EP1509589B1 - Automatic dishwashing detergent with improved glass anti-corrosion properties - Google Patents
Automatic dishwashing detergent with improved glass anti-corrosion properties Download PDFInfo
- Publication number
- EP1509589B1 EP1509589B1 EP03735481.8A EP03735481A EP1509589B1 EP 1509589 B1 EP1509589 B1 EP 1509589B1 EP 03735481 A EP03735481 A EP 03735481A EP 1509589 B1 EP1509589 B1 EP 1509589B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- automatic dishwashing
- water
- dishwashing agent
- soluble
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004851 dishwashing Methods 0.000 title claims description 135
- 239000011521 glass Substances 0.000 title claims description 18
- 238000005260 corrosion Methods 0.000 title claims description 16
- 239000003599 detergent Substances 0.000 title abstract description 73
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 60
- -1 zinc salt Chemical class 0.000 claims abstract description 57
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 139
- 229920000642 polymer Polymers 0.000 claims description 83
- 150000003751 zinc Chemical class 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 239000013543 active substance Substances 0.000 claims description 50
- 239000011159 matrix material Substances 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 9
- 230000035515 penetration Effects 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 8
- 239000001257 hydrogen Chemical group 0.000 claims description 6
- 229910052739 hydrogen Chemical group 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011670 zinc gluconate Substances 0.000 claims description 4
- 235000011478 zinc gluconate Nutrition 0.000 claims description 4
- 229960000306 zinc gluconate Drugs 0.000 claims description 4
- 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 claims description 4
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims description 3
- 150000003009 phosphonic acids Chemical class 0.000 claims description 3
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims description 3
- 239000011576 zinc lactate Substances 0.000 claims description 3
- 235000000193 zinc lactate Nutrition 0.000 claims description 3
- 229940050168 zinc lactate Drugs 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229940006174 zinc valerate Drugs 0.000 claims description 3
- 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 claims description 3
- BUDAIZWUWHWZPQ-UHFFFAOYSA-L zinc;pentanoate Chemical compound [Zn+2].CCCCC([O-])=O.CCCCC([O-])=O BUDAIZWUWHWZPQ-UHFFFAOYSA-L 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 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 claims description 2
- 229940100530 zinc ricinoleate Drugs 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 8
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- 239000003513 alkali Substances 0.000 abstract description 5
- 150000001340 alkali metals Chemical class 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910021478 group 5 element Inorganic materials 0.000 abstract 2
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
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- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- SFYBRCJPMDQKHA-UHFFFAOYSA-N zinc;dinitrate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SFYBRCJPMDQKHA-UHFFFAOYSA-N 0.000 description 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
-
- 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
- C11D2111/18—Glass; Plastics
Definitions
- the present invention is in the field of automatic dishwashing detergents.
- the present invention relates to automatic dishwashing detergents containing zinc salts and certain silicates.
- the so-called lower alkaline cleaners required for automatic dishwashing frequently contain mixtures of sodium disilicate and soda as alkali carriers, builders such as citric acid, for example in conjunction with polycarboxylates, and preferably low-foaming nonionic surfactants. Furthermore, bleaching agents, bleach activators, silver and corrosion inhibitors and, to enhance the cleaning power, enzymes may be included.
- the dishes set in baskets are cleaned by intensive contact with the aqueous detergent solution at about 65 ° C and pH values between 9 and 11 and then rinsed clear.
- the European patent application EP 0 383 482 (Procter & Gamble Company) finally describes automatic dishwashing agents containing insoluble zinc salts, which are distinguished by improved glass corrosion protection.
- the insoluble zinc salts must have a particle size below 1.7 millimeters to achieve such a lengthy effect.
- dishwasher detergents containing phosphate which contain a powdery to granular additive which contains, as essential constituents, a crystalline layered silicate of the general formula NaMSi x O 2x + 1yH 2 O, where M is sodium or hydrogen, x a Number is from 1.9 to 22 and y stands for a number of 0 bits 33, and (poly) polymeric polycarboxylic acid and in addition to glass or decor-preserving effects also have excellent cleaning performance.
- an object of the present invention to provide a machine dishwashing detergent which does not corrosively change the surfaces of glassware, even after repeated use, in particular does not cause turbidity, streaks or scratches, nor iridescence of the glass surfaces.
- an automatic dishwashing detergent additive should be provided which is suitable as a component of any type of dishwashing detergent, for example, as a component of powder, tablet, liquid formulations, cleansing foams or depot products, without limiting its formulation.
- the present application therefore relates to automatic dishwashing or dishwashing auxiliaries, comprising at least one soluble zinc salt and at least one crystalline layered silicate of the general formula (Ia) NaMSi x O 2x + 1 ⁇ y H 2 O (Ia), wherein M represents sodium or hydrogen, x is an integer from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33.
- the crystalline layer-form silicates of the formula (Ia) are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na 2 Si 22 O 45 .xN 2 O, Kenyaite), Na -SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 . xH 2 O, Makatite).
- Na-SKS for example Na-SKS-1 (Na 2 Si 22 O 45 .xN 2 O, Kenyaite), Na -SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 . xH 2 O, Makatite).
- x is 2.
- Na-SKS-5 ⁇ -Na 2 Si 2 O 5
- Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , Natrosilit
- Na-SKS-9 NaHSi 2 O 5 ⁇ H 2 O
- Na-SKS-10 NaHSi 2 O 5 ⁇ 3H 2 O kanemite
- Na-SKS-11 t-Na 2 Si 2 O 5
- Na-SKS-13 Na-SKS-13
- An overview of crystalline phyllosilicates can be found eg in the " Soap-oil-grease waxes, 116 vintage, no. 20/1990 "on pages 805 - 808 published article.
- preferred automatic dishwashing or automatic dishwashing assistants have a weight fraction of the crystalline layered silicate of the general formula (Ia) of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0 , 4 to 10 wt .-%, each based on the total weight of these agents, on.
- compositions according to the invention contain, in addition to the crystalline layered silicates mentioned, zinc salts, it being possible to use both inorganic and organic salts.
- zinc salt solubility Zinc acetate dihydrate 430 g / l (20 ° C) zinc acetylacetonate 4 g / l (20 ° C) zinc bromide 820 g / l (25 ° C) zinc chloride 4320 g / l (25 ° C) zinc gluconate 100 g / l (20 ° C) zinc iodide 4500 g / l (20 ° C) Zinc nitrate hexahydrate 1843 g / l (20 ° C) Zinc nitrate tetrahydrate Slightly soluble (20 ° C) Zinksulfal-Heptahydat 960 g / l (20 ° C) Zinc sulphate
- the soluble inorganic interest salts that is to say salts which in water (20 ° C.) have a solubility above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L, preferred component of agents according to the invention.
- the preferred soluble inorganic salts include the zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
- Another preferred subject matter of the present application are therefore automatic dishwashing or dishwashing dishwashing aids containing at least one zinc salt selected from the group consisting of soluble inorganic zinc salts from the group zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
- Soluble organic zinc salts have a solubility above 100 mg / L in water, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature).
- the group of soluble organic zinc salts includes, for example, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc valerate, and zinc salt of p-toluenesulfonic acid.
- machine dishwashing detergents or automatic dishwashing detergents according to the invention therefore contain at least one zinc salt selected from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate , Zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
- group of soluble organic zinc salts more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate , Zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
- compositions according to the invention may also contain mixtures of organic and inorganic zinc salts, in particular mixtures of soluble organic zinc salts with non-soluble inorganic zinc salts or mixtures of soluble organic zinc salts with soluble inorganic zinc salts or mixtures of insoluble organic zinc salts with soluble inorganic zinc salts.
- automatic dishwashing or automatic dishwashing aids in which the proportion by weight of the zinc salt relative to the total weight of this agent is 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0, are preferred , 4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts or mixtures thereof are used.
- compositions according to the invention are not subject to any restrictions with regard to their packaging and forms of presentation.
- Machine dishwashing or machine dishwashing aids in the context of the present invention can therefore be provided both in solid and in liquid form.
- active ingredients and / or active ingredient preparations in a timely manner.
- This time-controlled release can take place through different mechanisms or, in other words, due to different "switches”.
- these active substances are preferably added together but with a time offset to one or more further active ingredients and / or active substance preparations, such as builders (builders, cobuilders), surfactants, bleaches, bleach activators, enzymes , Dyes, fragrances, corrosion inhibitors or polymers are released.
- the zinc salt and / or the phyllosilicate can be released into the aqueous liquor both before and after the release of these active substances.
- the agents according to the invention are prepared, for example, as combination products of two or more substances or mixtures of substances in different preparation / physical state, then the composition according to the invention which contains the zinc salt and the layered silicate is preferably contained only in one of these agents.
- liquids, powders, granules, compactates, extrudates, casting bodies, gels, dispersions are considered as different types of preparation / physical states.
- the assembly of such different means to a combination product can be done for example by means of a common, preferably water-soluble packaging having one, two, three, four or more receiving chambers. Methods for producing such packages are known in the art. These methods include, for example, thermoforming, injection molding or casting. In the following, with reference to single and two-chamber packaging, some preferred combinations of differently prepared compositions are described:
- Receiving chamber 1 Inventive agent in a powder and liquid Composition according to the invention in a powder and further powder Inventive agent in a powder and granules Inventive agent in a powder and Kompaktat Inventive agent in a powder and extrudate Inventive agent in a powder and casting Inventive agent in a powder and dimensionally stable gel Inventive agent in a melt and liquid Composition according to the invention in a melt and further powder Inventive agent in a melt and granules Inventive agent in a melt and Kompaktat Composition according to the invention in a melt and extrudate Inventive agent in a melt and casting Inventive agent in a melt and dimensionally stable gel Inventive agent in a granule and liquid Composition according to the invention in granules and further powder Inventive agent in granules and granules Inventive agent in a granule and Kompaktat Composition according to the invention in a melt and extrudate Invent
- Water-soluble or water-dispersible packaging with two receiving chambers Receiving chamber 1 Receiving chamber 2 Composition according to the invention in a dispersion liquid Composition according to the invention in a dispersion powder Composition according to the invention in a dispersion granules Composition according to the invention in a dispersion compacted Composition according to the invention in a dispersion extrudate Composition according to the invention in a dispersion casting body Composition according to the invention in a dispersion Dimensionally stable gel Composition according to the invention in a dispersion dispersion Inventive agent in a powder liquid Inventive agent in a powder powder Inventive agent in a powder granules Inventive agent in a powder compacted Inventive agent in a powder extrudate Inventive agent in a powder casting body Inventive agent in a powder Dimensionally stable gel Inventive agent in a powder dispersion Inventive agent in a powder dispersion Inventive agent in a granule liquid Inventive agent
- the water-soluble and / or water-dispersible film for the preparation of the water-soluble and / or water-dispersible film, in principle all substances or mixtures of substances which can be formulated in the form of a film are suitable. However, particularly preferred is a process in which the water-soluble and / or water-dispersible film of (acetalized) Polyvinylakohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, starch and starch derivative (s), cellulose and cellulose derivative (s), in particular methylcellulose and / or mixtures of these substances this listing being exemplary and not limiting the invention.
- the film (s) comprises one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof ,
- Embodiments of the water-soluble films which are particularly preferred according to the invention also take into account the fact that the active substances and / or active-substance preparations contained in the receiving troughs are particularly advantageously - but not necessarily - water-solubility of the film material at a certain point in time of the washing, cleaning or thinning process Rinsing, for example, when reaching a certain temperature, or upon reaching a certain pH or a certain ionic strength of the wash liquor or due to other controllable events or conditions in the aqueous liquor can be fed.
- the thickness of the water-soluble film is between 1 .mu.m and 1000 .mu.m, preferably between 5 .mu.m and 500 .mu.m and in particular between 10 .mu.m and 200 .mu.m.
- Various film thicknesses with the aim of a delayed release of active substances and / or active substance preparations can also be realized, for example, advantageously by the multiple sealing of one or more receiving chambers by means of one or more identical or different water-soluble films.
- the thickness of the water-soluble film in the sense of the present invention then results as the sum of the thicknesses of the water-soluble individual films sealing one receiving trough.
- materials for the water-soluble films which - based on a specific, thickness-determining thickness - at certain temperatures, pH values, ionic strengths, or after a certain residence time in the aqueous liquor solve.
- a release process can capture the film as a whole or only a part thereof, so that parts of the film solve when setting a certain parameter combination, while other parts are not yet (but later) or not at all solved.
- the latter can be achieved by different quality of the material as well as by different amounts of material (thickness) or different geometries of the water-insoluble container. For example, it is possible to impede the access of water by the outer shape of the water-insoluble container and thus delay the dissolution process.
- the films may be made of materials of different water solubility, for example of polyvinyl alcohols (PVAL) with different residual acetate content.
- PVAL polyvinyl alcohols
- the water-soluble and / or water-dispersible film can also contain one or more washing and cleaning-active substances or consist of these substances (for example: polyvinyl alcohols as film material and builder) in addition to the ingredients mentioned.
- washing active, cleaning active or active ingredients that are only present in small amounts in the preparations and their uniform incorporation is therefore not unproblematic, in the film or a part of the film, for example, one which is in the state of Washing, cleaning or rinsing dissolves, in which just the active ingredient is needed to be incorporated, whereby it is released when dissolving the film at the right time in the fleet.
- An example of this may be fragrances which are desired in the final stage of the washing or cleaning or rinsing process, but also optical brighteners, UV protectants, dyes and other detergent-active, cleaning-active or rinse-active preparations.
- agents according to the invention which is likewise preferred in the context of the present application is the time-controlled release of one or more of the active substances (s) and / or active substance preparation (s) contained in these agents by the incorporation of matrix or coating materials of different solubility or melting temperature.
- the term "coating" encompasses not only the coating of one or more sides or surfaces of an article, such as a solid particulate agent, but also the complete coating, ie, the coating of this particulate article, as well as the sealing of a receiving well by a meltable substance by coating such a substance on a particulate or gel-like active / active substance preparation is referred to as a coating.
- active substances or “active substance preparations” includes both the zinc salts / sheet silicates which characterize the compositions according to the invention all others optionally included Ingredients.
- fusible substances have a melting point above 30 ° C. If active substance preparations are to be released at different times, for example during the various rinses of a cleaning process, this can be done, for example, by using one or different fusible matrices or coatings. If two or more different fusible matrices are used, the melting points are preferably adapted to the temperature profile of this cleaning process, the difference in the melting points being sufficient to ensure the separate dissolution of the individual matrices or coatings.
- Such substances are preferred for the different matrices and / or coatings, which differ in their melting point by at least 5 ° C, preferably by 10 ° C, more preferably by 15 ° C and in particular by at least 20 ° C, wherein it further preferred in that the melting point of at least one of the fusible substances forming a matrix or a coating is below 30 ° C, while the melting point of at least one further substance forming a further matrix or coating is above 30 ° C.
