent a radical from the group -CH2CH2 , -CH2CH2- CH2 , -CH2-CH(CH3), -CH2 -CH2-CH2-CH2, -CH2 -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 2 -CH 3 ),
- - w, x, y and z stand for values between 0.5 and 120, where x, y and/or z can also be 0.
- nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals can significantly improve the stability of the enzymes contained in the detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents.
- n is between 1 and 90, preferably between 10 and 80 and in particular between 20 and 60.
- R 1 is C7 to C13
- n is an integer from 16 to 28 and R 2 is Cs to C12.
- surfactants of the formula R 1 0 [CH 2 CH (CH 3) 0] x [CH 2 CH 2 0] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 bis 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x has values between 0.5 and 1.5 and y has a value of at least 15.
- the group of these nonionic surfactants includes, for example, the C2-26 fatty alcohol (PO)i-(EO)i5- 40 -2-hydroxyalkyl ethers, in particular also the Ce-io fatty alcohol (PO)i-(EO) 22 -2-hydroxydecyl ether .
- nonionic surfactants are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 0[CH 2 CH(R 3 )0]x[CH 2 ] k CH(0H)[CH 2 ]j0R 2 , in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2- butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5.
- each R 3 in the above formula R 1 0[CH 2 CH(R 3 )0]x[CH 2 ] k CH(0H)[CH 2 ]j 0R 2 can be different.
- R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
- H, -CH3 or -CFhCF are particularly preferred for the radical R 3 .
- Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
- each R 3 in the above formula can be different when x>2.
- the value 3 for x was selected here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
- R 1 , R 2 and R 3 are as defined above and x is a number from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
- the nonionic surfactants of the general formula R 1 --CH(OH)CH 2 0-(A0) W --R 2 have proven to be particularly effective
- R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
- R 2 represents a linear or branched hydrocarbon radical having from 2 to 26 carbon atoms
- - A is a radical from the group CH2CH2, CH2CH2CH2, CH2CH(CH3), preferably CH2CH2, and
- - w represents values between 1 and 120, preferably 10 to 80, in particular 20 to 40.
- the group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular the C8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C4- 22 fatty alcohol (EO) 40 -80-2-hydroxyalkyl ether.
- the at least one solid and/or the gel contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, with the proportion by weight of the nonionic surfactant based on the total weight of the gel preferably being 0.5% by weight to 30% by weight. , preferably 5% by weight to 25% by weight and in particular 10% by weight to 20% by weight.
- the nonionic surfactant of the solid and/or gel phase is selected from nonionic surfactants of the general formula R 1 -0(CH 2 CH 2 0) x CR 3 R 4 (0CH 2 CH 2 )y0-R 2 , in which R 1 and R 2 independently represent an alkyl group or alkenyl group having 4 to 22 carbon atoms; R 3 and R 4 are independently H or an alkyl or alkenyl group having from 1 to 18 carbon atoms and x and y are independently from 1 to 40.
- R 1 -0(CH 2 CH 2 0) x CR 3 R 4 (0CH 2 CH 2 ) y 0-R 2 in which the radicals R 1 and R 2 are, independently of one another, saturated alkyl radicals with 4 represent up to 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.
- the given carbon chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical mean values, which can be a whole or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which means that both the C chain lengths and the Degrees of ethoxylation or degrees of alkoxylation can result in mean values and fractional numbers as a result.
- nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.
- Nonionic surfactants which have a melting point above room temperature are particularly preferred in the at least one solid, preferably granular phase.
- Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferable for them to have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants, which have a waxy consistency at room temperature, are also preferred.
- the nonionic surfactant which is solid at room temperature preferably has propylene oxide units (PO) in the molecule.
- PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight, of the total molar mass of the nonionic surfactant.
- Particularly preferred nonionic surfactants are ethoxylated monohydroxy alkanols or alkyl phenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
- the alcohol or alkylphenol part of such nonionic surfactant molecules makes up preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.
- Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic identify surfactants.
- nonionic surfactants to be used particularly preferably in the solid phase with melting points above room temperature contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend which contains 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
- the proportion by weight of the nonionic surfactant in the total weight of the solid, preferably granular phase is from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight %.
- anionic surface-active substances are suitable as anionic surfactants in the agents.
- a water-solubilizing, anionic group such as. B. a carboxylate, sulfate or sulfonate group and a lipophilic alkyl group having about 8 to 30 carbon atoms.
- the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups.
- Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.
- Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
- cationic and/or amphoteric surfactants such as betaines or quaternary ammonium compounds can also be used. However, it is preferred that no cationic and/or amphoteric surfactants are used.
- the gel contains at least one further nonionic surfactant, preferably in an amount of 0.1 to 80% by weight.
- nonionic surfactants are described above.
- Substances from the Plurafac® LF (BASF) series are particularly suitable, as are the end-capped or non-capped non-ionic surfactants described above as hydroxy mixed ethers or fatty alcohol polyalkylene glycols.
- washing or cleaning agents according to the invention are further characterized in that they contain less than 1.0% by weight and in particular less than 0.1% by weight, preferably no anionic surfactant.
- the washing or cleaning agents according to the invention preferably dishwashing agents, in particular machine dishwashing agents, characterized in that the gel comprises less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight, of anionic surfactant, based in each case on the total weight of the gel.
- the gel is preferably essentially free of anionic surfactants. Substantially free means that the gel contains less than 0.05% by weight of anionic surfactant, based on the total weight of the gel.
- the gel contains less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.05% by weight, of fatty acid salts or soaps.
- the gel may include sugars.
- sugars include sugar alcohols, monosaccharides, disaccharides and oligosaccharides.
- the gel comprises at least one sugar alcohol other than glycerol, preferably at least one monosaccharide or disaccharide sugar alcohol.
- Mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol and xylitol are particularly preferred.
- Particularly preferred monosaccharide sugar alcohols are pentitols and/or hexitols. Xylitol and/or sorbitol is very particularly preferred.
- the gel may comprise disaccharides, in particular sucrose.
- the proportion of sucrose is 0% by weight to 30% by weight, in particular 5% by weight to 25% by weight, particularly preferably 10% by weight to 20% by weight, based on the weight of the gel phase .
- the sugar does not completely dissolve in the gel phase and causes the same to become cloudy.
- the use of sugar in particular in a proportion of 10% by weight to 15% by weight, reduces moisture development and thus improves adhesion to at least one solid phase.
- the at least one additional phase comprises at least one, preferably several ingredients, which are selected from which are selected from the group consisting of builders (preferably carbonates, citrates, aminopolycarboxylates and/or Amino carboxylates, preferably MGDA and/or GLDA or salts thereof, and/or bleaches (particularly percarbonate), and/or bleach activators and/or bleach catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase (n)), and/or nonionic surfactants and/or other processing aids.
- builders preferably carbonates, citrates, aminopolycarboxylates and/or Amino carboxylates, preferably MGDA and/or GLDA or salts thereof, and/or bleaches (particularly percarbonate), and/or bleach activators and/or bleach catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase (n)), and/or non
- the use of phosphates is largely or completely dispensed with.
- the agent preferably contains less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight, of phosphate(s).
- the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate(s).
- the builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates.
- the proportion by weight of the total builders in the total weight of agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.
- Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids/polycarboxylates being understood as meaning those carboxylic acids which have more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or carry five acid functions throughout the molecule.
- Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
- the polycarboxylic acids can also carry other functional groups, such as hydroxyl or amino groups.
- these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids (preferably aldaric acids, for example galactaric acid and glucaric acid), iminocarboxylic acids, aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine-N ,N-diacetic acid (also referred to as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methylglycine diacetic acid (MGDA) and their derivatives and mixtures of these.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.
- organic builders are polymeric polycarboxylates (organic polymers with a large number of (especially more than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.
- the free acids typically also have the property of an acidifying component. Particular mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.
- washing or cleaning agents according to the invention preferably dishwashing detergents, in particular machine dishwashing detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, particularly 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to 20% by weight, based in each case on the total weight of the agent.
- washing or cleaning agents according to the invention are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the proportion by weight of these builders, based on the total weight of the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, is preferably 5 to 70% by weight, preferably 15 to 60% by weight and in particular 20 to 50% by weight.
- the combination of two or more builders from the group mentioned above has proven advantageous for the cleaning and rinsing performance of washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents.
- one or more other builders can also be present.
- Preferred detergents or cleaning agents are characterized by a builder combination of citrate and carbonate and/or bicarbonate.
- a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight.
- the amount of citrate preferably from 5 to 35 wt machine dishwashing detergent, the total amount of these two builders preferably being 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight.
- one or more other builders can also be included.
- the detergents or cleaning agents according to the invention can contain phosphonates in particular as a further builder, to the extent permitted by regulations.
- a hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound.
- HEDP 1-hydroxyethane-1,1-diphosphonate
- Aminoalkanephosphonates are preferred
- Ethylenediamine tetramethylene phosphonate Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question.
- Phosphonates are present in agents according to the invention, to the extent permitted by regulations, preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight .- %, based on the total weight of the agent.
- citrate, (hydrogen) carbonate and phosphonate are particularly preferred. These can be used in the amounts mentioned above. In this combination, in particular, amounts of, in each case based on the total weight of the agent, 10 to 25% by weight of citrate, 10 to 30% by weight of carbonate (or bicarbonate) and 2.5 to 7.5% by weight
- dishwashing detergents in particular machine dishwashing detergents
- these contain at least one further phosphorus-free builder in addition to citrate and (hydrogen) carbonate and, if appropriate, phosphonate.
- this is selected from the aminocarboxylic acids, with the further phosphorus-free builder preferably being selected from methylglycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA.
- MGDA methylglycine diacetic acid
- GLDA glutamic acid diacetate
- ASDA aspartic acid diacetate
- HEIDA hydroxyethyliminodiacetate
- IDS iminodisuccinate
- EDDS ethylenediamine disuccinate
- a particularly preferred combination is, for example, citrate, (
- the percentage by weight of the further phosphorus-free builder, in particular of the MGDA and/or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, in particular 7 to 25% by weight.
- the use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules that contain as little water as possible and/or have a lower hygroscopicity (water absorption at 25° C., normal pressure) than non-granulated powder are advantageous.
- Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g/mol.
- Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g/mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1100 to 10000 g/mol, and particularly preferably from 1200 to 5000 g/mol, may in turn be preferred from this group.
- the content of (homo)polymeric polycarboxylates in the washing or cleaning agents according to the invention is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight. %.
- Detergents or cleaning agents according to the invention can also contain crystalline layered silicates of the general formula NaMSi x 0 2x+i y H2O as a builder, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
- Amorphous sodium silicates with an Na2O:S1O2 modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, which are preferably delayed in dissolution, can also be used and have secondary washing properties.
- the washing or cleaning agents according to the invention can also contain alkali metal hydroxides.
- These alkali carriers are used in the detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents and in particular in the at least one gel phase, preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5 Wt.
- Alternative washing or cleaning agents according to the invention, preferably dishwashing agents, in particular machine dishwashing agents are free from alkali metal hydroxides.
- Washing or cleaning agents according to the invention contain at least one solid as a further component and/or the at least one gel phase, preferably enzyme(s).
- enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.
- enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, which are correspondingly preferably used.
- Detergents or cleaning agents according to the invention preferably dishwashing detergents, in particular machine dishwashing detergents, preferably contain enzymes in total amounts of 1 ⁇ 10 -6 % by weight to 5% by weight, based on active protein.
- the protein concentration can be determined using known methods, for example the BCA method or the Biuret method.
- subtilisin type those of the subtilisin type are preferred.
- subtilisins BPN' and Carlsberg and their further developed forms the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, which can be assigned to the subtilases, but no longer to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
- amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments improved for use in detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents the aforementioned amylases.
- Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors.
- suitable precursors include, for example, the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange in positions D96LT213R and/or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.
- oxidoreductases for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect.
- organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators).
- a protein and/or enzyme can be protected against damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
- damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
- inhibition of proteolysis is particularly preferred, particularly if the agents also contain proteases.
- Detergents or cleaning agents preferably dishwashing detergents, in particular machine dishwashing detergents, can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
- Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized preparations that can be stored and transported.
- These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.
- the enzymes for the at least one solid and/or the gel can be encapsulated, 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 set gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer.
- Additional active substances for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers.
- Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
- such granules for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.
- the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
- Protease and amylase preparations used according to the invention contain between 1 and 40% by weight, preferably between 2 and 30% by weight, particularly preferably between 3 and 25% by weight, of the enzyme protein.
- the at least one solid and/or the gel of the washing or cleaning agent according to the invention can contain other ingredients.
- these include, for example, anionic, cationic and/or amphoteric surfactants, bleaches,
- Bleaching activators bleaching catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver preservatives, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (in particular in the at least one solid phase), additives to improve drainage and drying behavior, to adjust viscosity, to Stabilization, UV stabilizers, preservatives, antimicrobial active ingredients (disinfectants), pH adjusters in amounts of usually not more than 5% by weight.
- Agents according to the invention preferably contain at least one alkanolamine as a further solvent.
- the alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
- the alkanolamine is preferably contained in agents according to the invention in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight.
- preferred detergents or cleaning agents preferably dishwashing detergents, in particular machine dishwashing detergents, the gel is essentially free of alkanolamine, i.e.
- the gel contains less than 1% by weight, in particular less than 0.5% by weight, preferably less than 0 1% by weight, particularly preferably less than 0.05% by weight, of alkanolamine and the alkanolamine is contained only in the at least one solid phase.
- polyethyleneimines such as those available under the name Lupasol® (BASF)
- BASF can be used as glass corrosion inhibitors, preferably in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight .
- Polymers suitable as additives are in particular maleic acid-acrylic acid copolymer Na salt (for example Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example Sokalan® CP 10 from BASF, Ludwigshafen (Germany)), modified polycarboxylate sodium salt (for example Sokalan ® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet ® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (e.g.
- Silwet ® L-7608 from BASF, Ludwigshafen (Germany)
- polyether siloxanes copolymers of polymethyl siloxanes with ethylene oxide/propylene oxide segments (polyether blocks)
- preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren ® 5840, Tegopren ® 5843, Tegopren® 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878 from Evonik, Essen (Germany).
- Builder substances suitable as additives are, in particular, sodium polyaspartic acid salt, ethylenediamine triacetate coconut alkylacetamide (for example Rewopol® CHT 12 from Evonik, Essen (Germany)), sodium trimethylglycine diacetic acid salt and acetophosphonic acid.
- Tegopren ® 5843 and Tegopren ® 5863 mixtures with surfactant or polymer additives show synergisms.
- the use of Tegopren types 5843 and 5863 is less preferred when used on hard surfaces made of glass, in particular glassware, since these silicone surfactants can be absorbed by glass.
- the additives mentioned are omitted.
- a preferred washing or cleaning agent preferably a dishwashing detergent, in particular a machine dishwashing detergent, preferably also comprises a bleach, in particular an oxygen bleach and optionally a bleach activator and/or bleach catalyst.
- Detergents or cleaning agents according to the invention preferably dishwashing detergents, in particular machine dishwashing detergents, contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate as a preferred bleaching agent.
- Other usable bleaches are, for example, peroxypyrophosphates, citrate perhydrates and H2O2-supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
- Bleaching agents from the group of organic bleaching agents can also be used.
- Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
- Other typical organic bleaches are the peroxyacids, examples being the alkylperoxyacids and the arylperoxyacids.
- Sodium percarbonate is particularly preferred because of its good bleaching performance.
- a particularly preferred oxygen bleach is sodium percarbonate.
- Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Substances which contain 0- and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally carry substituted benzoyl groups. Polyacylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven to be particularly suitable.
- TAED tetraacetylethylenediamine
- the bleach catalysts are bleach-boosting transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
- Complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O and/or S, are particularly preferably used.
- Ligands which have nitrogen donor functions are preferably used.
- bleaching catalyst(s) in the agents according to the invention which contain, as macromolecular ligands, 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN ) and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN).
- Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
- TACN 1,4,7-triazacyclononane
- TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
- 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane Me/Me-TACN
- the detergent or cleaning agent portion comprises, in addition to at least one gel or a gel phase, at least or more additional phase(s) which is/are selected from a liquid phase, gel-like phase and/or solid, preferably granular, in particular particulate, preferably free-flowing, solid phase.
- the washing or cleaning agent according to the invention preferably dishwashing detergent, in particular machine dishwashing detergent, preferably comprises at least one gel or one gel phase and at least one solid, preferably granular phase.
- the detergent or cleaning agent, preferably dishwashing detergents, in particular machine dishwashing detergents can have one, two, three or more solid, preferably granular phases; it can also have one, two, three, four or more different gel phases.
- the washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents preferably comprises a solid, preferably granular phase and a gel phase.
- the washing or cleaning agent preferably dishwashing detergent, in particular machine dishwashing detergent, particularly preferably comprises two solid, preferably granular phases and a gel phase. It preferably comprises two solid, preferably granular, phases and two gel phases. Also preferred is an embodiment in which the washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprises three solid, preferably granular phases and one or two gel phases.
- the weight ratio of all of the at least one solid phase to all of the at least one gel phase is generally 40:1 to 2:1, in particular 20:1 to 4:1, preferably 14:1 to 6:1, for example 12:1 to 8:1 .
- the total weight of all phases in a detergent or cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing agent portion can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 13 to 17 g per washing or cleaning agent portion, preferably dishwashing agent portion , In particular machine dishwashing detergent portion amount. This weight ratio results in a good concentration of the respective ingredients of the solid or gel phase in a cleaning process.
- the at least one solid, preferably granular phase and the gel adjoin one another over the whole or part of the surface. It is preferred that the two phases directly adjoin one another.
- the stability is important in addition to the shortest possible setting time of the at least one gel phase. Stability here means that the components contained in the gel phase do not migrate into the at least one solid, preferably granular phase, but rather that the at least one solid, preferably granular phase and the gel are optically separate from one another even after prolonged storage and do not interact with one another, such as diffusion of liquid components from one phase to another or reaction of components in one phase with those in the other phase.
- Another subject of the present application is a method for cleaning hard surfaces, in particular dishes, in which the surface is treated in a manner known per se using a detergent or cleaning agent according to the invention, preferably dishwashing detergent, in particular automatic dishwashing detergent.
- a detergent or cleaning agent according to the invention preferably dishwashing detergent, in particular automatic dishwashing detergent.
- the surface is brought into contact with the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent.
- the cleaning takes place in particular with a cleaning machine, preferably with a dishwasher.
- a further subject of the present invention is also the use of a washing or cleaning agent, preferably dishwashing agent, in particular automatic dishwashing agent, as described above, for cleaning hard surfaces, in particular dishes, in particular in automatic dishwashers.
- a washing or cleaning agent preferably dishwashing agent, in particular automatic dishwashing agent, as described above
- dishwashing agent in particular automatic dishwashing agent
- the specific disclosures made above for the detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents apply accordingly.
- washing or cleaning agent according to the invention preferably dishwashing detergent, in particular automatic dishwashing detergent, as a whole or in the gel
- washing or cleaning agent preferably dishwashing detergent, in particular automatic dishwashing detergent
- washing or cleaning agent preferably dishwashing detergent, in particular automatic dishwashing detergent
- the preferred dishwashing agent according to the invention is described in a manner that does not limit cleaning agents.
- Detergents or cleaning agents comprising at least one gel, preferably one
- At least one further active ingredient preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20 °C, and with the proviso that for the mixture of components (number n) according to a) and b) or a), b) and c) applies :
- Detergent or cleaning agent according to one of the above points characterized in that ⁇ 5% by weight, preferably ⁇ 3% by weight, in particular ⁇ 1% by weight, of a component with
- 15.3 ⁇ r ⁇ 16.3 is included.
- Detergent or cleaning agent according to one of the above points characterized in that it contains ⁇ 5% by weight, preferably ⁇ 3% by weight, in particular ⁇ 1% by weight, of 1,3-propanediol.
- Detergent or cleaning agent according to one of the above points characterized in that ⁇ 5% by weight, preferably ⁇ 3% by weight, in particular ⁇ 1% by weight, of 1,3-propanediol and/or
- 1,2-propanediol is included.
- Detergent or cleaning agent according to one of the above points characterized in that at least one component according to a) which is liquid at 20°C is present.
- Detergent or cleaning agent according to one of the above points characterized in that at least one component according to a) which is liquid at 20°C and at least one component according to b) which is liquid at 20°C are present.
- Detergent or cleaning agent according to one of the above points characterized in that at least one component according to a), preferably one component a) which is liquid at 20°C, and at least two components, preferably two components according to b) which are liquid at 20°C, are present .
- Detergent or cleaning agent according to one of the above points characterized in that component a) is selected from the group consisting of water, glycerol and polyacrylates, in particular polyacrylates containing sulfonic acid groups.
- component b) is selected independently from the group consisting of organic solvents, nonionic surfactants and organic metal salts.
- component b) is independently selected from polyalkylene glycols (particularly polyethylene glycols, polypropylene glycols), carbonate esters (particularly glycerol carbonates, propylene carbonates, ethylene carbonates, diethyl carbonates, dimethyl carbonates), 3-methyl -1,3-Butanediol, fatty alcohol alkoxylates (possibly end-capped) and acetates, in particular zinc acetate.
- Detergent or cleaning agent according to one of the above points characterized in that the gel has a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular of at least 1.0 mm, very particularly preferably of at least 1.2 mm.
- Detergent or cleaning agent according to one of the above points characterized in that as component according to c) at least one zinc salt, preferably zinc chloride, zinc sulfate and/or zinc acetate, in particular zinc acetate, particularly preferably zinc acetate anhydrate, in an amount of 0.05 to 5 % by weight, preferably in an amount of 0.1 to 2.0% by weight, in particular 0.2 to 1% by weight, based on the total weight of the gel.
- Detergent or cleaning agent portion comprising at least one gel according to one of points 1 to 11 in a water-soluble envelope, preferably comprising polyvinyl alcohol, in particular a film comprising polyvinyl alcohol.
- Detergent or cleaning agent portion according to point 11 or 12 characterized in that it comprises at least one additional phase which is selected from a liquid phase, a gel phase and/or a particulate, preferably free-flowing, solid phase.
- Detergent or cleaning agent portion according to point 13 characterized in that at least one additional phase comprises at least one, preferably several ingredients selected from the group consisting of builders (preferably carbonates, citrates, amino carboxylates, preferably MGDA and/or GLDA or their Salts,) and/or bleaching agents (in particular percarbonate), and/or bleach activators and/or bleaching catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase(s)), and/or nonionic surfactants and/or other processing aids.
- Detergent or cleaning agent according to one of points 1 to 14 characterized in that it is a dishwashing detergent, in particular a dishwashing detergent for machine cleaning of dishes.
- a cleaning agent according to one of points 1 to 16 for machine cleaning of dishes, in particular for cleaning stubborn, greasy or greasy and protein-rich leftovers, eg fried bacon or gratinated cheese.
- Method for machine cleaning of dishes characterized in that a cleaning agent according to one of points 1 to 16 is used in a dishwasher. Examples:
- Cleaning agents according to the invention preferably dishwashing detergents, in particular machine dishwashing detergents, were produced which comprised a solid, preferably granular phase and a gel phase. Different geometries were realized here. Furthermore, detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, were produced which comprised two solid, preferably granular phases and a gel phase. Cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, were also produced, which comprised a solid, preferably granular phase and 3, 4 and 5 gel phases (of the same or different composition). The following information relates to % by weight of active substance based on the total weight of the phase in question (unless otherwise stated).
- the gels have compositions that are preferably in the following ranges (data based on the total amount of the gel phase):
- the solid granular phases and the gel could be combined with one another as desired.
- the spatial configuration of the gel phase which was liquid after mixing the ingredients and dimensionally stable within a maximum setting time of 5 minutes, was determined by the spatial configuration of the solid phase and by commercially available or self-designed forms.
- a water-soluble cover in the form of an open pouch was produced by deep-drawing a film containing PVOH.
- a liquid composition was poured into this open cavity, which gave the gel after curing, then solid phases in the form of a free-flowing solid were filled into a pouch comprising polyvinyl alcohol and the open pouch was then sealed by placing a second film and sealing by heat sealing.
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Abstract
The invention relates to special washing or cleaning agents, comprising at least one gel, preferably a gel that is solid at room temperature (20 °C), based in each case on the total weight of the gel, 3 to 40 wt.%, preferably 4 to 20 wt.%, in particular 5 to 18 wt.%, PVOH and/or the derivatives thereof; and a. at least one component having a parameter r <= 15.3 MPa1/2 and b. at least one component having a parameter r >= 16.3 MPa1/2; and c. optionally at least one additional active substance, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH regulators and additional process auxiliaries; wherein at least one of the components according to a) or b) is liquid at 20 °C.
Description
, Wasch- oder Reinigungsmittel“ , detergents or cleaning agents”
Die Erfindung betrifft Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, umfassend mindestens ein Gel, bevorzugt ein bei Raumtemperatur (20 °C) festes Gel, jeweils bezogen auf das Gesamtgewicht des Gels, 3 bis 40 Gew.-%, bevorzugt 4 bis 20 Gew.-%, insbesondere 5 bis 18 Gew.-%, PVOH und/oder dessen Derivate; sowie a. mindestens einer Komponente mit einem Parameter r <= 15,3 MPa1/2 und b. mindestens einer Komponente mit einem Parameter r >= 16,3 MPa1/2; sowie c. optional mindestens einen weiterer Aktivstoff, bevorzugt ausgewählt aus Farbstoffen, Glaskorrosionsinhibitoren, Parfüms, pH-Stellmitteln sowie weiteren Prozesshilfsmitteln; wobei mindestens eine der Komponenten gemäß a) oder b) bei 20 °C flüssig ist, und mit der Maßgabe, dass für die Mischung der Komponenten (Anzahl n) gemäß a) und b) oder a), b) und c) folgendes gilt:
mit
und The invention relates to cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, comprising at least one gel, preferably a gel that is solid at room temperature (20° C.), based in each case on the total weight of the gel, 3 to 40% by weight, preferably 4 to 20% by weight %, in particular 5 to 18% by weight, PVOH and/or its derivatives; as well as a. at least one component with a parameter r <= 15.3 MPa 1/2 and b. at least one component with a parameter r >= 16.3 MPa 1/2 ; as well as c. optionally at least one further active ingredient, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20° C., and with the proviso that the following applies to the mixture of the components (number n) according to a) and b) or a), b) and c). : With and
(dDMix - dD0 )2 + ( dPMix - dP0 )2 + ( dHMix - dH0 )2 = r2 wobei dD0 = 16,05 MPaz dP0 = 20,31 MPaz dH0 = 36,86 MPaz Und r= 14,0 bis 18,5 MPa1/2 ist. (dD Mix - dD 0 ) 2 + ( dP Mix - dP 0 ) 2 + ( dH Mix - dH 0 ) 2 = r 2 where dD 0 = 16.05 MPaz dP 0 = 20.31 MPaz dH 0 = 36.86 MPaz And r= 14.0 to 18.5 MPa 1/2 .
Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, liegen üblicherweise in fester Form (beispielsweise als Tabletten) oder in flüssiger Form (oder auch als fließendes Gel) vor. Insbesondere flüssige Reinigungsmittel erfreuen sich dabei zunehmender Beliebtheit beim Verbraucher. Vorportionierte Angebotsformen sind bei den Verbrauchern wegen der leichteren Dosierung beliebt. Dabei sind vorportionierte fließende Gele häufig problematisch, weil sie, beispielsweise, wenn in Ein- oder Mehrkammerbeutel konfektioniert, zu Leckagen neigen. Gleichzeitig ist es notwendig, dass solche Gele eine gute Reinigungs- und Klarspülleistung aufweisen. Detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, are usually in solid form (for example as tablets) or in liquid form (or else as a flowing gel). Liquid cleaning agents in particular are enjoying increasing popularity with consumers. Pre-portioned forms of presentation are popular with consumers because they are easier to dose. In this context, pre-portioned flowing gels are often problematic because they tend to leak, for example when packaged in single-chamber or multi-chamber bags. At the same time, it is necessary for such gels to have good cleaning and rinsing performance.
Aufgabe der vorliegenden Erfindung ist es, ein System bereitzustellen, das besonders geeignete Gelformulierungen, umfassend PVOH und/oder dessen Derivate, bereitstellt, sowie die Bereitstellung von Reinigungsmitteln, bevorzugt Geschirrspülmitteln, insbesondere maschinellen Geschirrspülmitteln, die sich einfach und kosteneffizient produzieren lassen, eine gute
Lagerstabilität aufweisen und zusätzlich eine gute Reinigungs- und/oder Klarspülleistung aufweisen. The object of the present invention is to provide a system that provides particularly suitable gel formulations comprising PVOH and / or its derivatives, as well as the provision of cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, which can be produced easily and cost-effectively, a good Have storage stability and also have good cleaning and / or rinsing performance.
Ein erster Gegenstand der vorliegenden Erfindung betrifft Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, umfassend ein Gel, bevorzugt ein bei Raumtemperatur (20 °C) festes Gel umfassend, jeweils bezogen auf das Gesamtgewicht des Gels, 3 bis 40 Gew.-%, bevorzugt 4 bis 20 Gew.-%, insbesondere 5 bis 18 Gew.-%, PVOH und/oder dessen Derivate; sowie a. mindestens einer Komponente mit einem Parameter r <= 15,3 und b. mindestens einer Komponente mit einem Parameter r >= 16,3; sowie c. optional mindestens einen weiterer Aktivstoff, bevorzugt ausgewählt aus Farbstoffen, Glaskorrosionsinhibitoren, Parfüms, pH-Stellmitteln sowie weiteren Prozesshilfsmitteln; wobei mindestens eine der Komponenten gemäß a) oder b) bei 20 °C flüssig ist, und mit der Maßgabe, dass für die Mischung der Komponenten (Anzahl n) gemäß a) und b) bzw. a), b) und c) folgendes gilt:
und A first subject matter of the present invention relates to washing or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, comprising a gel, preferably a gel which is solid at room temperature (20° C.), comprising 3 to 40% by weight, based in each case on the total weight of the gel. %, preferably 4 to 20% by weight, in particular 5 to 18% by weight, PVOH and/or its derivatives; as well as a. at least one component with a parameter r <= 15.3 and b. at least one component with a parameter r >= 16.3; as well as c. optionally at least one further active ingredient, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20° C., and with the proviso that for the mixture of the components (number n) according to a) and b) or a), b) and c) the following is applicable: and
(dDMix - dD0 )2 + ( dPMix - dP0 )2 + ( dHMix - dH0 )2 = r2 wobei dD0 = 16,05 MPaz dP0 = 20,31 MPaz dH0 = 36,86 MPaz Und r= 14,0 bis 18,5 MPa1/2 ist. (dD Mix - dD 0 ) 2 + ( dP Mix - dP 0 ) 2 + ( dH Mix - dH 0 ) 2 = r 2 where dD 0 = 16.05 MPaz dP 0 = 20.31 MPaz dH 0 = 36.86 MPaz And r= 14.0 to 18.5 MPa 1/2 .
Polyvinylalkohol kann verschiedene Lösungsmittel verdicken und dadurch Gele bilden. Dabei wird das PVOH durch nicht-kovalente intermolekulare Wechselwirkungen stabilisiert. Die Hansen- Löslichkeitsparameter basieren auf einem semi-empirischen Konzept, das von Charles M. Hansen entwickelt wurde. Dabei kann jeder Stoff über die drei Hansenparameter, Dispervise/Van-der- Waals Kräfte (dD); Dipolare Wechselwirkungen (dP) und die Fähigkeit zur Bildung von Wasserstoffbrückenbindungen (dH), charakterisiert werden. Polyvinyl alcohol can thicken various solvents, thereby forming gels. Here, the PVOH is stabilized by non-covalent intermolecular interactions. The Hansen solubility parameters are based on a semi-empirical concept developed by Charles M. Hansen. Each substance can be analyzed using the three Hansen parameters, disperse/van der Waals forces (dD); Dipolar interactions (dP) and the ability to form hydrogen bonds (dH) can be characterized.