- this mass softenable under the influence of temperature can be mixed by mixing the desired further ingredients with this meltable or softenable substance and heating the mixture to temperatures in the softening range of this substance is processed shaping at these temperatures.
- the softenable substances are used as coating agents, then such a coating can take place, for example, by dipping, spraying or circulating in a drum coater or coating pan.
- waxes, paraffins, polyalkylene glycols, etc. as meltable or softenable substances for the matrices or the coatings.
- meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius.
- the meltable or softenable substances preferably have a melting range of between about 35 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not denote the width of the melting range.
- the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.
- Another preferred possibility for the delayed release of active substances or active substance preparations is the staggered spatial arrangement of these substances in the receiving chamber of a preferably water-soluble packaging or within a casting or compact (onion model) with the aim of a staggered release.
- a spatially staggered arrangement is, for example, the layer or phase arrangement of the active ingredients or active substance preparations, for example, the layered tabletting or the layered pouring liquid active substances or mixtures of active ingredients and their subsequent solidification by solidification and / or crystallization are suitable. Since access of the solvent in compressed or cast moldings can take place only over their surface, this layered arrangement leads to the release of those active substances or active substance mixtures which are located on the surface of such a multiphase mixture. The phases are thus removed offset in time, the ingredients are released with a time delay.
- a program for the automatic cleaning of dishes usually includes various cleaning cycles, the nature and number of these cleaning cycles can be determined by the consumer by means of a program selection. Examples of such cleaning cycles are the pre-wash cycle, intermediate and main washes or the rinse cycle. All these different cleaning operations require for an optimum result of the targeted dosage of appropriate active ingredients or active mixtures.
- a controlled early or delayed release of zinc salts and / or phyllosilicates and / or other active substances may be beneficial, depending on the nature of the other active ingredients used.
- Solid forms of the machine dishwashing detergents or dishwashing auxiliaries according to the invention are, for example, fine- to coarse-grained powders, as obtained, for example, by spray-drying or granulation, compacted mixtures of roll compacting, but also solidified melts or shaped articles obtained by extrusion or tabletting.
- Such moldings can in the context of the present invention have virtually all useful manageable embodiments, for example, in the form of a bar, in bar or bar form, a cube, a cuboid and the like Room element with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the actual tablet to compact cylinder pieces with a height-to-diameter ratio above 1.
- Preferred tabletted or extruded means in the present invention, two or more phases, for example, by their composition, their Share of the total volume of the molding and / or can distinguish their visual appearance.
- the phases of such multiphase moldings can additionally be distinguished by a different dissolving behavior in the aqueous phase.
- Such moldings are suitable for the time-controlled release of certain ingredients (controlled release), for example in certain rinses of the machine wash program.
- one of the phases of the shaped body as the main constituent has meltable or softenable substances from the group of waxes, paraffins and / or polyalkylene glycols.
- the melted or softenable substances contained molded body or molded body component is at least largely water insoluble.
- the solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l.
- meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances.
- the release of the active substance takes place in this way upon reaching the melting or softening point.
- a further preferred procedure for obtaining a controlled release of ingredients, in particular the combination of zinc salt and sheet silicate according to the invention, from multiphase tablets is the compaction of the two or more individual phases with different pressures. Since the disintegration and dissolution properties of tablets or tablet phases are known to depend inter alia on the compaction pressure exerted on the tablet phase during tabletting, tablet phases having different disintegration and dissolution properties can be prepared solely by using different compaction pressures.
- the combination of zinc salt and layered silicate according to the invention are together in the phase which was exposed to the comparatively higher tabletting pressure and therefore decomposes later.
- automatic dishwashing assistants are those which are added in addition to a commercial detergent, for example in the form of a special glass preservative. Such a dosage can take place both before the beginning of each rinsing program and in the form of a depot product which causes a continuous release of the agent according to the invention.
- Preferred solid agents according to the invention are in the form of a dosing unit sufficient for a cleaning cycle.
- An example of such Kon Stammionsformen are dishwashing (auxiliary) stoffeltabletten.
- the agents according to the invention are in solid particulate form, but not in the form of separate metering units, the problem of segregation of individual constituents arises for these agents, and the segregation of the zinc salts and silicates contained in the agents according to the invention must be avoided.
- Examples of such particulate forms of supply are powders or granules.
- Preferred solid forms of the machine dishwashing detergent according to the invention contain, for example, fine to coarse-grained powders, as obtained, for example, by spray-drying or granulation.
- Such powders can be marketed as a commercial product or used as a premix for compaction, for example for tableting, and generally have a particle size in the range from 0.1 to 10 mm.
- it is preferred that these compounds have a particle size comparable to the powders.
- a preferred subject matter of the present application is therefore a machine dishwashing detergent, characterized in that the particle size of the zinc salts and / or crystalline layered silicates compounded with one or more active and / or builder substances is 0.1 and 10 mm, preferably 0.2 and 8 mm and in particular 0.5 and 5 mm, wherein preferred particulate compounds to avoid segregation additionally a density of 0.1 to 2.0 g / cm 3 , preferably from 0.2 to 1.6 g / cm 3 and in particular from 0.4 to 1.2 g / cm 3 .
- Automated dishwashing agents preferred according to the invention are characterized in particular by the particles of the zinc salts and / or crystalline layered silicates synthesized with one or more active and / or builder substances containing from 0.1 to 80% by weight of the zinc salts or crystalline layered silicates, particularly preferably from 0.2 to 70% by weight and particularly preferably from 0.5 to 60% by weight, in each case based on the total weight of the particles.
- the abovementioned particulate compounds are obtained according to the invention preferably by spray drying and / or granulation and / or extrusion and / or roller compaction and / or tabletting and / or solidification and / or crystallization, but in particular by spray drying and / or granulation.
- an aqueous slurry (“slurry") is prepared in a first step of the process, which may contain other thermally stable active and / or builders in addition to the zinc salts according to the invention, which neither volatilize nor decompose under the conditions of spray drying and this then transported via pumps in the spray tower and sprayed via located in the head of the tower nozzles.
- Ascending hot air dries the slurry and evaporates the adhering water so that the detergent ingredients at the outlet of the tower are obtained as fine powders. These may, if necessary, further Tempertur labile ingredients such.
- As bleaching agents or perfumes are admixed.
- compositions according to the invention can be carried out not only by the spray drying described above but also by a fluidized bed process in which fine granular bulk material stored on horizontal, perforated trays, which besides the zinc salts according to the invention can contain further active and / or builder substances, from below by gases (eg hot air) is flowed through. Under certain flow conditions, this creates a state that is similar to that of a boiling liquid; the layer causes bubbles, and the particles of the bulk material are within the layer in a constant, swirling up and down movement and remain so to speak in the balance.
- gases eg hot air
- the large surface of the fluidized material then allows, for example, the reaction with other substances such as solvents, solutions of active and / or builders, liquid active substances or other ingredients that are present as solid at room temperature, by increasing the temperature and / or addition of very limited amounts of liquid But soften additives at least superficially and / or form an adhesive and adhesive strength under the influence of temperature.
- Typical examples of the aforementioned substances are water and aqueous solutions, for example, aqueous solutions of zinc salts according to the invention can be used at room temperature liquid or solid surfactant compounds, especially nonionic surfactants, or polymer compounds of synthetic and / or natural origin, for example (co) -polymere carboxylates ,
- Another preferred procedure for the granulation is the use of mixers / compressors, as they are provided for this purpose, among other providers, for example, by the company Lödige and which are particularly suitable for the production of preformed particles according to the invention, as by the user Variation of different process parameters such as the number of revolutions of the mixer, the residence time of the individual components, the dosing of individual components during the mixing process, the geometry of the mixing elements used or the energy input offer the possibility of targeted control of the product properties of the resulting granules.
- the grain size and / or density of granules can be influenced in this way, and the assembly of zinc salts according to the invention with one or more further active and / or builder substance (s) in the aforementioned mixers / compressors is therefore within the scope of the present invention particularly preferred.
- Preferred in the context of the present invention are therefore mixtures of silicates and / or zinc salts with further active and / or builders, characterized in that the bulk densities of the individual components mixed with one another by a maximum of 200 g / l, preferably by a maximum of 150 g / l, preferably differ by a maximum of 100 g / l and in particular by a maximum of 50 g / l.
- the scaffolding and / or active substances which can be used in the above-described formulation of preferred automatic dishwashing compositions according to the invention include, among other conventional ingredients of detergents, for example builders, co-builders, surfactants, bleaches, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors or polymers.
- those automatic dishwashing or machine dishwashing auxiliaries are particularly preferred in the context of the present invention in which they are compounded with one or more active and / or builder substances
- Zinc salt compounds, active and / or builders from the group of phosphates, carbonates, bicarbonates, sulfates, silicates, citrates, citric acid, acetates, preferably in amounts of 20 to 99 wt.%, Particularly preferably from 30 to 98 wt .-% and particularly preferably from 40 to 95 wt .-%, each based on the total weight of the particles.
- active and / or builder substances which are particularly preferred for the preparation of the zinc salts in the context of the present invention are the surfactants, preferably the nonionic surfactants, and / or the polymeric carboxylates, in particular the polysulfocarboxylates.
- silicates present in the machine dishwashing detergents or dishwashing auxiliaries according to the invention are also preferably packaged with other active ingredients or builders in these compositions, active substances or builders from the group of organic monocarboxylic or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids being used here ,
- a further preferred subject matter of the present application is therefore dishwasher detergents or automatic dishwasher detergents, characterized in that the crystalline layered silicate (s) of the general formula (Ia) with one or more further active and / or Framework substance (s), preferably with one or more further active and / or builders from the group of organic mono- or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids, in particulate form, as a compound.
- the particulate present, with one or more active and / or builders formulated zinc salts and / or crystalline layered silicates may be provided to protect environmental influences and thus to improve their storage stability or to influence the dissolution behavior with a coating (coating).
- Coating materials and methods for coating particulate agents are widely described in the literature and will be explained below only with respect to particularly preferred embodiments.
- fusible or softenable substances are particularly preferred.
- coating means in the context of the present invention, in addition to the coating of single or multiple sides or surfaces of a particulate, inventively prepared agent also a complete coating, so the envelope of this particulate article.
- fusible substances have a melting point above 30 ° C on.
- the ready-made zinc salts and / or crystalline layered silicates are to be released at different times, for example during the various rinses of a cleaning process, this can be done, for example, by the use of different fusible coatings which differ in their melting point, the melting points of these substances preferably being on the Adjusted temperature course of this cleaning process and the difference of the melting points is sufficient to ensure the separate dissolution of the individual matrices or coatings. If, for example, it is envisaged to release zinc salts and crystalline layer-form silicates at separate times, then such substances are preferred for the different coatings which, with respect to their melting point, are at least 5 ° C., preferably around 10 ° C., more preferably around 15 ° C.
- the melting point of at least one of the fusible substances forming a coating is below 30 ° C, while the melting point of at least one further substance forming another matrix or coating, above 30 ° C is.
- Such coatings can be applied, for example, by dipping, spraying or tumbling in a drum coater or coating pan. Particular preference is given to using waxes, paraffins, polyalkylene glycols, etc., as the meltable or softenable substances for the coatings.
- meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius.
- the meltable or softenable substances preferably have a melting range of between about 45 ° C and about 75 ° C. That is, in the present case, that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range.
- the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.
- waxes are understood to mean a series of naturally or artificially produced substances which generally melt above 40 ° C. without decomposition and are already relatively low-viscosity and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility.
- the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
- the natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe fat, mineral waxes such as ceresin or ozokerite (groundwax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
- vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax
- animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe
- the chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
- Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances for the compositions which cure by cooling, and compounds from other substance classes which meet the stated requirements with regard to the softening point.
- suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, commercially available under the name Unimoll 66 ® (Bayer AG) is available, proven.
- synthetic waxes made of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea) is available.
- esters of lower alcohols can be used with fatty acids from natural sources.
- This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate.
- Shellac for example shellac KPS three-ring SP (Kalkhoff GmbH) can also be used as meltable or softenable substances.
- Wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms.
- the wax alcohols are present, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes.
- wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melisyl alcohol.
- the enclosure of the assembled zinc salts or crystalline layered silicates can optionally also contain wool wax alcohols which are understood to be understood triterpenoid and steroid alcohols, for example lanolin, available, for example, under the trade designation Argowax ® (Pamentier & Co).
- wool wax alcohols which are understood to be understood triterpenoid and steroid alcohols, for example lanolin, available, for example, under the trade designation Argowax ® (Pamentier & Co).
- fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds may likewise be used as part of the meltable or softenable substances.
- meltable or softenable substances are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains, with polyethylene glycols having molecular weights between 1500 and 36,000 are preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred. Also, corresponding processes, which are characterized in that the plastically deformable mass (s) at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains / are preferred.
- Coating agents which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as sole meltable or softenable substances are preferred here.
- Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which have the following general formula satisfy, where n can take values between 10 and 2000.
- Preferred PPG have molecular weights between 1000 and 10,000, corresponding to values of n between 17 and about 170.
- Polyethylene glycols which can preferably be used according to the invention are polymers of ethylene glycol, those of the general formula H- (O-CH 2 -CH 2 ) n -OH satisfy, where n can take values between 20 and about 1000.
- the abovementioned preferred molecular weight ranges correspond to preferred ranges of the value n in formula IV of about 30 to about 820 (exactly: from 34 to 818), more preferably from about 40 to about 150 (exactly: from 45 to 136). and especially from about 70 to about 120 (exactly: from 68 to 113).
- the coating materials contain paraffin wax.
- paraffin waxes have the advantage over the other natural waxes mentioned that no hydrolysis of the waxes takes place in an alkaline detergent environment (as is to be expected, for example, in the case of wax esters), since paraffin wax contains no hydrolyzable groups.
- Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes.
- the paraffin to be used according to the invention preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent leaving unwanted wax residue on the surfaces to be cleaned or the property to be cleaned. Such wax residues usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided.
- melt or softenable substances to be processed contain at least one paraffin wax with a melting range of 50 ° C to 60 ° C, preferred coating materials being characterized in that they contain a paraffin wax having a melting range of 50 ° C to 55 ° C.
- the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible.
- the more solid wax constituents in a wax at room temperature the more useful it is within the scope of the present invention.
- the proportion of solid wax constituents increases, the end-of-processability of the process end products increases against impacts or friction on other surfaces, resulting in longer-lasting protection.
- High levels of oils or liquid wax components can weaken the coating, opening pores and exposing the active ingredients to environmental conditions.
- the meltable or softenable substances may contain, in addition to paraffin as the main constituent, one or more of the abovementioned waxes or waxy substances.
- the mixture forming the meltable or softenable substances should be such that the composition and the coating formed therefrom are at least substantially insoluble in water.
- the solubility in water at a temperature of about 30 ° C should not exceed about 10 mg / l and preferably be below 5 mg / l.
- meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances.
- Preferred coating materials to be processed according to the invention are characterized in that they contain, as meltable or softenable substances, one or more substances having a melting range from 40 ° C. to 75 ° C. in amounts of from 6 to 30% by weight, preferably from 7.5 to 25 Wt.% And in particular from 10 to 20 wt .-%, each based on the weight of the coating material.
- the dissolution behavior of the zinc salt or silicate compounds can also be influenced by the abovementioned compaction methods.
- aids such as binders
- compacted silicates, in particular disilicates, and / or polycarboxylates and / or mixtures of various polycarboxylates are suitable as "depot substances" for the zinc salts or crystalline layered form due to their delayed solution / dispersion or due to gelling of these substances or substance mixtures in aqueous liquor silicates.
- polymer matrices are particularly preferred form of compounding machine dishwashing or automatic dishwashing auxiliaries according to the present invention.
- Such polymer matrices are universally applicable in various programs, are characterized by a simple and cost-effective method of preparation and may contain varying amounts of active agent.
- the preferred subject matter of the present application is therefore furthermore dishwasher detergents or dishwashing auxiliaries in which the zinc salt (s) and / or the crystalline layered silicate (s) are packaged in a polymer matrix.
- the active ingredient-containing polymer matrices can be produced cheaply and in a high variety of forms.
- the composition of the present invention can even be formulated as a package of automatic dishwashing detergents or as a basket into which the compositions are incorporated. It is also possible to combine both types of incorporation by, for example, a carrier basket of water-insoluble, active ingredient-containing polymer matrix containing a polymer body of water-soluble, active ingredient-containing polymer matrix.
- Such products can release different levels of active agents from the various matrices at different times, resulting in an optimal concentration of active ingredient at each point in the cleansing program.
- both the zinc salt and the silicates are packaged in a polymer matrix
- this preparation in preferred embodiments of the present invention can take place both in the same polymer matrix and in different matrices, which means that the zinc salt can be converted, for example, into polymer A pre-assembled, while the silicate was formulated in a polymer B.
- zinc salt and silicate can also be formulated by means of the same polymer, but in separate matrices.
- compositions of the invention can therefore be realized both with water-insoluble and with water-soluble polymers or mixtures thereof.
- Preferred automatic dishwashing or machine dishwashing aids are characterized in that the polymer matrix comprises one or more water-soluble polymer (s).
- the polymer matrices according to the invention can be formulated universally. For example, it is possible to provide pre-softeners, pre-rinsing agents, cleaning agents for the main rinse or rinse aid according to the invention.
- compositions according to the invention may also be combination products which combine two or more of the aforementioned agents.
- the formulation of inventive compositions as an addition product, which is hung for example in the dishwasher is easily possible.
- the active ingredient-containing polymer matrix can be particulate incorporated into the compositions of the invention, but it can also be a compact molded body, for example, either a core which fills a trough of a detergent tablet, or a shaped product, which as an addition product equal to a deodorant hanger in the dishwasher is introduced.
- baskets which are suitable for receiving detergent tablets can be prepared from the active ingredient-containing polymer matrix.
- the active ingredient-containing polymer matrix can also be used as a packaging for automatic dishwasher detergents. This is especially true for completely water-soluble active substance-containing polymer matrices attractive, since the consumer does not have to unpack the product, the direct contact with the product, which is perceived as undesirable, avoids and other packaging materials are saved.
- the polymer matrix of the agents preferred according to the invention comprises from 5 to 99.5% by weight of one or more polymers.
- polymers in the context of the following application, based on the IUPAC definition, denotes substances which are composed of a collective of chemically uniformly structured, but generally differing in terms of degree of polymerization, molecular weight and chain length macromolecules. According to this IUPAC definition, which does not take into account the concept of the term, a polymer "is a substance composed of a plurality of molecules in which one or more types of atoms or atomic groups (so-called constituent units, basic building blocks or repeating units) are repeated are strung together ".
- the different sized macromolecules of a polymer are composed of so many identical or similar low molecular weight building blocks (monomers) that the physical properties of the substance, especially the viscoelasticity, do not change noticeably with a slight increase or decrease in the number of building blocks.
- the size of the macromolecules implies that the end groups have relatively little effect on the properties of the polymers, so that their explicit specification in the structural formulas given below is usually dispensed with.
- the matrix-forming polymers of the compositions according to the invention may be of natural or synthetic origin.
- Preferred agents according to the invention are characterized in that the polymer matrix from 7.5 to 95 wt .-%, preferably 10 to 90 wt .-%, particularly preferably 12.5 to 85 wt .-%, more preferably 15 to 82.5 wt .-% and in particular 20 to 80 wt .-% of one or more polymers, wherein the weights are based on the active ingredient-containing polymer matrix.
- the average molar mass of the polymers contained in the preferred agents according to the invention is preferably at least 5000 g / mol, particularly preferably at least 10,000 g / mol and in particular at least 12,000 g / mol.
- the agents preferred according to the invention may contain both water-insoluble and water-soluble polymers and mixtures of these polymers.
- the polymer matrix comprises one or more water-insoluble polymers from the group polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polyurethanes, polyamides and mixtures thereof.
- the active ingredient-containing polymer matrix has, in addition to the polymer (s), a content of at least one zinc salt and / or at least one crystalline layered silicate of the general formula (I) or of the general formula (Ia) which can be liberated from the matrix.
- Agents preferred according to the invention are characterized in that they comprise at least one zinc salt and at least one crystalline layered silicate of the general formula (I) or the general formula (Ia), the sum of the proportions by weight of these constituents being from 1 to 90% by weight, preferably 1.5 to 80 wt .-%, particularly preferably 2 to 70 wt .-%, more preferably 2.5 to 60 wt .-% and in particular 3 to 50 wt .-%, each based on the total weight of the active ingredient-containing polymer matrix is.
- the automatic dishwasher detergents or automatic dishwashing auxiliaries according to the invention can contain the active ingredient-containing polymer matrix in different amounts.
- the proportions of the active ingredient-containing polymer matrix can vary in the overall composition.
- Preferred compositions according to the invention are those which, based on the total mass of the composition, are 1 to 40% by weight, preferably 1.5 to 35% by weight, more preferably 2 to 30% by weight and in particular 2.5 to 20 Wt .-% of the active ingredient-containing polymer matrix included.
- Particularly preferred polymer matrices contain at least one zinc salt in such amounts that the composition comprises zinc in oxidized form in proportions by weight of from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2 wt .-%, each based on the total weight of the polymer matrix contains.
- compositions according to the invention do not entail any restriction with regard to the forms of preparation or the formulations of these compositions.
- pre-soaking or pre-rinsing products, rinse aid, machine care or additional products can be provided as a composition according to the invention.
- a preferred embodiment of the composition of the invention provides that the polymer matrix is provided as a separate part to be introduced into the dishwasher, which releases the agents from the polymer matrix over several rinse cycles.
- This molding can either be a Dosierkörbchen for other products, such as the cleaner, but it can also embody the added benefit of glass preservation as a separate and independent molding.
- Possible shapes are based, for example, on the known dishwasher Dodorantien.
- Visually attractive is the design of the plastic part in translucent, opalescent or completely clear form, for example in the form of a stylized diamond.
- the active ingredient-containing polymer matrices can be easily converted by conventional methods.
- the shaping processing takes place according to the usual in the plastics processing industry process, in particular, the film production and processing, blow molding and injection molding are preferred. All methods have in common that a plastic granules are melted by means of an extruder and fed to forming tools. In this case, the plastic granules may already contain the agents for glass corrosion inhibition, but these can also be added during the melting in the extruder, which allows a particularly cost-effective production of inventively preferred active ingredient-containing polymer matrices.
- the automatic dishwasher detergents or automatic dishwashing auxiliaries according to the invention are packaged in a manner which makes it possible to selectively apply and meter the active substances contained in these agents.
- pen-shaped offer form similar to a glue stick, do not change their spatial-geometric shape during storage and transport, but these, the offer form is moved under the influence of pressure over a surface, in their contact area loses with the surface due to the shear forces occurring there.
- the agent is smeared as a result of the shearing forces acting on the surface and remains there after the end of the action of the shear forces in its new spatial-geometric shape, so in turn is dimensionally stable.
- Penetration number in the context of the present invention is the numerical value which results when determining the hardness of the agents according to the invention by means of a texture analyzer, model TA-XT2-I from Stable Micro Systems. To perform this measurement, the following test parameters are set: TA Fashion: Mass force in compression direction TA option: Simple test Trigger Value 0.2 g PPS 200
- the penetration rate is determined by pressing a specific measuring tool (TA-15 45 ° cone made of stainless steel) at a defined feed rate (0.5 mm / s) to a defined penetration depth (5.0 mm) into the test material and then with a defined speed (0.2 mm / s) is pulled out of this material.
- the tested test materials had a temperature of 23 ° C, the measurements were carried out at 20 ° C room temperature. Based on the test setup described above, the measuring instrument determined a numerical value in units of grams [g]. This numerical value is referred to in the context of the present application as a penetration number.
- the preferred dimensionally stable automatic dishwashing or machine dishwashing auxiliary penetration numbers of 200 to 1000 g, preferably from 250 to 900 g, more preferably from 300 to 800 g and in particular from 350 to 700 g.
- Another preferred subject of the present invention are therefore automatic dishwashing detergents or dishwashing auxiliaries according to the invention which are dimensionally stable and have a penetration number of from 200 to 1000 g, preferably from 250 to 900 g, more preferably from 300 to 800 g and in particular from 350 to 700 g.
- dimensionally stable in the context of the present invention denotes automatic dishwashing detergents or dishwashing auxiliaries which have an intrinsic dimensional stability which enables them, under normal conditions of manufacture, storage, transport and handling by the consumer, to be stable against breakage, to have non-disintegrating spatial form, which does not change even under the conditions mentioned for a long time, that is under the usual conditions of manufacture, storage, transport and handling by the consumer persists in the caused by the production spatial-geometric shape that is, for example, does not melt.
- the penetration number of 200 to 1000 g which is characteristic for preferred agents according to the invention, can not be realized in their pure form by active substances such as zinc salts or layered silicates. It is therefore necessary to provide a carrier material or matrix material for these active substances, which corresponds to the stated physical requirements for an agent according to the invention.
- a carrier material or matrix material for these active substances, which corresponds to the stated physical requirements for an agent according to the invention.
- such a matrix should be compatible with active agents contained in it, ie in particular should not react with them, but stabilize them.
- the carrier materials should not jeopardize the intended cleaning process, ie they should also be compatible with all other substances used during the cleaning and / or maintenance process.
- the matrix material should preferably be water-soluble or water-dispersible in order to prevent the occurrence of residues to avoid after the application of the agent according to the invention.
- preferably dimensionally stable dishwashing detergents or dishwashing auxiliaries are characterized in that they contain polyvinylpyrrolidone (s) and / or polyvinyl alcohol (s) and / or polyvinyl acetate (s) and / or polyacrylate (s) and / or Polyalkylene glycol (s) and / or fat (s) and / or fatty acid (s) and / or fatty acid esters and / or fatty acid amide (s) and / or fatty alcohols and / or wax (s) and / or parrafin (s) and / or Wax alcohols and / or surfactant (s), preferably nonionic (s) surfactant (s), and / or dextrin (s) and / or starch ethers, wherein the proportion by weight of this component / these components in the total weight of dimensionally stable machine dishwashing and / or Dishwashing auxiliary
- Automatic dishwashing detergents or automatic dishwashing auxiliaries according to the invention can also be formulated in the form of liquid or flowable agents, in addition to the solid or dimensionally stable forms described.
- the automatic dishwashing or machine dishwashing aids therefore have a viscosity of from 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and in particular from 1300 to 100,000 mPas.
- the viscosity of the compositions according to the invention is measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3).
- the term "liquid or flowable agents" will be used hereafter for agents which have a viscosity of from 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and especially from 1300 to 100,000 mPas.
- such preferred liquid or flowable compositions of the invention contain one or more non-aqueous solvents.
- non-aqueous solvents are derived, for example, from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides.
- nonaqueous solvents which are water-soluble, "water-soluble" solvents in the sense of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.
- Suitable nonaqueous solvents are preferably from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the given concentration range.
- the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy
- Nonionic surfactants which are liquid at room temperature are also preferred nonaqueous solvents in the context of the application.
- a liquid or free-flowing machine dishwashing detergent or machine dishwashing auxiliary which is particularly preferred in the context of the present invention is characterized in that it contains nonaqueous solvents, the solvent (s) preferably being selected from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate , Triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol, and n-propanol and / or iso-propanol.
- the solvent (s) preferably being selected from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate , Triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol, and n-propanol and / or iso-propanol.
- Polyethylene glycols which can preferably be used according to the invention are liquid at room temperature.
- PEG are polymers of ethylene glycol which are of the general formula (II) H- (O-CH 2 -CH 2 ) n -OH (II) n, where n can assume values between 1 (ethylene glycol, see below) and about 16.
- n can assume values between 1 (ethylene glycol, see below) and about 16.
- polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone -Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
- Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C.
- Glycerol was originally a by-product of fat saponification but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO 3 contact via the step of the glycide.
- Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO 2 to glycerol carbonate. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm -3 , which boils at 125-130 ° C (0.15 mbar).
- Ethylene Glycol (1,2-Ethanediol, "Glycol”) is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113.
- the solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C.
- ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.
- 1,3-Propanediol trimethylene glycol
- 1,0597 a neutral, colorless and odorless, sweet-tasting liquid of density 1,0597, which solidifies at -32 ° C and boils at 214 ° C.
- the preparation of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation.
- 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C.
- 1,2-Propanediol is prepared from propylene oxide by water addition.
- Propylene carbonate is a water-bright, easily mobile liquid, with a density of 1.21 gcm -3 , the melting point is -49 ° C, the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO 2 at 200 ° C and 80 bar.
- the nonaqueous solvent (s) is / are in amounts of from 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, more preferably from 1 to 50 wt .-%, most preferably from 2 to 40 wt .-% and in particular from 2.5 to 30 wt .-%, each based on the total agent included.
- non-aqueous is to be understood as meaning a state in which the content of free water in the agents is significantly below 5% by weight, based on the agent. It is preferred that the level of the automatic dishwashing or machine dishwashing aids of the invention be free, i. not present in the form of water of hydration and / or water of constitution below 10% by weight, preferably below 8% by weight and in particular even below 6% by weight, in each case based on the agent. Accordingly, water can be introduced into the agent substantially only in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as solid, but not as a liquid, solution or dispersion.
- preferred liquid or free-flowing automatic dishwasher detergents or dishwashing auxiliaries according to the invention comprise one or more nonionic surfactants, in short nonionic surfactants.
- the amounts in which the nonionic surfactants are used are according to the invention preferably between 5 and 30% by weight, whereby according to the invention those agents which are 1 to 25% by weight are particularly preferred, preferably 2 to 22.5% by weight, particularly preferably 3 to 20% by weight and in particular 4 to 17.5% by weight of nonionic surfactant (s).