Diese Variablen spannen einen dreidimensionalen Raum, den Hansenraum auf, mit dem für einen definierten Gelator Regionen, in denen gute Löslichkeit gegeben ist, sowie gelierende Regionen aufgefunden werden können.
Die Hansenparameter für bestimmte Substanzen können durch Tests ihrer Löslichkeit in Referenzlösungsmitteln mit bekannten Hansenparametern ermittelt werden. Aufgrund solcher Daten ist es dann möglich, die Lage dieser Substanz im Hansenraum zu bestimmen (Hansen Parameters Users Handbook, 2nd Edition, 15. Juni 2007) These variables span a three-dimensional space, the Hansen space, with which regions with good solubility and gelling regions can be found for a defined gelator. The Hansen parameters for specific substances can be determined by testing their solubility in reference solvents with known Hansen parameters. Based on such data it is then possible to determine the location of this substance in the Hansen space (Hansen Parameters Users Handbook, 2nd Edition, June 15, 2007)
Die Hansenparameter für die Mischung verschiedener Substanzen (dDMix, dPMix, dHiwx) ergibt sich gemäß unten stehender Gleichung 1 aus der Linearkombination der Hansenparameter der Komponenten in der Mischung. Dabei bleibt PVOH in dieser Gleichung unberücksichtigt. Die Summe aller Substanzen ergänzt sich dabei zu 1 (Gleichung 2). The Hansen parameters for the mixture of different substances (dD Mix , dP Mix , dHiwx) result from the linear combination of the Hansen parameters of the components in the mixture according to Equation 1 below. PVOH is not taken into account in this equation. The sum of all substances adds up to 1 (equation 2).
S?=i c ί = 1 (Gleichung 2) S?= i c ί = 1 (equation 2)
Der geeignete Ausschnitt des Hansenraums (dreidimensionaler Raum aufgespannt durch dD, dP und dH), in dem Gelierung und Löslichkeit gegeben ist, wird durch eine Kugelfunktion mit dem Radius r angepasst, für den die Gleichung 3 gilt. The appropriate section of the Hansen space (three-dimensional space spanned by dD, dP and dH), in which gelation and solubility are given, is fitted by a spherical function with radius r, for which Equation 3 applies.
(dDMix — dD0)2 + {dP Mix — dP0)2 + (dHMix — d//0)2 = r2 (Gleichung 3) (dD Mix - dD 0 ) 2 + {dP Mix - dP 0 ) 2 + (dH Mix - d// 0 ) 2 = r 2 (Equation 3)
Es wurde nun gefunden, dass Gele, umfassend PVOH und/der dessen Derivaten, in einer Menge, jeweils bezogen auf das Gesamtgewicht des Gels, von 3 bis 40 Gew.-%, bevorzugt von 4 bis 20 Gew.-%, insbesondere von 5 bis 18 Gew.-%, besonders vorteilhafte Eigenschaften aufweisen, wenn sie zusätzlich die folgenden Parameter erfüllen. dD0 = 16,05 MRάϊ dP0 = 20,31 MPc dH0 = 36,86 MPc Und r= 14,0 bis 18,5 MPa1/2 ist. It has now been found that gels comprising PVOH and/or its derivatives in an amount, based in each case on the total weight of the gel, from 3 to 40% by weight, preferably from 4 to 20% by weight, in particular from 5 up to 18% by weight, have particularly advantageous properties if they also meet the following parameters. dD 0 = 16.05 MRάϊ dP 0 = 20.31 MPc dH 0 = 36.86 MPc and r = 14.0 to 18.5 MPa 1/2 .
Bei r> 18,5 zeigt das Gel unvorteilhafte Synärese, d.h. Austritt von Lösungsmittel, bei Lagerung, während wenn r< 14,0 ist, das Gel zu weich wird und nicht mehr die gewünschten Eigenschaften bezüglich der Festigkeit und der Formstabilität hat. At r > 18.5 the gel shows unfavorable syneresis, i.e. leakage of solvent, on storage, while at r < 14.0 the gel becomes too soft and no longer has the desired properties in terms of strength and dimensional stability.
Besonders bevorzugt sind solche Lösungen der Gleichung 3, bei denen der Radius r von r= 15,0 bis 17,5 beträgt. Solutions of Equation 3 in which the radius r is r=15.0 to 17.5 are particularly preferred.
Dabei ist es von besonderem Vorteil zur Steuerung von bevorzugten Eigenschaften des Gels, insbesondere der Lagerstabilität und/oder Erstarrungszeit, wenn mindestens eine Komponente mit
einem Parameter ra<= 15,3 MPa05, und mindestens eine Komponente mit einem Parameter rb>= 16,3 MPa05 sowie optional mindestens ein weiterer Aktivstoff, bevorzugt ausgewählt aus Farbstoffen, Glaskorrosionsinhibitoren, Parfüms, pH-Stellmitteln sowie weiteren Prozesshilfsmitteln eingesetzt werden, die die oben genannten Gleichungen erfüllen. It is of particular advantage to control preferred properties of the gel, in particular the storage stability and / or setting time, if at least one component with a parameter r a <= 15.3 MPa 05 , and at least one component with a parameter rb>= 16.3 MPa 05 and optionally at least one other active ingredient, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing aids that satisfy the above equations.
Komponenten gemäß a) sind also Stoffe, deren Koordinaten im Hansenraum sich auf oder innerhalb der Kugelfunktion gemäß Gleichung 3 mit der Maßgabe dD0 = 16,05 MPc dP0 = 20,31 MPc dH0 = 36,86 MPc mit ra<= 15,3 MPa05 befinden. Components according to a) are substances whose coordinates in the Hansen space are on or within the spherical function according to Equation 3 with the proviso dD 0 = 16.05 MPc dP 0 = 20.31 MPc dH 0 = 36.86 MPc with r a <= 15.3 MPa 05 are located.
Komponenten gemäß b) sind also Stoffe, deren Koordinaten im Hansenraum sich auf oder außerhalb der Kugelfunktion gemäß Gleichung 3 mit der Maßgabe dD0 = 16,05 MPc dP0 = 20,31 MPc dH0 = 36,86 MPc mit rb>= 16,3 MPa05 befinden. Components according to b) are substances whose coordinates in the Hansen space are on or outside the spherical function according to Equation 3 with the proviso dD 0 = 16.05 MPc dP 0 = 20.31 MPc dH 0 = 36.86 MPc with rb>= 16 .3 MPa 05 are located.
Wie vorstehend beschrieben, können die Hansenparameter (dD, dP, dH) für die einzelnen Komponenten experimentell durch Tests ihrer Löslichkeit in Referenzlösungsmitteln mit bekannten Hansenparametern ermittelt werden. As described above, the Hansen parameters (dD, dP, dH) for the individual components can be determined experimentally by testing their solubility in reference solvents with known Hansen parameters.
Dabei ist es bevorzugt, dass mindestens eine der Komponenten gemäß a) oder b) bei 20 °C flüssig ist. It is preferred that at least one of the components according to a) or b) is liquid at 20.degree.
Durch diese Funktion ist der Fachmann in der Lage, Komponentenkombinationen (sowohl hinsichtlich der Stoffe der Komponentenmischung als auch deren Gewichtsanteile) zu bestimmen, die eine besonders geeignete Gelformulierung erzeugen. This function enables the person skilled in the art to determine combinations of components (both in terms of the substances in the component mixture and their proportions by weight) which produce a particularly suitable gel formulation.
Dabei sind weist die Mischung bevorzugt keine Separation der Mischung der Einzelkomponenten bei 80 °C in einem Zeitraum von 10 min, bevorzugt 20 min nach Mischung der Komponenten auf. The mixture preferably has no separation of the mixture of the individual components at 80° C. in a period of 10 minutes, preferably 20 minutes, after the components have been mixed.
Unter einem Gel, bzw. einer gelförmigen Phase, im weiteren auch Gelphase genannt, ist erfindungsgemäß eine Zusammensetzung (bzw. Phase) zu verstehen, welche ein intern strukturierendes Netzwerk aufweist. Dieses intern strukturierende (räumliche) Netzwerk wird durch die Dispersion eines festen, aber verteilten Stoff mit langen oder stark verzweigten Teilchen und/oder Gelbildner, hier Polyvinylalkohol und/oder dessen Derivaten, in mindestens einer Flüssigkeit (die mindestens eine Flüssigkeit ist flüssig bei 20 °C) gebildet. Solche Gelphasen verhalten sich thermoreversibel.
Das Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, kann dabei eine, zwei, drei, vier oder mehr Gele bzw. Gelphasen aufweisen. Die Gele/Gelphasen können dabei gleich oder verschieden sein. Im Falle mehrere Gele bzw. Gelphasen sind diese bevorzugt räumlich, optisch oder anhand ihrer Inhaltsstoffe unterscheidbar. Sind die Gele / Gelphasen verschieden, so können sie unterschiedliche Farbstoffe sowie unterschiedliche Zugaben von Aktivstoffen aufweisen. According to the invention, a gel or a gel-like phase, also referred to below as a gel phase, means a composition (or phase) which has an internally structuring network. This internal structuring (spatial) network is formed by the dispersion of a solid but distributed substance with long or highly branched particles and/or gelling agent, here polyvinyl alcohol and/or its derivatives, in at least one liquid (the at least one liquid is liquid at 20° C) formed. Such gel phases behave thermoreversibly. The washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, can have one, two, three, four or more gels or gel phases. The gels/gel phases can be the same or different. In the case of several gels or gel phases, these can preferably be distinguished spatially, optically or on the basis of their ingredients. If the gels/gel phases are different, they can have different dyes and different additions of active ingredients.
Das Gel ist formstabil. Bei der Herstellung wird der Polyvinylalkohol und/oder dessen Derivate mit Glycerin in Kontakt gebracht. Hierdurch erhält man eine fließfähige Mischung, welche in eine gewünschte Form gebracht werden kann. Nach einem gewissen Zeitraum erhält man ein Gel/eine Gelphase, die in der vorgegebenen Form bleibt, also formstabil ist. Dieser Zeitraum, die Erstarrungszeit, beträgt vorzugsweise 15 Minuten oder weniger, vorzugsweise 10 Minuten oder weniger, besonders bevorzugt 5 Minuten oder weniger. Dabei gibt das Gel auf Druck nach, verformt sich hierdurch jedoch nicht, sondern kehrt nach Wegfall des Drucks in den Ausgangszustand zurück. Das Gel ist vorzugsweise elastisch, insbesondere linear-elastisch. The gel is dimensionally stable. During production, the polyvinyl alcohol and/or its derivatives are brought into contact with glycerol. This gives a flowable mixture which can be brought into a desired shape. After a certain period of time, a gel/a gel phase is obtained which remains in the specified form, i.e. is dimensionally stable. This period of time, the setting time, is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes or less. The gel gives way under pressure, but does not deform as a result, but returns to its original state after the pressure is removed. The gel is preferably elastic, in particular linear-elastic.
Das Gel ist bevorzugt ein Formkörper. Ein Formkörper ist ein einzelner Körper, der sich in seiner aufgeprägten Form selbst stabilisiert. Dieser formstabile Körper wird aus einer Formmasse (z.B. eine Zusammensetzung) dadurch gebildet, dass diese Formmasse gezielt in eine vorgegebene Form gebracht wird, z.B. durch Gießen einer flüssigen Zusammensetzung in eine Gussform und anschließendem Aushärten der flüssigen Zusammensetzung, z.B. im Rahmen eines Sol-Gel- Prozesses. The gel is preferably a shaped body. A molded body is a single body that stabilizes itself in its imposed shape. This dimensionally stable body is formed from a molding compound (e.g. a composition) by deliberately bringing this molding compound into a predetermined shape, e.g. by pouring a liquid composition into a mold and then curing the liquid composition, e.g. as part of a sol-gel process.
An Formulierungen der wenigstens einen Gelphase werden bestimmte Mindestanforderungen gestellt. So muss, wie bereits ausgeführt, das Gel innerhalb einer möglichst kurzen Zeit erstarren. Lange Erstarrungszeiten würden zu einer langen Produktionsdauer und damit zu hohen Kosten führen. Erfindungsgemäß bedeutet Erstarrungszeit der Zeitraum, innerhalb dessen bei der Herstellung das Gel von einem fließfähigen in einen bei Raumtemperatur nicht-fließfähigen, formstabilen Zustand übergeht. Unter Raumtemperatur ist dabei eine Temperatur von 20 °C zu verstehen. Sofern hierin Temperaturen genannt sind, sind diese, soweit nichts anderes vermerkt, gemessen bei einem Druck von 1013 mbar zu verstehen. Certain minimum requirements are placed on formulations of the at least one gel phase. As already stated, the gel must solidify within the shortest possible time. Long solidification times would lead to a long production time and thus to high costs. According to the invention, the setting time means the period of time during which the gel changes from a flowable to a non-flowable, dimensionally stable state at room temperature during production. Room temperature is understood to mean a temperature of 20°C. Where temperatures are mentioned herein, unless otherwise noted, they are to be understood as measured at a pressure of 1013 mbar.
Das Gel ist eine feste Gelphase. Sie ist dabei bevorzugt schnittfest. Sie kann beispielsweise mit einem Messer nach der Erstarrung geschnitten werden, ohne dass sie, außer an der Stelle des durchgeführten Schnitts, weiter zerstört wird. The gel is a solid gel phase. It is preferably cut-resistant. It can, for example, be cut with a knife after it has solidified without being destroyed further, except at the point where the cut was made.
Eine Phase im Sinne der vorliegenden Erfindung ist ein räumlicher Bereich, in dem physikalische Parameter und die chemische Zusammensetzung homogen sind. Eine Phase unterscheidet sich von einer anderen Phase durch verschiedene Merkmale, beispielsweise Inhaltsstoffe,
physikalische Eigenschaften, äußeres Erscheinungsbild etc. Bevorzugt können verschiedene Phasen optisch unterschieden werden. A phase within the meaning of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various characteristics, such as ingredients, physical properties, external appearance, etc. Different phases can preferably be distinguished visually.
So ist für den Verbraucher die wenigstens eine Gelphase von anderen Phasen (feste, bevorzugt körnige, flüssige oder gelförmige) eindeutig zu unterschieden. Weist das erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, mehr als eine Gelphase auf, so können diese ebenfalls jeweils mit dem bloßen Auge voneinander unterschieden werden, weil sie sich beispielsweise in der Farbgebung voneinander unterscheiden. Gleiches gilt, wenn zwei oder mehr Gelphasen vorliegen. Auch in diesem Fall ist eine optische Unterscheidung der Phasen, beispielsweise auf Grund eines Farb- oder Transparenzunterschiedes möglich. Phasen im Sinne der vorliegenden Erfindung sind somit in sich abgeschlossene Bereiche, die vom Verbraucher optisch mit dem bloßen Auge voneinander unterschieden werden können. Die einzelnen Phasen können bei der Verwendung unterschiedliche Eigenschaften aufweisen, wie beispielsweise die Geschwindigkeit, mit der sich die Phase in Wasser löst und somit die Geschwindigkeit und die Reihenfolge der Freisetzung der in der jeweiligen Phase enthaltenen Inhaltsstoffe. Thus, the at least one gel phase can be clearly distinguished from other phases (solid, preferably granular, liquid or gel-like) for the consumer. If the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, has more than one gel phase, these can also be distinguished from one another with the naked eye because they differ from one another, for example in terms of color. The same applies if two or more gel phases are present. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a difference in color or transparency. Phases within the meaning of the present invention are therefore self-contained areas which the consumer can visually distinguish from one another with the naked eye. The individual phases can have different properties when used, such as the speed with which the phase dissolves in water and thus the speed and sequence of release of the ingredients contained in the respective phase.
Das Gel ist zudem vorzugsweise transluzent (durchscheinend) oder transparent, wodurch sich ein guter optischer Eindruck ergibt. Bevorzugt liegt die Transmission der Gelphase (ohne Farbstoff) in einem Bereich zwischen 100 % und 20 %, zwischen 100 % und 30 %, insbesondere zwischen 100 % und 40 %. Zur Messung der Lichtdurchlässigkeit (Transmission) wurde die Durchgängigkeit in % bei 600 nm gegen Wasser als Referenz bei 20 °C ermittelt. Die Masse wurde dafür in die vorgesehenen 11 mm Rundküvetten gegossen und nach 12 h Lagerzeit bei Raumtemperatur in einem LICO 300 Farbmesssystem nach Lange vermessen. In addition, the gel is preferably translucent (translucent) or transparent, which results in a good optical impression. The transmittance of the gel phase (without dye) is preferably in a range between 100% and 20%, between 100% and 30%, in particular between 100% and 40%. To measure the light transmittance (transmission), the permeability was determined in % at 600 nm against water as a reference at 20 °C. For this purpose, the mass was poured into the 11 mm round cuvettes provided and, after a storage time of 12 h at room temperature, measured in a LICO 300 color measuring system according to Lange.
Die erfindungsgemäßen Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, enthalten Polyvinylalkohol und/oder dessen Derivate, in einer Menge von 3 bis 40, insbesondere von 4 bis 30 Gew.-%, besonders bevorzugt in einer Menge von 5 bis 18 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Gels. The detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain polyvinyl alcohol and/or its derivatives in an amount of 3 to 40% by weight, in particular 4 to 30% by weight, particularly preferably in an amount of 5 to 18% by weight %, in each case based on the total weight of the gel.
Polyvinylalkohole sind thermoplastische Kunststoffe, die als weißes bis gelbliches Pulver meistens durch Hydrolyse von Polyvinylacetat hergestellt werden. Teilhydrolyiserter Polyvinylalkohol, welcher noch Mengen von bis zu 30 Mol% nicht hydroylisiertes Acetylgruppen aufweist, ist als Polyvinylalkohol im Sinne der Erfindung zu verstehen. Polyvinylalkohol (PVOH) ist beständig gegen fast alle wasserfreien organischen Lösemittel. Bevorzugt sind Polyvinylalkohole mit einer Molmasse von 30.000 bis 60.000 g/mol. Polyvinyl alcohols are thermoplastics that are usually produced as a white to yellowish powder by the hydrolysis of polyvinyl acetate. Partially hydrolyzed polyvinyl alcohol which still has amounts of up to 30 mol % of non-hydrolyzed acetyl groups is to be understood as polyvinyl alcohol in the context of the invention. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molar mass of 30,000 to 60,000 g/mol are preferred.
Besonders bevorzugt sind Polyvinylalkohole, die als weiß-gelbliche Pulver oder Granulate mit Polymerisationsgraden im Bereich von ca. 100 bis 2500 (Molmassen von ca. 4000 bis 100.000
g/mol) und Hydrolysegraden von 80 bis 99 Mol%, bevorzugt von 85 bis 90 Mol%, insbesondere von 87 bis 89 Mol%, beispielsweise 88 Mol% aufweisen, die dementsprechend noch einen Restgehalt an Acetyl-Gruppen enthalten. Particularly preferred are polyvinyl alcohols, which are available as yellowish-white powders or granules with degrees of polymerization in the range from about 100 to 2500 (molecular weights from about 4000 to 100,000 g/mol) and degrees of hydrolysis from 80 to 99 mol%, preferably from 85 to 90 mol%, in particular from 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.
Gemäß einer bevorzugten Ausführungsform umfasst das Gel PVOH (Polyvinylalkohol). Diese somit hergestellten Gele bzw. Gelphasen sind besonders hochschmelzend, formstabil (auch bei 40 °C) und verändern ihre Form auch bei Lagerung nicht oder nur unwesentlich. Insbesondere sind sie auch wenig reaktiv im Hinblick auf eine direkte negative Wechselwirkung mit Bestandteilen eines körnigen Gemenges, insbesondere einer zusätzlichen Pulverphase. PVOH kann sowohl wasserhaltige, aber auch wasserarme bzw. wasserfreie Gelphasen erzeugen. Bei der Verwendung von PVOH als Polymer für das Gel ergeben sich bei 80-90 °C oder 110-120 °C dünnflüssige Schmelzen, die dadurch besonders leicht verarbeitet werden können, insbesondere kann das Einfüllen der Gelphase in die wasserlösliche Umhüllung schnell und genau vorgenommen werden, ohne dass ein Verkleben stattfindet oder die Menge ungenau dosiert wird. Des Weiteren haften diese Gelphasen besonders gut an der wasserlöslichen Umhüllung, insbesondere, wenn diese aus ebenfalls aus PVOH hergestellt ist. Dies ist auch optisch von Vorteil. Durch die schnelle Verfestigung der wenigstens einen Gelphase mit PVOH kann die Weiterverarbeitung der Gelphasen besonders schnell erfolgen. Weiterhin ist die gute Löslichkeit der erzeugten Gelphasen für die Gesamtlöslichkeit des Wasch- oder Reinigungsmittels, besonders günstig. Außerdem sind Gelphasen mit solch kurzen Verfestigungszeiten vorteilhaft, für den Fall, dass eine darauf dosierte feste, bevorzugt körnige Phase, umfassend körnige Gemenge, insbesondere Pulver, nicht in das noch nicht völlig erstarrte oder zu weiche Gel einsinkt. Dies führt optisch zu wenig ansprechenden Wasch- oder Reinigungsmittelportionen. According to a preferred embodiment, the gel comprises PVOH (polyvinyl alcohol). The gels or gel phases produced in this way have a particularly high melting point, are dimensionally stable (even at 40° C.) and do not change their shape, if at all, only insignificantly, even during storage. In particular, they are also not very reactive with regard to a direct negative interaction with components of a granular mixture, in particular an additional powder phase. PVOH can produce both water-containing and water-poor or water-free gel phases. When using PVOH as a polymer for the gel, low-viscosity melts result at 80-90 °C or 110-120 °C, which are particularly easy to process. In particular, the gel phase can be filled into the water-soluble coating quickly and precisely , without sticking or the amount being dosed imprecisely. Furthermore, these gel phases adhere particularly well to the water-soluble coating, in particular if this is also made from PVOH. This is also a visual advantage. Due to the rapid solidification of the at least one gel phase with PVOH, the further processing of the gel phases can take place particularly quickly. Furthermore, the good solubility of the gel phases produced is particularly favorable for the overall solubility of the washing or cleaning agent. In addition, gel phases with such short setting times are advantageous in the event that a solid, preferably granular phase dosed thereon, comprising granular mixtures, in particular powder, does not sink into the gel that is not yet completely solidified or is too soft. This leads to visually unappealing washing or cleaning agent portions.
Besonders bevorzugt sind Polyvinylalkohole, die als weiß-gelbliche Pulver oder Granulate mit Polymerisationsgraden im Bereich von ca. 100 bis 2500 (Molmassen von ca. 4000 bis 100.000 g/mol) und Hydrolysegraden von 80 bis 99 Mol%, bevorzugt von 85 bis 90 Mol%, insbesondere von 87 bis 89 Mol%, beispielsweise 88 Mol% aufweisen, die dementsprechend noch einen Restgehalt an Acetyl-Gruppen enthalten. Particular preference is given to polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range from about 100 to 2500 (molar masses from about 4000 to 100,000 g/mol) and degrees of hydrolysis from 80 to 99 mol%, preferably from 85 to 90 mol %, in particular from 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.
PVOH Pulver, mit den vorstehend genannten Eigenschaften, welche zum Einsatz in der wenigstens einen Gelphasen geeignet sind, werden beispielsweise unter der Bezeichnung Mowiol® oder Poval® von Kuraray vertrieben. Geeignet ist z.B. auch Exceval® AQ4104 von Kuraray. Besonders geeignet sind Mowiol C30, die Poval® Qualitäten, insbesondere die Qualitäten 3-83, 3-88, 6-88, 4-85, und besonders bevorzugt 4-88, ganz besonders bevorzugt Poval 4-88 S2 sowie Mowiol® 4-88 von Kuraray. PVOH powders with the properties mentioned above, which are suitable for use in the at least one gel phase, are marketed, for example, by Kuraray under the name Mowiol® or Poval®. Exceval® AQ4104 from Kuraray, for example, is also suitable. Particularly suitable are Mowiol C30, the Poval® qualities, in particular the qualities 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, very particularly preferably Poval 4-88 S2 and Mowiol® 4- 88 by Kuraray.
Als Derivate des PVOH sind im Sinne der Erfindung bevorzugt Copolymere von Polyvinylalkohol mit anderen Monomeren, insbesondere Copolymer mit anionischen Monomeren. Als anionische
Monomere sind bevorzugt geeignet Vinylessigsäure, Alkylacrylate, Maleinsäure und deren Derivate, insbesondere Monoalkylmaleate (insbesondere Monomethylmaleat), Dialkylmaleate (insbesondere Dimethylmaleat), Maleinsäureanhydrid, Fumarsäure und deren Derivate, insbesondere Monoalkylfumarat (insbesondere Monomethylfumarat), Dialkylfumarat (insbesondere Dimethylfumarat), Fumarsäureanhydrid, Itaconsäure und deren Derivate, insbesondere Monomethylitaconat, Dialkylitaconat, Dimethylitaconat, Itaconsäureanhydrid, Citraconsäure (Methylmaleinsäure) und deren Derivate, Monoalkylcitraconsäure (insbesondere Methylcitraconat), Dialkylcitraconsäure (Dimethylcitraconat), Citraconsäureanhydrid, Mesaconsäure (Methylfumarsäure) und deren Derivate, Monoalkylmesaconat, Dialkylmesaconat, Mesaconsäureanhydrid, Glutaconsäure und deren Derivate, Monoalkylglutaconat,According to the invention, preferred derivatives of PVOH are copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers. As anionic Monomers are preferably suitable vinylacetic acid, alkyl acrylates, maleic acid and their derivatives, in particular monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, fumaric acid and their derivatives, especially monoalkyl fumarate (especially monomethyl fumarate), dialkyl fumarate (especially dimethyl fumarate), fumaric anhydride, itaconic acid and derivatives thereof, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and derivatives thereof, monoalkyl citraconic acid (especially methyl citraconic acid), dialkyl citraconic acid (dimethyl citraconic acid), citraconic acid anhydride, mesaconic acid (methyl fumaric acid) and derivatives thereof, monoalkyl mesaconate, dialkyl mesaconate, mesaconic acid anhydride, glutaconic acid and their derivatives derivatives, monoalkyl glutaconate,
Dialkylglutaconat, Glutaconsäureanhydrid, Vinylsulfonsäure, Alkylsulfonsäure, Ethylensulfonsäure, 2-Acrylamido-1 -methylpropansulfonsäure, 2-acrylamido-2-methylpropansulfonsäure, 2- Methylacrylamido-2-methylpropansulfonsäure, 2-Sulfoethylacrylat sowie deren Kombinationen sowie die Alkalimetallsalze oder Ester der vorstehend genannten Monomere. Dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate and combinations thereof and the alkali metal salts or esters of the abovementioned monomers.
Besonders bevorzugt sind als Derivate von PVOH solche, die ausgewählt sind aus Copolymeren von Polyvinylalkohol mit einem Monomer insbesondere ausgewählt aus der Gruppe der Monoalkylmaleate (insbesondere Monomethylmaleat), Dialkylmaleate (insbesondere Dimethylmaleat), Maleinsäureanhydrid, und deren Kombinationen, sowie die Alkalisalze oder Ester der vorstehend genannten Monomere. Für die geeigneten Molmassen gilt das für Polyvinylalkohole selbst angegebenen Werte. Im Rahmen der vorliegenden Erfindung ist es bevorzugt, dass das Gel einen Polyvinylalkohol und/oder dessen Derivate, bevorzugt Polyvinylalkohol, umfasst, dessen Hydrolysegrad vorzugsweise 70 bis 100 Mol-%, insbesondere 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und vor allem 82 bis 88 Mol-% beträgt. Particularly preferred derivatives of PVOH are those selected from copolymers of polyvinyl alcohol with a monomer selected in particular from the group of monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, and combinations thereof, and the alkali metal salts or esters of the above mentioned monomers. The values given for the polyvinyl alcohols themselves apply to the suitable molar masses. In the context of the present invention, it is preferred that the gel comprises a polyvinyl alcohol and/or derivatives thereof, preferably polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol %, in particular 80 to 90 mol %, particularly preferably 81 to 89 mol %. % and especially 82 to 88 mol%.
Die Wasserlöslichkeit von Polyvinylalkohol kann durch Nachbehandlung mit Aldehyden (Acetalisierung) oder Ketonen (Ketalisierung) verändert werden. Auch dieses sind als Derivate von Polyvinylalkohol zu verstehen. Als besonders bevorzugt und aufgrund ihrer ausgesprochen guten Kaltwasserlöslichkeit besonders vorteilhaft haben sich hierbei Polyvinylalkohole herausgestellt, die mit den Aldehyd- bzw. Ketogruppen von Sacchariden oder Polysacchariden oder Mischungen hiervon acetalisiert bzw. ketalisiert werden. Als äußerst vorteilhaft einzusetzen sind die Reaktionsprodukte aus Polyvinylalkohol und Stärke. Weiterhin lässt sich die Wasserlöslichkeit durch Komplexierung mit Ni- oder Cu-Salzen oder durch Behandlung mit Dichromaten, Borsäure, Borax verändern und so gezielt auf gewünschte Werte einstellen. The water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). These are also to be understood as derivatives of polyvinyl alcohol. Polyvinyl alcohols which are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous due to their extremely good solubility in cold water. The reaction products of polyvinyl alcohol and starch can be used extremely advantageously. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to desired values.
Optional kann mindestens ein weiterer Aktivstoff, bevorzugt ausgewählt aus Farbstoffen, Parfüms, pH-Stellmitteln sowie weiteren Prozesshilfsmitteln eingesetzt werden.
Bevorzugt umfasst das erfindungsgemäße Gel weniger als 1 Gew.-%, insbesondere weniger als 0,5 Gew.-%, besonders bevorzugt weniger als 0,1 Gew.-% mindestens einer Benzylidenalditol- Verbindung der Formel (I),
worin Optionally, at least one further active ingredient, preferably selected from dyes, perfumes, pH adjusters and other processing auxiliaries, can be used. The gel according to the invention preferably comprises less than 1% by weight, in particular less than 0.5% by weight, particularly preferably less than 0.1% by weight, of at least one benzylidene alditol compound of the formula (I), wherein
*- für eine kovalente Einfachbindung zwischen einem Sauerstoffatom des Alditol- Grundgerüsts und dem vorgesehenen Rest steht, n für 0 oder 1 , bevorzugt für 1 , steht, m für 0 oder 1 , bevorzugt für 1 , steht, *- stands for a covalent single bond between an oxygen atom of the alditol backbone and the intended residue, n stands for 0 or 1, preferably for 1, m stands for 0 or 1, preferably for 1, stands,
R1 , R2 und R3 unabhängig voneinander steht für ein Wasserstoffatom, ein Halogenatom, eine C1- C4-Alkylgruppe, eine Cyanogruppe, eine Nitrogruppe, eine Aminogruppe, eine Carboxylgruppe, eine Hydroxygruppe, eine Gruppe-C(=0)-NH-NH2, eine Gruppe -NHC(= R1, R2 and R3 independently represent a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group -C(=0)-NH-NH2, a group -NHC(=
0)-(C2-C4-Alkyl), eine C1-C4-Alkoxygruppe, eine C1-C4-Alkoxy-C2-C4-alkylgruppe, zwei der Reste gemeinsam mit dem Restmolekül einen 5- oder 6-gliedrigen Ring bilden, 0)-(C2-C4-alkyl), a C1-C4-alkoxy group, a C1-C4-alkoxy-C2-C4-alkyl group, two of the radicals together with the remainder molecule form a 5- or 6-membered ring,
R4, R5 und R6 unabhängig voneinander steht für ein Wasserstoffatom, ein Halogenatom, eine C1- C4-Alkylgruppe, eine Cyanogruppe, eine Nitrogruppe, eine Aminogruppe, eine Carboxylgruppe, eine Hydroxygruppe, eine Gruppe-C(=0)-NH-NH2, eine Gruppe -NHC(= R4, R5 and R6 independently represent a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group -C(=0)-NH-NH2, a group -NHC(=
0)-(C2-C4-Alkyl), eine C1-C4-Alkoxygruppe, eine C1-C4-Alkoxy-C2-C4-alkylgruppe, zwei der Reste gemeinsam mit dem Restmolekül einen 5- oder 6-gliedrigen Ring bilden. 0)-(C2-C4-alkyl), a C1-C4-alkoxy group, a C1-C4-alkoxy-C2-C4-alkyl group, two of the radicals together with the remainder molecule form a 5- or 6-membered ring.