- nonionic surfactants For a detailed description of these nonionic surfactants, reference is made to the following remarks on the preferred washing or cleaning-active ingredients of preferred compositions according to the invention in order to avoid repetitions at these points.
- compositions according to the invention may comprise further ingredients, the use of which, for example, the settling behavior or the pourability or flowability can be specifically controlled.
- the settling behavior or the pourability or flowability can be specifically controlled.
- non-aqueous systems in particular combinations of structurizers and thickeners have proven to be useful.
- the structurant a) comes from the group of bentonites and / or at least partially etherified sorbitols. These substances are used to ensure the physical stability of the agents and to adjust the viscosity. Although conventional thickeners such as polyacrylates or polyurethanes fail in non-aqueous media, the viscosity control with the substances mentioned succeeds in the non-aqueous system.
- Bentonites are contaminated clays caused by the weathering of volcanic tuffs. Due to their high content of montmorillonite, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonite according to the intended use. Bentonites are common as clay constituents in tropical soils and are used as sodium bentonite, e.g. mined in Wyoming / USA. Sodium bentonite has the most favorable application properties (swelling capacity), so that its use is preferred in the context of the present invention. Naturally occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. The naturally obtained Ca-bentonites are artificially converted by exchange of Ca for Na in the more swellable Na-bentonites.
- montmorillonites which can also be used in their pure form in the context of the present invention.
- Montmorillonites are too the clay silicates and here to the dioctahedral smectites belonging clay minerals, which crystallize monoclinic pseudohexagonal.
- Preferred automatic dishwashing detergents or dishwashing auxiliaries are characterized in that montmorillonites are used as structurants.
- Montmorillonites have a three-layer structure consisting of two tetrahedral layers, which are electrostatically crosslinked via the cations of an octahedral intermediate layer. The layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, ⁇ -picolin, ammonium compounds, hydroxy-aluminosilicate ions, etc.
- the above. Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity.
- Al can be exchanged for Mg, Fe 2+ , Fe 3+ , Zn, Cr, Cu and other ions.
- a negative charge of the layers results, which is balanced by other cations, especially Na + and Ca 2+ .
- At least partially etherified sorbitols can be used as structurants.
- Sorbitol is a hexavalent 6-valent alcohol (sugar alcohol) that is relatively easy to split one or two moles of water intramolecularly and forms cyclic ethers (eg, sorbitan and sorbide). The removal of water is also possible intermolecularly, forming noncyclic ethers of sorbitol and the alcohols in question. Again, the formation of mono-ethers and bis-ethers is possible, with higher degrees of etherification such as 3 and 4 may occur.
- At least partially etherified sorbitols to be used in the context of the present invention are doubly etherified sorbitols, of which the dibenzylidenesorbitol is particularly preferred.
- automatic dishwashing detergents which contain twice etherified sorbitols, in particular dibenzylidenesorbitol, as structurants are preferred.
- the preferred liquid or flowable compositions according to the invention may contain the structurants in amounts of from 0.1 to 1.0% by weight, based on the total agent and on the active substance of the structurizer.
- Preferred agents contain the modifier in amounts of from 0.2 to 0.9% by weight, preferably in amounts of from 0.25 to 0.75% by weight and in particular in amounts of from 0.3 to 0.5% by weight. %, in each case based on the total mean.
- the preferred liquid or flowable agents according to the invention may contain inorganic salts from the group of carbonates, sulfates and amorphous or crystalline disilicates.
- the said salts of all metals can be used, the alkali metal salts being preferred.
- Alkaline carbonate (s), alkali metal sulphate (s) and / or amorphous (s) and / or crystalline alkali metal disilicate (s), preferably sodium carbonate, sodium sulphate and / or amorphous or crystalline sodium disilicate, are particularly preferably used in the context of the present invention as thickener ,
- the preferred liquid or flowable compositions according to the invention contain the thickeners in amounts of from 5 to 30% by weight, based on the total agent.
- Particularly preferred compositions contain the thickener (s) in amounts of 7.5 to 28 wt .-%, preferably in amounts of 10 to 26 wt.% And in particular in amounts of 12.5 to 25 wt .-%, each based on the entire means.
- the solids present in the agents according to the invention are used as finely divided as possible. This is particularly advantageous in the case of inorganic thickeners and bleaching agents.
- automatic dishwashing detergents according to the invention are preferred in which the average particle size of the bleaching agents and thickeners as well as the optionally use builder is less than 75 ⁇ m, preferably less than 50 ⁇ m and in particular less than 25 ⁇ m.
- liquid automatic dishwashing compositions according to the invention may also contain other viscosity regulators or thickeners for adjusting a possibly desired higher viscosity.
- viscosity regulators or thickeners for adjusting a possibly desired higher viscosity.
- all known thickening agents can be used, ie those based on natural or synthetic polymers.
- Naturally derived polymers which are used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.
- Modified natural products come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers.
- preferred liquid or free-flowing automatic dishwashing or machine dishwashing aids comprise, as thickening agents, hydroxyethylcellulose and / or hydroxypropylcellulose, preferably in amounts of from 0.01 to 4.0% by weight, more preferably in amounts of from 0.01 to 3, 0 wt .-% and in particular in amounts of 0.01 to 2.0 wt.%, Each based on the total agent.
- a large group of thickeners which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
- Thickeners from said substance classes are widely available commercially and are sold for example under the trade name Acusol ® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ® -GT- 282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ® -xg (anionic heteropolysaccharide based on ⁇ -D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH ) deuteron ® -XN (nonionic polysaccharide Schoner GmbH), DICRYLAN ® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® -91 (ethylene-maleic
- a preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons.
- Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
- the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
- thickeners are polyurethanes or modified polyacrylates, which, based on the total agent, for example, in amounts of 0.1 to 5 wt .-% can be used.
- Polyurethanes are prepared by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula IV in which R 1 is a low molecular weight or polymeric diol radical, R 2 is an aliphatic or aromatic group and n is a natural number.
- R 1 is preferably a linear or branched C 2-12 -alk (en) yl group, but may also be a residue of a higher-valent alcohol, whereby crosslinked polyurethanes are formed, which differ from the formula VIII given above in that the Rest R 1 further -O-CO-NH groups are bonded.
- TDI 2,4- and 2,6-toluene diisocyanate
- MDI C 6 H 4 -CH 2 -C 6 H 4
- thickener based on polyurethane are, for example, under the names Acrysol ® PM 12 V (mixture of 3-5% modified starch and 14-16% polyurethane resin in water, Rohm & Haas), Borchigel ® L75-N (non-ionic polyurethane dispersion, 50% in water, Borchers), Coatex ® BR-100-P (PUR-dispersion, 50% in water / butyl glycol, Dimed), Nopco ® DSX-1514 (polyurethane dispersion, 40% in water / Butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% polyurethane emulsion in water / Digylcolether, Rohm & Haas) and Rilanit ® VPW-3116 (polyurethane dispersion, 43% in water, Henkel) available.
- Acrysol ® PM 12 V mixture of 3-5% modified starch and 14-16% polyurethane resin in
- aqueous dispersions when using aqueous dispersions, care must be taken that the water content of the agents according to the invention remains within the abovementioned limits. If the use of the aqueous dispersions for these reasons is not possible, dispersions in other solvents, or even the solids can be used.
- Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula V.
- R 3 is H or a branched or unbranched C 1-4 -alk (en) yl radical
- X is NR 5 or O
- R 4 is an optionally alkoxylated branched or unbranched, possibly substituted C 8-22 -alk (s ) ylrest
- R 5 is H or R 4 and n is a natural number.
- such modified polyacrylates are esters or amides of acrylic acid or of an ⁇ -substituted acrylic acid. Preferred among these polymers are those in which R 3 is H or a methyl group.
- Preferred alkoxylation levels are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.
- the designation of the radicals bound to X represents a statistical mean value which, in individual cases, can vary with regard to chain length or degree of alkoxylation.
- the formula V indicates only formulas for idealized homopolymers. In the context of the present invention, however, it is also possible to use copolymers in which the proportion of monomer units which satisfy the formula V is at least 30% by weight. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO - groups.
- Modified polyacrylates which are preferably used for the purposes of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula Va in which R 4 is a preferably unbranched, saturated or unsaturated C 8-22 -alkenoyl radical, R 6 and R 7 independently of one another are H or CH 3 , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number between 2 and 30, preferably between 10 and 20.
- Products of formula Va are commercially available for example under the name Acusol ® 820 (Rohm & Haas) in the form of 30 wt .-% strength dispersion in water available.
- R 4 is a stearyl
- R 6 is a hydrogen atom
- R 7 is H or CH 3
- the degree of ethoxylation a is 20.
- the above water content of the Mitttel said applies.
- preferred liquid or free-flowing automatic dishwasher detergents or dishwashing auxiliaries are characterized in that they additionally contain 0.01 to 5 wt.%, Preferably 0.02 to 4 wt.%, Particularly preferably 0.05 to 3 wt .-% and in particular 0.1 to 1.5 wt .-%, of a polymeric thickener, preferably from the group of polyurethanes or modified polyacrylates, with particular preference to thickeners of formula VI in the R 3 is H or a branched or unbranched C 1-4 -alk (en) yl radical, X is NR 5 or O, R 4 is an optionally alkoxylated branched or unbranched, possibly substituted C 8-22 -alk (s ) yl radical, R 5 is H or R 4 and n is a natural number.
- a polymeric thickener preferably from the group of polyurethanes or modified polyacrylates
- X is NR 5 or O
- R 4 is an optionally alk
- the solid or dimensionally stable and liquid or free-flowing automatic dishwashing or dishwashing auxiliaries according to the invention can be offered to the consumer in conventional containers, for example bottles, screw jars, canisters, balloons, cups or spray vessels, from which they are dosed for use. Higher viscosity products can also be offered in tubes or dispensers as known from toothpaste or sealants.
- Such containers are today usually made of non-water-soluble polymers and may for example consist of all common water-insoluble packaging materials, which are well known to those skilled in the art. In particular, polymers based on hydrocarbons may be mentioned as preferred polymers.
- Particularly preferred polymers include polyethylene, polypropylene (more preferably oriented polypropylene) and polymer blends such as blends of said polymers with polyethylene terephthalate. Also suitable are one or more polymers from the group consisting of polyvinyl chloride, polysulfones, polyacetals, water-insoluble cellulose derivatives, cellulose acetate, cellulose propionate, cellulose acetobutyrate and mixtures of said polymers or copolymers comprising said polymers.
- a particularly preferred embodiment of the present invention aims to provide the consumer with pre-portioned means according to the invention so that he can use the dosing advantages known to him from the "tablet" offering and combine them with the rapid dissolution and release rates and the performance advantages of the agents according to the invention can.
- Such pre-portioned agents according to the invention may also be present in water-insoluble packaging, so that the consumer must open them before use in a suitable manner.
- it is also possible and preferred to package portioned compositions according to the invention so that the consumer can give them without further handling steps directly, ie together with the packaging, into the dishwasher.
- Such packages include water-soluble or decomposable packages such as bags of water-soluble film (so-called pouches), bags or other packaging of water-soluble or decomposable nonwovens or flexible or rigid bodies of water-soluble polymers, preferably in the form of filled hollow body, which for example by deep drawing, injection molding , Blow molding, calendering, etc. can be made.
- a preferred subject matter of the present invention are therefore automatic dishwashing detergents or dishwashing auxiliaries according to the invention, which are packaged in portions in a water-soluble casing.
- Dishwasher detergents or dishwashing auxiliaries according to the invention preferably comprise a completely or partially water-soluble coating.
- the shape of the wrapper is not limited to specific shapes. Basically, all Archimedean and Platonic bodies, ie three-dimensional shaped bodies, come into question as forms of envelopment. Examples of the shape of the wrapper are capsules, cubes, spheres, ovoid moldings, cuboids, cones, rods or bags. Also hollow body with one or more compartments are suitable as a sheath for the Geschirthesesmittel.
- the wrappers are in the form of capsules, such as those used in pharmacy for the administration of drugs, spheres or bags. The latter are preferably welded or glued on at least one side, wherein the adhesive used in particularly preferred embodiments of the invention is an adhesive that is water-soluble.
- the water-soluble polymer material which partially or completely surrounds the automatic dishwashing or dishwashing auxiliary is a water-soluble packaging.
- This is understood to mean a flat part which partially or completely surrounds the dishwashing detergent.
- the exact form of such packaging is not critical and can be largely adapted to the conditions of use.
- processed plastic foils or sheets, capsules and other conceivable forms come into consideration for various forms (such as hoses, cushions, cylinders, bottles, disks or the like).
- Particularly preferred according to the invention are films which, for example, can be bonded and / or sealed to packagings such as hoses, cushions or the like, after they have been filled with partial portions of the cleaning agents according to the invention or with the cleaning agents according to the invention.
- plastic film packaging of water-soluble polymer materials are basically known from the prior art.
- both hollow body of any shape which can be produced by injection molding, bottle blowing, deep drawing, etc., as well as hollow body of films, in particular bags (so-called pouches) as packages for portioned inventive Medium preferred.
- Preferred automatic dishwasher detergents or dishwashing auxiliaries according to the invention are thus characterized in that the water-soluble casing comprises a bag of water-soluble film and / or an injection-molded part and / or a blow-molded part and / or a deep-drawn part.
- the one or more enclosures are / are completed. This has the advantage that the Geschirthesessch are optimally protected against the effects of the environment, especially against moisture.
- the invention can be further developed such that the detergents contain at least one gas to protect the contents of the enclosure (s) from moisture, see below.
- Suitable materials for the completely or partially water-soluble coating are in principle all materials in question, which can completely or partially dissolve in the aqueous phase under the given conditions of a washing process, rinsing or cleaning process (temperature, pH, concentration of detergent components).
- the polymer materials may particularly preferably the groups (optionally partially acetalized) polyvinyl alcohol, polyvinylpyrrolidone, poly-ethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, in particular modified starches, and mixtures (polymer blends, composites, coextrudates, etc.) of belong to the materials mentioned.
- Particularly preferred are gelatin and polyvinyl alcohols and the two materials mentioned in each case in combination with starch or modified starch.
- Preferred automatic dishwasher detergents or dishwashing auxiliaries according to the invention are characterized in that the coating comprises one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.
- the coating comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalised) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
- PVAL polyvinyl alcohol
- PVAL polyvinylpyrrolidone
- Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
- polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
- the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
- polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
- Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
- the water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
- the coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
- the 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% ,
- Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the coating, it being preferred according to the invention for the coating to comprise a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol . 1 , preferably from 11,000 to 90,000 gmol -1 , more preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
- the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
- polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
- Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
- particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
- polyvinyl alcohols are ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).
- the water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
- Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility.
- To use extremely advantageous are the reaction products of PVAL and starch.
- the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
- Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
- PVAL films under the name "SOLUBLON® ®” from Syntana bottlesgesellschaft E. Harke GmbH & Co. available PVAL films. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.
- PVP Polyvinylpyrrolidones
- PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
- Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
- Polyethylene oxides PEOX for short, are polyalkylene glycols of the general formula H- [O-CH 2 -CH 2 ] n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
- Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
- the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
- the use of gelatin as the water-soluble shell material is especially in pharmacy in the form of hard or soft gelatin capsules extremely widespread. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.
- dishwashing detergents whose packaging consists of at least partially water-soluble film of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and mixtures thereof.
- Starch is a homoglycan, wherein the glucose units are linked a-glycosidically.
- Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000).
- small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose.
- starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention.
- Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
- the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
- Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
- Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
- Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
- Preferred casings of at least partially water-soluble film comprise at least one polymer having a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol.
- the casing has different material thicknesses, automatic dishwashing agents or automatic dishwashing auxiliaries according to the invention being preferred in which the wall thickness of the casing is 10 to 5000 ⁇ m, preferably 20 to 3000 ⁇ m, particularly preferably 25 to 2000 ⁇ m and in particular 100 to 1500 ⁇ m ,
- the water-soluble film forming the coating preferably has a thickness of 1 to 300 ⁇ m, preferably 2 to 200 ⁇ m, more preferably 5 to 150 ⁇ m and in particular 10 to 100 ⁇ m, up.
- these water-soluble films can be produced by various production methods. Blow molding, calendering and casting processes should be mentioned here in principle.
- the films are blown starting from a melt with air through a mandrel to a hose.
- the calendering process which is likewise one of the preferred production processes
- the raw materials plasticized by suitable additives are atomized to form the films.
- an aqueous polymer preparation is placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film is peeled off as a film.
- this film is additionally powdered before or during the removal.
- an embodiment is preferred in accordance with which the coating is water-soluble as a whole, ie, dissolves completely under normal use during mechanical cleaning when the conditions for release are reached.
- Particularly preferred as completely water-soluble coatings z.
- gelatin capsules advantageously of soft gelatin, or bags of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably spheres of soft gelatin.
- the essential advantage of this embodiment is that the sheath within a practically relevant short time - as a non-limiting example can be a few seconds to 5 min - at least partially dissolves under precisely defined conditions in the cleaning liquor and thus according to the requirements, the coated content, ie the cleaning-active material or several materials in the fleet brings.
- the water-soluble coating comprises regions which are less soluble or not water-soluble or only water-soluble at relatively high temperatures and regions which are readily soluble in water or soluble in water at low temperature.
- the coating does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility.
- areas of good water solubility are to be distinguished from areas with less good water solubility, with poor or even absent water solubility or areas in which the water solubility reaches the desired value only at a higher temperature or only at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand.
- an envelope provided with pores or holes is formed, into which water and / or liquor can penetrate, which can dissolve washing-active, rinse-active or cleaning-active ingredients and remove them from the casing.
- wrapping systems in the form of multi-chamber bags or in the form of nested hollow bodies (eg balls: "onion system") can also be provided.
- controlled release systems of the detergent-active, rinse-active or cleaning-active ingredients can be produced.
- wraps can be provided in which a uniform polymeric material comprises small areas of incorporated compounds (for example, salts) which are more rapidly soluble in water than the polymeric material.
- incorporated compounds for example, salts
- several polymer materials with different water solubility can be mixed (polymer blend), so that the faster soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the slower soluble.
- the less readily water-soluble or water-insoluble areas or areas of the enclosure which are water-soluble at higher temperatures are areas of a material chemically substantially that of the water-soluble or water-soluble areas but has a higher layer thickness and / or has a modified degree of polymerization of the same polymer and / or has a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer.
- PVAL for example with saccharides, polysaccharides, such as starch
- the water-soluble shell material is preferably transparent.
- transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%.
- a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.
- Dishwashing detergents according to the invention which are packaged in transparent envelopes or containers, can contain a stabilizing agent as an essential constituent.
- Stabilizing agents in the context of the invention are materials which protect the detergent components in their water-soluble, transparent sheaths from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
- antioxidants are particularly suitable stabilizing agents in the context of the invention.
- the formulations may contain antioxidants.
- antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
- Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic palmitate, organosulfur compounds such as the esters of 3,3'-thiodipropionic acid with C 1-8 alkanols, especially C 10-18 alkanols, metal ion deactivators capable of auto-oxidation catalyzing metal ions such as Copper, such as nitrilotriacetic acid and its derivatives and their mixtures.
- Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.
- UV absorbers can improve the light stability of the formulation ingredients. These are understood to be organic substances (light protection filters) which are able to absorb ultraviolet rays and to release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
- substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ® Fast H), phenyl-substituted in the 3-position acrylates (cinnamic acid derivatives) , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's urocanic acid suitable.
- the biphenyl and especially stilbene derivatives which are available commercially as Tinosorb ® FD or Tinosorb ® FR available ex Ciba.
- 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3- (4-methylbenzylidene) camphor may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl sal
- 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
- Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
- UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds.
- the UV-A and UV-B filters can also be used in mixtures be used.
- insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose.
- suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
- silicates (talc) barium sulfate or zinc stearate can be used.
- the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
- the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
- the pigments can also be surface-treated, ie hydrophilized or hydrophobized.
- Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck).
- Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones.
- micronized zinc oxide is used.
- UV absorbers may be present in the dishwashing detergents in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight.
- fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives.
- fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives.
- Fluorescent substances can be present in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.
- the abovementioned stabilizers are used in any mixtures.
- the stabilizers are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.
- preferred automatic dishwashing or machine dishwashing aids comprise at least one washing or cleaning substance from the group of bleaches, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, hydrotropes, Foam inhibitors, antimicrobial agents, germicides, fungicides, corrosion inhibitors, non-aqueous solvents.
- a further subject of the present application is the use of a machine dishwashing detergent or automatic dishwashing auxiliary according to the invention for reducing the glass corrosion in automatic dishwashing.
- the table shows that the machine dishwashing detergent according to the invention, which contains the combination of a zinc salt and a crystalline layered silicate, under the conditions mentioned significantly better Galskorrosionseigenschaften than dishwashing detergents containing only zinc salt or only silicate.
- the corrosion-inhibiting effect of the active ingredient combination of zinc salt and silicate is significantly above the sum of the effects observed for the individual substances.
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Abstract
Description
Die vorliegende Erfindung liegt auf dem Gebiet der maschinellen Geschirrspülmittel. Insbesondere betrifft die vorliegende Erfindung maschinelle Geschirrspülmittel, die Zinksalze sowie bestimmte Silikate enthalten.The present invention is in the field of automatic dishwashing detergents. In particular, the present invention relates to automatic dishwashing detergents containing zinc salts and certain silicates.
Mit der fortschreitenden Automatisierung verschiedenster Wasch- und Reinigungsprozesse in Haushalt und Industrie haben maschinelle Wasch- und Reinigungsmittel für Textilien und Geschirr in den vergangenen Jahrzehnten zunehmend an Bedeutung gewonnen.With the progressive automation of various washing and cleaning processes in the home and industry, machine washing and cleaning agents for textiles and tableware have become increasingly important in recent decades.
Die für das maschinelle Geschirrspülen erforderlichen sogenannten niederalkalischen Reiniger enthalten als Alkaliträger häufig Mischungen aus Natriumdisilikat und Soda, Builder wie Citronensäure beispielsweise in Verbindung mit Polycarboxylaten sowie vorzugsweise schwachschäumende, nichtionische Tenside. Weiterhin können Bleichmittel, Bleichaktivatoren, Silber- und Korrosionschutzmittel und, zur Verstärkung des Reinigungsvermögens, Enzyme enthalten sein. In einem typischen maschinellen Reinigungsgang wird das in Körben eingestellte Geschirr durch intensiven Kontakt mit der wässrigen Reinigerlösung bei etwa 65°C und pH-Werten zwischen 9 und 11 gesäubert und anschließend klargespült.The so-called lower alkaline cleaners required for automatic dishwashing frequently contain mixtures of sodium disilicate and soda as alkali carriers, builders such as citric acid, for example in conjunction with polycarboxylates, and preferably low-foaming nonionic surfactants. Furthermore, bleaching agents, bleach activators, silver and corrosion inhibitors and, to enhance the cleaning power, enzymes may be included. In a typical machine cleaning cycle, the dishes set in baskets are cleaned by intensive contact with the aqueous detergent solution at about 65 ° C and pH values between 9 and 11 and then rinsed clear.
Ein wichtiges Kriterium zur Beurteilung eines maschinellen Geschirrspülmittels ist neben dessen Reinigungsleistung das optische Erscheinungsbild des trockenen Geschirrs nach erfolgter Reinigung. Eventuell auftretende Calciumcarbonat-Ablagerungen auf Geschirr oder im Maschineninnenraum können beispielsweise die Kundenzufriedenheit beeinträchtigen und haben damit ursächlichen Einfluß auf den wirtschaftlichen Erfolg eines derartigen Reinigungsmittels. Ein weiteres seit langem bestehendes Problem beim maschinellen Geschirrspülen ist die Korrosion von Glasspülgut, die sich in der Regel durch Auftreten von Trübungen, Schlieren und Kratzern aber auch durch ein Irisieren der Glasoberfläche äußern kann. Die beobachteten Effekte beruhen dabei im wesentlichen auf zwei Vorgängen, dem Austritt von Alkali- und Erdalkaliionen aus dem Glas in Verbindung mit einer Hydrolyse des Silikat-Netzwerks, zum anderen in einer Ablagerung silikatischer Verbindungen auf der Glasoberfläche. Zur Vermeidung derartiger Korrosionsvorgänge gibt es im Stand der Technik eine Reihe von Vorschlägen, beispielsweise bezüglich des Einsatzes von Zinksalzen.An important criterion for the evaluation of a machine dishwashing detergent, apart from its cleaning performance, is the visual appearance of the dry dishes after cleaning. Possibly occurring calcium carbonate deposits on dishes or in the machine interior, for example, affect customer satisfaction and thus have causal influence on the economic success of such a detergent. Another long-standing problem with automatic dishwashing is the corrosion of glassware, which can usually manifest itself by the appearance of turbidity, streaks and scratches, but also by iridescence of the glass surface. The observed effects are based essentially on two processes, the leakage of alkali and alkaline earth ions from the glass in conjunction with hydrolysis of the silicate network, on the other hand in a deposition of silicate compounds on the glass surface. To avoid such corrosion processes, there are in the prior art a number of proposals, for example with regard to the use of zinc salts.
Nach der Lehre der amerikanischen Patentschrift
Die europäische Patentanmeldung
Aber auch die Verwendung von Silikaten zur Verhinderung der Glaskorrosion beim maschinellen Geschirrspülen wurde beschrieben.However, the use of silicates to prevent glass corrosion in automatic dishwashing has also been described.
So offenbart die internationale Patentanmeldung
Gegenstand der internationalen Patentanmeldung
Der vorliegenden Erfindung lag nun die Aufgabe zugrunde, ein maschinelles Geschirrspülmittel bereitzustellen, das auch bei wiederholter Benutzung die Oberflächen gläsernen Spülguts nicht korrosiv verändert, insbesondere keine Trübungen, Schlieren oder Kratzer aber auch kein Irisieren der Glasoberflächen verursacht. Vorzugsweise sollte ein Additiv für ein maschinelles Geschirreinigungsmittel bereitgestellt werden, das sich als Bestandteil maschineller Geschirrspülmittel jedweder Angebotsform beispielsweise als Bestandteil von Pulver-, Tabletten-, Flüssigformulierungen, Reinlgungsschäumen oder Depotprodukten eignet, ohne diese rezepturell einzuschränken.It is an object of the present invention to provide a machine dishwashing detergent which does not corrosively change the surfaces of glassware, even after repeated use, in particular does not cause turbidity, streaks or scratches, nor iridescence of the glass surfaces. Preferably, an automatic dishwashing detergent additive should be provided which is suitable as a component of any type of dishwashing detergent, for example, as a component of powder, tablet, liquid formulations, cleansing foams or depot products, without limiting its formulation.
Es wurde nun gefunden, daß die zuvor genannten Aufgaben durch solche maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel gelöst werden, die neben mindestens einem löslichen Zinksalz weiterhin mindestens ein kristallines schichtförmiges Silikat enthalten.It has now been found that the abovementioned objects are achieved by means of such automatic dishwasher detergents or dishwashing auxiliaries which, in addition to at least one soluble zinc salt, also contain at least one crystalline layered silicate.
Gegenstand der vorliegenden Anmeldung sind daher maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, enthaltend mindestens ein lösliches Zinksatz sowie mindestens ein kristallines schichtförmiges Silikat der allgemeinen Formel (Ia)
NaMSixO2x+1 · y H2O (Ia),
worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, ist und y für eine Zahl von 0 bis 33 steht.The present application therefore relates to automatic dishwashing or dishwashing auxiliaries, comprising at least one soluble zinc salt and at least one crystalline layered silicate of the general formula (Ia)
NaMSi x O 2x + 1 · y H 2 O (Ia),
wherein M represents sodium or hydrogen, x is an integer from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33.
Als besonders vorteilhaft für die korrosionsinhibierende Wirkung erfindungsgemäßer Mittel hat es sich dabei erwiesen, wenn das/die lösliche(n) Zinksalz(e) sowie das/die kristalline(n) schichtförmige(n) Silikat(e) der allgemeinen Formel (la) im Verhältnis 10:1 bis 1:50, vorzugsweise von 5:1 bis 1:30 und insbesondere von 3:1 bis 1:10 in diesen Mitteln enthalten sind.It has proved to be particularly advantageous for the corrosion-inhibiting effect of agents according to the invention if the soluble zinc salt (s) and / or the crystalline layered silicate (s) of the general formula (Ia) Ratio 10: 1 to 1:50, preferably from 5: 1 to 1:30 and in particular from 3: 1 to 1:10 are contained in these agents.
Die kristallinen schichtförmigen Silikate der Formel (Ia) werden beispielsweise von der Fa. Clariant GmbH (Deutschland) unter dem Handelsnamen Na-SKS vertrieben, z.B. Na-SKS-1 (Na2Si22O45·xN2O, Kenyait), Na-SKS-2 (Na2Si14O29·xH2O, Magadiit), Na-SKS-3 (Na2Si8O17·xH2O) oder Na-SKS-4 (Na2Si4O9·xH2O, Makatit).The crystalline layer-form silicates of the formula (Ia) are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na 2 Si 22 O 45 .xN 2 O, Kenyaite), Na -SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 . xH 2 O, Makatite).