Insbesondere umfasst das erfindungsgemäße Gel weniger als 1 Gew.-%, insbesondere weniger als 0,5 Gew.-%, besonders bevorzugt weniger als 0,1 Gew.-% der Verbindungen ausgewählt aus 1 ,3:2,4-Di-0-benzyliden-D-sorbitol; 1 ,3:2,4-Di-0-(p-methyl- benzyliden)-D-sorbitol; 1 ,3:2,4-Di-0-(p- chlorobenzyliden)-D-sorbitol; 1 ,3:2,4-Di-0-(2,4-dimethylbenzyliden)-D- sorbitol; 1 ,3:2,4-Di-Q-(p-
ethylbenzyliden)-D-sorbitol; 1 ,3:2,4-Di-0-(3,4-dimethylbenzyliden)-D-sorbitol oder Mischungen daraus. In particular, the gel according to the invention comprises less than 1% by weight, in particular less than 0.5% by weight, particularly preferably less than 0.1% by weight, of the compounds selected from 1,3:2,4-Di-O -benzylidene-D-sorbitol; 1,3:2,4-di-0-(p-methyl-benzylidene)-D-sorbitol; 1,3:2,4-di-O-(p-chlorobenzylidene)-D-sorbitol; 1,3:2,4-di-0-(2,4-dimethylbenzylidene)-D-sorbitol; 1,3:2,4-Di-Q-(p- ethylbenzylidene)-D-sorbitol; 1,3:2,4-di-0-(3,4-dimethylbenzylidene)-D-sorbitol or mixtures thereof.
Gemäß einer bevorzugten Ausführungsform umfasst das erfindungsgemäße Gel als einzigen Gelbildner Polyvinylalkohol wie vorstehend beschrieben. Andere Gelbildner außer PVOH sind bevorzugt nicht im Gel enthalten. According to a preferred embodiment, the gel according to the invention comprises polyvinyl alcohol as the only gel former, as described above. Gel formers other than PVOH are preferably not contained in the gel.
Gemäß einer bevorzugten Ausführungsform ist im Gel mindestens eine bei 20 °C flüssige Komponente gemäß a), also eine Komponente mit einem Parameter ra kleiner oder gleich 15,3 MPa05, bevorzugt kleiner als 15,3 MPa05, insbesondere bevorzugt kleiner als 15,2 MPa05, ganz besonders bevorzugt kleiner als 15,0 MPa05 enthalten. Das verbesserte die Lösungsfähigkeit des PVOH-Gelbildners und führt so zu einer einfacheren Verarbeitbarkeit des Gels. According to a preferred embodiment, the gel contains at least one component according to a), which is liquid at 20° C., i.e. a component with a parameter ra less than or equal to 15.3 MPa 05 , preferably less than 15.3 MPa 05 , particularly preferably less than 15 2 MPa 05 , very particularly preferably less than 15.0 MPa 05 . This improves the ability of the PVOH gelling agent to dissolve, making the gel easier to process.
Gemäß einer besonders bevorzugten Ausführungsform ist im Gel mindestens eine bei 20 °C flüssige Komponente gemäß a), also eine Komponente mit einem Parameter rb größer oder gleich 16,3, und mindestens eine bei 20 °C flüssige Komponente gemäß b) enthalten. Dadurch kann die Einstellung der Parameter insbesondere im Hinblick auf die Lösungsfähigkeit und die Gelbildungseigenschaften, insbesondere die Erstarrungszeit und Härte des Gels, noch besser gesteuert werden. According to a particularly preferred embodiment, the gel contains at least one component according to a) which is liquid at 20° C., ie a component with a parameter rb greater than or equal to 16.3, and at least one component according to b) which is liquid at 20° C. As a result, the setting of the parameters, in particular with regard to the ability to dissolve and the gel-forming properties, in particular the setting time and hardness of the gel, can be controlled even better.
Gemäß einer besonders bevorzugten Ausführungsform sind im Gel mindestens eine Komponente gemäß a), bevorzugt eine bei 20 °C flüssige Komponente gemäß a), und mindestens zwei Komponenten gemäß b), bevorzugt zwei bei 20 °C flüssige Komponenten gemäß b), enthalten. Die Einstellung und Kontrolle der besonders wichtigen Gelierungsparameter hinsichtlich Lagerstabilität und Erstarrungszeit gelingt dadurch viel einfacher. According to a particularly preferred embodiment, the gel contains at least one component according to a), preferably one component according to a) which is liquid at 20° C. and at least two components according to b), preferably two components according to b) which are liquid at 20° C. This makes it much easier to set and control the particularly important gelation parameters with regard to storage stability and setting time.
Gemäß einer besonders bevorzugten Ausführungsform ist die Komponente a) ausgewählt aus der Gruppe gebildet aus Wasser, Glycerin und den oligomeren oder polymeren Carboxylaten, bevorzugt Polycarboxylaten wie sie unten ausführlich beschrieben werden, insbesondere bevorzugt Polyacrylaten, ganz besonders bevorzugt sulfonsäuregruppenhaltigen Polyacrylaten. According to a particularly preferred embodiment, component a) is selected from the group consisting of water, glycerol and the oligomeric or polymeric carboxylates, preferably polycarboxylates as described in detail below, particularly preferably polyacrylates, very particularly preferably polyacrylates containing sulfonic acid groups.
Dabei ist mindestens eine der Komponenten gemäß a), bevorzugt zwei oder mehr, insbesondere drei oder mehr der Komponenten gemäß a) in den erfindungsgemäßen Gelen enthalten. At least one of the components according to a), preferably two or more, in particular three or more, of the components according to a) is present in the gels according to the invention.
Besonders bevorzugt sind als bei 20 °C flüssige Komponente gemäß a) Glyzerin oderWasser sowie Mischungen daraus. Particular preference is given to components a) which are liquid at 20° C. are glycerol or water and mixtures thereof.
Bevorzugt umfasst das Gel Oligomere oder polymere Carboxylate, wie zum Beispiel Citrate, Aminocarboxylate und/oder Polycarboxylate, wie sie unten ausführlich beschrieben werden. Beispielsweise genannt seien z.B. Acrylat-Homopolymere oder Acrylatcopolymer, z.B.
Maleinsäure-Acrylsäure-Copolymer-Na-Salz oder Sulfopolymere. Diese können entweder als Gerüststoffe und/oder als Verdickungspolymer wirken. Als Polycarboxylat wird vorzugsweise ein copolymeres Polyacrylat, vorzugsweise ein Sulfopolymer vorzugsweise ein copolymeres Polysulfonat, vorzugsweise ein hydrophob modifiziertes copolymeres Polysulfonat eingesetzt. Die Copolymere können zwei, drei, vier oder mehr unterschiedliche Monomereinheiten aufweisen. Bevorzugte Copolymere Polysulfonate enthalten neben Sulfonsäuregruppen-haltigem(n) Monomer(en) wenigstens ein Monomer aus der Gruppe der ungesättigten Carbonsäuren. The gel preferably comprises oligomers or polymeric carboxylates, such as citrates, amino carboxylates and/or polycarboxylates, as described in detail below. Examples which may be mentioned are acrylate homopolymers or acrylate copolymers, e.g Maleic acid-acrylic acid copolymer sodium salt or sulfopolymers. These can act either as builders and/or as a thickening polymer. A copolymeric polyacrylate, preferably a sulphopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the polycarboxylate. The copolymers can have two, three, four or more different monomer units. In addition to monomer(s) containing sulfonic acid groups, preferred copolymers polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.
Gemäß einer besonders bevorzugten Ausführungsform enthält die gelförmige Phase als eine der Komponenten gemäß a) also einer Komponente mit einem Hansen Parameter r kleiner oder gleich 15,3, ein Polymer umfassend mindestens ein Sulfonsäuregruppenhaltiges Monomer. According to a particularly preferred embodiment, the gel-like phase contains as one of the components according to a), ie a component with a Hansen parameter r less than or equal to 15.3, a polymer comprising at least one sulfonic acid-containing monomer.
Als ungesättigte Carbonsäure(n) wird/werden mit besonderem Vorzug ungesättigte Carbonsäuren der Formel R1(R2)C=C(R3)COOH eingesetzt, in der R1 bis R3 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder-COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettig er oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist. The unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R 1 (R 2 )C═C(R 3 )COOH, in which R 1 to R 3 independently represent —H, —CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -OH or -COOH as defined above or for -COOH or- COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
Besonders bevorzugte ungesättigte Carbonsäuren sind Acrylsäure, Methacrylsäure, Ethacrylsäure, a-Chloroacrylsäure, a-Cyanoacrylsäure, Crotonsäure, a-Phenyl-Acrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Citraconsäure, Methylenmalonsäure, Sorbinsäure, Zimtsäure oder deren Mischungen. Einsetzbar sind selbstverständlich auch die ungesättigten Dicarbonsäuren. Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.
Bei den Sulfonsäuregruppen-haltigen Monomeren sind solche der Formel R5(R6)C=C(R7)-X-S03H bevorzugt, in der R5 bis R7 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit - NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für -COOH oder-COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettiger oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(0)-NH-C(CH3)2-, - C(0)-NH-C(CH3)2-CH2- und -C(0)-NH-CH(CH3)-CH2-. In the case of the sulfonic acid group-containing monomers, preference is given to those of the formula R 5 (R 6 )C═C(R 7 )—X—SO 3 H, in which R 5 to R 7 independently represent —H, —CH 3 , a straight-chain or branched saturated Alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH2, -OH or -COOH or -COOH or -COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group selected from -(CH2)n- with n = 0 to 4, -COO-(CH2)k - with k = 1 to 6, -C(0)-NH-C(CH3)2-, - C(0)-NH-C(CH 3 )2-CH 2 - and -C(0)-NH- CH(CH3 ) -CH2 -.
Unter diesen Monomeren bevorzugt sind solche der Formeln H2C=CH-X-S03H, H2C=C(CH3)-X-S03H oder H03S-X-(R6)C=C(R7)-X-S03H,
in denen R6 und R7 unabhängig voneinander ausgewählt sind aus -H, -Chh, -CH2CH3, - CH2CH2CH3 und -CH(CH3)2 und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(0)-NH-C(CH3)2-, - C(0)-NH-C(CH3)2-CH2- und -C(0)-NH-CH(CH3)-CH2-. Preferred among these monomers are those of the formulas H 2 C=CH-X-S0 3 H, H 2 C=C(CH 3 )-X-S0 3 H or H0 3 SX-(R 6 )C=C(R 7 ) -X-S0 3 H, in which R 6 and R 7 are independently selected from -H, -Chh, -CH2CH3, -CH2CH2CH3 and -CH(CH 3 )2 and X is an optionally present spacer group selected from -(CH2)n- with n = 0 to 4, -COO-(CH2)k- with k = 1 to 6, -C(0)-NH-C(CH3)2-, -C(0)-NH-C(CH 3 ) 2-CH 2 - and -C(0)-NH-CH(CH 3 )-CH 2 -.
Gemäß einer besonders bevorzugten Ausführungsform enthält die das Gel / die Gelphase ein Polymer umfassend als sulfonsäuregruppenhaltiges Monomer Acrylamidopropansulfonsäuren, Methacrylamidomethylpropansulfonsäuren oder Acrylamidomethylpropansulfonsäure. According to a particularly preferred embodiment, the gel/gel phase contains a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as the monomer containing sulfonic acid groups.
Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acrylamido-1- propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methyl-1 - propansulfonsäure, 2-Methacrylamido-2-methyl-1-propansulfonsäure, 3-Methacrylamido-2- hydroxy-propansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2- propenl -Sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 3- Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Mischungen der genannten Säuren oder deren wasserlösliche Salze. In den Polymeren können die Sulfonsäuregruppen ganz oder teilweise in neutralisierter Form vorliegen, das heißt dass das acide Wasserstoffatom der Sulfonsäuregruppe in einigen oder allen Sulfonsäuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Der Einsatz von teil- oder vollneutralisierten Sulfonsäuregruppen-haltigen Copolymeren ist erfindungsgemäß bevorzugt. Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propenesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts. In the polymers, some or all of the sulfonic acid groups can be present in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
Die Monomerenverteilung der erfindungsgemäß bevorzugt eingesetzten Copolymere beträgt bei Copolymeren, die nur Carbonsäuregruppen-haltige Monomere und Sulfonsäuregruppen-haltige Monomere enthalten, vorzugsweise jeweils 5 bis 95 Gew.-%, besonders bevorzugt beträgt der Anteil des Sulfonsäuregruppen-haltigen Monomers 50 bis 90 Gew.-% und der Anteil des Carbonsäuregruppen-haltigen Monomers 10 bis 50 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewählt aus den zuvor genannten. Die Molmasse der erfindungsgemäß bevorzugt eingesetzten Sulfo-Copolymere kann variiert werden, um die Eigenschaften der Polymere dem gewünschten Verwendungszweck anzupassen. Bevorzugte Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, sind dadurch gekennzeichnet, dass die Copolymere Molmassen von 2000 bis 200.000 g mol-1, vorzugsweise von 4000 bis 25.000 g mol-1 und insbesondere von 5000 bis 15.000 g mol-1 aufweisen. The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which only contain carboxylic acid group-containing monomers and sulfonic acid group-containing monomers is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight; the monomers are preferably selected from those mentioned above. The molar mass of the sulfo-copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired application. Preferred detergents or cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, are characterized in that the copolymers have molecular weights of 2000 to 200,000 g mol -1 , preferably 4000 to 25,000 g mol -1 and in particular 5000 to 15,000 g mol -1 .
In einerweiteren bevorzugten Ausführungsform umfassen die Copolymere neben Carboxylgruppen-haltigem Monomer und Sulfonsäuregruppen-haltigem Monomer weiterhin wenigstens ein nichtionisches, vorzugsweise hydrophobes Monomer. Durch den Einsatz dieser
hydrophob modifizierten Polymere konnte insbesondere die Klarspülleistung erfindungsgemäßer Geschirrspülmittel verbessert werden. In a further preferred embodiment, the copolymers also comprise at least one nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups. By using this hydrophobically modified polymers, it was possible in particular to improve the rinsing performance of dishwashing detergents according to the invention.
Besonders bevorzugt umfasst das Gel weiterhin ein anionisches Copolymer, wobei als anionisches Copolymer ein Copolymer, umfassend i) Carbonsäuregruppen-haltige Monomere ii) Sulfonsäuregruppen-haltige Monomere iii) nichtionische Monomere, insbesondere hydrophobe Monomere eingesetzt wird. The gel particularly preferably also comprises an anionic copolymer, a copolymer comprising i) carboxylic acid group-containing monomers ii) sulfonic acid group-containing monomers iii) nonionic monomers, in particular hydrophobic monomers, being used as anionic copolymer.
Als nichtionische Monomere werden vorzugsweise Monomere der allgemeinen Formel R1 (R 2)C=C(R 3)-X-R4 eingesetzt, in der R1 bis R 3 unabhängig voneinander für -H, -Ch oder - C2H5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH2-, - C(0)0- und -C(0)-NH-, und R4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht. The nonionic monomers used are preferably monomers of the general formula R 1 (R 2 )C═C(R 3 )—XR 4 , in which R 1 to R 3 independently represent —H, —Ch or —C2H5, X represents one optionally present spacer group, which is selected from -CH2-, -C(0)0- and -C(0)-NH-, and R 4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
Besonders bevorzugte nichtionische Monomere sind Buten, Isobuten, Penten, 3-Methylbuten, 2- Methylbuten, Cyclopenten, Hexen, Hexen-1 , 2-Methlypenten-1 , 3-Methlypenten-1 , Cyclohexen, Methylcyclopenten, Cyclohepten, Methylcyclohexen, 2,4,4-Trimethylpenten-1 , 2,4,4- Trimethylpenten-2,2,3-Dimethylhexen-1 , 2,4-Diemthylhexen-1 , 2,5-Dimethlyhexen-1 , 3,5-Dimethyl- hexen-1 , 4,4-Dimethylhexan-1 , Ethylcyclohexyn, 1-Octen, a-Olefine mit 10 oder mehr Kohlenstoffatomen wie beispielsweise 1-Decen, 1-Dodecen, 1-Hexadecen, 1-Oktadecen und C22- a-Olefin, 2-Styrol, a-Methylstyrol, 3-Methylstyrol, 4-Propylstryol, 4-Cyclohexylstyrol, 4- Dodecylstyrol, 2-Ethyl-4-Benzylstyrol, 1 -Vinylnaphthalin, 2- Vinylnaphthalin, Acrylsäuremethylester, Acrylsäureethylester, Acrylsäurepropylester, Acrylsäurebutylester, Acrylsäurepentylester, Acrylsäurehexylester, Methacrylsäuremethylester, A/-(Methyl)acrylamid, Acrylsäure-2- Ethylhexylester, Methacrylsäure-2-Ethylhexylester, A/-(2-Ethylhexyl)acrylamid,Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, 1-hexene, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 ,4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1 , 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22 α-olefin, 2-styrene , a-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate , A/-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, A/-(2-ethylhexyl)acrylamide,
Acrylsäureoctylester, Methacrylsäureoctylester, A/-(Octyl)acrylamid, Acrylsäurelaurylester, Methacrylsäurelaurylester, A/-(Lauryl)acrylamid, Acrylsäurestearylester, Methacrylsäure- stearylester, A/-(Stearyl)acrylamid, Acrylsäurebehenylester, Methacrylsäurebehenylester und N- (Behenyl)acrylamid oder deren Mischungen, insbesondere Acrylsäure, Ethylacrylat, 2-Acrylamido- 2-methylpropansulfonsäure (AMPS) sowie deren Mischungen. Octyl acrylate, octyl methacrylate, A/-(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, A/-(lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, A/-(stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or their Mixtures, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.
Gemäß einer bevorzugten Ausführungsform sind die sulfonsäuregruppenhaltigen Polymere in einer Menge von 0 bis 30, insbesondere 0 bis 20 Gew.-% im Gel enthalten. According to a preferred embodiment, the polymers containing sulfonic acid groups are present in the gel in an amount of 0 to 30% by weight, in particular 0 to 20% by weight.
Gemäß einer besonders bevorzugten Ausführungsform ist die mindestens eine Komponente b) unabhängig voneinander ausgewählt aus der Gruppe gebildet aus organischen Lösungsmitteln,
deren Koordinaten im Hansenraum den Wert von rb größer oder gleich 16,3 MPa0·5 bei dD0 = 16,05 MPc dP0 = 20,31 MPc dH0 = 36,86 MPc aufweisen, sowie nichtionischen Tensiden und organischen Metallsalzen. According to a particularly preferred embodiment, the at least one component b) is independently selected from the group consisting of organic solvents, whose coordinates in the Hansen space have the value of rb greater than or equal to 16.3 MPa 0 · 5 at dD 0 = 16.05 MPc dP 0 = 20.31 MPc dH 0 = 36.86 MPc, as well as nonionic surfactants and organic metal salts.
Gemäß einer besonders bevorzugten Ausführungsform ist Wasch- oder Reinigungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Komponente b) im Gel ausgewählt ist aus der Gruppe gebildet durch Polyalkylenglycole (insbesondere Polyethylenglycole, Polypropylenglykole), Carbonatestern, (insbesondere Glycerolcarbonate, Propylene carbonate, Ethylencarbonate, Diethylcarbonate, Dimethylcarbonate), 3-Methyl-1 ,3- Butanediol, Fettalkoholalkoxylaten (ggf. endgruppenvorschlossen), Acetaten und Zinksalzen, insbesondere Zinkacetaten, insbesondere Zinkacetat. According to a particularly preferred embodiment, the washing or cleaning agent according to one of the preceding claims, characterized in that component b) in the gel is selected from the group formed by polyalkylene glycols (especially polyethylene glycols, polypropylene glycols), carbonate esters (especially glycerol carbonates, propylene carbonates, Ethylene carbonates, diethyl carbonates, dimethyl carbonates), 3-methyl-1,3-butanediol, fatty alcohol alkoxylates (possibly end-capped), acetates and zinc salts, in particular zinc acetates, in particular zinc acetate.
Als weitere Komponente gemäß b) enthält das Gel bevorzugt Polypropylenglykol, bevorzugt in einer Menge von 0,1 bis 30 Gew.-%. Es können selbstverständlich Mischungen verschiedener Polypropylenglykole eingesetzt werden. Diese sind beispielsweise kommerziell unter dem Handelsnamen Pluriol ® (BASF) erhältlich. As a further component according to b), the gel preferably contains polypropylene glycol, preferably in an amount of 0.1 to 30% by weight. Mixtures of different polypropylene glycols can of course be used. These are commercially available, for example, under the trade name Pluriol® (BASF).
Gemäß einer bevorzugten Ausführungsform beträgt das mittlere Molekulargewicht des Propylenglykols von 500 bis 10000 g/mol, insbesondere von 1000 bis 6000 g/mol. According to a preferred embodiment, the average molecular weight of the propylene glycol is from 500 to 10,000 g/mol, in particular from 1000 to 6000 g/mol.
Gemäß einer besonders bevorzugten Ausführungsform ist Polypropylenglykol in einer Menge von 0,6 bis 25 Gew.-%, bevorzugt in einer Menge von 1 bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Gels, enthalten. According to a particularly preferred embodiment, polypropylene glycol is contained in an amount of 0.6 to 25% by weight, preferably in an amount of 1 to 15% by weight, based in each case on the total weight of the gel.
Bevorzugte Komponenten gemäß b) sind Carbonatestern, (insbesondere Glycerin carbonat (Glycerol carbonate, 4-Hydroxymethyl-1 ,3-dioxolan-2-on), Propylencarbonat (4-Methyl-1 ,3- dioxolan-2-on), Ethylencarbonate (1 ,3-Dioxolan-2-on), Diethylcarbonat, Dimethylcarbonat).
Preferred components according to b) are carbonate esters (in particular glycerol carbonate (glycerol carbonate, 4-hydroxymethyl-1,3-dioxolan-2-one), propylene carbonate (4-methyl-1,3-dioxolan-2-one), ethylene carbonate ( 1,3-dioxolan-2-one), diethyl carbonate, dimethyl carbonate).
Insbesondere bevorzugt sind Glycerincarbonat, Proplyencarbonat und/oder Ethylencarbonat. Glycerol carbonate, propylene carbonate and/or ethylene carbonate are particularly preferred.
Erfindungsgemäß enthält die Gelphase bevorzugt mindestens ein Polyethylenglykol. According to the invention, the gel phase preferably contains at least one polyethylene glycol.
Dabei sind insbesondere solche Polyethylenglykole mit einer mittleren Molmasse zwischen etwa 100 und 8000 geeignet. Es können auch Mischungen davon eingesetzt werden. Besonders bevorzugt werden die vorstehend genannten Polyethylenglykole in Mengen von 1 bis 40 Gew.-%, bevorzugt 5 bis 35 Gew.-%, insbesondere von 10 bis 30 Gew.-%, beispielsweise 12 bis 25 bevorzugt jeweils bezogen auf das Gesamtgewicht der Gelphase bzw. des Gels eingesetzt; ganz besonders bevorzugt sind 12 bis 18,5 Gew.-% Polyethylenglykol, insbesondere 13,5 bis 16,5 Gew.-% Polyethylenglykol, bevorzugt Polyethylenglykol im Gel enthalten.
Bevorzugt sind die eingesetzten Polyethylenglykole flüssig bei 20 °C, 1 bar. Erfindungsgemäß werden bevorzugt Polyethylenglykol(e) mit einer mittleren Molmasse von 200 bis 600 g/mol in der wenigstens einen Gelphase bzw. den Gelphasen eingesetzt. Dabei werden in Kombination mit Polyvinylalkohol Polyethylenglykole mit einer mittleren Molmasse zwischen etwa 200 und etwa 600 g/mol, bevorzugt zwischen 300 und 500 g/mol, insbesondere bevorzugt zwischen 350 und 450 g/mol, beispielsweise um 400 g/mol INCI: PEG400) eingesetzt. Erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, sind somit dadurch gekennzeichnet, dass sie Polyethylenglykol(e) mit einer mittleren Molmasse von 300 bis 500 g/mol, insbesondere von 350 bis 450 g/mol aufweisen. Polyethylene glycols with an average molar mass of between about 100 and 8000 are particularly suitable. Mixtures thereof can also be used. The abovementioned polyethylene glycols are particularly preferred in amounts of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 12 to 25% by weight, preferably based on the total weight of the gel phase or .of the gel used; 12 to 18.5% by weight of polyethylene glycol, in particular 13.5 to 16.5% by weight of polyethylene glycol, preferably polyethylene glycol, are very particularly preferably present in the gel. The polyethylene glycols used are preferably liquid at 20° C. and 1 bar. According to the invention, preference is given to using polyethylene glycol(s) with an average molar mass of 200 to 600 g/mol in the at least one gel phase or the gel phases. In this case, in combination with polyvinyl alcohol, polyethylene glycols with an average molar mass of between about 200 and about 600 g/mol, preferably between 300 and 500 g/mol, particularly preferably between 350 and 450 g/mol, for example around 400 g/mol INCI: PEG400) deployed. Washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are thus characterized in that they contain polyethylene glycol(s) with an average molar mass of 300 to 500 g/mol, in particular 350 to 450 g/mol.
Überraschenderweise hat sich gezeigt, dass die Zugabe von Polyethylenglykolen, insbesondere von solchen mit mittleren Molmassen von 200 bis 600 g/mol zu der wenigstens einen Gelphase, insbesondere bei Gelphasen, umfassend Polyvinylalkohol, zu einer Beschleunigung der Verfestigungszeit der Gelphasen führt. Es können dabei Werte von wenigen Minuten und sogar unter einer Minute erreicht werden. Dies ist insbesondere für die produktionstechnischen Abläufe von großem Vorteil, da die Weiterverarbeitung der Gelphasen im verfestigten Zustand viel schneller und damit in der Regel kostengünstiger erfolgen kann. Überraschenderweise wurde gefunden, dass die Anwesenheit von Polyethylenglykol(en) mit einer mittleren Molmasse von 200 bis 600 g/mol in Kombination mit Polyvinylalkohol und/oder dessen Derivaten entscheidend dazu beiträgt, die Erstarrungszeiten zu verringern. Ohne auf die Theorie festgelegt zu sein, wird davon ausgegangen, dass solche Polyethylenglykole, insbesondere solche mit einer Molmasse von 350 bis 450 g/mol, insbesondere um 400 g/mol die Sol-Gel-Temperatur erhöht. Surprisingly, it has been shown that the addition of polyethylene glycols, especially those with an average molar mass of 200 to 600 g/mol, to the at least one gel phase, especially in the case of gel phases comprising polyvinyl alcohol, accelerates the setting time of the gel phases. Values of a few minutes and even less than a minute can be achieved. This is of great advantage in particular for the production processes, since the further processing of the gel phases in the solidified state can be carried out much more quickly and therefore generally more cost-effectively. It has surprisingly been found that the presence of polyethylene glycol(s) with an average molar mass of 200 to 600 g/mol in combination with polyvinyl alcohol and/or its derivatives makes a decisive contribution to reducing the solidification times. Without being bound to theory, it is assumed that such polyethylene glycols, in particular those with a molar mass of 350 to 450 g/mol, increase the sol-gel temperature, in particular by 400 g/mol.
In einer besonders bevorzugten Ausführungsform beträgt die Menge von Polyethylenglykol(en) mit einer mittleren Molmasse von 350 bis 450 g/mol, beispielsweise um 400 g/mol, 10 bis 22 Gew.-% bezogen auf das Gesamtgewicht des Gels. In a particularly preferred embodiment, the amount of polyethylene glycol(s) with an average molar mass of 350 to 450 g/mol, for example around 400 g/mol, is 10 to 22% by weight, based on the total weight of the gel.
Gemäß einerweiteren Ausführungsform können neben den genannten Polyethylenglykolen mit einer mittleren Molmasse von 200 bis 600 g/mol weitere Polyethylenglykolen, insbesondere weitere Polyethylenglykole, mit einer mittleren Molmasse zwischen etwa 800 und 8000 in der wenigstens einen Gelphase enthalten sein. Besonders bevorzugt werden die vorstehend genannten Polyethylenglykole in Mengen von 1 bis 40 Gew.-%, bevorzugt 5 bis 35 Gew.-%, insbesondere von 10 bis 30 Gew.-%, beispielsweise 15 bis 25 bevorzugt jeweils bezogen auf das Gesamtgewicht des Gels eingesetzt. According to a further embodiment, in addition to the polyethylene glycols mentioned with an average molecular weight of 200 to 600 g/mol, further polyethylene glycols, in particular further polyethylene glycols, with an average molecular weight between about 800 and 8000 can be contained in the at least one gel phase. The abovementioned polyethylene glycols are particularly preferably used in amounts of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 15 to 25% by weight, based on the total weight of the gel .
Nichtionische Tenside, wie sie weiter unten ausführlich beschrieben sind, können ebenfalls als bevorzugte Komponenten gemäß b) eingesetzt werden. Als nichtionische Tenside können alle dem Fachmann bekannten nichtionischen Tenside eingesetzt werden. Bevorzugt werden
schwachschäumende nichtionische Tenside eingesetzt, insbesondere alkoxylierte Fettsäurealkylether (Fettsäurepolyalkylenglykole). Besonders bevorzugte nichtionische Tenside sind weiter unter als besonders bevorzugt näher spezifiziert. Nonionic surfactants, as described in detail below, can also be used as preferred components according to b). All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. To be favoured low-foaming nonionic surfactants used, in particular alkoxylated fatty acid alkyl ethers (fatty acid polyalkylene glycols). Particularly preferred nonionic surfactants are specified in more detail below as being particularly preferred.
Als weitere Komponente gemäß b) ist bevorzugt mindestens ein wasserlösliches Zinksalz enthalten. At least one water-soluble zinc salt is preferably present as a further component according to b).
Neben der Wirkung solcher Zinksalze als Glaskorrosionsinhibitoren wurde gefunden, dass die Anwesenheit von Zinksalzen in der Gelphase zur Stabilisierung des Gels sowie zur Verbesserung der Verarbeitbarkeit beiträgt. In addition to the effect of such zinc salts as glass corrosion inhibitors, it has been found that the presence of zinc salts in the gel phase contributes to stabilizing the gel and improving processability.
Gemäß einerweiteren bevorzugten Ausführungsform der vorliegenden Erfindung enthalten Waschoder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, welche als Wasch- oder Reinigungsmittelportion, bevorzugt Geschirrspülmittelportion, insbesondere maschinelle Geschirrspülmittelportion, die bevorzugt die für einen Reinigungsgang notwendigen Aktivstoffe enthalten, konfektioniert sind, als Gesamtmenge der wasserlöslichen Zinksalze, insbesondere Zinksulfat und/oder Zinkacetat, insbesondere Zinkacetat, in der Waschoder Reinigungsmittelportion, bevorzugt Geschirrspülmittelportion, insbesondere maschinellen Geschirrspülmittelportion, bevorzugt 0,0004 bis 0,5 g, bevorzugt 0,001 bis 0,2 g, insbesondere 0,02 bis 0,06 g. According to a further preferred embodiment of the present invention, detergents or cleaning agents, preferably dishwashing agents, in particular automatic dishwashing agents, which are packaged as washing or cleaning agent portions, preferably dishwashing agent portions, in particular automatic dishwashing agent portions, which preferably contain the active ingredients necessary for a cleaning cycle, are packaged as the total amount of the water-soluble zinc salts , in particular zinc sulphate and/or zinc acetate, in particular zinc acetate, in the washing or cleaning agent portion, preferably dishwashing agent portion, in particular automatic dishwashing agent portion, preferably 0.0004 to 0.5 g, preferably 0.001 to 0.2 g, in particular 0.02 to 0.06 g .