Für die Zwecke der vorliegenden Erfindung besonders geeignet sind Mittel, die kristalline Schichtsilikate der Formel (Ia) enthalten, in denen x für 2 steht. Von diesen eignen sich vor allem Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (ß-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5·H2O), Na-SKS-10 (NaHSi2O5·3H2O Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (δ-Na2Si2O5). Einen Überblick über kristalline Schichtsilikate findet sich z.B. in dem in "
Bevorzugte maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel weisen im Rahmen der vorliegenden Anmeldung einen Gewichtsanteil des kristallinen schichtförmigen Silikats der allgemeinen Formel (la) von 0,1 bis 20 Gew.-%, vorzugsweise von 0,2 bis 15 Gew.-% und insbesondere von 0,4 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht dieser Mittel, auf.In the context of the present application, preferred automatic dishwashing or automatic dishwashing assistants have a weight fraction of the crystalline layered silicate of the general formula (Ia) of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0 , 4 to 10 wt .-%, each based on the total weight of these agents, on.
Erfindungsgemäße Mittel enthalten neben den genannten kristallinen schichtförmigen Silikaten Zinksalze, wobei bevorzugt sowohl anorganische als auch organische Salze einsetzbar sind. Eine r nicht abschließende Auflistung einiger bevorzugter Zinksalze zeigt die folgende Tabelle.
Im Rahmen der vorliegenden Anmeldung sind die loslichen anorganischen Zinsalze, das heißt Salze, die in Wasser (20°C) eine Löslichkeit oberhalb 100 mg/L, vorzugsweise oberhalb 500 mg/L, besonders bevorzugt oberhalb 1 g/L und insbesondere oberhalb 5 g/L aufweisen, bevorzugter Bestandteil erfindungsgemäßer Mittel. Zu den bevorzugten löslichen anorganischen Salzen zählen das Zinkbromid, das zinkchlorid, das Zinklodid, das Zinknitrat und das Zinksulfat Ein weiterer bevorzugter Gegenstand der vorliegenden Anmeldung sind daher maschinelle Geschirrspülmittel oder maschmelle Geschirrspüthilfsmittel, welche mindestens ein Zinksalz ausgewählt aus der Gruppe der löslichen anorganischen Zinksalze, insbesondere aus der Gruppe Zinkbromid, Zinkchlorid Zinkiodid, Zinknitrat und Zinksulfat enthalten.In the context of the present application, the soluble inorganic interest salts, that is to say salts which in water (20 ° C.) have a solubility above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L, preferred component of agents according to the invention. The preferred soluble inorganic salts include the zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. Another preferred subject matter of the present application are therefore automatic dishwashing or dishwashing dishwashing aids containing at least one zinc salt selected from the group consisting of soluble inorganic zinc salts from the group zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
Lösliche organische Zinksalze weisen 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 auf (alle Löslichkeiten bei 20°C Wassertemperatur). Zu der Gruppe der löslichen organischen Zinksalze gehören beispielsweise das Zinkacetat, das Zinkacetylacetonat, das Zinkbenzoat, das Zinkformiat, das Zinklactat, das Zinkgluconat, das Zinkvalerat sowie das Zinksalze der p-Toluolsulfonsäure.Soluble organic zinc salts have a solubility above 100 mg / L in water, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The group of soluble organic zinc salts includes, for example, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc valerate, and zinc salt of p-toluenesulfonic acid.
In einer weiteren bevorzugten Ausführungsförm enthalten erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Gaschirrspülhilfsmittel daher mindestens ein Zinksalz ausgewählt aus der Gruppe der löslichen organischen Zinksalze, besonders bevorzugt aus der Gruppe der löslichen Zinksalze monomerer oder polymerer organischer Säuren, insbesondere aus der Gruppe Zinkacetat, Zinkacetylacetonat, Zinkbenzoat, Zinkformlat, Zinklactat, Zinkgluconat, Zinkricinoleat, Zinkabietat, Zinkvalerat, Zink-p-toluolsulfonat.In a further preferred embodiment, machine dishwashing detergents or automatic dishwashing detergents according to the invention therefore contain at least one zinc salt selected from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate , Zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
Selbstverständlich können bevorzugte erfindungsgemäße Mittel auch Gemische organischer und anorganischer Zinksalze, insbesondere Mischungen löslicher organischer Zinksalze mit nicht löslichen anorganischen Zinksalzen oder Mischungen lösliche organischer Zinksalze mit löslichen anorganischen Zinksalzen oder Mischungen nicht löslicher organischer Zinksalze mit löslichen anorganischen Zinksalzen, enthalten.Of course, preferred compositions according to the invention may also contain mixtures of organic and inorganic zinc salts, in particular mixtures of soluble organic zinc salts with non-soluble inorganic zinc salts or mixtures of soluble organic zinc salts with soluble inorganic zinc salts or mixtures of insoluble organic zinc salts with soluble inorganic zinc salts.
Als bevorzugt gelten im Rahmen der vorliegenden Anmeldung dabei maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, bei denen der Gewichtsanteil des Zinksalz bezogen auf das Gesamtgewicht dieses Mittels 0,1 bis 10 Gew.-%, vorzugsweise 0,2 bis 7 Gew.-% und insbesondere 0,4 bis 4 Gew.-% beträgt und zwar unabhängig davon welche Zinksalze eingesetzt werden, insbesondere also unabhängig davon ob organische oder anorganische Zinksalze oder deren Mischungen eingesetzt werden.For the purposes of the present application, automatic dishwashing or automatic dishwashing aids in which the proportion by weight of the zinc salt relative to the total weight of this agent is 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0, are preferred , 4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts or mixtures thereof are used.
Erfindungsgemäße Mittel unterliegen keiner Einschränkung bezüglich ihrer Konfektionierung und Anbietungsformen. Maschinelle Geschirrspülmittel .oder maschinelle Geschirrspülhilfsmittel im Rahmen der vorliegenden Erfindung können daher sowohl in fester als auch in flüssiger Form bereitgestellt werden.Compositions according to the invention are not subject to any restrictions with regard to their packaging and forms of presentation. Machine dishwashing or machine dishwashing aids in the context of the present invention can therefore be provided both in solid and in liquid form.
In Abhängigkeit von dem Anwendungsbereich des erfindungsgemäßen Verfahrens kann es notwendig oder erwünscht sein, verschiedene oder gleiche in den erfindungsgemäßen Mitteln enthaltene Aktivstoffe und/oder Aktivstoffzubereitungen in zeitlich kontrollierter Weise freizusetzen. Diese zeitlich kontrollierte Freisetzung kann dabei durch unterschiedliche Mechanismen oder, mit anderen Worten, aufgrund unterschiedlicher "Schalter" erfolgen. Bezogen auf die in den erfindungsgemäßen Mitteln enthaltenen Zinksalze und schichtförmigen Silikate bedeutet dies, das diese Aktivsubstanzen vorzugsweise gemeinsam, jedoch zeitlich versetzt zu einem oder mehreren weiteren Aktivstoffen und/oder Aktivstoffzubereitungen, wie beispielsweise Gerüststoffen (Builder, Cobuilder), Tensiden, Bleichmitteln Bleichaktivatoren, Enzymen, Farbstoffen, Duftstoffen, Korrosionschutzmitteln oder Polymeren freigesetzt werden. Dabei können das Zinksalz und/oder das Schichtsilikat sowohl vor als auch nach der Freisetzung dieser Aktivsubstanzen in die wässrige Flotte freigesetzt werden.Depending on the scope of the method of the invention, it may be necessary or desirable to use different or the same in the compositions of the invention Release active ingredients and / or active ingredient preparations in a timely manner. This time-controlled release can take place through different mechanisms or, in other words, due to different "switches". Based on the zinc salts and layered silicates contained in the compositions according to the invention, this means that these active substances are preferably added together but with a time offset to one or more further active ingredients and / or active substance preparations, such as builders (builders, cobuilders), surfactants, bleaches, bleach activators, enzymes , Dyes, fragrances, corrosion inhibitors or polymers are released. The zinc salt and / or the phyllosilicate can be released into the aqueous liquor both before and after the release of these active substances.
Mögliche "Schalter", welche das Freisetzungsverhalten von Aktivstoffen oder Aktivstoffzubereitungen beeinflussen sind beispielsweise
- der Aggregatzustand und die Konfektionsform der Mittel; flüssige Mittel lösen sich häufig schneller als feste Mittel; feste Mittel mit großer Oberfläche (z.B. Pulver, Granulate) lösen sich schneller als feste Mittel mit vergleichsweise kleiner Oberfläche (z.B. Tabletten);
- die mechanische Stabilität, welche - in Abhängigkeit von der Zeit, von der Temperatur oder von anderen Parametern - ein die Desintegration bestimmender Faktor sein kann;
- die Temperatur, d. h. das Erreichen eines bestimmten Temperaturwertes im Verlauf des Temperaturprofils des Wasch-, Reinigungs- oder Spülvorgangs; die Steuerung über die Temperatur stellt insbesondere bei Geschirrspülmitteln wegen der mit jeder Stufe des Spülvorgangs steigenden Temperatur eine zuverlässige und damit bevorzugte Ausführungsform dar;
- der pH-Wert, d. h. die Einstellung eines bestimmten pH-Wertes im Verlauf eines Wasch-, Reinigungs- oder Spülvorgangs durch Komponenten der waschaktiven, reinigungsaktiven oder spülaktiven Zubereitung oder das Verlassen eines bestimmten pH-Wertes nach Zerfall einer den pH-Wert beeinflussenden oder bestimmenden Komponente;
- die Ionenstärke;
- die Anwesenheit von Enzymen
- der Einsatz von vorzugsweise wasserlöslichen Verpackungsmaterialien, sowie deren Permeabilität für eine bestimmte - vornehmlich gasförmige oder flüssige - Komponente; usw..
- the state of aggregation and the ready-made form of the means; Liquid funds often dissolve faster than fixed funds; Solid agents with a large surface area (eg powder, granules) dissolve faster than solid agents with a comparatively small surface (eg tablets);
- the mechanical stability, which - depending on time, temperature or other parameters - may be a factor determining disintegration;
- the temperature, ie the achievement of a certain temperature value in the course of the temperature profile of the washing, cleaning or rinsing process; the control over the temperature represents a reliable and therefore preferred embodiment, in particular for dishwashing detergents, because of the rising temperature with each stage of the flushing process;
- the pH value, ie the setting of a specific pH value during the course of a washing, cleaning or rinsing process by components of the detergent-active, cleaning-active or rinse-active preparation or the leaving of a specific pH value after decomposition of a pH influencing or determining agent Component;
- the ionic strength;
- the presence of enzymes
- the use of preferably water-soluble packaging materials, as well as their permeability to a specific - primarily gaseous or liquid - component; etc..
Die vorgenannten Parameter stellen nur Beispiele dar, welche die Erfindung nicht beschränken sollen.The aforementioned parameters are only examples which are not intended to limit the invention.
Werden die erfindungsgemäßen Mittel beispielsweise als Kombinationsprodukte aus zwei oder mehr Substanzen oder Substanzgemischen in unterschiedlicher Konfektionsform/Aggregatzustand hergestellt, so ist das erfindungsgemäße Mittel, welches das Zinksalz und das Schichtsilikat enthält, vorzugsweise nur in einem dieser Mittel enthalten. Als unterschiedliche Konfektionsformen/Aggregatzustände gelten dabei in der vorliegenden Anmeldung beispielsweise Flüssigkeiten, Pulver, Granulate, Kompaktate, Extrudate, Gießkörper, Gele, Dispersionen. Die Konfektionierung derartiger unterschiedlicher Mittel zu einem Kombinationsprodukt kann dabei beispielsweise mittels einer gemeinsamen, vorzugsweise wasserlöslichen Verpackung erfolgen, welche eine, zwei, drei, vier oder mehr Aufnahmekammern aufweist. Verfahren zur Herstellung derartiger Verpackungen sind dem Fachmann bekannt. Zu diesen Verfahren zählen beispielsweise Tiefzieh-, Spritzguß- oder Gießverfahren. In der Folge sind anhand von Ein- und Zwei-Kammer-Verpackungen einige erfindungsgemäß bevorzugte Kombinationen unterschiedlich konfektionierter Mittel beschrieben:If the agents according to the invention are prepared, for example, as combination products of two or more substances or mixtures of substances in different preparation / physical state, then the composition according to the invention which contains the zinc salt and the layered silicate is preferably contained only in one of these agents. In the present application, for example, liquids, powders, granules, compactates, extrudates, casting bodies, gels, dispersions are considered as different types of preparation / physical states. The assembly of such different means to a combination product can be done for example by means of a common, preferably water-soluble packaging having one, two, three, four or more receiving chambers. Methods for producing such packages are known in the art. These methods include, for example, thermoforming, injection molding or casting. In the following, with reference to single and two-chamber packaging, some preferred combinations of differently prepared compositions are described:
Wasserlösliche oder wasserdispergierbare Verpackung mit einer Aufnahmekammer:
Wasserlösliche oder wasserdispergierbare Verpackung mit zwei Aufnahmekammern:
Für die Herstellung der wasserlöslichen und/oder wasserdispergierbaren Folie eignen sich prinzipiell alle Substanzen oder Substanzgemische, die sich in Form einer Folie konfektionieren lassen. Besonders bevorzugt ist jedoch ein Verfahren, in dem die wasserlösliche und/oder wasserdispergierbare Folie aus (acetalisiertem) Polyvinylakohol, Polyvinylpyrrolidon, Polyethylenoxid, Gelatine, Stärke und Stärkederivat(en), Cellulose und Cellulosederivat(en), insbesondere Methylcellulose und/oder Mischungen dieser Substanzen besteht, wobei diese Aufzählung als beispielhaft und die Erfindung nicht einschränkend zu werten ist.For the preparation of the water-soluble and / or water-dispersible film, in principle all substances or mixtures of substances which can be formulated in the form of a film are suitable. However, particularly preferred is a process in which the water-soluble and / or water-dispersible film of (acetalized) Polyvinylakohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, starch and starch derivative (s), cellulose and cellulose derivative (s), in particular methylcellulose and / or mixtures of these substances this listing being exemplary and not limiting the invention.
In einer weiteren, ebenfalls bevorzugten Ausführungsform ist es erfindungsgemäß von Vorteil, wenn die Folie(n) ein oder mehrere Materialien aus der Gruppe Acrylsäure-haltige Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester und Polyether und deren Mischungen umfaßt/umfassen.In a further, likewise preferred embodiment, it is advantageous according to the invention for the film (s) to comprise one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof ,
Mit besonderem Vorteil kann/können ein oder mehrere Material(ien) aus der folgenden beispielhaften, jedoch nicht beschränkenden Aufzählung genannt werden:
- Mischungen aus 50 bis 100 % Polyvinylalkohol oder Poly(vinylalkohol - co - vinylacetat) mit Molekulargewichten im Bereich von 10.000 bis 200.000 g/mol und Acetatgehalten von 0 bis 30 Mol-%; diese können Verarbeitungszusätze wie Weichmacher (Glycerin, Sorbit, Wasser, PEG usw.), Gleitmittel (Stearinsäure und andere Mono-, Di- und Tricarbonsäuren), sogenannte "Slipmittel" (z. B. "Aerosil"), organische und anorganische Pigmente, Salze, Blasformmittel (Citronensäure-Natriumbicarbonat-Mischungen) enthalten;
- Acrylsäure-haltige Polymere, wie z. B. Copolymere, Terpolymere oder Tetrapolymere, die mindestens 20 % Acrylsäure enthalten und ein Molekulargewicht von 5.000 bis 500.000 g/mol besitzen; als Comonomere sind besonders bevorzugt Acrylsäureester wie Ethylacrylat, Methylacrylat, Hydroxy-ethylacrylat, Ethylhexylacrylat, Butylacrylat, und Salze der Acrylsäure wie Natriumacrylat, Methacrylsäure und deren Salze und deren Ester wie Methylmethacrylat, Ethylmethacrylat, Trimethylammoniummethylmethacrylatchlorid (TMAEMC), Methacrylatamidopropyl-trimethylammoniumchlorid (MAPTAC). Weitere Monomere wie Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon sind ebenfalls mit Vorteil verwendbar;
- Polyalkylenoxide, bevorzugt Polyethylenoxide mit Molekulargewichten von 600 bis 100.000 g/mol und deren durch Pfropfcopolymerisation mit Monomeren wie Vinylacetat, Acrylsäure und deren Salzen und deren Estern, Methacrylsäure und deren Salzen und deren Estern, Acrylamid, Styrol, Styrolsulfonat und Vinylpyrrolidon modifizierte Derivate (Beispiel: Poly-(ethylenglykol - graft - vinylacetat). Der Polyglykol-Anteil sollte 5 bis 100 Gew.-% betragen, der Pfropfanteil sollte 0 bis 95 Gew.-% betragen; letzterer kann aus einem oder aus mehreren Monomeren bestehen. Besonders bevorzugt ist ein Pfropfanteil von 5 bis 70 Gew.-%; dabei sinkt die Wasserlöslichkeit mit dem Pfropfanteil;
- Polyvinylpyrrolidon (PVP) mit einem Molekulargewicht von 2.500 bis 750.000 g/mol;
- Polyacrylamid mit einem Molekulargewicht von 5.000 bis 5.000.000 g/mol;
- Polyethyloxazolin und Polymethyloxazolin mit einem Molekulargewicht von 5.000 bis 100.000 g/mol;
- Polystyrolsulfonate und deren Copolymere mit Comonomeren wie Ethyl-(meth-)acrylat, Methyl(meth-)acrylat, Hydroxyethyl(meth-)acrylat, Ethylhexyl(meth-)acrylat, Butyl(meth-)acrylat und den Salzen der (Meth-) Acrylsäure wie Natrium-(meth-)acrylat, Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon; der Comonomer-Gehalt sollte 0 bis 80 Mol-% betragen, und das Molekulargewicht sollte im Bereich von 5.000 bis 500.000 g/mol liegen;
- Polyurethane, insbesondere die Umsetzungsprodukte von Diisocyanaten (z. B. TMXDI) mit Polyalkylenglykolen, insbesondere Polyethylenglykolen des Molekulargewichts 200 bis 35.000, oder mit anderen difunktionellen Alkoholen zu Produkten mit Molekulargewichten von 2.000 bis 100.000 g/mol;
- Polyester mit Molekulargewichten von 4.000 bis 100.000 g/mol, basierend auf Dicarbonsäuren (z. B. Terephthalsäure, Isophthalsäure, Phthalsäure, Sulfoisophthalsäure, Oxalsäure, Bernsteinsäure, Sulfobernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure usw.) und Diolen (z. B. Polyethylenglykole, beispielsweise mit Molekulargewichten von 200 bis 35.000 g/mol);
- Celluloseether/ester, z. B. Celluloseacetate, Cellulosebutyrate, Methylcellulose, Hydroxypropylcellulose, Hydroxyethylcellulose, Methylhydroxypropylcellulose usw.;
- Polyvinylmethylether mit Molekulargewichten von 5.000 bis 500.000 g/mol.
- Mixtures of 50 to 100% polyvinyl alcohol or poly (vinyl alcohol-co-vinyl acetate) having molecular weights in the range of 10,000 to 200,000 g / mol and acetate contents of 0 to 30 mol%; these may include processing additives such as plasticizers (glycerin, sorbitol, water, PEG, etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called "slip agents" (eg "Aerosil"), organic and inorganic pigments, salts, blowing agents (citric acid-sodium bicarbonate mixtures);
- Acrylic acid-containing polymers, such as. Copolymers, terpolymers or tetrapolymers containing at least 20% of acrylic acid and having a molecular weight of from 5,000 to 500,000 g / mol; Particularly preferred comonomers are acrylic acid esters such as ethyl acrylate, methyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and their salts and their esters such as methyl methacrylate, ethyl methacrylate, trimethylammonium methyl methacrylate chloride (TMAEMC), methacrylatamidopropyl trimethyl ammonium chloride (MAPTAC). Other monomers such as acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone are also useful with advantage;
- Polyalkylene oxides, preferably polyethylene oxides having molecular weights of 600 to 100,000 g / mol and their derivatives by graft copolymerization with monomers such as vinyl acetate, acrylic acid and their salts and their esters, methacrylic acid and its salts and their esters, acrylamide, styrene, styrenesulfonate and vinylpyrrolidone modified derivatives (Example: The amount of polyglycol should be from 5 to 100% by weight, the amount of graft should be from 0 to 95% by weight, the latter being composed of one or more monomers Graft content of from 5 to 70% by weight, in which case the solubility in water drops with the grafting component;
- Polyvinylpyrrolidone (PVP) having a molecular weight of 2,500 to 750,000 g / mol;
- Polyacrylamide having a molecular weight of 5,000 to 5,000,000 g / mol;
- Polyethyloxazoline and polymethyloxazoline having a molecular weight of 5,000 to 100,000 g / mol;
- Polystyrenesulfonates and their copolymers with comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and the salts of (meth) Acrylic acid such as sodium (meth) acrylate, acrylamide, styrene, vinyl acetate, maleic anhydride, vinylpyrrolidone; the comonomer content should be 0 to 80 mol%, and the molecular weight should be in the range of 5,000 to 500,000 g / mol;
- Polyurethanes, in particular the reaction products of diisocyanates (eg TMXDI) with polyalkylene glycols, in particular polyethylene glycols of molecular weight 200 to 35,000, or with other difunctional alcohols to products with molecular weights of 2,000 to 100,000 g / mol;
- Polyesters having molecular weights of 4,000 to 100,000 g / mol, based on dicarboxylic acids (eg terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid etc.) and diols (eg polyethylene glycols, for example, with molecular weights of 200 to 35,000 g / mol);
- Cellulose ethers / esters, eg. Cellulose acetates, cellulose butyrates, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose, etc .;
- Polyvinyl methyl ether with molecular weights of 5,000 to 500,000 g / mol.
Erfindungsgemäß besonders bevorzugte Ausführungsformen der wasserlöslichen Folien berücksichtigen auch, daß mit besonderem Vorteil - wenn auch nicht zwingend - die in den Aufnahmemulden enthaltenen Aktivstoffe und/oder Aktivstoffzubereitungen durch eine-vorzugsweise steuerbare - Wasserlöslichkeit des Folienmaterials zu einem bestimmten Zeitpunkt des Wasch-, Reinigungs- oder Spülvorgangs, beispielsweise bei Erreichen einer bestimmten Temperatur, oder bei Erreichen eines bestimmten pH-Werts oder einer bestimmten Ionenstärke der Waschflotte oder auch aufgrund anderer steuerbarer Ereignisse oder Bedingungen in die wäßrige Flotte eingespeist werden können.Embodiments of the water-soluble films which are particularly preferred according to the invention also take into account the fact that the active substances and / or active-substance preparations contained in the receiving troughs are particularly advantageously - but not necessarily - water-solubility of the film material at a certain point in time of the washing, cleaning or thinning process Rinsing, for example, when reaching a certain temperature, or upon reaching a certain pH or a certain ionic strength of the wash liquor or due to other controllable events or conditions in the aqueous liquor can be fed.
Die Qualität des Materials wie auch dessen Quantität/Stärke nehmen auf diese Löslichkeitseigenschaften direkten Einfluß. Es ist daher im Rahmen der vorliegenden Erfindung ein solches Verfahren besonders bevorzugt, das dadurch gekennzeichnet ist, daß die Dicke der wasserlöslichen Folie zwischen 1 µm und 1000 µm, vorzugsweise zwischen 5 µm und 500 µm und insbesondere zwischen 10 µm und 200 µm beträgt. Verschiedene Foliendicken mit dem Ziel einer verzögerten Freisetzung von Aktivstoffen und/oder Aktivstoffzubereitungen lassen sich beispielsweise auch vorteilhaft durch die mehrfache Versiegelung einer oder mehrerer Aufnahmekammern mittels einer oder mehrerer gleicher oder unterschiedlicher wasserlöslicher Folien realisieren. Die Dicke der wasserlöslichen Folie im Sinne der vorliegenden Erfindung ergibt sich dann als die Summe der Dicken der eine Aufnahmemulde versiegelnden, übereinanderliegenden wasserlöslichen Einzelfolien.The quality of the material as well as its quantity / strength directly influence these solubility properties. It is therefore in the context of the present invention, such a method is particularly preferred, which is characterized in that the thickness of the water-soluble film is between 1 .mu.m and 1000 .mu.m, preferably between 5 .mu.m and 500 .mu.m and in particular between 10 .mu.m and 200 .mu.m. Various film thicknesses with the aim of a delayed release of active substances and / or active substance preparations can also be realized, for example, advantageously by the multiple sealing of one or more receiving chambers by means of one or more identical or different water-soluble films. The thickness of the water-soluble film in the sense of the present invention then results as the sum of the thicknesses of the water-soluble individual films sealing one receiving trough.
Besonders bevorzugt sind Materialien für die wasserlöslichen Folien, die sich - eine bestimmte, die Stabilität mitbestimmende Dicke zugrundegelegt - bei bestimmten Temperaturen, pH-Werten, Ionenstärken, oder nach einer bestimmten Verweilzeit in der wäßrigen Flotte lösen. Dabei kann ein solcher Lösevorgang die Folie als ganzes erfassen oder nur einen Teil davon, so daß sich Teile der Folie bei Einstellung einer bestimmten Parameterkombination lösen, während sich andere Teile noch nicht (sondern erst später) oder auch gar nicht lösen. Letzteres kann durch unterschiedliche Qualität des Materials wie auch durch unterschiedlichen Materialmengen (Dicke) oder auch unterschiedliche Geometrien des wasserunlöslichen Behältnisses erreicht werden. Beispielsweise ist es möglich, durch die äußere Form des wasserunlöslichen Behältnisses den Wasserzutritt zu erschweren und damit den Lösevorgang zu verzögern. In einer anderen bevorzugten Ausführungsform ist es möglich, die Folien unterschiedlich dick (gleichwohl aus demselben Material) zu gestalten und damit an den dünneren Stellen ein früheres Lösen zu ermöglichen. Werden solche unterschiedlich dicken wasserlöslichen Folien zur Abdeckung unterschiedlicher Aufnahmemulden eingesetzt, werden die in diesen Aufnahmemulden befindlichen Aktivstoffe zu unterschiedlichen Zeiten freigesetzt. In einer weiteren ebenfalls bevorzugten Ausführungsformen können die Folien aus Materialien unterschiedlicher Wasserlöslichkeit hergestellt werden, beispielsweise aus Polyvinalalkoholen (PVAL) mit unterschiedlichem Rest-Acetatgehalt.Particular preference is given to materials for the water-soluble films, which - based on a specific, thickness-determining thickness - at certain temperatures, pH values, ionic strengths, or after a certain residence time in the aqueous liquor solve. In this case, such a release process can capture the film as a whole or only a part thereof, so that parts of the film solve when setting a certain parameter combination, while other parts are not yet (but later) or not at all solved. The latter can be achieved by different quality of the material as well as by different amounts of material (thickness) or different geometries of the water-insoluble container. For example, it is possible to impede the access of water by the outer shape of the water-insoluble container and thus delay the dissolution process. In another preferred embodiment, it is possible to make the films of different thicknesses (nevertheless of the same material) and thus to allow earlier dissolution at the thinner locations. Be such different thicknesses of water-soluble films to cover used different receiving troughs, the active substances contained in these receiving troughs are released at different times. In a further likewise preferred embodiment, the films may be made of materials of different water solubility, for example of polyvinyl alcohols (PVAL) with different residual acetate content.
In einer besonders bevorzugten Ausführungsform kann die wasserlösliche und/oder wasserdispergierbare Folie neben den genannten Inhaltsstoffen auch eine oder mehrere wasch- und reinigungsaktive Substanzen enthalten oder aus diesen Substanzen bestehen (Bsp.: Polyvinylalkohole als Folienmaterial und Builder). Im erstgenannten Fall können beispielsweise waschaktive, reinigungsaktive oder spülaktive Wirkstoffe, die nur in kleinen Mengen in den Zubereitungen zugegen sind und deren gleichmäßige Einarbeitung deswegen nicht unproblematisch ist, in die Folie oder einen Teil der Folie, beispielsweise einen solchen, der sich in dem Stadium des Wasch-, Reinigungs- oder Spülgangs löst, in dem gerade der Wirkstoff benötigt wird, eingearbeitet werden, wodurch er beim Auflösen der Folie zum richtigen Zeitpunkt in die Flotte freigesetzt wird. Ein Beispiel hierfür mögen Duftstoffe sein, die in der letzten Phase des Wasch- oder Reinigungs- oder Spülvorgangs erwünscht sind, jedoch auch optische Aufheller, UV-Schutzsubstanzen, Farbstoffe und andere waschaktive, reinigungsaktive oder spülaktive Zubereitungen.In a particularly preferred embodiment, the water-soluble and / or water-dispersible film can also contain one or more washing and cleaning-active substances or consist of these substances (for example: polyvinyl alcohols as film material and builder) in addition to the ingredients mentioned. In the former case, for example, washing active, cleaning active or active ingredients that are only present in small amounts in the preparations and their uniform incorporation is therefore not unproblematic, in the film or a part of the film, for example, one which is in the state of Washing, cleaning or rinsing dissolves, in which just the active ingredient is needed to be incorporated, whereby it is released when dissolving the film at the right time in the fleet. An example of this may be fragrances which are desired in the final stage of the washing or cleaning or rinsing process, but also optical brighteners, UV protectants, dyes and other detergent-active, cleaning-active or rinse-active preparations.
Eine weitere im Rahmen der vorliegenden Anmeldung ebenfalls bevorzugte Ausgestaltungsform erfindungsgemäßer Mittel ist die zeitlich kontrollierte Freisetzung eines oder mehrerer der in diesen Mitteln enthaltenen Aktivstoffe(s) und/oder Aktivstoffzubereitung(en) durch die Einarbeitung von Matrix- oder Beschichtungsmaterialien unterschiedlicher Löslichkeit oder Schmelztemperatur.A further embodiment of agents according to the invention which is likewise preferred in the context of the present application is the time-controlled release of one or more of the active substances (s) and / or active substance preparation (s) contained in these agents by the incorporation of matrix or coating materials of different solubility or melting temperature.