Das bedeutet, dass die einzelne Wasch- oder Reinigungsmittelportion, bevorzugt Geschirrspülmittelportion, insbesondere maschinellen Geschirrspülmittelportion, welche zur Durchführung eines einzelnen Reinigungsgangs genutzt wird, insbesondere in einen Reinigungsgang einer maschinellen Geschirrspülmaschine gegeben wird, 0,0005 bis 1 g, bevorzugt 0,01 bis 0,5 g, insbesondere 0,02 bis 0,06 g wasserlösliche Zinksalze, insbesondere Zinksulfat und/oder Zinkacetat, insbesondere Zinkacetat, enthält. This means that the individual detergent or cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing agent portion, which is used to carry out a single cleaning cycle, in particular in a cleaning cycle of a machine dishwasher, is 0.0005 to 1 g, preferably 0.01 to 0 5 g, in particular 0.02 to 0.06 g of water-soluble zinc salts, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate.
Besonders bevorzugt enthält eine einzelne erfindungsgemäße Wasch- oder Reinigungsmittelportion, bevorzugt Geschirrspülmittelportion, insbesondere maschinellen Geschirrspülmittelportion, die insbesondere in einen Reinigungsgang einer maschinellen Geschirrspülmaschine gegeben wird, 0,001 bis 0,5 g, insbesondere 0,02 bis 0,05 g wasserlösliche Zinksalze, insbesondere Zinksulfat und/oder Zinkacetat, insbesondere Zinkacetat, bezogen auf die Gesamtmenge des Wasch- oder Reinigungsmittels, bevorzugt Geschirrspülmittels, insbesondere maschinellen Geschirrspülmittels. Particularly preferably, an individual detergent or cleaning agent portion according to the invention, preferably a dishwashing detergent portion, in particular an automatic dishwashing detergent portion, which is added in particular to a cleaning cycle of an automatic dishwasher, contains 0.001 to 0.5 g, in particular 0.02 to 0.05 g, of water-soluble zinc salts, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, based on the total amount of the detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent.
Das erfindungsgemäß bevorzugt einzusetzende Zinksalz ist wasserlöslich, das bedeutet, es in Wasser eine Löslichkeit oberhalb 100 mg/l, vorzugsweise oberhalb 500 mg/l, besonders bevorzugt oberhalb 1 g/l und insbesondere oberhalb 5 g/l (alle Löslichkeiten bei 20°C Wassertemperatur).
Das anorganische Zinksalz ist vorzugsweise ausgewählt aus der Gruppe bestehend aus Zinkbromid, Zinkchlorid, Zinkiodid, Zinknitrat und Zinksulfat. Das organische Zinksalz ist vorzugsweise ausgewählt aus der Gruppe bestehend aus Zinksalzen monomerer oder polymerer organischer Säuren, insbesondere aus der Gruppe Zinkacetat, Zinkacetylacetonat, ZinkPCA (Zink- 5-oxopyrrolidine-2-carboxylate), Zinkbenzoat, Zinkchlorid, Zinkformiat, Zinklactat, Zinkgluconat, Zinkricinoleat, Zinkabietat, Zinkvalerat und Zink-p-toluolsulfonat. The zinc salt to be used with preference according to the invention is water-soluble, which means that it has a solubility in water of more than 100 mg/l, preferably more than 500 mg/l, particularly preferably more than 1 g/l and in particular more than 5 g/l (all solubilities at 20° C water temperature). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc PCA (zinc 5-oxopyrrolidine-2-carboxylate), zinc benzoate, zinc chloride, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate , zinc abietate, zinc valerate and zinc p-toluenesulfonate.
In einer erfindungsgemäß besonders bevorzugten Ausführungsform wird als wasserlösliches Zinksalz Zinkchlorid, Zinkacetat oder Zinksulfat, insbesondere wasserfreies Zinksalz (Anhydrat), besonders bevorzugt Zinkacetat (Anhydrat), eingesetzt. In a particularly preferred embodiment according to the invention, the water-soluble zinc salt used is zinc chloride, zinc acetate or zinc sulfate, in particular anhydrous zinc salt (anhydrate), particularly preferably zinc acetate (anhydrate).
Als weitere Komponente gemäß b) ist bevorzugt mindestens ein wasserlösliches Zinksalz, insbesondere Zinksulfat und/oder Zinkacetat, insbesondere Zinkacetat, in einer Menge von 0,05 bis 5 Gew.-%, insbesondere von 0,1 bis 2,0 Gew.-%, ganz besonders bevorzugt von 0,2 bis 1 ,0 Gew.-%, bezogen auf das Gesamtgewicht des Gels enthalten. Another component according to b) is preferably at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, in an amount of from 0.05 to 5% by weight, in particular from 0.1 to 2.0% by weight. , very particularly preferably from 0.2 to 1.0% by weight, based on the total weight of the gel.
Das Zinksalz ist in der Gelphase vorzugsweise in einer Menge von 0,05 Gew.-% bis 3 Gew.-%, besonders bevorzugt in einer Menge von 0,1 Gew.-% bis 2,4 Gew.-%, insbesondere in einer Menge von 0,2 Gew.-% bis 1 ,0 Gew.-%, enthalten, bezogen auf das Gesamtgewicht des Gelphase. The zinc salt is present in the gel phase preferably in an amount of from 0.05% to 3% by weight, more preferably in an amount of from 0.1% to 2.4% by weight, especially in a Amount of 0.2% by weight to 1.0% by weight, based on the total weight of the gel phase.
Zinksalze können darüber hinaus auch in einer ggf. vorhandenen festen Phase enthalten sein. In diesem Fall ist das Zinksalz in erfindungsgemäßen Mitteln vorzugsweise in einer Menge von 0,01 Gew.-% bis 5 Gew.-%, besonders bevorzugt in einer Menge von 0,05 Gew.-% bis 3 Gew.-%, insbesondere in einer Menge von 0,1 Gew.-% bis 2 Gew.-%, enthalten, bezogen auf das Gesamtgewicht des Wasch- oder Reinigungsmittels, bevorzugt Geschirrspülmittels, insbesondere maschinellen Geschirrspülmittels. Zinc salts can also be contained in a solid phase that may be present. In this case, the zinc salt in agents according to the invention is preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1% by weight to 2% by weight, based on the total weight of the detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent.
Gemäß einer besonders bevorzugten Ausführungsform umfasst das Gel mindestens ein weiterer Inhaltsstoffe gemäß Komponente c), der ausgewählt ist aus Farbstoffen, Glaskorrosionsinhibitoren, sowie weiteren Prozesshilfs mittel, insbesondere Parfüm, pH-Stellmittel. According to a particularly preferred embodiment, the gel comprises at least one other ingredient according to component c), which is selected from dyes, glass corrosion inhibitors, and other processing aids, in particular perfume, pH adjusters.
Gemäß einer besonders bevorzugten Ausführungsform beträgt der Wassergehalt des Gels von 0 bis 55 Gew.-%, bevorzugt von 1 und 50 Gew.-%, bezogen auf das Gesamtgewicht des Gels, beträgt. According to a particularly preferred embodiment, the water content of the gel is from 0 to 55% by weight, preferably from 1 to 50% by weight, based on the total weight of the gel.
Gemäß einer besonders bevorzugten Ausführungsform umfasst das Gel weniger als 5 Gew.-%, bevorzugt weniger als 3 Gew.-%, insbesondere weniger als 1 Gew.-% einer Komponente mit 15,3<r<16,3.
Gemäß einerweiteren, ganz besonders bevorzugten Ausführungsform umfasst das Gel weniger als 5 Gew.-%, bevorzugt weniger als 3 Gew.-%, insbesondere weniger als 1 Gew.-% 1 ,3- Propandiol. Die Abwesenheit von 1 ,3-Propandiol ermöglicht es, die kritischen Gelparameter, wie Härte des Gels, Erstarrungszeit, Synärese und/oder Lagerstabilität, durch eine Kombination der Komponenten gemäß a) und der Komponenten gemäß b) einzustellen. According to a particularly preferred embodiment, the gel comprises less than 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight, of a component with 15.3<r<16.3. According to a further, very particularly preferred embodiment, the gel comprises less than 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight, of 1,3-propanediol. The absence of 1,3-propanediol makes it possible to set the critical gel parameters, such as hardness of the gel, setting time, syneresis and/or storage stability, by combining the components according to a) and the components according to b).
Propandiole, insbesondere 1 ,3-Propandiol, führen außerdem zu Wechselwirkungen mit wasserlöslichen Umhüllungen und/oder anderen Komponenten, insbesondere gecoateten Komponenten, wobei sich unschöne Verfärbungen an den gecoateten Komponenten ausbilden können, deren verfärbtes Erscheinungsbild dann vom Endverbraucher als nicht attraktiv bzw. sogar zum Teil als nicht mehr einwandfrei verwendbar angesehen wird. Das Coating kann auch bei Anwesenheit von Propandiolen aufgeweicht werden, so dass ggf. die Schutzwirkung des Coatings für den eingekapselten Aktivstoff nicht mehr gegeben ist. Propanediols, in particular 1,3-propanediol, also lead to interactions with water-soluble coatings and/or other components, in particular coated components, with unsightly discolorations being able to form on the coated components, the discolored appearance of which is then perceived by the end user as unattractive or even harmful Part is considered to be no longer perfectly usable. The coating can also be softened in the presence of propanediols, so that the protective effect of the coating for the encapsulated active ingredient may no longer be available.
1 ,3 Propandiol hat in der großtechnischen Produktion deutliche Nachteile, da es bei der Dosierung des Gels zum Teil verdampft und schnell wieder in der Umgebung kondensiert. Die Absaugung dieses Lösungsmittels ist dadurch erschwert. Dabei sollte eine Kontamination weiterer Oberflächen von Anlagen oder anderen Produktkomponenten (wie z.B. eines wasserlöslichen Films) mit 1 ,3 Propandiol als Folge des Verdampfens möglichst vermieden werden, um negative Wechselwirkungen zu verhindern. 1,3 propanediol has clear disadvantages in large-scale production, since some of it evaporates when the gel is dosed and quickly condenses again in the environment. This makes it difficult to suck off this solvent. Contamination of other surfaces of plants or other product components (e.g. a water-soluble film) with 1,3-propanediol as a result of evaporation should be avoided as far as possible in order to prevent negative interactions.
Gemäß einer anderen, besonders bevorzugten Ausführungsform beträgt der Anteil an 1 ,3- Propandiol und 1 ,2-Propandiol, bezogen auf das Gesamtgewicht des Gels, bevorzugt < 5 Gew.-%, bevorzugt weniger als 3 Gew.-%, insbesondere weniger als 1 Gew.-% bezogen auf das Gesamtgewicht des Gels. According to another, particularly preferred embodiment, the proportion of 1,3-propanediol and 1,2-propanediol, based on the total weight of the gel, is preferably <5% by weight, preferably less than 3% by weight, in particular less than 1% by weight based on the total weight of the gel.
Diese und weitere Aspekte, Merkmale und Vorteile der Erfindung werden für den Fachmann aus dem Studium der folgenden detaillierten Beschreibung und Ansprüche ersichtlich. Dabei kann jedes Merkmal aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Ferner ist es selbstverständlich, dass die hierin enthaltenen Beispiele die Erfindung beschreiben und veranschaulichen sollen, diese aber nicht einschränken und insbesondere die Erfindung nicht auf diese Beispiele beschränkt ist. Alle Prozentangaben sind, sofern nicht anders angegeben, Gewichts-%. Numerische Bereiche, die in dem Format „von x bis y“ angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden.
„Mindestens ein“, wie hierin verwendet, bedeutet 1 oder mehr, d.h. 1 , 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Bezogen auf einen Inhaltsstoff bezieht sich die Angabe auf die Art des Inhaltsstoffs und nicht auf die absolute Zahl der Moleküle. „Mindestens ein Bleichkatalysator“ bedeutet somit beispielsweise mindestens eine Art von Bleichkatalysator, d.h. dass eine Art von Bleichkatalysator oder eine Mischung mehrerer verschiedener Bleichkatalysatoren gemeint sein kann. Zusammen mit Gewichtsangaben bezieht sich die Angabe auf alle Verbindungen der angegebenen Art, die in der Zusammensetzung/Mischung enthalten sind, d.h. dass die Zusammensetzung über die angegebene Menge der entsprechenden Verbindungen hinaus keine weiteren Verbindungen dieser Art enthält. 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 from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it should be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples. All percentages are % by weight unless otherwise stated. Numeric ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included. "At least one" as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With regard to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. “At least one bleach catalyst” thus means, for example, at least one type of bleach catalyst, ie it can mean one type of bleach catalyst or a mixture of several different bleach catalysts. Together with weight information, the information relates to all compounds of the specified type that are contained in the composition/mixture, ie the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.
Wenn hierin auf Molmassen Bezug genommen wird, beziehen sich diese Angaben immer auf die zahlenmittlere Molmasse Mn, sofern nicht explizit anders angeben. Das Zahlenmittel der Molmasse kann beispielsweise mittels Gel-Permeations-Chromatographie (GPC) gemäß DIN 55672-1 :2007- 08 mit THF als Eluent bestimmt werden. Die massenmittlere Molmasse M kann ebenfalls mittels GPC bestimmt werden, wie für Mn beschrieben. When reference is made herein to molar masses, this information always relates to the number-average molar mass M n , unless explicitly stated otherwise. The number average molar mass can be determined, for example, by means of gel permeation chromatography (GPC) in accordance with DIN 55672-1:2007-08 with THF as the eluent. The mass-average molar mass M can also be determined by means of GPC , as described for Mn.
Alle Prozentangaben, die im Zusammenhang mit den hierin beschriebenen Zusammensetzungen gemacht werden, beziehen sich, sofern nicht explizit anders angegeben auf Gew.-%, jeweils bezogen auf die betreffende Mischung bzw. Phase. Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein relate to % by weight, in each case based on the mixture or phase in question.
Weiterhin muss das Gel lagerstabil sein, und zwar bei üblichen Lagerbedingungen. Die erfindungsgemäße Gelphase ist Bestandteil eines Wasch- oder Reinigungsmittels, bevorzugt Geschirrspülmittels, insbesondere maschinellen Geschirrspülmittels. Solche Wasch- oder Reinigungsmittel werden in einem Haushalt üblicherweise über einen gewissen Zeitraum gelagert. Die Lagerung erfolgt üblicherweise in der Nähe der Wasch- bzw. Spülmaschine. Für eine solche Lagerung sollte das Gel stabil sein. Somit sollte das Gel insbesondere auch nach einer Lagerzeit von beispielsweise 4 bis 12 Wochen, insbesondere 10 bis 12 Wochen oder länger bei einer Temperatur von bis zu 40°C, besonders bei 30 °C, insbesondere bei 25 °C oder bei 20 °C stabil sein und sich in dieser Zeit nicht verformen oder sonst wie in der Konsistenz ändern. Furthermore, the gel must be storage-stable under normal storage conditions. The gel phase according to the invention is a component of a washing or cleaning agent, preferably a dishwashing detergent, in particular a machine dishwashing detergent. Such detergents or cleaning agents are usually stored in a household for a certain period of time. They are usually stored near the washing machine or dishwasher. For such storage, the gel should be stable. Thus, the gel should be stable even after a storage time of, for example, 4 to 12 weeks, especially 10 to 12 weeks or longer at a temperature of up to 40°C, especially at 30°C, especially at 25°C or at 20°C be and do not deform during this time or otherwise change in consistency.
Liegen das Gel und eine feste, insbesondere eine Pulverphase in direktem Kontakt miteinander vor, dringt das Gel in der Lagerzeit von 4 Wochen bei 25 °C bevorzugt maximal 1 mm in die Zwischenräume der unmittelbar unterliegenden Pulverphase ein. If the gel and a solid, in particular a powder phase are in direct contact with one another, the gel penetrates into the interstices of the immediately underlying powder phase by a maximum of 1 mm during the storage period of 4 weeks at 25°C.
Nachteilig wäre eine Volumenänderung oder Schrumpfung während der Lagerung, da hierdurch die Akzeptanz des Produktes beim Verbraucher gering wäre. Auch ein Austritt von Flüssigkeit oder das Ausschwitzen von Bestandteilen aus der Gelphase ist unerwünscht. Auch hier ist zum einen der optische Eindruck von Relevanz. Durch den Austritt von Flüssigkeit, wie beispielsweise Lösungsmittel, kann die Stabilität der Gelphase beeinflusst werden, so dass die Bestandteile nicht
mehr stabil enthalten sind und dadurch auch die Wasch- bzw. Reinigungswirkung beeinflusst werden kann. A change in volume or shrinkage during storage would be disadvantageous, since this would result in poor acceptance of the product by consumers. Escape of liquid or exudation of components from the gel phase is also undesirable. On the one hand, the visual impression is also relevant here. The stability of the gel phase can be affected by the escape of liquid, such as solvents, so that the components cannot are contained more stably and thereby the washing or cleaning effect can be influenced.
Die Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, sind insbesondere keine Filme. Sie stellen vielmehr Formkörper dar, die eine nicht filmartige Dicke aufweisen. Sie weisen daher eine Schichtdicke von mindestens 0,3 mm, bevorzugt von mindestens 0,7 mm, insbesondere von mindestens 1 ,0 mm, ganz besonders bevorzugt von mindestens 1 ,2 mm auf. Dabei wird die Schichtdicke in der Ebene mit der geringsten Ausdehnung gemessen. The detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, preferably dishwashing agents, in particular machine dishwashing agents, are in particular not films. Rather, they represent moldings that have a non-film-like thickness. They therefore have a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular at least 1.0 mm, very particularly preferably at least 1.2 mm. The layer thickness is measured in the plane with the smallest expansion.
Ein weiterer Gegenstand der vorliegenden Erfindung betrifft eine Wasch- oder Reinigungsmittelportion, umfassend mindestens ein Gel, wie vorstehend beschrieben, in einer wasserlöslichen Umhüllung. Another subject of the present invention relates to a detergent or cleaning agent portion, comprising at least one gel as described above, in a water-soluble casing.
Gemäß einer weiteren besonders bevorzugten Ausführungsform handelt es sich bei den Waschoder Reinigungsmitteln, bevorzugt Geschirrspülmitteln, insbesondere maschinellen Geschirrspülmitteln, um eine Wasch- oder Reinigungsmittelportion, bevorzugt Geschirrspülmittelportion, insbesondere maschinelle Geschirrspülmittelportion, in einer wasserlöslichen Umhüllung. Diese kann eine oder mehreren Kammern/Kompartimente aufweisen. According to a further particularly preferred embodiment, the washing or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, are a washing or cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing agent portion, in a water-soluble casing. This can have one or more chambers/compartments.
Dabei ist das Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, bevorzugt als Wasch- oder Reinigungsmitteleinmalportion konfektioniert, so dass es zur Durchführung eines Geschirrspülmaschinendurchlaufs eingesetzt wird und dabei (weitestgehend) im Wesentlichen bis vollständig verbraucht wird. The washing or cleaning agent, preferably dishwashing agent, in particular machine dishwashing agent, is preferably packaged as a single portion washing or cleaning agent, so that it is used to carry out a dishwasher cycle and is (largely) essentially or completely consumed.
Die wasserlösliche Umhüllung wird vorzugsweise aus einem wasserlöslichen Folienmaterial, welches ausgewählt ist aus der Gruppe, bestehend aus Polymeren oder Polymergemischen, gebildet. Die Umhüllung kann aus einer oder aus zwei oder mehr Lagen aus dem wasserlöslichen Folienmaterial gebildet werden. Das wasserlösliche Folienmaterial der ersten Lage und der weiteren Lagen, falls vorhanden, kann gleich oder unterschiedlich sein. The water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The cover can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if any, can be the same or different.
Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält. Wasserlösliche Umhüllungen, die Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthalten, weisen eine gute Stabilität bei einer ausreichend hohen Wasserlöslichkeit, insbesondere Kaltwasserlöslichkeit, auf. It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility.
Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im
Bereich von 10.000 bis 1.000.000 gmol 1, vorzugsweise von 20.000 bis 500.000 gmol 1, besonders bevorzugt von 30.000 bis 100.000 gmol-1 und insbesondere von 40.000 bis 80.000 gmol-1 liegt. Suitable water-soluble films for producing the water-soluble envelope are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in Range from 10,000 to 1,000,000 gmol 1 , preferably from 20,000 to 500,000 gmol 1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
Die Herstellung von Polyvinylalkohol geschieht üblicherweise durch Hydrolyse von Polyvinylacetat, da der direkte Syntheseweg nicht möglich ist. Ähnliches gilt für Polyvinylalkoholcopolymere, die aus entsprechend aus Polyvinylacetatcopolymeren hergestellt werden. Bevorzugt ist, wenn wenigstens eine Lage der wasserlöslichen Umhüllung einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht. Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.
In einer bevorzugten Ausführungsform besteht die wasserlösliche Verpackung zu mindestens 20 Gew.-%, besonders bevorzugt zu mindestens 40 Gew.-%, ganz besonders bevorzugt zu mindestens 60 Gew.-% und insbesondere zu mindestens 80 Gew.-% aus einem Polyvinylalkohol, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-%, beträgt. In a preferred embodiment, the water-soluble packaging consists of at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight of a polyvinyl alcohol whose Degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
Einem zur Herstellung der wasserlöslichen Umhüllung geeignetem Polyvinylalkohol-enthaltendem Folienmaterial kann zusätzlich ein Polymer ausgewählt aus der Gruppe umfassend (Meth)Acrylsäure-haltige (Co)Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether, Polymilchsäure oder Mischungen der vorstehenden Polymere zugesetzt sein. Ein bevorzugtes zusätzliches Polymer sind Polymilchsäuren. A polyvinyl alcohol-containing film material suitable for producing the water-soluble casing can also have a polymer selected from the group consisting of (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added. A preferred additional polymer are polylactic acids.
Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol Dicarbonsäuren als weitere Monomere. Geeignete Dicarbonsäure sind Itaconsäure, Malonsäure, Bernsteinsäure und Mischungen daraus, wobei Itaconsäure bevorzugt ist. Ebenfalls bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesättige Carbonsäure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Polyvinylalkoholcopolymere neben Vinylalkohol Acrylsäure, Methacrylsäure, Acrylsäureester, Methacrylsäureester oder Mischungen daraus. In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred. Polyvinyl alcohol copolymers which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
Es kann bevorzugt sein, dass das Folienmaterial weitere Zusatzstoffe enthält. Das Folienmaterial kann beispielsweise Weichmacher wie Dipropylenglycol, Ethylenglycol, Diethylenglycol, Propylenglycol, Glycerin, Sorbitol, Mannitol oder Mischungen daraus enthalten. Weitere Zusatzstoffe umfassen beispielsweise Freisetzungshilfen, Füllmittel, Vernetzungsmittel, Tenside, Antioxidationsmittel, UV-Absorber, Antiblockmittel, Antiklebemittel oder Mischungen daraus. It can be preferred that the film material contains further additives. The film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof.
Geeignete wasserlösliche Folien zum Einsatz in den wasserlöslichen Umhüllungen der wasserlöslichen Verpackungen gemäß der Erfindung sind Folien, die von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8720, M8630, M8312, M8440, M7062, C8400 oder M8900
vertrieben werden. Weiter geeignet sind Folien, welche unter der Bezeichnung SH2601 , SH2504, SH2707 oder SH2701 von Nippon Gohsei vertrieben werden. Andere geeignete Folien umfassen Folien mit der Bezeichnung Solublon® PT, Solublon® GA, Solublon® KC oder Solublon® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray. Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packaging according to the invention are films available from MonoSol LLC, for example under the designation M8720, M8630, M8312, M8440, M7062, C8400 or M8900 to be expelled. Films sold by Nippon Gohsei under the name SH2601, SH2504, SH2707 or SH2701 are also suitable. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or films VF-HP from Kuraray.
Die wasserlösliche Umhüllung weist bevorzugt zumindest teilweise einen Bitterstoff mit einem Bitterwert zwischen 1 .000 und 200.000, insbesondere solche ausgewählt aus Chininsulfat (Bitterwert = 10.000), Naringin (Bitterwert = 10.000), Saccharoseoctaacetat (Bitterwert = 100.000), Chininhydrochlorid und Mischungen daraus auf. Insbesondere ist die äußere Oberfläche der wasserlöslichen Umhüllung zumindest teilweise mit einem Bitterstoff mit einem Bitterwert zwischen 1 .000 und 200.000 beschichtet. In diesem Zusammenhang ist es insbesondere zu bevorzugen, dass die wasserlösliche Umhüllung zu mindestens 50 %, vorzugsweise zu mindestens 75 % und ganz besonders bevorzugt mindestens 90 % mit dem Bitterstoff mit einem Bitterwert zwischen 1 .000 und 200.000 beschichtet ist. Das Aufbringen des Bitterstoffs mit einem Bitterwert zwischen 1 .000 und 200.000 kann beispielsweise mittels Bedruckung, Besprühens oder Bestreichung erfolgen. The water-soluble coating preferably at least partially has a bitter substance with a bitterness between 1,000 and 200,000, in particular those selected from quinine sulfate (bitter value=10,000), naringin (bitter value=10,000), sucrose octaacetate (bitter value=100,000), quinine hydrochloride and mixtures thereof. In particular, the outer surface of the water-soluble casing is at least partially coated with a bitter substance with a bitterness between 1,000 and 200,000. In this context, it is particularly preferable that the water-soluble coating is coated to an extent of at least 50%, preferably at least 75% and very particularly preferably at least 90% with the bitter substance with a bitterness value between 1,000 and 200,000. The application of the bitter substance with a bitter value between 1,000 and 200,000 can be done, for example, by printing, spraying or brushing.
Erfindungsgemäß weist die wasserlösliche Umhüllung bevorzugt mindestens eine kontinuierlich umlaufende Siegelnaht auf, die im Wesentlichen in einer Ebene liegt. Dies ist prozesstechnisch günstig, da für eine umlaufende Siegelnaht, welche im Wesentlichen in einer Ebene liegt, nur ein einziger Versiegelungsschritt, ggf. unter Benutzung nur eines einzigen Siegelwerkzeug, notwendig ist. Die kontinuierlich umlaufende Siegelnaht führt zu einem besseren Verschluss gegenüber solchen Umhüllungen mit mehreren Siegelnähten und einer hervorragenden Dichtigkeit der Siegelnaht und damit der Umhüllung selbst. Austreten von Produkt aus der Umhüllung, z.B. auf die Oberfläche der Portion wäre nachteilig, da der Konsument dann mit dem Produkt in Kontakt käme. Genau dies soll aber bei einer Wasch- oder Reinigungsmittelportion, bevorzugt Geschirrspülmittelportion, insbesondere maschinellen Geschirrspülmittelportion, mit einer wasserlöslichen Umhüllung möglichst vermieden werden. According to the invention, the water-soluble casing preferably has at least one continuous circumferential sealing seam, which essentially lies in one plane. This is favorable in terms of process technology, since only a single sealing step, possibly using only a single sealing tool, is necessary for a circumferential sealing seam which lies essentially in one plane. The continuously circumferential sealing seam leads to a better closure compared to such casings with several sealing seams and an excellent tightness of the sealing seam and thus of the casing itself. Leaking of product from the casing, e.g. on the surface of the portion would be disadvantageous, since the consumer would then be exposed to the product came into contact. However, this is precisely what should be avoided as far as possible in the case of a detergent or cleaning agent portion, preferably a dishwashing agent portion, in particular a machine dishwashing agent portion, with a water-soluble coating.
Die wasserlösliche Umhüllung kann bevorzugt aus mindestens 2 Verpackungsteilen hergestellt werden. Bevorzugt sind die mindestens zwei Verpackungsteile wasserlöslich, damit in der Geschirrspülmaschine keine Verpackungsteile Zurückbleiben, die dann zu Problemen in der Geschirrspülmaschine führen können. Dabei ist es nicht notwendig, dass die mindestens zwei Verpackungsteile unterschiedlich sind. Sie können bevorzugt aus dem gleichen Material und auf die gleiche Art und Weise hergestellt sein. In einer bevorzugten Ausführungsform handelt es sich dabei um zwei Teile einer wasserlöslichen Folie, insbesondere um zwei Teile einer wasserlöslichen Folie gleicher Zusammensetzung. The water-soluble casing can preferably be made from at least 2 packaging parts. The at least two packaging parts are preferably water-soluble, so that no packaging parts remain in the dishwasher, which could then lead to problems in the dishwasher. It is not necessary for the at least two packaging parts to be different. They can preferably be made from the same material and in the same way. In a preferred embodiment, these are two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.
In einer weiteren Ausführungsform können die mindestens zwei Verpackungsteile aus unterschiedlichem Material, z.B. aus unterschiedlichen Folien oder aus Material mit zwei
unterschiedlichen Eigenschaften (z.B. warm- und kaltwasserlösliche Folie) hergestellt sein. In dieser Ausführungsform ist es bevorzugt, dass eine wasserlösliche Folie und ein anderes Verpackungsteil, welches durch Spritzguss hergestellt wurde, kombiniert werden. In a further embodiment, the at least two packaging parts made of different materials, for example different films or material with two different properties (e.g. hot and cold water soluble film). In this embodiment, it is preferable that a water-soluble film and another packaging member made by injection molding are combined.
Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung umfasst die wasserlösliche Umhüllung mindestens eine zumindest teilweise plastisch verformte Folie. Insbesondere kann diese plastische Verformung der Folie durch dem Fachmann bekannte Methoden wie Tiefziehen (mit und ohne Anlegen eines Vakuums), Blas- oder Stempelformen hergestellt werden. Insbesondere umfasst die wasserlösliche Umhüllung mindestens eine zumindest teilweise plastisch verformte Folie, die durch Tiefziehen hergestellt wurde. According to a particularly preferred embodiment of the present invention, the water-soluble cover comprises at least one at least partially plastically deformed film. In particular, this plastic deformation of the film can be produced by methods known to those skilled in the art, such as deep drawing (with and without applying a vacuum), blow molding or stamping. In particular, the water-soluble covering comprises at least one at least partially plastically deformed film that was produced by deep-drawing.
Gemäß einer besonders bevorzugten Ausführungsform weist die wasserlösliche Umhüllung eine Schichtdicke von 30 bis 100 pm, insbesondere von 40 bis 800 pm. According to a particularly preferred embodiment, the water-soluble coating has a layer thickness of from 30 to 100 μm, in particular from 40 to 800 μm.
Die wenigstens eine feste, bevorzug körnige Phase und das Gel können innerhalb der wasserlöslichen Umhüllung in beliebiger Kombination zueinander angeordnet sein. So kann eine feste, bevorzugt körnige Phase auf oder neben einer Gelphase angeordnet sein. In dieser Ausführungsform weist das erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, eine feste, bevorzugt körnige Phase und eine Gelphase bzw. Gel auf. Es ist auch denkbar, dass eine feste, bevorzugt körnige Phase von Gelphasen umgeben ist. Auch ein Einbetten einer Phase in eine andere ist erfindungsgemäß umfasst. In einer weiteren, besonders bevorzugten Anordnung liegt das Gel in gegossener Form, beispielsweise in Form eines Gelkerns vor, der von einer festen Phase umgeben ist. Es können auch 2 oder mehr voneinander getrennte Kavitäten vorhanden sein, die mit der wenigstens einen Gelphase gefüllt werden. In dieser Ausführungsform umfasst das Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, zwei Gelphasen, wobei die zwei Gelphasen unterschiedliche Zusammensetzungen aufweisen können. The at least one solid, preferably granular phase and the gel can be arranged within the water-soluble envelope in any combination with one another. A solid, preferably granular phase can be arranged on or next to a gel phase. In this embodiment, the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, has a solid, preferably granular phase and a gel phase or gel. It is also conceivable that a solid, preferably granular phase is surrounded by gel phases. Embedding one phase in another is also included according to the invention. In a further particularly preferred arrangement, the gel is in cast form, for example in the form of a gel core surrounded by a solid phase. There can also be 2 or more separate cavities that are filled with at least one gel phase. In this embodiment, the washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprises two gel phases, it being possible for the two gel phases to have different compositions.
Gemäß einer bevorzugten Ausführungsform sind 3, 4, 5 oder 6 oder mehr voneinander getrennte Kavitäten vorhanden, die mit einer oder mehreren der Gelphasen gefüllt werden. Bevorzugt umfassen solche Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, 3, 4, 5 oder 6 oder mehr Gelphasen, wobei diese Gelphase die gleichen oder auch unterschiedliche Zusammensetzungen aufweisen können. According to a preferred embodiment, there are 3, 4, 5 or 6 or more separate cavities which are filled with one or more of the gel phases. Such detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprise 3, 4, 5 or 6 or more gel phases, it being possible for these gel phases to have the same or also different compositions.
Ein bevorzugter Gegenstand der vorliegenden Erfindung ist ein Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelles Geschirrspülmittel, welches, zusätzlich zu der wenigstens einen Gelphase, mindestens eine feste, insbesondere partikuläre Phase sowie optional mindestens eine weitere flüssige/gelförmige oder feste, bevorzugt körnige Phase umfasst.
„Fest“ bedeutet in diesem Zusammenhang, dass die Zusammensetzung bei Standardbedingungen (Temperatur 25°C, Druck 1013 mbar) in fester Form vorliegt. Geeignete feste, bevorzugt körnige Phasen sind zum einen körnige Gemenge einer festförmigen Zusammensetzung, wie zum Beispiel Pulver und/oder Granulate, insbesondere pulverförmige Phasen. Erfindungsgemäß ebenfalls geeignet sind feste Zusammensetzungen/Phasen, welche eine gegenüber dem losen Pulver verstärkte Formstabilität aufweisen, beispielsweise Pulver- oder Granulatzubereitung, welche vor oder nach dem Einschließen in die Folie durch Kompression verdichtet wurden, z.B. durch Rückstellkräfte der Folie nach dem Tiefziehen oder auch direkt komprimierte Zusammensetzungen, wie Komprimate oder Tabletten. Diese mindestens eine feste, bevorzugt körnige Phasen können in direktem Kontakt mit der gelförmigen Phase stehen. Erfindungsgemäß sind weiterhin Wasch- oder Reinigungsmittelportionen, bevorzugt Geschirrspülmittelportionen, insbesondere maschinellen Geschirrspülmittelportionen, insbesondere Mehrkammerbeutel, bei denen die feste und das Gel / die Gelphase in räumlicher Nähe, aber getrennt voneinander vorliegen. Dabei können die beiden Kammern beispielsweise durch eine Folie, insbesondere eine wasserlösliche Folie, oder auch durch eine Siegelnaht (bevorzugt von einer Siegelnaht von 3 mm oder weniger) getrennt sein. Erfindungsgemäß sind daher übereinanderliegende als auch nebeneinander angeordnete Kammern eines Mehrkammerpouches. Weiterhin sind auch Gemische von Ein- oder Mehrkammerbeutel, welche eine erfindungsgemäße gelförmige Phase und davon getrennt mindestens eine feste, bevorzugt körnige Phase umfassen, die durch Anordnung, z.B. durch Faltung und Fixierung eines Pouches, oder durch Lagerung in einem Abstand von geringer als 3 mm in Kontakt kommen, beispielsweise in einem Verpackungsbeutel oder einer Vorrichtung zur portionierten Dosierung, erfindungsgemäß. A preferred subject of the present invention is a detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent, which, in addition to the at least one gel phase, at least one solid, in particular particulate phase and optionally at least one other liquid / gel-like or solid, preferably granular phase includes. “Solid” in this context means that the composition is in solid form under standard conditions (temperature 25°C, pressure 1013 mbar). Suitable solid, preferably granular phases are, on the one hand, granular mixtures of a solid composition, such as, for example, powder and/or granules, in particular pulverulent phases. Also suitable according to the invention are solid compositions/phases which have greater dimensional stability than the loose powder, for example powder or granulate preparations which have been compacted by compression before or after being enclosed in the film, e.g. by restoring forces of the film after deep-drawing or directly compressed compositions such as compresses or tablets. This at least one solid, preferably granular phase can be in direct contact with the gel-like phase. According to the invention are also detergent or cleaning agent portions, preferably dishwashing detergent portions, in particular machine dishwashing detergent portions, in particular multi-chamber bags, in which the solid and the gel/the gel phase are present in close proximity but separate from one another. The two chambers can be separated, for example, by a film, in particular a water-soluble film, or by a sealed seam (preferably a sealed seam of 3 mm or less). According to the invention, chambers of a multi-chamber pouch are arranged one above the other or next to one another. Furthermore, mixtures of single or multi-chamber bags, which comprise a gel-like phase according to the invention and separately from it at least one solid, preferably granular phase, which can be arranged, for example by folding and fixing a pouch, or by storage at a distance of less than 3 mm come into contact, for example in a packaging bag or a device for portioned dosing, according to the invention.
Als pulverförmige Phase im Sinne der vorliegenden Erfindung ist ein körniges Gemenge zu verstehen, welches aus einer Vielzahl an losen, festförmigen Partikeln gebildet wird, die wiederum sogenannte Körner umfassen. Erfindungsgemäß umfasst der Begriff pulverförmige Phase Pulver und/oder Granulate gemäß der folgenden Definition. A granular mixture is to be understood as a powdery phase within the meaning of the present invention, which is formed from a large number of loose, solid particles, which in turn comprise so-called grains. According to the invention, the term powdery phase includes powders and/or granules according to the following definition.
Ein Korn ist eine Bezeichnung für die partikulären Bestandteile von Pulvern (Körner sind die losen, festförmigen Partikel), Stäuben (Körner sind die losen festförmigen Partikel), Granulaten (lose, festförmige Partikel sind Agglomerate aus mehreren Körnern) und anderen körnigen Gemengen. Eine bevorzugte Ausführungsform des körnigen Gemenges der Zusammensetzung der festen Phase ist das Pulver und/oder das Granulat, wenn hier von „Pulver“ oder „Granulat“ gesprochen wird, ist ebenfalls umfasst, dass es sich dabei auch um Mischungen verschiedener Pulver oder verschiedener Granulate handelt. Entsprechend sind mit Pulver und Granulat auch Mischungen verschiedener Pulver mit verschiedenen Granulaten gemeint. Die besagten festförmigen Partikel des körnigen Gemenges weisen wiederum bevorzugt einen Partikeldurchmesser X (Volumenmittel) von 10 bis 1500 pm, weiter bevorzugt von 200 gm bis 1200 pm, besonders bevorzugt von 600 pm bis 1100 pm, auf. Diese Partikelgrößen können durch Siebung oder mittels
eines Partikelgrößenanalysators Camsizer der Fa. Retsch bestimmt werden. Das als feste, bevorzugt körnige Phase dienende körnige Gemenge der festförmigen Zusammensetzung der vorliegenden Erfindung liegt bevorzugt in rieselfähiger Form (besonders bevorzugt als rieselfähiges Pulver und/oder rieselfähiges Granulat) vor. Das Mittel der erfindungsgemäßen Portion umfasst somit wenigstens eine feste, bevorzugt körnige Phase eines rieselfähigen, körnigen Gemenges einer festförmigen Zusammensetzung, insbesondere eines Pulvers sowie wenigstens eine, wie zuvor, definierte Gelphase. A grain is a designation for the particulate components of powders (grains are the loose, solid particles), dusts (grains are the loose, solid particles), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures. A preferred embodiment of the granular mixture of the composition of the solid phase is the powder and/or the granulate, if “powder” or “granulate” is mentioned here, it also includes mixtures of different powders or different granulates . Correspondingly, powder and granules also mean mixtures of different powders with different granules. Said solid particles of the granular mixture in turn preferably have a particle diameter X (volume average) of 10 to 1500 μm, more preferably of 200 μm to 1200 μm, particularly preferably of 600 μm to 1100 μm. These particle sizes can by sieving or by means a particle size analyzer Camsizer from Retsch. The granular mixture of the solid composition of the present invention, which serves as the solid, preferably granular phase, is preferably in a free-flowing form (particularly preferably as a free-flowing powder and/or free-flowing granules). The agent of the portion according to the invention thus comprises at least one solid, preferably granular phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one gel phase, as defined above.
Ein besonders bevorzugter Gegenstand der vorliegenden Erfindung sind Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, insbesondere eine Wasch- oder Reinigungsmittelportion, bevorzugt Geschirrspülmittelportion, insbesondere maschinelle Geschirrspülmittelportion, bei denen das Gel / die Gelphase in direktem Kontakt, beispielsweise in einer Kammer, mit der mindestens einen festen Phase enthalten ist. A particularly preferred subject of the present invention are detergents or cleaning agents, preferably dishwashing agents, in particular automatic dishwashing agents, in particular a portion of washing or cleaning agent, preferably dishwashing agent portion, in particular automatic dishwashing agent portion, in which the gel/the gel phase is in direct contact, for example in a chamber, is included with the at least one solid phase.
Des Weiteren ist es bevorzugt, dass die wenigstens eine feste, bevorzugt körnige Phase und das Gel in einem unmittelbaren Kontakt miteinander stehen. In diesem Fall soll es keine negative Wechselwirkung zwischen der festen Phase und der Gelphase geben. Keine negative Wechselwirkung bedeutet hier beispielsweise, dass keine Inhaltsstoffe oder Lösungsmittel aus einer Phase in die andere übertreten oder dass die Stabilität, insbesondere Lagerstabilität, bevorzugt bei 4 Wochen und 30 °C Lagertemperatur, und/oder die Ästhetik des Produktes in irgendeiner Form, beispielsweise durch Farbveränderung, Ausbildung von feucht-wirkenden Rändern, unscharf werdenden Grenze zwischen den beiden Phasen oder ähnlichem, beeinträchtigt wird. Furthermore, it is preferred that the at least one solid, preferably granular phase and the gel are in direct contact with one another. In this case there should be no negative interaction between the solid phase and the gel phase. No negative interaction means here, for example, that no ingredients or solvents pass from one phase to the other or that the stability, in particular storage stability, preferably at 4 weeks and 30 °C storage temperature, and / or the aesthetics of the product in any form, for example by Color change, the formation of edges that appear moist, the boundary between the two phases becoming blurred, or the like.
Überraschenderweise hat sich gezeigt, dass durch eine Formulierung einer Gelphase, bevorzugt formstabilen Gelphase, umfassend mindestens ein Polypropylenglykol, bevorzugt mit einem mittleren Molekulargewicht von 1000 bis 6000 g/mol, bevorzugt in einer Menge von 1 bis 15 Gew.- %, welche mit einem körnigen Gemenge einer festförmigen Zusammensetzung, insbesondere einer pulverförmigen Phase kombiniert wird, dieses Ziel erreicht werden kann. Dabei ist es besonders geeignet, wenn das körnige Gemenge einer festförmigen Zusammensetzung, insbesondere die pulverförmige Phase rieselfähig ist, da somit prozessbedingt eine gezieltere Füllung der wasserlöslichen Umhüllung, insbesondere bei Füllung einer durch Tiefziehen hergestellten Kavität, erzielt werden kann. Darüber hinaus kann die optische Erscheinung des körnigen Gemenges einer festförmigen Zusammensetzung, insbesondere des Pulvers im Vergleich zu einerverpressten Tablette besser geändert werden, insbesondere Texturunterschiede, wie grobe und feine Partikel sowie Partikel oder Bereiche mit unterschiedlichen Farben, gesamt oder als farbige Sprenkel, können so zur Verbesserung eines optisch ansprechenden Erscheinungsbildes eingesetzt werden. Das körnige Gemenge der festförmigen
Zusammensetzung, insbesondere das Pulver bietet darüber hinaus auch ohne Zusatz von Sprengmitteln eine verbesserte Löslichkeit im Vergleich zu verpressten Tabletten. Surprisingly, it has been shown that by formulating a gel phase, preferably dimensionally stable gel phase, comprising at least one polypropylene glycol, preferably having an average molecular weight of 1000 to 6000 g/mol, preferably in an amount of 1 to 15% by weight, which with a granular mixture of a solid composition, in particular a powdered phase is combined, this goal can be achieved. It is particularly suitable if the granular mixture of a solid composition, in particular the powdery phase, is free-flowing, since a more targeted filling of the water-soluble covering can be achieved as a result of the process, in particular when filling a cavity produced by deep drawing. In addition, the visual appearance of the granular mixture of a solid composition, in particular the powder, can be changed better compared to a compressed tablet, in particular differences in texture, such as coarse and fine particles as well as particles or areas with different colors, overall or as colored speckles, can thus be Improving a visually appealing appearance are used. The granular mixture of the solid The composition, in particular the powder, also offers improved solubility compared to compressed tablets, even without the addition of disintegrants.
Insbesondere bei den erfindungsgemäßen mehrphasigen Einmalportionen mit mindestens einer festen Phase ist es wichtig, dass das Gel formstabil ist, damit möglichst wenig Interaktionen zwischen der festen und der Gelphase stattfinden können. Particularly in the case of the multi-phase single-use portions according to the invention with at least one solid phase, it is important that the gel is dimensionally stable so that as few interactions as possible can take place between the solid and the gel phase.
Die wenigstens eine feste, bevorzugt körnige Phase der vorliegenden Erfindung umfasst ein körniges Gemenge einer festförmigen Zusammensetzung, insbesondere liegt sie in pulverfömiger und rieselfähiger Form vor. Das erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, umfasst somit wenigstens eine feste pulverförmige und rieselfähige Phase, sowie wenigstens eine Gelphase, das mindestens eine wasserlösliche Zinksalz, insbesondere Zinksulfat und/oder Zinkacetat, insbesondere Zinkacetat, sowie wenigstens ein Polyvinylalkohol, als Gelbildner mindestens PVOH und/oder dessen Derivate, insbesondere bevorzugt mindestens PVOH, sowie Glycerin umfasst. The at least one solid, preferably granular phase of the present invention comprises a granular mixture of a solid composition, in particular it is in powdered and free-flowing form. The washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, thus comprises at least one solid powdery and free-flowing phase, and at least one gel phase, the at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, and at least one polyvinyl alcohol, at least PVOH and/or derivatives thereof, particularly preferably at least PVOH, and glycerol as gel formers.
Die Rieselfähigkeit eines körnigen Gemenges, insbesondere eines pulverförmigen Feststoffes, der pulverförmigen Phase, bevorzugt des Pulvers und/oder Granulats betrifft sein Vermögen, unter eigenem Gewicht frei zu rieseln. Die Rieselfähigkeit wird bestimmt, in dem die Auslaufzeit von 1000 ml Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittelpulver aus einem genormten, an seiner Auslaufrichtung zunächst verschlossenen Rieseltesttrichter mit einem Auslauf von 16,5 mm Durchmesser durch Messen der Zeit für den vollständigen Auslauf des körnigen Gemenges, insbesondere der pulverförmigen Phase, bevorzugt des Pulvers und/oder Granulats, z.B. des Pulvers nach dem Öffnen des Auslaufs gemessen und mit der Auslaufgeschwindigkeit (in Sekunden) eines Standardprüfsands verglichen wird, dessen Auslaufgeschwindigkeit als 100 % definiert wird. Das definierte Sandgemisch zur Kalibrierung der Rieselapparatur ist trockener Seesand. Dabei wird Seesand mit einem Teilchendurchmesser von 0,4 bis 0,8 mm verwendet, erhältlich beispielsweise von Carl Roth, Deutschland CAS-Nr. [14808- 60-7] Zur Trocknung wird der Seesand vor der Messung 24 h bei 60 °C im Trockenschrank auf einer Platte bei einer maximalen Schichthöhe von 2 cm, getrocknet. The pourability of a granular mixture, in particular of a powdery solid, of the powdery phase, preferably of the powder and/or granulate, relates to its ability to pour freely under its own weight. The pourability is determined by measuring the flow time of 1000 ml of detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing powder, from a standardized flow test funnel that is initially closed in its outlet direction and has an outlet diameter of 16.5 mm by measuring the time it takes for it to flow out completely of the granular mixture, in particular the powdery phase, preferably the powder and/or granules, e.g. the powder is measured after opening the outlet and compared with the outlet speed (in seconds) of a standard test sand, the outlet speed of which is defined as 100%. The defined sand mixture for calibrating the trickle apparatus is dry sea sand. Sea sand with a particle diameter of 0.4 to 0.8 mm is used, available for example from Carl Roth, Germany CAS no. [14808- 60-7] Before the measurement, the sea sand is dried for 24 h at 60 °C in a drying cabinet on a plate with a maximum layer height of 2 cm.
Bevorzugte Ausführungsformen der erfindungsgemäßen festen Phasen weisen einen Schüttwinkel/Böschungswinkel von 26 bis 35, von 27 bis 34, von 28 bis 33, wobei der Schüttwinkel gemäß der unten genannten Methode nach 24 h nach der Herstellung des körnigen Gemenges der festförmigen Zusammensetzung, insbesondere der pulverförmigen festen Phase, bevorzugt des Pulvers und/oder Granulats und Lagerung bei 20 °C bestimmt wird, auf. Solche Schüttwinkel haben den Vorteil, dass die Befüllung der Kavitäten mit der wenigstens einen festen Phase vergleichsweise schnell und präzise erfolgen kann.
Zur Bestimmung des Schüttwinkels (oder auch Böschungswinkel genannt) der wenigstens einen festen, bevorzugt körnigen Phase wird ein Pulvertrichter mit 400ml Inhalt und einem Ablauf mit einem Durchmesser von 25mm gerade in ein Stativ gehängt. Der Trichter wird mittels eines manuell zu bedienenden Rändelrads mit einer Geschwindigkeit von 80 mm/min nach oben gefahren, so dass das körnige Gemenge, insbesondere die pulverförmige Phase, bevorzugt das Pulver und/oder Granulat, z.B. das Pulver herausrieselt. Dadurch bildet sich ein sogenannter Schüttkegel. Die Schüttkegelhöhe und der Schüttkegeldurchmesser werden für die einzelnen festen Phasen bestimmt. Aus dem Quotienten der Schüttkegelhöhe und dem Schüttkegeldurchmesser * 100 berechnet sich der Böschungswinkel. Preferred embodiments of the solid phases according to the invention have an angle of repose/repose of 26 to 35, 27 to 34, 28 to 33, the angle of repose according to the method mentioned below after 24 hours after the preparation of the granular mixture of the solid composition, in particular the powdery solid phase, preferably the powder and/or granules and storage at 20° C., is determined. Such angles of repose have the advantage that the cavities can be filled with the at least one solid phase comparatively quickly and precisely. To determine the angle of repose (or also known as the angle of repose) of the at least one solid, preferably granular phase, a powder funnel with a capacity of 400 ml and an outlet with a diameter of 25 mm is hung straight on a tripod. The hopper is moved upwards at a speed of 80 mm/min using a manually operated knurled wheel, so that the granular mixture, in particular the powdered phase, preferably the powder and/or granules, eg the powder, trickles out. This forms a so-called material cone. The height of the cone of repose and the diameter of the cone of repose are determined for the individual solid phases. The angle of repose is calculated from the quotient of the heap of repose and the diameter of the cone of repose * 100.
Besonders geeignet sind solche körnigen Gemenge einer festförmigen Zusammensetzung, insbesondere solche pulverförmigen Phasen, bevorzugt die Pulver und/oder Granulate, z.B. die Pulver die eine Rieselfähigkeit in % zum vorstehend angegebenen Standardprüfstoff von größer als 40 %, bevorzugt größer als 50, insbesondere größer als 55%, besonders bevorzugt größer als 60%, insbesondere bevorzugt zwischen 63 % und 80 %, beispielsweise zwischen 65 % und 75 % aufweisen. Insbesondere geeignet sind solche körnigen Gemenge einer festförmigen Zusammensetzung, insbesondere solche Pulver und/oder Granulate, die eine Rieselfähigkeit in % zum vorstehend angegebenen Standardprüfstoff von größer als 40 %, bevorzugt größer als 45 %, insbesondere größer als 50 %, besonders bevorzugt größer als 55 %, insbesondere bevorzugt größer als 60 % aufweisen, wobei die Messung der Rieselfähigkeit 24 h nach der Herstellung des Pulvers und Lagerung bei 20 °C durchgeführt wird. Particularly suitable are such granular mixtures of a solid composition, in particular such powdery phases, preferably the powders and/or granules, e.g. the powders which have a flowability in % of the standard test material specified above of greater than 40%, preferably greater than 50, in particular greater than 55 %, particularly preferably greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75%. Particularly suitable are those granular mixtures of a solid composition, in particular those powders and/or granules, which have a pourability in % of the standard test substance specified above of greater than 40%, preferably greater than 45%, in particular greater than 50%, particularly preferably greater than 55 %, particularly preferably greater than 60%, the pourability being measured 24 hours after the powder has been produced and stored at 20°C.
Geringere Werte für die Rieselfähigkeit sind eher nicht geeignet, da aus prozesstechnischer Sicht eine genaue Dosierung des körnigen Gemenges, insbesondere der pulverförmigen Phase, bevorzugt des Pulvers und/oder Granulats, z.B. des Pulvers notwendig ist. Insbesondere die Werte größer 50 %, insbesondere größer 55 %, bevorzugt größer 60 % (wobei die Messung der Rieselfähigkeit 24 h nach der Herstellung des Pulvers und Lagerung bei 20 °C durchgeführt wird) haben sich als vorteilhaft erwiesen, da sich durch die gute Dosierbarkeit der körnigen Gemenge, insbesondere der pulverförmigen Phasen, bevorzugt der Pulver und/oder Granulate, z.B. Pulver nur geringe Schwankungen in der dosierten Menge bzw. der Zusammensetzung ergeben. Die genauere Dosierung führt zu einer gleichbleibenden Produktleistung, wirtschaftliche Verluste durch Überdosierung werden so vermieden. Weiterhin ist es vorteilhaft, dass die körnigen Gemenge, insbesondere die pulverförmige Phase, bevorzugt das Pulver und/oder Granulat, z.B. das Pulver gut dosierbar sind, so erreicht man einen schnelleren Ablauf des Dosierprozesses. Weiterhin wird durch eine solch gute Rieselfähigkeit besser vermieden, dass das körnige Gemenge, insbesondere die pulverförmige Phase, bevorzugt das Pulver und/oder Granulat, z.B. das Pulver auf den Teil der wasserlöslichen Umhüllung gelangt, die für die Herstellung der Siegelnaht vorgesehen ist und daher möglichst körnchenfrei, insbesondere pulverfrei bleiben soll.
Das als feste, bevorzugt körnige Phase dienende körnige Gemenge der festförmigen Zusammensetzung der vorliegenden Erfindung liegt bevorzugt in rieselfähiger Form (besonders bevorzugt als rieselfähiges Pulver und/oder rieselfähiges Granulat) vor. Das Mittel der erfindungsgemäßen Portion umfasst somit wenigstens eine feste, bevorzugt körnige Phase eines rieselfähigen, körnigen Gemenges einer festförmigen Zusammensetzung, insbesondere eines Pulvers sowie wenigstens eine zuvor definierte Gelphase. Lower values for the pourability are rather unsuitable since, from the point of view of process technology, precise dosing of the granular mixture, in particular the powdered phase, preferably the powder and/or granules, for example the powder, is necessary. In particular, the values greater than 50%, in particular greater than 55%, preferably greater than 60% (the flowability being measured 24 h after the production of the powder and storage at 20° C.) have proven to be advantageous because the good dosability the granular mixture, in particular the pulverulent phases, preferably the powder and/or granules, eg powder, result in only slight fluctuations in the metered quantity or the composition. The more precise dosing leads to a constant product performance, economic losses due to overdosing are thus avoided. Furthermore, it is advantageous that the granular mixture, in particular the pulverulent phase, preferably the powder and/or granulate, eg the powder, can be easily dosed, so that the dosing process runs more quickly. Furthermore, such a good flowability better prevents the granular mixture, in particular the powdery phase, preferably the powder and/or granules, e.g. the powder, from getting onto the part of the water-soluble cover that is intended for the production of the sealed seam and is therefore possible should remain granule-free, in particular powder-free. The granular mixture of the solid composition of the present invention, which serves as the solid, preferably granular phase, is preferably in a free-flowing form (particularly preferably as a free-flowing powder and/or free-flowing granules). The means of the portion according to the invention thus comprises at least one solid, preferably granular phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one previously defined gel phase.
Das erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, umfasst vorzugsweise wenigstens ein Tensid. Dieses Tensid ist ausgewählt aus der Gruppe der anionischen, nichtionischen und kationischen Tenside. Das erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, kann auch Mischungen aus mehreren Tensiden, die aus derselben Gruppe ausgewählt sind, enthalten. The washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprises at least one surfactant. This surfactant is selected from the group of anionic, nonionic and cationic surfactants. The washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, can also contain mixtures of two or more surfactants selected from the same group.
Erfindungsgemäß umfassen die wenigstens eine feste, bevorzugt körnige Phase und/oder das Gel wenigstens ein Tensid. Es ist möglich, dass nur die wenigstens eine feste, bevorzugt körnige Phase oder nur das Gel wenigstens ein Tensid umfassen. Umfassen beide Phasen ein Tensid, so handelt es sich vorzugsweise um voneinander verschiedene Tenside. Es ist jedoch auch möglich, dass feste und Gelphase dasselbe Tensid oder dieselben Tenside aufweisen. Erfindungsgemäße wenigstens eine feste und/oder Gelphasen enthalten vorzugsweise mindestens ein nichtionisches Tensid. Als nichtionische Tenside können alle dem Fachmann bekannten nichtionischen Tenside eingesetzt werden. Bevorzugt werden schwachschäumende nichtionische Tenside eingesetzt, insbesondere alkoxylierte, vor allem ethoxylierte, schwachschäumende nichtionische Tenside, wie beispielsweise Alkylglykoside, alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, Polyhydroxyfettsäureamide oder Aminoxide. Besonders bevorzugte nichtionische Tenside werden im Folgenden näher spezifiziert. According to the invention, the at least one solid, preferably granular phase and/or the gel comprise at least one surfactant. It is possible for only the at least one solid, preferably granular phase or only the gel to comprise at least one surfactant. If both phases comprise a surfactant, they are preferably different surfactants. However, it is also possible for the solid and gel phases to have the same surfactant or surfactants. At least one solid and/or gel phase according to the invention preferably contains at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants, such as, for example, alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides or amine oxides. Particularly preferred nonionic surfactants are specified in more detail below.
Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
Mit besonderem Vorzug werden ethoxylierte Niotenside, die aus C6-20-Monohydroxyalkanolen oder C6-2o-Alkylphenolen oder Ci6-20-Fettalkoholen und mehr als 12 Mol, vorzugsweise mehr als 15 Mol und insbesondere mehr als 20 Mol Ethylenoxid pro Mol Alkohol gewonnen wurden, eingesetzt. Ein besonders bevorzugtes Niotensid wird aus einem geradkettigen Fettalkohol mit 16 bis 20 Kohlenstoffatomen (Ci6-20-Alkohol), vorzugsweise einem Cis-Alkohol und mindestens 12 Mol, vorzugsweise mindestens 15 Mol und insbesondere mindestens 20 Mol Ethylenoxid gewonnen. Hierunter sind die sogenannten „narrow ränge ethoxylates" besonders bevorzugt.
Bevorzugt einzusetzende Tenside stammen aus den Gruppen der alkoxylierten Niotenside, insbesondere der ethoxylierten primären Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen ((PO/EO/PO)-Tenside). Solche (PO/EO/PO)-Niotenside zeichnen sich darüber hinaus durch gute Schaumkontrolle aus. Particular preference is given to ethoxylated nonionic surfactants obtained from C6-20 monohydroxyalkanols or C6-20 alkylphenols or C16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol, deployed. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (Ci6-20 alcohol), preferably a cis alcohol, and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Among these, the so-called “narrow range ethoxylates” are particularly preferred. Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are also distinguished by good foam control.
Als besonders bevorzugte Niotenside haben sich im Rahmen der vorliegenden Erfindung für die schwachschäumende Niotenside erwiesen, welche alternierende Ethylenoxid- und Alkylenoxideinheiten aufweisen. Unter diesen sind wiederum Tenside mit EO-AO-EO-AO-Blöcken bevorzugt, wobei jeweils eine bis zehn EO- beziehungsweise AO-Gruppen aneinander gebunden sind, bevor ein Block aus den jeweils anderen Gruppen folgt. Hier sind nichtionische Tenside der allgemeinen Formel
bevorzugt, in der R1 für einen geradkettigen oder verzweigten, gesättigten oder einbeziehungsweise mehrfach ungesättigten C6-24-Alkyl- oder — Alkenylrest steht; jede Gruppe R2 beziehungsweise R3 unabhängig voneinander ausgewählt ist aus -CH3, -CH2CH3, -CH2CH2- CH3, -CH(CH3)2 und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen. In the context of the present invention, particularly preferred nonionic surfactants have been found for the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, preference is in turn given to surfactants with EO-AO-EO-AO blocks, in which case one to ten EO or AO groups are bonded to one another before a block of the other groups follows. Here are nonionic surfactants of the general formula preferably in which R 1 is a straight-chain or branched, saturated or one or more times unsaturated C6-24 -alkyl or - alkenyl radical; each group R 2 or R 3 is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH 3 ) 2 and the indices w, x, y, z are independently integers from 1 to 6 .
Bevorzugte Niotenside der vorstehenden Formel lassen sich durch bekannte Methoden aus den entsprechenden Alkoholen R1-OH und Ethylen- beziehungsweise Alkylenoxid hersteilen. Der Rest R1 in der vorstehenden Formel kann je nach Herkunft des Alkohols variieren. Werden native Quellen genutzt, weist der Rest R1 eine gerade Anzahl von Kohlenstoffatomen auf und ist in der Regel unverzweigt, wobei die linearen Reste aus Alkoholen nativen Ursprungs mit 12 bis 18 C- Atomen, zum Beispielaus Kokos-, Palm-, Talgfett- oder Oleylalkohol, bevorzugt sind. Aus synthetischen Quellen zugängliche Alkohole sind beispielsweise die Guerbetalkohole oder in 2- Stellung methylverzweigte beziehungsweise lineare und methylverzweigte Reste im Gemisch, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Unabhängig von der Art des zur Herstellung der in den Mitteln enthaltenen Niotenside eingesetzten Alkohols sind Niotenside bevorzugt, bei denen R1 in der vorstehenden Formel für einen Alkylrest mit 6 bis 24, vorzugsweise 8 bis 20, besonders bevorzugt 9 bis 15 und insbesondere 9 bis 11 Kohlenstoffatomen steht. Preferred nonionic surfactants of the above formula can be prepared from the corresponding alcohols R 1 —OH and ethylene or alkylene oxide by known methods. The radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, with the linear radicals from alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred. Alcohols obtainable from synthetic sources are, for example, the Guerbet alcohols or a mixture of methyl-branched or linear and methyl-branched radicals in the 2-position, such as are usually present in oxo alcohol radicals. Regardless of the type of alcohol used to produce the nonionic surfactants contained in the agents, nonionic surfactants are preferred in which R 1 in the above formula is an alkyl radical with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
Als Alkylenoxideinheit, die alternierend zur Ethylenoxideinheit in den bevorzugten Niotensiden enthalten ist, kommt neben Propylenoxid insbesondere Butylenoxid in Betracht. Aber auch weitere Alkylenoxide, bei denen R2 beziehungsweise R3 unabhängig voneinander ausgewählt sind aus - CH2CH2-CH3 beziehungsweise -CH(CH3)2 sind geeignet. Bevorzugt werden Niotenside der vorstehenden Formel eingesetzt, bei denen R2 beziehungsweise R3 für einen Rest -CH3, w und x
unabhängig voneinander für Werte von 3 oder 4 und y und z unabhängig voneinander für Werte von 1 oder 2 stehen. A suitable alkylene oxide unit, which is present in the preferred nonionic surfactants alternating with the ethylene oxide unit, is, in addition to propylene oxide, in particular butylene oxide. However, other alkylene oxides in which R 2 or R 3 are independently selected from -CH2CH2-CH3 or -CH(CH3)2 are also suitable. Preference is given to using nonionic surfactants of the above formula in which R.sup.2 or R.sup.3 is a --CH.sub.3 radical, w and x are independently 3 or 4, and y and z are independently 1 or 2.
Weitere bevorzugt eingesetzte nichtionische Tenside der festen Phase sind nichtionische Tenside der allgemeinen Formel R10(Alk0)xM(0Alk)y0R2, wobei Other nonionic surfactants preferably used in the solid phase are nonionic surfactants of the general formula R 1 0(Alk0) x M(0Alk) y 0R 2 , where
R1 und R2 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen; Alk für einen verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht; x und y unabhängig voneinander für Werte zwischen 1 und 70 stehen; und M für einen Alkylrest aus der Gruppe CH2, CHR3, CR3R4, CH2CHR3 und CHR3CHR4 steht, wobei R3 und R4 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen stehen. R 1 and R 2 independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl group having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M is an alkyl radical from the group CH 2 , CHR 3 , CR 3 R 4 , CH2CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 are independently branched or unbranched, saturated or unsaturated alkyl radicals having 1 to 18 carbon atoms.
Bevorzugt sind hierbei nichtionische Tenside der allgemeinen Formel Nonionic surfactants of the general formula are preferred here
R1-CH(0H)CH2-0(CH2CH20)xCH2CHR(0CH2CH2)y-CH2CH(0H)-R2, wobei R, R1 und R2 unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22R 1 -CH(0H)CH 2 -0(CH 2 CH 2 0)xCH 2 CHR(0CH 2 CH 2 )y -CH 2 CH(0H)-R 2 where R, R 1 and R 2 are independently an alkyl radical or alkenyl radical with 6 to 22
Kohlenstoffatomen; x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen. carbon atoms; x and y independently represent values between 1 and 40.
Bevorzugt sind hierbei insbesondere Verbindungen der allgemeinen Formel R1-CH(0H)CH2-0(CH2CH20)xCH2CHR(0CH2CH2)y0-CH2CH(0H)-R2, in denen R für einen linearen, gesättigten Alkylrest mit 8 bis 16 Kohlenstoffatomen, vorzugsweise 10 bis 14 Kohlenstoffatomen steht und n und m unabhängig voneinander Werte von 20 bis 30 aufweisen. Entsprechende Verbindungen können beispielsweise durch Umsetzung von Alkyldiolen HO-CHR-CH2-OH mit Ethylenoxid erhalten werden, wobei im Anschluss eine Umsetzung mit einem Alkylepoxid zum Verschluss der freien OH-Funktionen unter Ausbildung eines Dihydroxyethers erfolgt. Particular preference is given here to compounds of the general formula R 1 -CH(0H)CH 2 -0(CH 2 CH 2 0)xCH 2 CHR(0CH 2 CH 2 )y0-CH 2 CH(0H)-R 2 in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently have values of 20 to 30. Corresponding compounds can be obtained, for example, by reacting alkyl diols HO-CHR-CH2-OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close the free OH functions with formation of a dihydroxy ether.
Bevorzugte nichtionische Tenside sind hierbei solche der allgemeinen Formel R1-CH(0H)CH20- (A0)w-(A0)x-(A"0)y-(A'"0)z-R2, in der Preferred nonionic surfactants here are those of the general formula R 1 -CH(OH)CH 2 0-(A0)w-(A0)x-(A"0) y- (A'"0)zR 2 , in which
- R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder -Alkenylrest steht; - R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;
- R2 für Wasserstoff oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht; - R 2 represents hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
- A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH2CH2, -CH2CH2- CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-, -CH2-CH(CH2-CH3) stehen,- A, A', A" and A'" independently represent a radical from the group -CH2CH2 , -CH2CH2- CH2 , -CH2-CH(CH3), -CH2 -CH2-CH2-CH2, -CH2 -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 2 -CH 3 ),
- w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können. - w, x, y and z stand for values between 0.5 and 120, where x, y and/or z can also be 0.
Durch den Zusatz der vorgenannten nichtionischen Tenside der allgemeinen Formel
R1-CH(OH)CH2O-(AO)w-(A'O)x-(A"0)y-(A"O)z-R2, nachfolgend auch als „Hydroxymischether" bezeichnet, kann überraschenderweise die Reinigungsleistung erfindungsgemäßer Zubereitungen deutlich verbessert werden und zwar sowohl im Vergleich zu Tensid-freien System wie auch im Vergleich zu Systemen, die alternative nichtionischen Tenside, beispielsweise aus der Gruppe der polyalkoxylierten Fettalkohole enthalten. By adding the aforementioned nonionic surfactants of the general formula R 1 -CH(OH)CH2O-(AO)w-(A′O)x-(A″O)y-(A″O) z -R 2 , also referred to below as “hydroxy mixed ether”, can surprisingly improve the cleaning performance Preparations according to the invention are significantly improved, both in comparison to surfactant-free systems and in comparison to systems that contain alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
Durch den Einsatz dieser nichtionischen Tenside mit einer oder mehreren freien Hydroxylgruppe an einem oder beiden endständigen Alkylresten kann die Stabilität der in den erfindungsgemäßen Wasch- oder Reinigungsmitteln, bevorzugt Geschirrspülmitteln, insbesondere maschinellen Geschirrspülmitteln enthaltenen Enzyme deutlich verbessert werden. The use of these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals can significantly improve the stability of the enzymes contained in the detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents.
Bevorzugt sind insbesondere solche endgruppenverschlossenen poly(oxyalkylierten) Niotenside, die, gemäß der folgenden Formel
neben einem Rest R1, welcher für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen steht, weiterhin einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest R2 mit 1 bis 30 Kohlenstoffatomen aufweisen, wobei n für Werte zwischen 1 und 90, vorzugsweise für Werte zwischen 10 und 80 und insbesondere für Werte zwischen 20 und 60 steht. Insbesondere bevorzugt sind Tenside der vorstehenden Formel, in denen R1 für C7 bis C13, n für eine ganze natürliche Zahl von 16 bis 28 und R2für Cs bis C12 steht. Preference is given in particular to those end-capped poly(oxyalkylated) nonionic surfactants which, according to the following formula in addition to a radical R 1 , which is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, also a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 with 1 to 30 carbon atoms, where n is between 1 and 90, preferably between 10 and 80 and in particular between 20 and 60. Particular preference is given to surfactants of the above formula in which R 1 is C7 to C13, n is an integer from 16 to 28 and R 2 is Cs to C12.
Besonders bevorzugt sind Tenside der Formel R10[CH2CH(CH3)0]x[CH2CH20]yCH2CH(0H)R2, in der R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 18 Kohlenstoffatomen oder Mischungen hieraus steht, R2einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x für Werte zwischen 0,5 und 1 ,5 sowie y für einen Wert von mindestens 15 steht. Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C2-26 Fettalkohol-(PO)i-(EO)i5-40-2- hydroxyalkylether, insbesondere auch die Ce-io Fettalkohol-(PO)i-(EO)22-2-hydroxydecylether. Particularly preferred are surfactants of the formula R 1 0 [CH 2 CH (CH 3) 0] x [CH 2 CH 2 0] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 bis 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x has values between 0.5 and 1.5 and y has a value of at least 15. The group of these nonionic surfactants includes, for example, the C2-26 fatty alcohol (PO)i-(EO)i5- 40 -2-hydroxyalkyl ethers, in particular also the Ce-io fatty alcohol (PO)i-(EO) 22 -2-hydroxydecyl ether .
Besonders bevorzugt sind weiterhin solche endgruppenverschlossenen poly(oxyalkylierten) Niotenside der Formel R10[CH2CH20]x[CH2CH(R3)0]yCH2CH(0H)R2, in der R1 und R2 unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht, R3 unabhängig voneinander ausgewählt ist aus -CH3, -CH2CH3, -CH2CH2-CH 3, -CH(CH3)2, vorzugsweise jedoch für -CH3Steht, und x und y unabhängig voneinander für Werte zwischen 1 und
32 stehen, wobei Niotenside mit R3= -Chh und Werten für x von 15 bis 32 und y von 0,5 und 1 ,5 ganz besonders bevorzugt sind. Particular preference is also given to end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 0[CH 2 CH 2 0]x[CH 2 CH(R 3 )0] y CH 2 CH(0H)R 2 , in which R 1 and R 2 is independently a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2 , but preferably represents -CH3, and x and y independently represent values between 1 and 32, where nonionic surfactants with R 3 = -Chh and values for x from 15 to 32 and y from 0.5 to 1.5 are very particularly preferred.
Weitere bevorzugt einsetzbare Niotenside sind die endgruppenverschlossenen poly(oxyalkylierten) Niotenside der Formel R10[CH2CH(R3)0]x[CH2]kCH(0H)[CH2]j0R2, in der R1 und R2für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R3 für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x für Werte zwischen 1 und 30, k und j für Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen. Wenn der Wert x > 2 ist, kann jedes R3 in der oben stehenden Formel R10[CH2CH(R3)0]x[CH2]kCH(0H)[CH2]j0R2 unterschiedlich sein. R1 und R2sind vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. Für den Rest R3sind H, -CH3 oder-CFhCF besonders bevorzugt. Besonders bevorzugte Werte fürx liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15. Other preferably usable nonionic surfactants are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 0[CH 2 CH(R 3 )0]x[CH 2 ] k CH(0H)[CH 2 ]j0R 2 , in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2- butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5. When the value of x > 2, each R 3 in the above formula R 1 0[CH 2 CH(R 3 )0]x[CH 2 ] k CH(0H)[CH 2 ]j 0R 2 can be different. R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH3 or -CFhCF are particularly preferred for the radical R 3 . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
Wie vorstehend beschrieben, kann jedes R3 in der oben stehenden Formel unterschiedlich sein, falls x > 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht x beispielsweise für 3, kann der Rest R3 ausgewählt werden, um Ethylenoxid- (R3= H) oder Propylenoxid- (R3= CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefügt sein können, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 für x ist hierbei beispielhaft gewählt worden und kann durchaus größer sein, wobei die Variationsbreite mit steigenden x-Werten zunimmt und beispielsweise eine große Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)- Gruppen einschließt, oder umgekehrt. As described above, each R 3 in the above formula can be different when x>2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R 3 group may be selected to form ethylene oxide (R 3 = H) or propylene oxide (R 3 = CH 3 ) moieties which may be joined in any order, e.g. (EO)(PO )(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO )(PO). The value 3 for x was selected here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
Besonders bevorzugte endgruppenverschlossene poly(oxyalkylierte) Alkohole der oben stehenden Formel weisen Werte von k = 1 und j = 1 auf, so dass sich die vorstehende Formel zu R10[CH2CH(R3)0]XCH2CH(0H)CH20R2 vereinfacht. In der letztgenannten Formel sind R1, R2 und R3 wie oben definiert und x steht für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R1 und R29 bis 14 C-Atome aufweisen, R3 für H steht und x Werte von 6 bis 15 annimmt. Als besonders wirkungsvoll haben sich schließlich die nichtionischen Tenside der allgemeine Formel R1- CH(0H)CH20-(A0)W-R2 erwiesen, in der Particularly preferred endcapped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1 such that the above formula translates to R 1 0[CH 2 CH(R 3 )0] X CH 2 CH(0H )CH 2 0R 2 simplified. In the latter formula, R 1 , R 2 and R 3 are as defined above and x is a number from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Surfactants in which the radicals R 1 and R 2 has 9 to 14 carbon atoms, R 3 is H and x has values from 6 to 15. Finally, the nonionic surfactants of the general formula R 1 --CH(OH)CH 2 0-(A0) W --R 2 have proven to be particularly effective
- R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C 6-24-Alkyl- oder-Alkenylrest steht; - R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
- R2 für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
- A für einen Rest aus der Gruppe CH2CH2, CH2CH2CH2, CH2CH(CH3), vorzugsweise für CH2CH2 steht, und - R 2 represents a linear or branched hydrocarbon radical having from 2 to 26 carbon atoms; - A is a radical from the group CH2CH2, CH2CH2CH2, CH2CH(CH3), preferably CH2CH2, and
- w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht. - w represents values between 1 and 120, preferably 10 to 80, in particular 20 to 40.
Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C4-22 Fettalkohol-(EO)io-8o-2- hydroxyalkylether, insbesondere auch die C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4- 22 Fettalkohol-(EO)40-80-2-hydroxyalkylether. The group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular the C8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C4- 22 fatty alcohol (EO) 40 -80-2-hydroxyalkyl ether.
Bevorzugt enthält die wenigstens eine feste und/oder das Gel mindestens ein nichtionisches Tensid, vorzugsweise ein nichtionisches Tensid aus der Gruppe der Hydroxymischether, wobei der Gewichtsanteil des nichtionischen Tensids am Gesamtgewicht des Gels vorzugsweise 0,5 Gew.-% bis 30 Gew.-%, bevorzugt 5 Gew.-% bis 25 Gew.-% und insbesondere 10 Gew.-% bis 20 Gew.-% beträgt. Preferably, the at least one solid and/or the gel contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, with the proportion by weight of the nonionic surfactant based on the total weight of the gel preferably being 0.5% by weight to 30% by weight. , preferably 5% by weight to 25% by weight and in particular 10% by weight to 20% by weight.
In einerweiteren bevorzugten Ausführungsform ist das nichtionische Tensid der festen und/oder Gelphase ausgewählt aus nichtionischen Tensiden der allgemeinen Formel R1-0(CH2CH20)xCR3R4(0CH2CH2)y0-R2, in der R1 und R2 unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen; R3 und R4 unabhängig voneinander für H oder für einen Alkylrest oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen und x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen. In a further preferred embodiment, the nonionic surfactant of the solid and/or gel phase is selected from nonionic surfactants of the general formula R 1 -0(CH 2 CH 2 0) x CR 3 R 4 (0CH 2 CH 2 )y0-R 2 , in which R 1 and R 2 independently represent an alkyl group or alkenyl group having 4 to 22 carbon atoms; R 3 and R 4 are independently H or an alkyl or alkenyl group having from 1 to 18 carbon atoms and x and y are independently from 1 to 40.
Bevorzugt sind hierbei insbesondere Verbindungen der allgemeinen Formel R1-0(CH2CH20)xCR3R4(0CH2CH2)y0-R2, in der R3 und R4 für H stehen und die Indices x und y unabhängig voneinander Werte von 1 bis 40, vorzugsweise von 1 bis 15 annehmen. In this connection, particular preference is given to compounds of the general formula R 1 -0(CH 2 CH 2 0)xCR 3 R 4 (0CH 2 CH 2 ) y 0-R 2 , in which R 3 and R 4 represent H and the indices x and y independently assume values from 1 to 40, preferably from 1 to 15.
Besonders bevorzugt sind insbesondere Verbindungen der allgemeinen Formel R1-0(CH2CH20)xCR3R4(0CH2CH2)y0-R2, in der die Reste R1 und R2 unabhängig voneinander gesättigte Alkylreste mit 4 bis 14 Kohlenstoffatome darstellen und die Indices x und y unabhängig voneinander Werte von 1 bis 15 und insbesondere von 1 bis 12 annehmen. Particular preference is given in particular to compounds of the general formula R 1 -0(CH 2 CH 2 0) x CR 3 R 4 (0CH 2 CH 2 ) y 0-R 2 , in which the radicals R 1 and R 2 are, independently of one another, saturated alkyl radicals with 4 represent up to 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.
Weiterhin bevorzugt sind solche Verbindungen der allgemeinen Formel R1-0(CH2CH20)xCR3R4(0CH2CH2)y0-R2, in der einer der Reste R1 und R2 verzweigt ist. Preference is also given to compounds of the general formula R 1 -0(CH 2 CH 2 0)xCR 3 R 4 (0CH 2 CH 2 ) y 0-R 2 in which one of the radicals R 1 and R 2 is branched.
Ganz besonders bevorzugt sind Verbindungen der allgemeinen Formel Compounds of the general formula are very particularly preferred
R1-0(CH2CH20)xCR3R4(0CH2CH2)y0-R2, in der die Indices x und y unabhängig voneinander Werte von 8 bis 12 annehmen. R 1 -0(CH 2 CH 2 0) x CR 3 R 4 (0CH 2 CH 2 )y0-R 2 in which the indices x and y assume values from 8 to 12 independently of one another.
Die angegebenen C-Kettenlängen sowie Ethoxylierungsgrade beziehungsweise Alkoxylierungsgrade der Niotenside stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Aufgrund der Herstellverfahren bestehen Handelsprodukte der genannten Formeln zumeist nicht aus einem individuellen Vertreter, sondern aus Gemischen, wodurch sich sowohl für die C-Kettenlängen als auch für die
Ethoxylierungsgrade beziehungsweise Alkoxylierungsgrade Mittelwerte und daraus folgend gebrochene Zahlen ergeben können. The given carbon chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical mean values, which can be a whole or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which means that both the C chain lengths and the Degrees of ethoxylation or degrees of alkoxylation can result in mean values and fractional numbers as a result.
Selbstverständlich können die vorgenannten nichtionischen Tenside (Niotenside) nicht nur als Einzelsubstanzen, sondern auch als Tensidgemische aus zwei, drei, vier oder mehr Tensiden eingesetzt werden. Of course, the aforementioned nonionic surfactants (nonionic surfactants) can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.
Insbesondere bevorzugt sind in der wenigstens einen festen, bevorzugt körnigen Phase solche nichtionische Tenside, die einen Schmelzpunkt oberhalb Raumtemperatur aufweisen. Nichtionische(s) Tensid(e) mit einem Schmelzpunkt oberhalb von 20°C, vorzugsweise oberhalb von 25°C, besonders bevorzugt zwischen 25 und 60°C und insbesondere zwischen 26,6 und 43,3°C, ist/sind besonders bevorzugt. Nonionic surfactants which have a melting point above room temperature are particularly preferred in the at least one solid, preferably granular phase. Nonionic surfactant(s) with a melting point above 20°C, preferably above 25°C, more preferably between 25 and 60°C and especially between 26.6 and 43.3°C is/are particularly preferred .
Geeignete nichtionische Tenside, die Schmelz- beziehungsweise Erweichungspunkte im genannten Temperaturbereich aufweisen, sind beispielsweise schwachschäumende nichtionische Tenside, die bei Raumtemperatur fest oder hochviskos sein können. Werden Niotenside eingesetzt, die bei Raumtemperatur hochviskos sind, so ist bevorzugt, dass diese eine Viskosität oberhalb von 20 Pa s, vorzugsweise oberhalb von 35 Pa s und insbesondere oberhalb 40 Pa s aufweisen. Auch Niotenside, die bei Raumtemperatur wachsartige Konsistenz besitzen, sind bevorzugt. Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferable for them to have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants, which have a waxy consistency at room temperature, are also preferred.
Das bei Raumtemperatur feste Niotensid besitzt vorzugsweise Propylenoxideinheiten (PO) im Molekül. Vorzugsweise machen solche PO-Einheiten bis zu 25 Gew.-%, besonders bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids aus. Besonders bevorzugte nichtionische Tenside sind ethoxylierte Monohydroxyalkanole oder Alkylphenole, die zusätzlich Polyoxyethylen-Polyoxypropylen Blockcopolymereinheiten aufweisen. Der Alkohol- beziehungsweise Alkylphenolteil solcher Niotensidmoleküle macht dabei vorzugsweise mehr als 30 Gew.-%, besonders bevorzugt mehr als 50 Gew.-% und insbesondere mehr als 70 Gew.-% der gesamten Molmasse solcher Niotenside aus. Bevorzugte Mittel sind dadurch gekennzeichnet, dass sie ethoxylierte und propoxylierte Niotenside enthalten, bei denen die Propylenoxideinheiten im Molekül bis zu 25 Gew.-%, bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids ausmachen. The nonionic surfactant which is solid at room temperature preferably has propylene oxide units (PO) in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight, of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxy alkanols or alkyl phenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes up preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic identify surfactants.
Weitere besonders bevorzugt in der festen Phase einzusetzende Niotenside mit Schmelzpunkten oberhalb Raumtemperatur enthalten 40 bis 70% eines Polyoxypropylen/Polyoxyethylen/Polyoxy- propylen-Blockpolymerblends, der 75 Gew.-% eines umgekehrten Block-Copolymers von Polyoxyethylen und Polyoxypropylen mit 17 Mol Ethylenoxid und 44 Mol Propylenoxid und 25 Gew.-% eines Block-Copolymers von Polyoxyethylen und Polyoxypropylen, initiiert mit
Trimethylolpropan und enthaltend 24 Mol Ethylenoxid und 99 Mol Propylenoxid pro Mol Trimethylolpropan, enthält. Other nonionic surfactants to be used particularly preferably in the solid phase with melting points above room temperature contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend which contains 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
Der Gewichtsanteil des nichtionischen Tensids am Gesamtgewicht der festen, bevorzugt körnigen Phase beträgt in einer bevorzugten Ausführungsform von 0,1 bis 20 Gew.-%, besonders bevorzugt von 0,5 bis 15 Gew.-%, insbesondere von 2,5 bis 10 Gew.-%. In a preferred embodiment, the proportion by weight of the nonionic surfactant in the total weight of the solid, preferably granular phase is from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight %.
Als anionische Tenside eignen sich in den Mitteln alle anionischen oberflächenaktiven Stoffe.All anionic surface-active substances are suitable as anionic surfactants in the agents.
Diese sind gekennzeichnet durch eine wasserlöslich machende, anionische Gruppe wie z. B. eine Carboxylat-, Sulfat- oder Sulfonat-Gruppe und eine lipophile Alkylgruppe mit etwa 8 bis 30 C- Atomen. Zusätzlich können im Molekül Glykol- oder Polyglykolether-Gruppen, Ester-, Ether- und Amidgruppen sowie Hydroxylgruppen enthalten sein. Geeignete anionische Tenside liegen vorzugsweise in Form der Natrium-, Kalium- und Ammonium- sowie der Mono-, Di- und Trialkanolammoniumsalze mit 2 bis 4 C-Atomen in der Alkanolgruppe vor, aber auch Zink, Mangan(ll), Magnesium, Calcium oder Mischungen hieraus können als Gegenionen dienen. Bevorzugte anionische Tenside sind Alkylsulfate, Alkylpolyglykolethersulfate und Ethercarbonsäuren mit 10 bis 18 C-Atomen in der Alkylgruppe und bis zu 12 Glykolethergruppen im Molekül. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate or sulfonate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
Anstelle der genannten Tenside oder in Verbindung mit ihnen können auch kationische und/oder amphotere Tenside, wie Betaine oder quartäre Ammoniumverbindungen, eingesetzt werden. Es ist allerdings bevorzugt, dass keine kationischen und/oder amphoteren Tenside eingesetzt werden. Instead of the surfactants mentioned or in combination with them, cationic and/or amphoteric surfactants such as betaines or quaternary ammonium compounds can also be used. However, it is preferred that no cationic and/or amphoteric surfactants are used.
Gemäß einer besonders bevorzugten Ausführungsform enthält das Gel mindestens ein weiteres nichtionisches Tensid, bevorzugt in einer Menge von 0,1 bis 80 Gew.-% enthalten ist. According to a particularly preferred embodiment, the gel contains at least one further nonionic surfactant, preferably in an amount of 0.1 to 80% by weight.
Besonders geeignete nichtionische Tenside sind vorstehend beschrieben. Besonders bevorzugt eignen sich die Substanzen der Serie Plurafac® LF (BASF), sowie die vorstehend als Hydroxymischether oder Fettalkoholpolyalkylenglykole beschriebenen endgruppenverschlossenen oder nicht-endgruppenverschlossenen nichtionischen Tenside. Particularly suitable nonionic surfactants are described above. Substances from the Plurafac® LF (BASF) series are particularly suitable, as are the end-capped or non-capped non-ionic surfactants described above as hydroxy mixed ethers or fatty alcohol polyalkylene glycols.
Bevorzugte erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, sind weiterhin dadurch gekennzeichnet, dass sie in der wenigstens einen festen und/oder der wenigstens einen Gelphase, insbesondere in der festen Phase, weniger als 1 ,0 Gew.-% und insbesondere weniger als 0,1 Gew.-%, bevorzugt kein anionisches Tensid enthalten. Preferred washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are further characterized in that they contain less than 1.0% by weight and in particular less than 0.1% by weight, preferably no anionic surfactant.
Gemäß einer besonders bevorzugten Ausführungsform sind die erfindungsgemäßen Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel,
dadurch gekennzeichnet, dass das Gel weniger als 1 Gew.-%, insbesondere weniger als 0,5 Gew.- %, insbesondere weniger als 0,1 Gew.-% Aniontensid, jeweils bezogen auf das Gesamtgewicht des Gels umfasst. Bevorzugt ist das Gel im Wesentlichen frei von Aniontensiden. Im Wesentlichen frei bedeutet, dass das Gel weniger als 0,05 Gew.-% Aniontensid jeweils bezogen auf das Gesamtgewicht des Gels enthält. According to a particularly preferred embodiment, the washing or cleaning agents according to the invention, preferably dishwashing agents, in particular machine dishwashing agents, characterized in that the gel comprises less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight, of anionic surfactant, based in each case on the total weight of the gel. The gel is preferably essentially free of anionic surfactants. Substantially free means that the gel contains less than 0.05% by weight of anionic surfactant, based on the total weight of the gel.
Es hat sich in diesem Zusammenhang gezeigt, dass die Anwesenheit von 1 Gew.-% Aniontensid in der wenigstens einen Gelphase zu schlechterem Schaumverhalten sowie schlechterem Klarspülverhalten der Gesamtzusammensetzung führt. Weiterhin beeinflussen höhere Mengen an Aniontensiden die Aushärtung negativ. Gemäß einer besonders bevorzugten Ausführungsform enthält das Gel weniger als 1 Gew.-%, bevorzugt weniger als 0,5 Gew.-%, insbesondere weniger als 0,05 Gew.-% Fettsäuresalze bzw. Seifen. In this context, it has been shown that the presence of 1% by weight of anionic surfactant in the at least one gel phase leads to poorer foaming behavior and poorer rinsing behavior of the composition as a whole. Furthermore, higher amounts of anionic surfactants have a negative effect on curing. According to a particularly preferred embodiment, the gel contains less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.05% by weight, of fatty acid salts or soaps.
Gemäß einerweiteren Ausführungsform kann das Gel Zucker aufweisen. Zucker umfassen erfindungsgemäß Zuckeralkohole, Monosaccharide, Disaccharide sowie Oligosaccharide. In einer bevorzugten Ausführungsform umfasst das Gel mindestens einen von Glycerin verschiedenen Zuckeralkohol, bevorzugt mindestens ein Monosaccharid- oder Disaccharid-Zuckeralkohol. Insbesondere bevorzugt sind Mannitol, Isomalt, Lactit, Sorbitol, Threit, Erythrit, Arabit und Xylitol. Besonders bevorzugte Monosaccharid-Zuckeralkohole sind Pentitole und/oder Hexitole. Ganz besonders bevorzugt ist Xylitol und/oder Sorbitol. In another embodiment, the gel may include sugars. According to the invention, sugars include sugar alcohols, monosaccharides, disaccharides and oligosaccharides. In a preferred embodiment, the gel comprises at least one sugar alcohol other than glycerol, preferably at least one monosaccharide or disaccharide sugar alcohol. Mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol and xylitol are particularly preferred. Particularly preferred monosaccharide sugar alcohols are pentitols and/or hexitols. Xylitol and/or sorbitol is very particularly preferred.
In einerweiteren Ausführungsform kann das Gel Disaccharide, insbesondere Saccharose, umfassen. Der Anteil an Saccharose beträgt 0 Gew.-% bis 30 Gew.-%, insbesondere 5 Gew.-% bis 25 Gew.-%, besonders bevorzugt 10 Gew.-% bis 20 Gew.-%, bezogen auf das Gewicht der Gelphase. In höheren Mengen löst sich der Zucker nicht vollständig in der Gelphase und führt zu einer Trübung derselben. Durch den Einsatz von Zucker, insbesondere in einem Anteil von 10 Gew. -5 bis 15 Gew.-% wird die Feuchteentwicklung reduziert und damit die Haftung zur wenigstens einen festen Phase verbessert. In a further embodiment the gel may comprise disaccharides, in particular sucrose. The proportion of sucrose is 0% by weight to 30% by weight, in particular 5% by weight to 25% by weight, particularly preferably 10% by weight to 20% by weight, based on the weight of the gel phase . In higher amounts, the sugar does not completely dissolve in the gel phase and causes the same to become cloudy. The use of sugar, in particular in a proportion of 10% by weight to 15% by weight, reduces moisture development and thus improves adhesion to at least one solid phase.
Gemäß einer besonders bevorzugten Ausführungsform enthält die wenigstens eine zusätzliche Phase, bevorzugt eine feste, körnige Phase, mindestens einen, bevorzugt mehrere Inhaltsstoffe umfasst, welche ausgewählt sind aus welche ausgewählt sind aus der Gruppe gebildet aus Gerüststoffen (bevorzugt Carbonate, Citrat, Aminopolycarboxylate und/oder Aminocarboxylate, bevorzugt MGDA und/oder GLDA bzw. deren Salze, und/oder Bleichmitteln (insbesondere Percarbonat), und/oder Bleichaktivatoren und/oder Bleichkatalysatoren, und/oder Silberschutzmitteln, und/oder Enzymen (bevorzugt Protease(n) und/oder Amylase(n)), und/oder nichtionische Tensiden und/oder weitere Prozesshilfsmitteln.
Der Einsatz von Buildersubstanzen (Gerüststoffen) wie Silikaten, Aluminiumsilikaten (insbesondere Zeolithen), Salze organischer Di- und Polycarbonsäuren sowie Mischungen dieser Stoffe, vorzugsweise wasserlöslicher Buildersubstanzen, kann von Vorteil sein. According to a particularly preferred embodiment, the at least one additional phase, preferably a solid, granular phase, comprises at least one, preferably several ingredients, which are selected from which are selected from the group consisting of builders (preferably carbonates, citrates, aminopolycarboxylates and/or Amino carboxylates, preferably MGDA and/or GLDA or salts thereof, and/or bleaches (particularly percarbonate), and/or bleach activators and/or bleach catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase (n)), and/or nonionic surfactants and/or other processing aids. The use of builders (builders) such as silicates, aluminum silicates (in particular zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, can be advantageous.
In einer erfindungsgemäß besonders bevorzugten Ausführungsform wird auf den Einsatz von Phosphaten (auch Polyphosphaten) weitgehend oder vollständig verzichtet. Das Mittel enthält in dieser Ausführungsform vorzugsweise weniger als 5 Gew.-%, besonders bevorzugt weniger als 3 Gew.-%, insbesondere weniger als 1 Gew.-% Phosphat(e). Besonders bevorzugt ist das Mittel in dieser Ausführungsform völlig phosphatfrei, d.h. die Mittel enthalten weniger als 0,1 Gew.-% Phosphat(e). In an embodiment which is particularly preferred according to the invention, the use of phosphates (including polyphosphates) is largely or completely dispensed with. In this embodiment, the agent preferably contains less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight, of phosphate(s). In this embodiment, the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate(s).
Zu den Gerüststoffen zählen insbesondere Carbonate, Citrate, Phosphonate, organische Gerüststoffe und Silikate. Der Gewichtsanteil der gesamten Gerüststoffe am Gesamtgewicht erfindungsgemäßer Mittel beträgt vorzugsweise 15 bis 80 Gew.-% und insbesondere 20 bis 70 Gew.-%. The builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates. The proportion by weight of the total builders in the total weight of agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.
Erfindungsgemäß geeignete organische Gerüststoffe sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren (Polycarboxylate), wobei unter Polycarbonsäuren/Polycarboxylaten solche Carbonsäuren verstanden werden, die mehr als eine, insbesondere zwei bis acht Säurefunktionen, bevorzugt zwei bis sechs, insbesondere zwei, drei, vier oder fünf Säurefunktionen im gesamten Molekül tragen. Bevorzugt sind als Polycarbonsäuren somit Dicarbonsäuren, Tricarbonsäuren, Tetracarbonsäuren und Pentacarbonsäuren, insbesondere Di-, Tri- und Tetracarbonsäuren. Dabei können die Polycarbonsäuren noch weitere funktionelle Gruppen, wie beispielsweise Hydroxyl- oder Aminogruppen, tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren (bevorzugt Aldarsäuren, beispielsweise Galactarsäure und Glucarsäure), Iminocarbonsäuren, Aminocarbonsäuren, insbesondere Aminodicarbonsäuren, Aminotricarbonsäuren, Aminotetracarbonsäuren wie beispielsweise Nitrilotriessigsäure (NTA), Glutamin-N,N-diessigsäure (auch als N,N-Bis(carboxymethyl)-L-glutaminsäure oder GLDA bezeichnet), Methylglycindiessigsäure (MGDA) und deren Derivate sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, GLDA, MGDA und Mischungen aus diesen. Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids/polycarboxylates being understood as meaning those carboxylic acids which have more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or carry five acid functions throughout the molecule. Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids can also carry other functional groups, such as hydroxyl or amino groups. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids (preferably aldaric acids, for example galactaric acid and glucaric acid), iminocarboxylic acids, aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine-N ,N-diacetic acid (also referred to as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methylglycine diacetic acid (MGDA) and their derivatives and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.
Weiterhin geeignet als organische Gerüststoffe sind polymere Polycarboxylate (organische Polymere mit einer Vielzahl, an (insbesondere größer zehn) Carboxylatfunktionen im Makromolekül), Polyaspartate, Polyacetale und Dextrine.
Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen. Also suitable as organic builders are polymeric polycarboxylates (organic polymers with a large number of (especially more than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins. In addition to their builder effect, the free acids typically also have the property of an acidifying component. Particular mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.
Besonders bevorzugte erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, enthalten als einen ihrer wesentlichen Gerüststoffe ein oder mehrere Salze der Citronensäure, also Citrate. Diese sind vorzugsweise in einem Anteil von 2 bis 40 Gew.-%, insbesondere von 5 bis 30 Gew.-%, besonders von 7 bis 28 Gew.-%, besonders bevorzugt 10 bis 25 Gew.-%, ganz besonders bevorzugt 15 bis 20 Gew.-% enthalten, jeweils bezogen auf das Gesamtgewicht des Mittels. Particularly preferred washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, particularly 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to 20% by weight, based in each case on the total weight of the agent.
Besonders bevorzugt ist ebenfalls der Einsatz von Carbonat(en) und/oder Hydrogencarbonat(en), vorzugsweise Alkalicarbonat(en), besonders bevorzugt Natriumcarbonat (Soda), in Mengen von 2 bis 50 Gew.-%, vorzugsweise von 4 bis 40 Gew.-% und insbesondere von 10 bis 30 Gew.-%, ganz besonders bevorzugt 10 bis 24 Gew.-%, jeweils bezogen auf das Gewicht des Mittels. Particular preference is also given to using carbonate(s) and/or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate (soda), in amounts of 2 to 50% by weight, preferably 4 to 40% by weight. -% and in particular from 10 to 30% by weight, very particularly preferably 10 to 24% by weight, based in each case on the weight of the agent.
Besonders bevorzugte erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, sind dadurch gekennzeichnet, dass sie mindestens zwei Gerüststoffe aus der Gruppe der Silikate, Phosphonate, Carbonate, Aminocarbonsäuren und Citrate enthalten, wobei der Gewichtsanteil dieser Gerüststoffe, bezogen auf das Gesamtgewicht des erfindungsgemäßen Wasch- oder Reinigungsmittels, bevorzugt Geschirrspülmittels, insbesondere maschinellen Geschirrspülmittels, bevorzugt 5 bis 70 Gew.-%, vorzugsweise 15 bis 60 Gew.- % und insbesondere 20 bis 50 Gew.-% beträgt. Die Kombination von zwei oder mehr Gerüststoffen aus der oben genannten Gruppe hat sich für die Reinigungsund Klarspülleistung erfindungsgemäßer Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, als vorteilhaft erwiesen. Über die hier erwähnten Gerüststoffe hinaus können noch ein oder mehrere andere Gerüststoffe zusätzlich enthalten sein. Particularly preferred washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the proportion by weight of these builders, based on the total weight of the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, is preferably 5 to 70% by weight, preferably 15 to 60% by weight and in particular 20 to 50% by weight. The combination of two or more builders from the group mentioned above has proven advantageous for the cleaning and rinsing performance of washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents. In addition to the builders mentioned here, one or more other builders can also be present.
Bevorzugte Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, sind durch eine Gerüststoffkombination aus Citrat und Carbonat und/oder Hydrogencarbonat gekennzeichnet. In einer erfindungsgemäß ganz besonders bevorzugten Ausführungsform wird eine Mischung aus Carbonat und Citrat eingesetzt, wobei die Menge an Carbonat vorzugsweise von 5 bis 40 Gew.-%, insbesondere 10 bis 35 Gew.-%, ganz besonders bevorzugt 15 bis 30 Gew.-% und die Menge an Citrat vorzugsweise von 5 bis 35 Gew.- %, insbesondere 10 bis 25 Gew.-%, ganz besonders bevorzugt 15 bis 20 Gew.-%, jeweils bezogen auf die Gesamtmenge des Wasch- oder Reinigungsmittels, bevorzugt Geschirrspülmittels, insbesondere maschinellen Geschirrspülmittels, beträgt, wobei die Gesamtmenge dieser beiden Gerüststoffe vorzugsweise 20 bis 65 Gew.-%, insbesondere 25 bis 60 Gew.-%, bevorzugt 30 bis
50 Gew.-%, beträgt. Darüber hinaus können noch ein oder mehrere weitere Gerüststoffe zusätzlich enthalten sein. Preferred detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized by a builder combination of citrate and carbonate and/or bicarbonate. In a very particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight. and the amount of citrate preferably from 5 to 35 wt machine dishwashing detergent, the total amount of these two builders preferably being 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight. In addition, one or more other builders can also be included.
Die erfindungsgemäßen Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, können als weiteren Gerüststoff insbesondere Phosphonate, soweit regulatorisch zulässig, enthalten. Als Phosphonat-Verbindung wird vorzugsweise ein Hydroxyalkan- und/oder Aminoalkanphosphonat eingesetzt. Unter den Hydroxyalkanphosphonaten ist das 1- Hydroxyethan-1 ,1-diphosphonat (HEDP) von besonderer Bedeutung. Als Aminoalkanphosphonate kommen vorzugsweiseThe detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, can contain phosphonates in particular as a further builder, to the extent permitted by regulations. A hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Aminoalkanephosphonates are preferred
Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriamin- pentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Phosphonate sind in erfindungsgemäßen Mitteln, soweit regulatorisch zulässig, vorzugsweise in Mengen von 0,1 bis 10 Gew.-%, insbesondere in Mengen von 0,5 bis 8 Gew.-%, ganz besonders bevorzugt von 2,5 bis 7,5 Gew.- %, jeweils bezogen auf das Gesamtgewicht des Mittels, enthalten. Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. Phosphonates are present in agents according to the invention, to the extent permitted by regulations, preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight .- %, based on the total weight of the agent.
Besonders bevorzugt ist der kombinierte Einsatz von Citrat, (Hydrogen-)Carbonat und Phosphonat. Diese können in den oben genannten Mengen eingesetzt werden. Insbesondere werden bei dieser Kombination Mengen von, jeweils bezogen auf das Gesamtgewicht des Mittels, 10 bis 25 Gew.-% Citrat, 10 bis 30 Gew.-% Carbonat (oder Hydrogencarbonat), sowie 2,5 bis 7,5 Gew.-%The combined use of citrate, (hydrogen) carbonate and phosphonate is particularly preferred. These can be used in the amounts mentioned above. In this combination, in particular, amounts of, in each case based on the total weight of the agent, 10 to 25% by weight of citrate, 10 to 30% by weight of carbonate (or bicarbonate) and 2.5 to 7.5% by weight
Phosphonat eingesetzt. phosphonate used.
Weitere besonders bevorzugte Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, sind dadurch gekennzeichnet, dass sie neben Citrat und (Hydrogen-) Carbonat sowie ggf. Phosphonat mindestens einen weiteren phosphorfreien Gerüststoff enthalten. Insbesondere ist dieser ausgewählt aus den Aminocarbonsäuren, wobei der weitere phosphorfreie Gerüststoff vorzugsweise ausgewählt ist aus Methylglycindiessigsäure (MGDA), Glutaminsäurediacetat (GLDA), Asparaginsäurediacetat (ASDA), Hydroxyethyliminodiacetat (HEIDA), Iminodisuccinat (IDS) und Ethylendiamindisuccinat (EDDS), besonders bevorzugt aus MGDA oder GLDA. Eine besonders bevorzugte Kombination ist beispielsweise Citrat, (Hydrogen-)Carbonat und MGDA sowie ggf. Phosphonat. Further particularly preferred detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized in that they contain at least one further phosphorus-free builder in addition to citrate and (hydrogen) carbonate and, if appropriate, phosphonate. In particular, this is selected from the aminocarboxylic acids, with the further phosphorus-free builder preferably being selected from methylglycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA. A particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.
Der Gew.-%-Anteil des Weiteren phosphorfreien Gerüststoffs, insbesondere des MGDA und/oder GLDA, beträgt vorzugsweise 0 bis 40 Gew.-%, insbesondere 5 bis 30 Gew.-%, vor allem 7 bis 25 Gew.-%. Besonders bevorzugt ist der Einsatz von MGDA bzw. GLDA, insbesondere MGDA, als Granulat. Von Vorteil sind dabei solche MGDA-Granulate, die möglichst wenig Wasser enthalten und/oder eine im Vergleich zum nicht granulierten Pulver geringere Hygroskopizität (Wasseraufnahme bei 25 °C, Normaldruck) aufweisen. Die Kombination von mindestens drei, insbesondere mindestens vier Gerüststoffen aus der oben genannten Gruppe hat sich für die Reinigungs- und Klarspülleistung erfindungsgemäßer Wasch- oder Reinigungsmittel, bevorzugt
Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, als vorteilhaft erwiesen. The percentage by weight of the further phosphorus-free builder, in particular of the MGDA and/or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, in particular 7 to 25% by weight. The use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules that contain as little water as possible and/or have a lower hygroscopicity (water absorption at 25° C., normal pressure) than non-granulated powder are advantageous. The combination of at least three, in particular at least four, builders from the group mentioned above has proven to be preferred for the cleaning and rinsing performance of washing or cleaning agents according to the invention Dishwashing detergents, in particular machine dishwashing detergents, proved to be advantageous.
Daneben können noch weitere Gerüststoffe enthalten sein. Other builders can also be included.
Als organische Gerüststoffe sind weiterhin polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol. Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 1000 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 1100 bis 10000 g/mol, und besonders bevorzugt von 1200 bis 5000 g/mol, aufweisen, bevorzugt sein. Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g/mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g/mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1100 to 10000 g/mol, and particularly preferably from 1200 to 5000 g/mol, may in turn be preferred from this group.
Der Gehalt der erfindungsgemäßen Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, an (homo)polymeren Polycarboxylaten beträgt vorzugsweise 0,5 bis 20 Gew.-%, bevorzugt 2 bis 15 Gew.-% und insbesondere 4 bis 10 Gew.-%. The content of (homo)polymeric polycarboxylates in the washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight. %.
Erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, können als Gerüststoff weiterhin kristalline schichtförmige Silikate der allgemeinen Formel NaMSix02x+i y H2O, worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1 ,9 bis 22, vorzugsweise von 1 ,9 bis 4, wobei besonders bevorzugte Werte für x 2, 3 oder 4 sind, und y für eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20 steht. Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2Ü : S1O2 von 1 :2 bis 1 :3,3, vorzugsweise von 1 :2 bis 1 :2,8 und insbesondere von 1 :2 bis 1 :2,6, welche vorzugsweise löseverzögert sind und Sekundärwascheigenschaften aufweisen. Detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, can also contain crystalline layered silicates of the general formula NaMSi x 0 2x+i y H2O as a builder, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with an Na2O:S1O2 modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, which are preferably delayed in dissolution, can also be used and have secondary washing properties.
In Ergänzung zu den vorgenannten Gerüststoffen können die erfindungsgemäßen Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, weiterhin Alkalimetallhydroxide enthalten. Diese Alkaliträger werden in den Wasch- oder Reinigungsmitteln, bevorzugt Geschirrspülmitteln, insbesondere maschinellen Geschirrspülmitteln und insbesondere in den wenigstens einen Gelphasen bevorzugt nur in geringen Mengen, vorzugsweise in Mengen unterhalb 10 Gew.-%, bevorzugt unterhalb 6 Gew.-%, vorzugsweise unterhalb 5 Gew.-%, besonders bevorzugt zwischen 0,1 und 5 Gew.-% und insbesondere zwischen 0,5 und 5 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Wasch- oder Reinigungsmittels, bevorzugt Geschirrspülmittels, insbesondere maschinellen Geschirrspülmittels eingesetzt. Alternative erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, sind frei von Alkalimetallhydroxiden. In addition to the aforementioned builders, the washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, can also contain alkali metal hydroxides. These alkali carriers are used in the detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents and in particular in the at least one gel phase, preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5 Wt. Alternative washing or cleaning agents according to the invention, preferably dishwashing agents, in particular machine dishwashing agents, are free from alkali metal hydroxides.
Als weiteren Bestandteil enthalten erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, in der wenigstens einen festen
und/oder der wenigstens einen Gelphase vorzugsweise Enzym(e). Hierzu gehören insbesondere Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, Perhydrolasen oder Oxidoreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Wasch- oder Reinigungsmitteln, bevorzugt Geschirrspülmitteln, insbesondere maschinellen Geschirrspülmitteln, verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10-6 Gew.-% bis 5 Gew.-% bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren oder dem Biuret- Verfahren bestimmt werden. Washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain at least one solid as a further component and/or the at least one gel phase, preferably enzyme(s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, which are correspondingly preferably used. Detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably contain enzymes in total amounts of 1×10 -6 % by weight to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the Biuret method.
Unter den Proteasen sind solche vom Subtilisin-Typ bevorzugt. Beispiele hierfür sind die Subtilisine BPN' und Carlsberg sowie deren weiterentwickelte Formen, die Protease PB92, die Subtilisine 147 und 309, die Alkalische Protease aus Bacillus lentus, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7. Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN' and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, which can be assigned to the subtilases, but no longer to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
Beispiele für erfindungsgemäß einsetzbare Amylasen sind die a-Amylasen aus Bacillus licheniformis, aus B. amyloliquefaciens, aus B. stearothermophilus, aus Aspergillus niger und A. oryzae sowie die für den Einsatz in Wasch- oder Reinigungsmitteln, bevorzugt Geschirrspülmitteln, insbesondere maschinellen Geschirrspülmitteln verbesserten Weiterentwicklungen der vorgenannten Amylasen. Des Weiteren sind für diesen Zweck die a-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus B. agaradherens (DSM 9948) hervorzuheben. Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments improved for use in detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents the aforementioned amylases. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
Erfindungsgemäß einsetzbar sind weiterhin Lipasen oder Cutinasen, insbesondere wegen ihrer Triglycerid-spaltenden Aktivitäten, aber auch, um aus geeigneten Vorstufen in situ Persäuren zu erzeugen. Hierzu gehören beispielsweise die ursprünglich aus Humicola lanuginosa (Thermomyces lanuginosus) erhältlichen, beziehungsweise weiterentwickelten Lipasen, insbesondere solche mit dem Aminosäureaustausch in den Positionen D96LT213R und/oder N233R, besonders bevorzugt alle der Austausche D96L, T213R und N233R. Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange in positions D96LT213R and/or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.
Weiterhin können Enzyme eingesetzt werden, die unter dem Begriff Hemicellulasen zusammengefasst werden. Hierzu gehören beispielsweise Mannanasen, Xanthanlyasen, Pektinlyasen (=Pektinasen), Pektinesterasen, Pektatlyasen, Xyloglucanasen (=Xylanasen), Pullulanasen und ß-Glucanasen.
Zur Erhöhung der bleichenden Wirkung können erfindungsgemäß Oxidoreduktasen, beispielsweise Oxidasen, Oxygenasen, Katalasen, Peroxidasen, wie Halo-, Chloro-, Bromo-, Lignin-, Glucoseoder Mangan-Peroxidasen, Dioxygenasen oder Laccasen (Phenoloxidasen, Polyphenoloxidasen) eingesetzt werden. Vorteilhafterweise werden zusätzlich vorzugsweise organische, besonders bevorzugt aromatische, mit den Enzymen wechselwirkende Verbindungen zugegeben, um die Aktivität der betreffenden Oxidoreduktasen zu verstärken (Enhancer) oder um bei stark unterschiedlichen Redoxpotentialen zwischen den oxidierenden Enzymen und den Anschmutzungen den Elektronenfluss zu gewährleisten (Mediatoren). Ein Protein und/oder Enzym kann besonders während der Lagerung gegen Schädigungen wie beispielsweise Inaktivierung, Denaturierung oder Zerfall etwa durch physikalische Einflüsse, Oxidation oder proteolytische Spaltung geschützt werden. Bei mikrobieller Gewinnung der Proteine und/oder Enzyme ist eine Inhibierung der Proteolyse besonders bevorzugt, insbesondere wenn auch die Mittel Proteasen enthalten. Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, können zu diesem Zweck Stabilisatoren enthalten; die Bereitstellung derartiger Mittel stellt eine bevorzugte Ausführungsform der vorliegenden Erfindung dar. It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and ß-glucanases. According to the invention, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators). A protein and/or enzyme can be protected against damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and/or enzymes, inhibition of proteolysis is particularly preferred, particularly if the agents also contain proteases. Detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
Reinigungsaktive Proteasen und Amylasen werden in der Regel nicht in Form des reinen Proteins sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt. Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized preparations that can be stored and transported. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.
Alternativ können die Enzyme für die wenigstens eine feste und/oder das Gel 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 Schüttei- 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 for the at least one solid and/or the gel can be encapsulated, 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 set gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer. Additional active substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.
Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.
Wie aus den vorherigen Ausführungen ersichtlich, bildet das Enzym-Protein nur einen Bruchteil des Gesamtgewichts üblicher Enzym-Zubereitungen. Erfindungsgemäß eingesetzte Protease- und Amylase-Zubereitungen enthalten zwischen 1 und 40 Gew.-%, bevorzugt zwischen 2 und 30 Gew.- %, besonders bevorzugt zwischen 3 und 25 Gew.-% des Enzymproteins. Bevorzugt werden insbesondere solche Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, die, jeweils bezogen auf ihr Gesamtgewicht, 0,1 bis 12 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-% und insbesondere 0,5 bis 8 Gew.-% der jeweiligen Enzym- Zubereitungen enthalten. Furthermore, it is possible to formulate two or more enzymes together, so that a single granulate has several enzyme activities. As can be seen from the above, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention contain between 1 and 40% by weight, preferably between 2 and 30% by weight, particularly preferably between 3 and 25% by weight, of the enzyme protein. Preference is given in particular to detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, which, based on their total weight, contain from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight of the respective enzyme preparations.
Neben den bisher angeführten Bestandteilen können die wenigstens eine feste und/oder das Gel des erfindungsgemäßen Wasch- oder Reinigungsmittels, bevorzugt Geschirrspülmittels, insbesondere maschinellen Geschirrspülmittels weitere Inhaltsstoffe enthalten. Hierzu zählen beispielsweise anionische, kationische und/oder amphotere Tenside, Bleichmittel,In addition to the ingredients mentioned so far, the at least one solid and/or the gel of the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular automatic dishwashing detergent, can contain other ingredients. These include, for example, anionic, cationic and/or amphoteric surfactants, bleaches,
Bleichaktivatoren, Bleichkatalysatoren, weitere Lösungsmittel, Verdicker, Sequestrierungsmittel, Elektrolyte, Korrosionsinhibitoren, insbesondere Silberschutzmittel, Glaskorrosionsinhibitoren, Schauminhibitoren, Farbstoffe, Duftstoffe (insbesondere in der wenigstens einen festen Phase), Additive zur Verbesserung des Ablauf- und Trocknungsverhaltens, zur Einstellung der Viskosität, zur Stabilisierung, UV-Stabilisatoren, Konservierungsmittel, antimikrobielle Wrkstoffe (Desinfektionsmittel), pH-Stellmittel in Mengen von üblicherweise nicht mehr als 5 Gew.-% enthalten sein. Bleaching activators, bleaching catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver preservatives, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (in particular in the at least one solid phase), additives to improve drainage and drying behavior, to adjust viscosity, to Stabilization, UV stabilizers, preservatives, antimicrobial active ingredients (disinfectants), pH adjusters in amounts of usually not more than 5% by weight.
Als weiteres Lösungsmittel enthalten erfindungsgemäße Mittel vorzugsweise mindestens ein Alkanolamin. Das Alkanolamin ist hierbei vorzugsweise ausgewählt aus der Gruppe bestehend aus Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen. Das Alkanolamin ist in erfindungsgemäßen Mitteln vorzugsweise in einer Menge von 0,5 bis 10 Gew.-%, insbesondere in einer Menge von 1 bis 6 Gew.-%, enthalten. In bevorzugten Wasch- oder Reinigungsmitteln, bevorzugt Geschirrspülmitteln, insbesondere maschinellen Geschirrspülmitteln, ist das Gel im wesentlichen frei von Alkanolamin, d.h. das Gel enthält weniger als 1 Gew.-%, insbesondere weniger als 0,5 Gew.-%, bevorzugt weniger als 0,1 Gew.-%, insbesondere bevorzugt weniger als 0,05 Gew.-% Alkanolamin und das Alkanolamin ist nur in der wenigstens einen festen Phase enthalten. Agents according to the invention preferably contain at least one alkanolamine as a further solvent. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is preferably contained in agents according to the invention in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight. In preferred detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, the gel is essentially free of alkanolamine, i.e. the gel contains less than 1% by weight, in particular less than 0.5% by weight, preferably less than 0 1% by weight, particularly preferably less than 0.05% by weight, of alkanolamine and the alkanolamine is contained only in the at least one solid phase.
Zusätzlich zu den o.g. Zinksalzen können Polyethylenimine, wie sie beispielsweise unter dem Namen Lupasol® (BASF) erhältlich sind, vorzugsweise in einer Menge von 0 bis 5 Gew.-%, insbesondere 0,01 bis 2 Gew.-%, als Glaskorrosionsinhibitoren eingesetzt werden. In addition to the zinc salts mentioned above, polyethyleneimines, such as those available under the name Lupasol® (BASF), can be used as glass corrosion inhibitors, preferably in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight .
Als Additive geeignete Polymere sind insbesondere Maleinsäure-Acrylsäure-Copolymer-Na-Salz (beispielsweise Sokalan® CP 5 der Firma BASF, Ludwigshafen (Deutschland)), modifiziertes Polyacrylsäure-Na-Salz (beispielsweise Sokalan® CP 10 der Firma BASF, Ludwigshafen
(Deutschland)), modifiziertes Polycarboxylat-Na-Salz (beispielsweise Sokalan® HP 25 der Firma BASF, Ludwigshafen (Deutschland)), Polyalkylenoxid, modifiziertes Heptamethyltrisiloxan (beispielsweise Silwet® L-77 der Firma BASF, Ludwigshafen (Deutschland)), Polyalkylenoxid, modifiziertes Heptamethyltrisiloxan (beispielsweise Silwet® L-7608 der Firma BASF, Ludwigshafen (Deutschland)) sowie Polyethersiloxane (Copolymere von Polymethylsiloxanen mit Ethylenoxid- /Propylenoxidsegmenten (Polyetherblöcken)), vorzugsweise wasserlösliche lineare Polyethersiloxane mit terminalen Polyetherblöcken wie Tegopren® 5840, Tegopren® 5843, Tegopren® 5847, Tegopren® 5851 , Tegopren® 5863 oder Tegopren® 5878 der Firma Evonik, Essen (Deutschland). Als Additive geeignete Buildersubstanzen sind insbesondere Polyasparaginsäure- Na-Salz, Ethylendiamintriacetatkokosalkylacetamid (beispielsweise Rewopol® CHT 12 der Firma Evonik, Essen (Deutschland)), Methylglycindiessigsäure-Tri-Na-Salz und Acetophosphonsäure. Mischungen mit tensidischen oder polymeren Additiven zeigen im Falle von Tegopren® 5843 und Tegopren® 5863 Synergismen. Der Einsatz der Tegopren-Typen 5843 und 5863 ist jedoch bei der Anwendung auf harte Oberflächen aus Glas, insbesondere Glasgeschirr, weniger bevorzugt, da diese Silikontenside auf Glas aufziehen können. In einer besonderen Ausführungsform der Erfindung wird auf die genannten Additive verzichtet. Polymers suitable as additives are in particular maleic acid-acrylic acid copolymer Na salt (for example Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example Sokalan® CP 10 from BASF, Ludwigshafen (Germany)), modified polycarboxylate sodium salt (for example Sokalan ® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet ® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (e.g. Silwet ® L-7608 from BASF, Ludwigshafen (Germany)) and polyether siloxanes (copolymers of polymethyl siloxanes with ethylene oxide/propylene oxide segments (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren ® 5840, Tegopren ® 5843, Tegopren® 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878 from Evonik, Essen (Germany). Builder substances suitable as additives are, in particular, sodium polyaspartic acid salt, ethylenediamine triacetate coconut alkylacetamide (for example Rewopol® CHT 12 from Evonik, Essen (Germany)), sodium trimethylglycine diacetic acid salt and acetophosphonic acid. In the case of Tegopren ® 5843 and Tegopren ® 5863, mixtures with surfactant or polymer additives show synergisms. However, the use of Tegopren types 5843 and 5863 is less preferred when used on hard surfaces made of glass, in particular glassware, since these silicone surfactants can be absorbed by glass. In a particular embodiment of the invention, the additives mentioned are omitted.
Ein bevorzugtes Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelles Geschirrspülmittel, umfasst vorzugsweise weiterhin ein Bleichmittel, insbesondere ein Sauerstoffbleichmittel sowie gegebenenfalls einen Bleichaktivator und/oder Bleichkatalysator.A preferred washing or cleaning agent, preferably a dishwashing detergent, in particular a machine dishwashing detergent, preferably also comprises a bleach, in particular an oxygen bleach and optionally a bleach activator and/or bleach catalyst.
Diese sind, soweit vorhanden, ausschließlich in der wenigstens einen festen Phase enthalten. If present, these are contained exclusively in the at least one solid phase.
Als bevorzugtes Bleichmittel enthalten erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, ein Sauerstoffbleichmittel aus der Gruppe Natriumpercarbonat, Natriumperborattetrahydrat und Natriumperboratmonohydrat. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Weiterhin können auch Bleichmittel aus der Gruppe der organischen Bleichmittel eingesetzt werden. Typische organische Bleichmittel sind die Diacylperoxide, wie zum Beispiel Dibenzoylperoxid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden. Wegen seiner guten Bleichleistung wird das Natriumpercarbonat besonders bevorzugt. Ein besonders bevorzugtes Sauerstoffbleichmittel ist Natriumpercarbonat. Detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate as a preferred bleaching agent. Other usable bleaches are, for example, peroxypyrophosphates, citrate perhydrates and H2O2-supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples being the alkylperoxyacids and the arylperoxyacids. Sodium percarbonate is particularly preferred because of its good bleaching performance. A particularly preferred oxygen bleach is sodium percarbonate.
Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die 0- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls
substituierte Benzoylgruppen tragen. Bevorzugt werden mehrfach acylierte Alkylendiamine, wobei sich Tetraacetylethylendiamin (TAED) als besonders geeignet erwiesen hat. Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Substances which contain 0- and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally carry substituted benzoyl groups. Polyacylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven to be particularly suitable.
Bei den Bleichkatalysatoren handelt es sich um bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo- Salenkomplexe oder - carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe- Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar. Mit besonderem Vorzug werden Komplexe des Mangans in der Oxidationsstufe II, III, IV oder IV eingesetzt, die vorzugsweise einen oder mehrere makrocyclische(n) Ligand(en) mit den Donorfunktionen N, NR, PR, O und/oder S enthalten. Vorzugsweise werden Liganden eingesetzt, die Stickstoff-Donorfunktionen aufweisen. Dabei ist es besonders bevorzugt, Bleichkatalysator(en) in den erfindungsgemäßen Mitteln einzusetzen, welche als makromolekularen Liganden 1 ,4,7-Trimethyl-1 ,4,7-triazacyclononan (Me-TACN), 1 ,4,7- Triazacyclononan (TACN), 1 ,5,9-Trimethyl-1 ,5,9-triazacyclododecan (Me-TACD), 2-Methyl-1-1 ,4,7- trimethyl-1 ,4,7-triazacyclononan (Me/Me-TACN) und/oder 2-Methyl-1 ,4,7-triazacyclononan (Me/TACN) enthalten. Geeignete Mangankomplexe sind beispielsweise [Mhip 2(m-0)i(m- 0AC)2(TACN)2](CI04)2, [MnmMnlv^-0)2^-0Ac)i(TACN)2](BPh4)2, [Mnlv 4(p-0)6(TACN)4](CI04)4, [Mhiii2(m-O)i(m-OA0)2(Mb-TAΰN)2](ΰIO4)2, [MnIMMnlv(p-0)i(p-0Ac)2(Me-TACN)2](CI04)3, [Mhin 2(m- 0)3(Me-TACN)2](PF6)2 und [Mnlv2^-0)3(Me/Me-TACN)2](PF6)2(mit OAc = 0C(0)CH3). The bleach catalysts are bleach-boosting transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts. Complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O and/or S, are particularly preferably used. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleaching catalyst(s) in the agents according to the invention which contain, as macromolecular ligands, 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN ) and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN). Suitable manganese complexes are, for example, [Mh ip 2 (m-0)i(m-0AC) 2 (TACN)2](CI0 4 )2, [Mn m Mn lv ^-0)2^-0Ac)i(TACN)2 ](BPh4)2, [Mn lv 4 (p-0)6(TACN) 4 ](CI0 4 ) 4 , [M hiii 2(mO)i(m-OA0)2(Mb-TAΰN) 2 ](ΰIO 4 )2, [Mn IM Mn lv (p-0)i(p-0Ac)2(Me-TACN)2](CI0 4 )3, [M hin 2 (m-0) 3 (Me-TACN) 2 ](PF6)2 and [Mn lv 2^-0)3(Me/Me-TACN)2](PF 6 )2 (with OAc = 0C(0)CH 3 ).
Gemäß einer bevorzugten Ausführungsform umfasst die Wasch- oder Reinigungsmittelportion neben mindestens einem Gel bzw. einer Gelphase mindestens oder mehr zusätzliche Phase(n), die ausgewählt ist/sind aus einer flüssigen Phase, gelförmigen Phase und/oder festen, bevorzugt körnigen, insbesondere partikulären, bevorzugt rieselfähigen, festen Phase. According to a preferred embodiment, the detergent or cleaning agent portion comprises, in addition to at least one gel or a gel phase, at least or more additional phase(s) which is/are selected from a liquid phase, gel-like phase and/or solid, preferably granular, in particular particulate, preferably free-flowing, solid phase.
Das erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, umfasst bevorzugt wenigstens ein Gel bzw. eine Gelphase und wenigstens eine feste, bevorzugt körnige Phase. Das Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, kann eine, zwei, drei oder mehr voneinander verschiedene feste, bevorzugt körnige Phasen aufweisen; ebenso kann es eine, zwei, drei, vier oder mehr voneinander verschiedene Gelphasen aufweisen. Bevorzugt umfasst das erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, eine feste, bevorzugt körnige Phase und eine Gelphase. The washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, preferably comprises at least one gel or one gel phase and at least one solid, preferably granular phase. The detergent or cleaning agent, preferably dishwashing detergents, in particular machine dishwashing detergents, can have one, two, three or more solid, preferably granular phases; it can also have one, two, three, four or more different gel phases. The washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprises a solid, preferably granular phase and a gel phase.
Besonders bevorzugt umfasst das Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, zwei feste, bevorzugt körnige Phasen und eine Gelphase. Bevorzugt umfasst es zwei feste, bevorzugt körnige Phasen und zwei Gelphasen. Weiterhin bevorzugt ist eine Ausführungsform, in der das Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinelle Geschirrspülmittel, drei feste, bevorzugt körnige Phasen und eine oder zwei Gelphasen umfasst.
Dabei beträgt das Gewichtsverhältnis der Gesamtheit der wenigstens einen festen Phase zur Gesamtheit der wenigstens einen Gelphase in der Regel Phase 40:1 bis 2:1 , insbesondere 20:1 bis 4:1 , bevorzugt 14:1 bis 6:1 beispielsweise 12:1 bis 8:1 . Das Gesamtgewicht aller Phase in einer Wasch- oder Reinigungsmittelportion, bevorzugt Geschirrspülmittelportion, insbesondere maschinellen Geschirrspülmittelportion, kann zwischen 8 und 30 g, insbesondere 10 bis 25 g, bevorzugt 12 bis 21 g, beispielsweise 13 bis 17 g pro Wasch- oder Reinigungsmittelportion, bevorzugt Geschirrspülmittelportion, insbesondere maschinellen Geschirrspülmittelportion, betragen. In diesem Gewichtsverhältnis ergibt sich eine gute Konzentration an den jeweiligen Inhaltsstoffen der festen beziehungsweise Gelphase in einem Reinigungsvorgang. The washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, particularly preferably comprises two solid, preferably granular phases and a gel phase. It preferably comprises two solid, preferably granular, phases and two gel phases. Also preferred is an embodiment in which the washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprises three solid, preferably granular phases and one or two gel phases. The weight ratio of all of the at least one solid phase to all of the at least one gel phase is generally 40:1 to 2:1, in particular 20:1 to 4:1, preferably 14:1 to 6:1, for example 12:1 to 8:1 . The total weight of all phases in a detergent or cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing agent portion, can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 13 to 17 g per washing or cleaning agent portion, preferably dishwashing agent portion , In particular machine dishwashing detergent portion amount. This weight ratio results in a good concentration of the respective ingredients of the solid or gel phase in a cleaning process.
Erfindungsgemäß grenzen die wenigstens eine feste, bevorzugt körnige Phase und das Gel voll- oder teilflächig aneinander. Dabei ist es bevorzugt, dass die beiden Phasen unmittelbar aneinandergrenzen. According to the invention, the at least one solid, preferably granular phase and the gel adjoin one another over the whole or part of the surface. It is preferred that the two phases directly adjoin one another.
Grenzen die wenigstens eine feste, bevorzugt körnige Phase und das Gel unmittelbar voll- oder teilflächig aneinander, ist die Stabilität neben einer möglichst kurzen Erstarrungszeit der wenigstens einen Gelphase wichtig. Stabilität bedeutet hier, dass in der Gelphase enthaltende Bestandteile nicht in die wenigstens eine feste, bevorzugt körnige Phase übertreten, sondern auch nach einer längeren Lagerung die wenigstens eine feste, bevorzugt körnige Phase und das Gel optisch getrennt voneinander vorliegen und nicht miteinander in Wechselwirkung treten, wie z.B. Diffusion flüssiger Bestandteile von einer in die andere Phase oder Reaktion von Bestandteilen einer Phase mit denen in der anderen Phase. If the at least one solid, preferably granular phase and the gel directly adjoin one another over the whole or part of the surface, the stability is important in addition to the shortest possible setting time of the at least one gel phase. Stability here means that the components contained in the gel phase do not migrate into the at least one solid, preferably granular phase, but rather that the at least one solid, preferably granular phase and the gel are optically separate from one another even after prolonged storage and do not interact with one another, such as diffusion of liquid components from one phase to another or reaction of components in one phase with those in the other phase.
Ein weiterer Gegenstand der vorliegenden Anmeldung ist ein Verfahren zur Reinigung von harten Oberflächen, insbesondere von Geschirr, in dem die Oberfläche in an sich bekannterWeise unter Verwendung eines erfindungsgemäßen Wasch- oder Reinigungsmittels, bevorzugt Geschirrspülmittels, insbesondere maschinellen Geschirrspülmittels bearbeitet wird. Insbesondere wird dabei die Oberfläche mit dem erfindungsgemäßen Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, in Kontakt gebracht. Die Reinigung erfolgt dabei insbesondere mit einer Reinigungsmaschine, bevorzugt mit einer Geschirrspülmaschine. Another subject of the present application is a method for cleaning hard surfaces, in particular dishes, in which the surface is treated in a manner known per se using a detergent or cleaning agent according to the invention, preferably dishwashing detergent, in particular automatic dishwashing detergent. In particular, the surface is brought into contact with the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent. The cleaning takes place in particular with a cleaning machine, preferably with a dishwasher.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ebenso die Verwendung eines Waschoder Reinigungsmittels, bevorzugt Geschirrspülmittels, insbesondere maschinellen Geschirrspülmittels, wie vorstehend beschrieben, zur Reinigung von harten Oberflächen, insbesondere von Geschirr, insbesondere in maschinellen Geschirrspülmaschinen.
Für die Verwendung bzw. das Verfahren gilt entsprechend das vorstehend für die Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, konkret offenbarte. A further subject of the present invention is also the use of a washing or cleaning agent, preferably dishwashing agent, in particular automatic dishwashing agent, as described above, for cleaning hard surfaces, in particular dishes, in particular in automatic dishwashers. For the use or the process, the specific disclosures made above for the detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, apply accordingly.
Soweit in der vorliegenden Anmeldung festgehalten ist, dass das erfindungsgemäße Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, im Ganzen oder im Gel, etwas umfasst, ist ebenfalls als offenbart anzusehen, dass Wasch- oder Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, bzw. die jeweilige Phase daraus bestehen kann. Im nachfolgenden Ausführungsbeispiel wird das erfindungsgemäße, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, in nicht Reinigungsmittel limitierender Weise beschrieben. Insofar as it is stated in the present application that the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular automatic dishwashing detergent, as a whole or in the gel, comprises something, it is also to be regarded as disclosed that washing or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent , or the respective phase can consist of it. In the exemplary embodiment below, the preferred dishwashing agent according to the invention, in particular automatic dishwashing agent, is described in a manner that does not limit cleaning agents.
Durch diese Anmeldung werden u.a. die folgenden Gegenstände bereitgestellt: Items provided by this application include:
1 . Wasch- oder Reinigungsmittel, umfassend mindestens ein Gel, bevorzugt ein bei1 . Detergents or cleaning agents, comprising at least one gel, preferably one
Raumtemperatur (20 °C) festes Gel, umfassend, jeweils bezogen auf das Gesamtgewicht des Gels, 3 bis 40 Gew.-%, bevorzugt 4 bis 20 Gew.-%, insbesondere 5 bis 18 Gew.-%, PVOH und/oder dessen Derivate; sowie a. mindestens einer Komponente mit einem Parameter r <= 15,3 MPa1/2 und b. mindestens einer Komponente mit einem Parameter r >= 16,3 MPa1/2; sowie c. optional mindestens einen weiterer Aktivstoff, bevorzugt ausgewählt aus Farbstoffen, Glaskorrosionsinhibitoren, Parfüms, pH-Stellmitteln sowie weiteren Prozesshilfsmitteln; wobei mindestens eine der Komponenten gemäß a) oder b) bei 20 °C flüssig ist, und mit der Maßgabe, dass für die Mischung der Komponenten (Anzahl n) gemäß a) und b) bzw. a), b) und c) gilt:
mit Room temperature (20°C) solid gel comprising, based in each case on the total weight of the gel, 3 to 40% by weight, preferably 4 to 20% by weight, in particular 5 to 18% by weight, PVOH and/or its derivatives; as well as a. at least one component with a parameter r <= 15.3 MPa 1/2 and b. at least one component with a parameter r >= 16.3 MPa 1/2 ; as well as c. optionally at least one further active ingredient, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20 °C, and with the proviso that for the mixture of components (number n) according to a) and b) or a), b) and c) applies : With
Und wobei dD0 = 16,05 MPc dP0 = 20,31 MPc dH0 = 36,86 MPa Und r = 14,0 bis 18,5 MPa1/2. And where dD 0 = 16.05 MPc dP 0 = 20.31 MPc dH 0 = 36.86 MPa And r = 14.0 to 18.5 MPa 1/2 .
2. Wasch- oder Reinigungsmittel nach Punkt 1 , dadurch gekennzeichnet, dass der Radius r von r= 15,0 bis 17,5 beträgt.
Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass < 5 Gew.-%, bevorzugt < 3 Gew.-%, insbesondere < 1 Gew.-% einer Komponente mit2. Detergent or cleaning agent according to point 1, characterized in that the radius r is r=15.0 to 17.5. Detergent or cleaning agent according to one of the above points, characterized in that <5% by weight, preferably <3% by weight, in particular <1% by weight, of a component with
15.3<r<16.3 enthalten ist. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass < 5 Gew.-%, bevorzugt < 3 Gew.-%, insbesondere < 1 Gew.-% 1 ,3-Propandiol enthalten ist. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass < 5 Gew.-%, bevorzugt < 3 Gew.-%, insbesondere < 1 Gew.-% 1 ,3-Propandiol und/oder15.3<r<16.3 is included. Detergent or cleaning agent according to one of the above points, characterized in that it contains <5% by weight, preferably <3% by weight, in particular <1% by weight, of 1,3-propanediol. Detergent or cleaning agent according to one of the above points, characterized in that <5% by weight, preferably <3% by weight, in particular <1% by weight, of 1,3-propanediol and/or
1 ,2-Propandiol enthalten ist. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass mindestens eine bei 20 °C flüssige Komponente gemäß a) enthalten ist. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass mindestens eine bei 20 °C flüssige Komponente gemäß a) und mindestens eine bei 20 °C flüssige Komponente gemäß b) enthalten sind. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass mindestens eine Komponente gemäß a), bevorzugt eine bei 20 °C flüssige Komponente a), und mindestens zwei Komponenten, bevorzugt zwei bei 20 °C flüssige Komponenten gemäß b) enthalten sind. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass die Komponente a) ausgewählt ist aus der Gruppe gebildet aus Wasser, Glycerin, und Polyacrylaten, insbesondere sulfonsäuregruppenhaltigen Polyacrylaten. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass die Komponente b) unabhängig voneinander ausgewählt ist aus der Gruppe gebildet aus organischen Lösungsmitteln, nichtionischen Tensiden und organischen Metallsalzen. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass die Komponente b) unabhängig voneinander ausgewählt ist aus Polyalkylenglycolen (insbesondere Polyethylenglycolen, Polypropylenglykolen), Carbonatestern, (insbesondere Glycerolcarbonate, Propylene carbonate, Ethylencarbonate, Diethylcarbonate, Dimethylcarbonate), 3-Methyl-1 ,3-Butanediol, Fettalkoholalkoxylaten (ggf. endgruppenvorschlossen) und Acetaten, insbesondere Zinkacetat. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass das Gel eine Schichtdicke von mindestens 0,3 mm, bevorzugt von mindestens 0,7 mm,
insbesondere von mindestens 1 ,0 mm, ganz besonders bevorzugt von mindestens 1 ,2 mm aufweist. Wasch- oder Reinigungsmittel nach einem der vorstehenden Punkte, dadurch gekennzeichnet, dass als Komponente gemäß c) mindestens ein Zinksalz, bevorzugt Zinkchlorid, Zinksulfat und/oder Zinkacetat, insbesondere Zinkacetat, besonders bevorzugt Zinkacetat-Anhydrat, in einer Menge von 0,05 bis 5 Gew.-%, bevorzugt in einer Menge von 0,1 bis 2,0 Gew.-%, insbesondere 0,2 bis 1 Gew.-%, bezogen auf das Gesamtgewicht des Gels, enthalten ist. Wasch- oder Reinigungsmittelportion, umfassend mindestens ein Gel gemäß einem der Punkten 1 bis 11 in einer wasserlöslichen Umhüllung, bevorzugt umfassend Polyvinylalkohol, insbesondere einem Polyvinylalkohol umfassenden Film. Wasch- oder Reinigungsmittelportion nach Punkt 11 oder 12, dadurch gekennzeichnet, dass sie mindestens eine zusätzliche Phase umfasst, die ausgewählt ist aus einer flüssigen Phase, gelförmigen Phase und/oder partikulären, bevorzugt rieselfähigen, festen Phase. Wasch- oder Reinigungsmittelportion nach Punkt 13, dadurch gekennzeichnet, dass wenigstens eine zusätzliche Phase mindestens einen, bevorzugt mehrere Inhaltsstoffe umfasst, welche ausgewählt sind aus der Gruppe gebildet aus Gerüststoffe (bevorzugt Carbonate, Citrate, Aminocarboxylate, bevorzugt MGDA und/oder GLDA bzw. deren Salze,) und/oder Bleichmittel (insbesondere Percarbonat), und/oder Bleichaktivatoren und/oder Bleichkatalysatoren, und/oder Silberschutzmittel, und/oder Enzyme (bevorzugt Protease(n) und/oder Amylase(n)), und/oder nichtionische Tenside und/oder weitere Prozesshilfsmitteln. Wasch- oder Reinigungsmittel nach einem der Punkte 1 bis 14, dadurch gekennzeichnet, dass es ein Geschirrspülmittel, insbesondere ein Geschirrspülmittel zur maschinellen Reinigung von Geschirr ist. Verwendung eines Reinigungsmittels nach einem der Punkte 1 bis 16 zur maschinellen Reinigung von Geschirr, insbesondere zur Reinigung von hartnäckigen, fettigen bzw. fettig und proteinreichen Speiseresten, z.B. gebratenem Speck oder überbackenem Käse. Verfahren zur maschinellen Reinigung von Geschirr, dadurch gekennzeichnet, dass ein Reinigungsmittel nach einem der Punkte 1 bis 16 in einer Geschirrspülmaschine zum Einsatz kommt.
Ausführungsbeispiele: 1,2-propanediol is included. Detergent or cleaning agent according to one of the above points, characterized in that at least one component according to a) which is liquid at 20°C is present. Detergent or cleaning agent according to one of the above points, characterized in that at least one component according to a) which is liquid at 20°C and at least one component according to b) which is liquid at 20°C are present. Detergent or cleaning agent according to one of the above points, characterized in that at least one component according to a), preferably one component a) which is liquid at 20°C, and at least two components, preferably two components according to b) which are liquid at 20°C, are present . Detergent or cleaning agent according to one of the above points, characterized in that component a) is selected from the group consisting of water, glycerol and polyacrylates, in particular polyacrylates containing sulfonic acid groups. Detergent or cleaning agent according to one of the above points, characterized in that component b) is selected independently from the group consisting of organic solvents, nonionic surfactants and organic metal salts. Detergent or cleaning agent according to one of the above points, characterized in that component b) is independently selected from polyalkylene glycols (particularly polyethylene glycols, polypropylene glycols), carbonate esters (particularly glycerol carbonates, propylene carbonates, ethylene carbonates, diethyl carbonates, dimethyl carbonates), 3-methyl -1,3-Butanediol, fatty alcohol alkoxylates (possibly end-capped) and acetates, in particular zinc acetate. Detergent or cleaning agent according to one of the above points, characterized in that the gel has a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular of at least 1.0 mm, very particularly preferably of at least 1.2 mm. Detergent or cleaning agent according to one of the above points, characterized in that as component according to c) at least one zinc salt, preferably zinc chloride, zinc sulfate and/or zinc acetate, in particular zinc acetate, particularly preferably zinc acetate anhydrate, in an amount of 0.05 to 5 % by weight, preferably in an amount of 0.1 to 2.0% by weight, in particular 0.2 to 1% by weight, based on the total weight of the gel. Detergent or cleaning agent portion comprising at least one gel according to one of points 1 to 11 in a water-soluble envelope, preferably comprising polyvinyl alcohol, in particular a film comprising polyvinyl alcohol. Detergent or cleaning agent portion according to point 11 or 12, characterized in that it comprises at least one additional phase which is selected from a liquid phase, a gel phase and/or a particulate, preferably free-flowing, solid phase. Detergent or cleaning agent portion according to point 13, characterized in that at least one additional phase comprises at least one, preferably several ingredients selected from the group consisting of builders (preferably carbonates, citrates, amino carboxylates, preferably MGDA and/or GLDA or their Salts,) and/or bleaching agents (in particular percarbonate), and/or bleach activators and/or bleaching catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase(s)), and/or nonionic surfactants and/or other processing aids. Detergent or cleaning agent according to one of points 1 to 14, characterized in that it is a dishwashing detergent, in particular a dishwashing detergent for machine cleaning of dishes. Use of a cleaning agent according to one of points 1 to 16 for machine cleaning of dishes, in particular for cleaning stubborn, greasy or greasy and protein-rich leftovers, eg fried bacon or gratinated cheese. Method for machine cleaning of dishes, characterized in that a cleaning agent according to one of points 1 to 16 is used in a dishwasher. Examples:
Es wurden erfindungsgemäße Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, hergestellt, die eine feste, bevorzugt körnige Phase und eine Gelphase umfassten. Hierbei wurden unterschiedliche Geometrien realisiert. Weiterhin wurden Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, hergestellt, die zwei feste, bevorzugt körnige Phasen und eine Gelphase umfassten. Ebenfalls wurden Reinigungsmittel, bevorzugt Geschirrspülmittel, insbesondere maschinellen Geschirrspülmittel, hergestellt, die eine feste, bevorzugt körnige Phase sowie 3, 4 und 5 Gelphasen, (gleicher oder unterschiedlicher Zusammensetzung) umfassten. Die folgenden Angaben beziehen sich auf Gew. -% Aktivsubstanz bezogen auf das Gesamtgewicht der jeweiligen Phase (sofern nichts anderes angegeben). Cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, were produced which comprised a solid, preferably granular phase and a gel phase. Different geometries were realized here. Furthermore, detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, were produced which comprised two solid, preferably granular phases and a gel phase. Cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, were also produced, which comprised a solid, preferably granular phase and 3, 4 and 5 gel phases (of the same or different composition). The following information relates to % by weight of active substance based on the total weight of the phase in question (unless otherwise stated).
Tabelle 1 : Die festen körnigen Gemenge einer festförmigen Zusammensetzung, insbesondere pulverförmigen und rieselfähigen Phasen wiesen dabei die folgende bevorzugte Zusammensetzung auf:
Table 1: The solid, granular mixtures of a solid composition, in particular powdery and free-flowing phases, had the following preferred composition:
Tabelle 2: Die Gele haben Zusammensetzungen, die bevorzugt in den folgenden Bereichen liegen (Angaben jeweils bezogen auf die Gesamtmenge der Gelphase):
Table 2: The gels have compositions that are preferably in the following ranges (data based on the total amount of the gel phase):
Tabelle 3: Besonders bevorzugte Gele weisen folgende Zusammensetzungen auf.
Table 3: Particularly preferred gels have the following compositions.
Die festen körnigen Phasen und das Gel konnten beliebig miteinander kombiniert werden. Die räumliche Ausgestaltung der Gelphase, die nach dem Vermischen der Inhaltsstoffe flüssig und innerhalb einer Erstarrungszeit von maximal 5 Minuten formstabil war, wurde durch die räumliche Ausgestaltung der festen Phase sowie durch handelsübliche oder selbst designte Formen vorgegeben. Es wurde eine wasserlösliche Umhüllung in Form eines offenen Pouches durch Tiefziehen einer PVOH-haltigen Folie hergestellt. In diese offene Kavität wurde eine flüssige Zusammensetzung gegossen, welche nach dem Aushärten das Gel ergab, darauf wurden festen Phasen in Form eines rieselfähigen Feststoffes in einem Pouch umfassend Polyvinylalkohol eingefüllt und der offene Pouch dann durch Auflegen einer zweiten Folie und Versiegelung mittels Heißsiegelung versiegelt. The solid granular phases and the gel could be combined with one another as desired. The spatial configuration of the gel phase, which was liquid after mixing the ingredients and dimensionally stable within a maximum setting time of 5 minutes, was determined by the spatial configuration of the solid phase and by commercially available or self-designed forms. A water-soluble cover in the form of an open pouch was produced by deep-drawing a film containing PVOH. A liquid composition was poured into this open cavity, which gave the gel after curing, then solid phases in the form of a free-flowing solid were filled into a pouch comprising polyvinyl alcohol and the open pouch was then sealed by placing a second film and sealing by heat sealing.
(*1) Fettalkoholalkoxylat, bevorzugt 20-40 EO, endcapped (*1) Fatty alcohol alkoxylate, preferably 20-40 EO, endcapped
Für E1 ergibt sich die Berechnung des Wertes r wie folgt (Tabelle 5): Tabelle 5:
Daraus ergibt sich mit For E1, the value r is calculated as follows (Table 5): Table 5: This results in with
(dDM ix dD0)2 + ( dPMix dP0)2 + ( dHMix dH0)2 = r2 (dD Mix dD 0 ) 2 + ( dPMix dP 0 ) 2 + ( dHMix dH 0 ) 2 = r 2
Und dD0 = 16,05 MPc dP0 = 20,31 MPc dH0 = 36,86 MPc ein Wert für r= 15,0. And dD 0 = 16.05 MPc dP 0 = 20.31 MPc dH 0 = 36.86 MPc a value for r= 15.0.
Gemäß Tabelle 3 wurden die Gelformulierungen hergestellt. According to Table 3, the gel formulations were prepared.
Die Gele wurden bei erhöhter Temperatur gerührt (80-90 °C bei Wasserhaltigen Gelen, 110-120 °C bei wasserarmen Gelen). Diese Gelphasen wurden anschließend wie unter Tabelle 2 beschrieben in Gießlinge gegossen. Dabei wurde festgestellt, dass die so hergestellten Gelphasen, auch ohne 1 ,3 Propandiol, mit Verfestigungszeiten von kleiner 10 min besonders gute Verarbeitungseigenschaften aufwiesen. The gels were stirred at elevated temperature (80-90°C for water-containing gels, 110-120°C for low-water gels). These gel phases were then poured into castings as described under Table 2. It was found that the gel phases produced in this way, even without 1,3 propanediol, had particularly good processing properties with setting times of less than 10 minutes.
Überraschend wurde gefunden, dass diese Gele besonders gut auf hartnäckigen Belägen auf harten Oberflächen, insbesondere auf Spülgut wirken. Eine besonders positive Reinigungsleistung gelingt bei fettigen bzw. fettig-proteinhaltigen Rückständen sowie angebrannten und/oder angebackenen Speisereste. Auch wird überraschend eine gute Klarspülleistung gefunden.
Surprisingly, it was found that these gels work particularly well on stubborn deposits on hard surfaces, in particular on items to be washed. A particularly positive cleaning performance is achieved with greasy or greasy-protein residues as well as burnt and/or baked-on food residues. Surprisingly, good rinsing performance is also found.
Claims
1 . Wasch- oder Reinigungsmittel, umfassend mindestens ein Gel, bevorzugt ein bei1 . Detergents or cleaning agents, comprising at least one gel, preferably one
Raumtemperatur (20 °C) festes Gel, umfassend, jeweils bezogen auf das Gesamtgewicht des Gels, 3 bis 40 Gew.-%, bevorzugt 4 bis 20 Gew.-%, insbesondere 5 bis 18 Gew.-%, PVOH und/oder dessen Derivate; sowie a. mindestens eine Komponente mit einem Parameter r <= 15,3 MPa1/2 und b. mindestens eine Komponente mit einem Parameter r >= 16,3 MPa1/2; sowie c. optional mindestens einen weiterer Aktivstoff, bevorzugt ausgewählt aus Farbstoffen, Glaskorrosionsinhibitoren, Parfüms, pH-Stellmitteln sowie weiteren Prozesshilfsmitteln; wobei mindestens eine der Komponenten gemäß a) oder b) bei 20 °C flüssig ist, und mit der Maßgabe, dass für die Mischung der Komponenten (Anzahl n) gemäß a) und b) bzw. a), b) und c) gilt:
mit
und Room temperature (20°C) solid gel comprising, based in each case on the total weight of the gel, 3 to 40% by weight, preferably 4 to 20% by weight, in particular 5 to 18% by weight, PVOH and/or its derivatives; as well as a. at least one component with a parameter r <= 15.3 MPa 1/2 and b. at least one component with a parameter r >= 16.3 MPa 1/2 ; as well as c. optionally at least one further active ingredient, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20 °C, and with the proviso that for the mixture of components (number n) according to a) and b) or a), b) and c) applies : With and
( dDMix — dD0 )2 + ( dPMix — dP0 )2 + ( dHMix — dH0 )2 = r2 wobei dD0 = 16,05 MPa dP0 = 20,31 MPc dH0 = 36,86 MPc ( dD Mix - dD 0 ) 2 + ( dPMix - dP 0 ) 2 + ( dHMix - dH 0 ) 2 = r 2 where dD 0 = 16.05 MPa dP 0 = 20.31 MPc dH 0 = 36.86 MPc
Und r= 14,0 bis 18,5 MPa1/2 ist. And r= 14.0 to 18.5 MPa 1/2 .
2. Wasch- oder Reinigungsmittel nach 1 , dadurch gekennzeichnet, dass der Radius r von r= 15,0 bis 17,5 beträgt. 2. Detergent or cleaning agent according to 1, characterized in that the radius r is r=15.0 to 17.5.
3. Wasch- oder Reinigungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass mindestens eine bei 20 °C flüssige Komponente gemäß a) enthalten ist. 3. Detergent or cleaning agent according to one of the preceding claims, characterized in that at least one component according to a) which is liquid at 20° C. is present.
4. Wasch- oder Reinigungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass mindestens eine bei 20 °C flüssige Komponente gemäß a) und mindestens eine bei 20 °C flüssige Komponente gemäß b) enthalten sind.
4. Detergent or cleaning agent according to one of the preceding claims, characterized in that at least one component according to a) which is liquid at 20° C. and at least one component according to b) which is liquid at 20° C. are present.
5. Wasch- oder Reinigungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass mindestens eine Komponente gemäß a), bevorzugt eine bei 20 °C flüssige Komponente a), und mindestens zwei Komponenten, bevorzugt zwei bei 20 °C flüssige Komponenten gemäß b) enthalten sind. 5. Detergent or cleaning agent according to one of the preceding claims, characterized in that at least one component according to a), preferably one component a) which is liquid at 20° C., and at least two components, preferably two components which are liquid at 20° C. according to b) are included.
6. Wasch- oder Reinigungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Komponente a) ausgewählt ist aus der Gruppe gebildet aus Wasser, Glycerin und Polyacrylaten, insbesondere sulfonsäuregruppenhaltigen Polyacrylaten. 6. Detergent or cleaning agent according to one of the preceding claims, characterized in that component a) is selected from the group consisting of water, glycerol and polyacrylates, in particular polyacrylates containing sulfonic acid groups.
7. Wasch- oder Reinigungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Komponente b) unabhängig voneinander ausgewählt ist aus der Gruppe gebildet aus organischen Lösungsmitteln, nichtionischen Tensiden und organischen Metallsalzen. 7. Detergent or cleaning agent according to one of the preceding claims, characterized in that component b) is selected independently from the group consisting of organic solvents, nonionic surfactants and organic metal salts.
8. Wasch- oder Reinigungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Komponente b) unabhängig voneinander ausgewählt ist aus Polyalkylenglycolen (insbesondere Polyethylenglycolen, Polypropylenglykolen), Carbonatestern, (insbesondere Glycerolcarbonate, Propylene carbonate, Ethylencarbonate, Diethylcarbonate, Dimethylcarbonate), 3-Methyl-1 ,3-Butanediol, Fettalkoholalkoxylaten (ggf. endgruppenvorschlossen) und Acetaten, insbesondere Zinkacetat. 8. Detergent or cleaning agent according to one of the preceding claims, characterized in that component b) is independently selected from polyalkylene glycols (in particular polyethylene glycols, polypropylene glycols), carbonate esters (in particular glycerol carbonates, propylene carbonates, ethylene carbonates, diethyl carbonates, dimethyl carbonates), 3 -Methyl-1,3-butanediol, fatty alcohol alkoxylates (possibly end-capped) and acetates, in particular zinc acetate.
9. Wasch- oder Reinigungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Gel weniger als 5 Gew.-%, bevorzugt weniger als 3 Gew.-%, insbesondere weniger als 1 Gew.-% 1 ,3-Propandiol umfasst. 9. Detergent or cleaning agent according to one of the preceding claims, characterized in that the gel comprises less than 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight, of 1,3-propanediol.
10. Wasch- oder Reinigungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Gel eine Schichtdicke von mindestens 0,3 mm, bevorzugt von mindestens 0,7 mm, insbesondere von mindestens 1 ,0 mm, ganz besonders bevorzugt von mindestens 1 ,2 mm aufweist. 10. Detergent or cleaning agent according to one of the preceding claims, characterized in that the gel has a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular at least 1.0 mm, very particularly preferably at least 1 2mm.
11. Wasch- oder Reinigungsmittelportion, umfassend mindestens ein Gel gemäß einem der Ansprüchen 1 bis 10 in einer wasserlöslichen Umhüllung, bevorzugt umfassend Polyvinylalkohol, insbesondere einem Polyvinylalkohol umfassenden Film. 11. Detergent or cleaning agent portion comprising at least one gel according to any one of claims 1 to 10 in a water-soluble envelope, preferably comprising polyvinyl alcohol, in particular a film comprising polyvinyl alcohol.
12. Wasch- oder Reinigungsmittelportion nach Anspruch 10 oder 11 , dadurch gekennzeichnet, dass sie mindestens eine zusätzliche Phase umfasst, die ausgewählt ist aus einer flüssigen Phase, gelförmigen Phase und/oder partikulären, bevorzugt rieselfähigen, festen Phase. 12. Detergent or cleaning agent portion according to claim 10 or 11, characterized in that it comprises at least one additional phase which is selected from a liquid phase, a gel phase and/or a particulate, preferably free-flowing, solid phase.
13. Wasch- oder Reinigungsmittelportion nach Anspruch 12, dadurch gekennzeichnet, dass wenigstens eine zusätzliche Phase mindestens einen, bevorzugt mehrere Inhaltsstoffe
umfasst, welche ausgewählt sind aus der Gruppe gebildet aus Gerüststoffe (bevorzugt Carbonate, Citrate, Aminopolycarboxylate, bevorzugt MGDA und/oder GLDA bzw. deren Salze) und/oder Bleichmittel (insbesondere Percarbonat), und/oder Bleichaktivatoren und/oder Bleichkatalysatoren, und/oder Silberschutzmittel, und/oder Enzyme (bevorzugt Protease(n) und/oder Amylase(n)), und/oder nichtionische Tenside und/oder weitere Prozesshilfsmitteln. 13. Detergent or cleaning agent portion according to claim 12, characterized in that at least one additional phase has at least one, preferably several ingredients which are selected from the group formed from builders (preferably carbonates, citrates, aminopolycarboxylates, preferably MGDA and/or GLDA or their salts) and/or bleaches (especially percarbonate), and/or bleach activators and/or bleach catalysts, and/or or silver protectants, and/or enzymes (preferably protease(s) and/or amylase(s)), and/or nonionic surfactants and/or other processing aids.
14. Wasch- oder Reinigungsmittel nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass es ein Geschirrspülmittel, insbesondere ein Geschirrspülmittel zur maschinellen Reinigung von Geschirr ist. 14. Detergent or cleaning agent according to one of claims 1 to 13, characterized in that it is a dishwashing detergent, in particular a dishwashing detergent for machine cleaning of dishes.
15. Verwendung eines Wasch- oder Reinigungsmittels nach einem der Ansprüche 1 bis 14 zur maschinellen Reinigung von Geschirr, insbesondere zur Reinigung von hartnäckigen, fettigen bzw. fettig und proteinreichen Speiseresten, z.B. gebratenem Speck oder überbackenem Käse.
15. Use of a detergent or cleaning agent according to one of Claims 1 to 14 for machine cleaning of dishes, in particular for cleaning stubborn, greasy or greasy and protein-rich food residues, e.g. fried bacon or gratinated cheese.
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WO2018138124A1 (en) * | 2017-01-24 | 2018-08-02 | Henkel Ag & Co. Kgaa | Detergent or cleaning agent portion having at least two phases |
EP3770242A1 (en) * | 2019-07-22 | 2021-01-27 | Henkel AG & Co. KGaA | Cleaning composition with enzyme |
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DE102018212204A1 (en) | 2018-07-23 | 2020-01-23 | Henkel Ag & Co. Kgaa | Detergent with protection against glass corrosion |
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ALQARNI MOHAMMED H ET AL: "Solubility data, Hansen solubility parameters and thermodynamic behavior of pterostilbene in some pure solvents and different (PEG-400 + water) cosolvent compositions", JOURNAL OF MOLECULAR LIQUIDS, ELSEVIER, AMSTERDAM, NL, vol. 331, 20 February 2021 (2021-02-20), XP086549726, ISSN: 0167-7322, [retrieved on 20210220], DOI: 10.1016/J.MOLLIQ.2021.115700 * |
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