Nach dem zuvor Gesagten lassen sich Unterschiede in der Freisetzungsgeschwindigkeit von Aktivstoffen und/oder Aktivstoffgemischen durch den Einsatz von Matrixmaterialien oder Beschichtungen erzielen, welche unterschiedliche Schmelztemperaturen aufweisen. Besonders bevorzugt ist dabei die Verwendung von schmelzbaren oder erweichbaren Substanzen als Matrix- oder Beschichtungsmaterial für die Aktivstoffe oder Aktivstoffzubereitungen. (Die Bezeichnung "Beschichtung" umfaßt im Rahmen der vorliegenden Erfindung neben der Beschichtung einzelner oder mehrerer Seiten oder Oberflächen eines Gegenstandes wie beispielsweise eines festen partikulären Mittels auch die vollständige Beschichtung, also die Umhüllung dieses partikulären Gegenstandes. Auch die Versiegelung einer Aufnahmemulde durch eine schmelzbare Substanz durch Aufgießen einer solchen Substanz auf eine(n) partikuläre(n) oder gelförmige(n) Aktivstoff/Aktivstoffzubereitung wird als Beschichtung bezeichnet. Unter die Bezeichung "Aktivstoffe" oder "Aktivstoffzubereitungen" fallen sowohl die für die erfindungsgemäßen Mittel kennzeichnenden Zinksalze/Schichtsilikate als auch alle übrigen optional enthaltenen Inhaltsstoffe.) Erfindungsgemäß bevorzugte schmelzbare Substanzen weisen dabei einen Schmelzpunkt oberhalb 30°C auf. Sollen Aktivstoffzubereitungen zu unterschiedlichen Zeiten beispielsweise während der verschiedenen Spülgänge eines Reinigungsprozesses freigesetzt werden, so kann dies beispielsweise durch den Einsatz einer oder verschiedener schmelzbarer Matrizes oder Beschichtungen erfolgen. Werden zwei oder mehr unterschiedliche schmelzbare Matrizes eingesetzt, so sind die Schmelzpunkte vorzugsweise an den Temperaturverlauf dieses Reinigungsprozesses angepaßt, wobei die Differenz der Schmelzpunkte ausreicht, um das gesonderte Auflösen der einzelnen Matrizes oder Beschichtungen zu gewährleisten. Dabei werden solche Substanzen für die unterschiedliche Matrizes und/oder Beschichtungen bevorzugt, die sich bezüglich ihres Schmelzpunktes um mindestens 5°C, vorzugsweise um 10°C, besonders bevorzugt um 15°C und insbesondere um mindestens 20°C unterscheiden, wobei es weiterhin bevorzugt ist, daß der Schmelzpunkt mindestens einer der schmelzbaren Substanzen, die eine Matrix oder eine Beschichtung bilden unterhalb 30°C liegt, während der Schmelzpunkt mindestens einer weiteren Substanz, die eine weitere Matrix oder Beschichtung bilden, oberhalb 30°C liegt.According to the above, differences in the release rate of active substances and / or active substance mixtures can be achieved by the use of matrix materials or coatings which have different melting temperatures. The use of fusible or softenable substances as matrix or coating material for the active substances or active substance preparations is particularly preferred. In the context of the present invention, the term "coating" encompasses not only the coating of one or more sides or surfaces of an article, such as a solid particulate agent, but also the complete coating, ie, the coating of this particulate article, as well as the sealing of a receiving well by a meltable substance by coating such a substance on a particulate or gel-like active / active substance preparation is referred to as a coating. The term "active substances" or "active substance preparations" includes both the zinc salts / sheet silicates which characterize the compositions according to the invention all others optionally included Ingredients.) According to preferred fusible substances have a melting point above 30 ° C. If active substance preparations are to be released at different times, for example during the various rinses of a cleaning process, this can be done, for example, by using one or different fusible matrices or coatings. If two or more different fusible matrices are used, the melting points are preferably adapted to the temperature profile of this cleaning process, the difference in the melting points being sufficient to ensure the separate dissolution of the individual matrices or coatings. Such substances are preferred for the different matrices and / or coatings, which differ in their melting point by at least 5 ° C, preferably by 10 ° C, more preferably by 15 ° C and in particular by at least 20 ° C, wherein it further preferred in that the melting point of at least one of the fusible substances forming a matrix or a coating is below 30 ° C, while the melting point of at least one further substance forming a further matrix or coating is above 30 ° C.
Ist es vorgesehen eine erweichbare Substanz als Matrix für einen Aktivstoff oder eine Aktivstoffzubereitung einzusetzten, so läst sich diese unter Temperatureinwirkung erweichbare Masse konfektionieren, indem die gewünschten weiteren Inhaltsstoffe mit diesem schmelz- oder erweichbaren Stoff vermischt und die Mischung auf Temperaturen im Erweichungsbereich dieses Stoffes erwärmt und bei diesen Temperaturen formgebend verarbeitet wird. Werden die erweichbaren Substanzen als Beschichtungsmittel eingesetzt, so kann eine derartige Beschichtung beispielsweise durch Tauchen, Besprühen oder Umwälzen in einem Trommelcoater oder Dragierkessel erfolgen. Besonders bevorzugt werden als schmelz- oder erweichbare Substanzen für die Matrizes oder die Beschichtungen Wachse, Paraffine, Polyalkylenglycole usw. eingesetzt.If it is envisaged to use a softenable substance as a matrix for an active substance or an active substance preparation, then this mass softenable under the influence of temperature can be mixed by mixing the desired further ingredients with this meltable or softenable substance and heating the mixture to temperatures in the softening range of this substance is processed shaping at these temperatures. If the softenable substances are used as coating agents, then such a coating can take place, for example, by dipping, spraying or circulating in a drum coater or coating pan. Particular preference is given to using waxes, paraffins, polyalkylene glycols, etc. as meltable or softenable substances for the matrices or the coatings.
Es hat sich als vorteilhaft erwiesen, wenn die schmelz- oder erweichbaren Substanzen keinen scharf definierten Schmelzpunkt zeigt, wie er üblicherweise bei reinen, kristallinen Substanzen auftritt, sondern einen unter Umständen mehrere Grad Celsius umfassenden Schmelzbereich aufweisen. Die schmelz- oder erweichbaren Substanzen weisen vorzugsweise einen Schmelzbereich auf, der zwischen etwa 35°C und etwa 75°C liegt. Das heißt im vorliegenden Fall, daß der Schmelzbereich innerhalb des angegebenen Temperaturintervalls auftritt und bezeichnet nicht die Breite des Schmelzbereichs. Vorzugsweise beträgt die Breite des Schmelzbereichs wenigstens 1°C, vorzugsweise etwa 2 bis etwa 3°C.It has proved to be advantageous if the meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius. The meltable or softenable substances preferably have a melting range of between about 35 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not denote the width of the melting range. Preferably, the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.
Die oben genannten Eigenschaften werden außer von Paraffinen und Polyethylenglykolen in der Regel auch von sogenannten Wachsen erfüllt. Genauere Beschreibungen dieser Stoffgruppen finden sich weiter unten in der Beschreibung. Auf diese Ausführungen wird zur Vermeidung von Wiederholungen an dieser Stelle verwiesen.Apart from paraffins and polyethylene glycols, the abovementioned properties are as a rule also fulfilled by so-called waxes. Find more detailed descriptions of these groups of substances further down in the description. Reference is made to these statements to avoid repetition at this point.
Eine weitere bevorzugte Möglichkeit zur zeitlich verzögerten Freisetzung von Aktivstoffen oder Aktivstoffzubereitungen ist die gestaffelte räumliche Anordnung dieser Substanzen in der Aufnahmekammer einer vorzugsweise wasserlöslichen Verpackung oder innerhalb eines Gieß- oder Preßkörpers (Zwiebelmodell) mit dem Ziel einer zeitlich gestaffelten Freisetzung. Eine derartige räumlich gestaffelte Anordnung ist beispielsweise die schicht- oder phasenweise Anordnung der Aktivstoffe oder Aktivstoffzubereitungen, für die sich beispielsweise die schichtweise Tablettierung oder das schichtweise Eingießen flüssiger Aktivstoffe oder Aktivstoffgemische und deren nachfolgende Verfestigung durch Erstarren und/oder Kristallisation eignen. Da ein Zutritt des Lösungsmittels bei verpreßten oder gegossenen Formkörpern nur über deren Oberfläche erfolgen kann, führt diese schichtweise Anordnung zur Freisetzung derjenigen Aktivstoffe oder Aktivstoffgemische, welche sich an der Oberfläche eines solchen mehrphasigen Gemischs befinden. Die Phasen werden folglich zeitlich versetzt abgetragen, deren Inhaltsstoffe werden zeitlich versetzt freigesetzt.Another preferred possibility for the delayed release of active substances or active substance preparations is the staggered spatial arrangement of these substances in the receiving chamber of a preferably water-soluble packaging or within a casting or compact (onion model) with the aim of a staggered release. Such a spatially staggered arrangement is, for example, the layer or phase arrangement of the active ingredients or active substance preparations, for example, the layered tabletting or the layered pouring liquid active substances or mixtures of active ingredients and their subsequent solidification by solidification and / or crystallization are suitable. Since access of the solvent in compressed or cast moldings can take place only over their surface, this layered arrangement leads to the release of those active substances or active substance mixtures which are located on the surface of such a multiphase mixture. The phases are thus removed offset in time, the ingredients are released with a time delay.
Die zuvor beschriebenen Methoden zur zeitlich kontrollierten Freisetzung von Aktivstoffen und/oder Aktivstoffgemischen sind selbstverständlich nicht Selbstzweck, sondern dienen der gezielten Steuerung des Reinigungsverfahrens. So umfaßt ein Programm für die maschinelle Reinigung von Geschirr in der Regel verschiedene Reinigungsgänge, wobei die Art und Anzahl dieser Reinigungsgänge durch den Verbraucher mittels einer Programmwahl bestimmt werden können. Beispiele für derartige Reinigungsgänge sind der Vorspülgang, Zwischen- und Hauptspülgänge oder der Klarspülgang. All diese unterschiedlichen Reinigungsgänge bedürfen für ein optimales Ergebnis der gezielten Dosierung entsprechender Aktivstoffe oder Aktivstoffgemische. Insbesondere zur Optimierung der erfindungsgemäß eingesetzten Wirkstoffkombination von Zinksalzen mit Schichtsilikaten kann dabei in Abhängigkeit von der Natur der weiteren eingesetzten Aktivstoffe eine kontrollierte frühzeitige oder verzögerte Freisetzung von Zinksalzen und/oder Schichtsilikaten und/oder weiteren Aktivstoffen förderlich sein.Of course, the previously described methods for the timely release of active substances and / or mixtures of active substances are not an end in themselves, but are used for targeted control of the purification process. Thus, a program for the automatic cleaning of dishes usually includes various cleaning cycles, the nature and number of these cleaning cycles can be determined by the consumer by means of a program selection. Examples of such cleaning cycles are the pre-wash cycle, intermediate and main washes or the rinse cycle. All these different cleaning operations require for an optimum result of the targeted dosage of appropriate active ingredients or active mixtures. In particular, for optimizing the active ingredient combination of zinc salts with phyllosilicates used according to the invention, a controlled early or delayed release of zinc salts and / or phyllosilicates and / or other active substances may be beneficial, depending on the nature of the other active ingredients used.
Feste Angebotsformen der erfindungsgemäßen maschinellen Geschirrspülmittel oder maschinellen Geschirrspülhilfsmittel sind beispielsweise fein- bis grobkörnige Pulver, wie sie zum Beispiel durch Sprühtrocknung oder Granulation erhalten werden, verdichtete Stoffgemische aus der Walzenkompaktierung, aber auch erstarrte Schmelzen oder durch Extrusion bzw. Tablettierung erhaltene Formkörper. Derartige Formkörper können im Rahmen der vorliegenden Erfindung praktisch alle sinnvoll handhabbaren Ausgestaltungen aufweisen, beispielsweise also in Form einer Tafel, in Stab- bzw. Barrenform, eines Würfel, eines Quader und entsprechendes Raumelement mit ebenen Seitenflächen sowie insbesondere zylinderförmige Ausgestaltungen mit kreisförmigem oder ovalem Querschnitt aufweisen. Diese letzte Ausgestaltung erfaßt dabei die Darbietungsform von der eigentlichen Tablette bis zu kompakten Zylinderstücken mit einem Verhältnis von Höhe zu Durchmesser oberhalb 1. Bevorzugte tablettierte oder extrudierte Mittel weisen im Rahmen der vorliegenden Erfindung zwei oder mehr Phasen auf, die sich beispielsweise durch ihre Zusammensetzung, ihren Anteil am Gesamtvolumen des Formkörpers und/oder ihr optisches Erscheinungsbild unterscheiden können.Solid forms of the machine dishwashing detergents or dishwashing auxiliaries according to the invention are, for example, fine- to coarse-grained powders, as obtained, for example, by spray-drying or granulation, compacted mixtures of roll compacting, but also solidified melts or shaped articles obtained by extrusion or tabletting. Such moldings can in the context of the present invention have virtually all useful manageable embodiments, for example, in the form of a bar, in bar or bar form, a cube, a cuboid and the like Room element with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the actual tablet to compact cylinder pieces with a height-to-diameter ratio above 1. Preferred tabletted or extruded means in the present invention, two or more phases, for example, by their composition, their Share of the total volume of the molding and / or can distinguish their visual appearance.
Die Phasen derartiger mehrphasiger Formkörper können sich zusätzlich durch ein unterschiedliches Auflöseverhalten in wässriger Phase auszeichnen. Derartige Formkörper eignen sich zur zeitlich kontrollierten Freisetzung bestimmter Inhaltsstoffe (controlled release), beispielsweise in bestimmten Spülgängen des maschinellen Spülprogramms. In einer bevorzugten Ausführungsform weist eine der Phasen des Formkörpers als Hauptbestandteil schmelz- oder erweichbare Substanzen aus der Gruppe der Wachse, Paraffine und/oder Polyalkylenglycole auf. Weiterhin hat es sich als vorteilhaft erwiesen, wenn der diese schmelz- oder erweichbaren Substanzen enthaltene Formkörper bzw. Formkörperbestandteil wenigstens weitgehend wasserunlöslich ist. Die Löslichkeit in Wasser sollte bei einer Temperatur von etwa 30°C etwa 10 mg/l nicht übersteigen und vorzugsweise unterhalb 5 mg/l liegen. In solchen Fällen sollten die schmelz- oder erweichbaren Substanzen jedoch eine möglichst geringe Wasserlöslichkeit, auch in Wasser mit erhöhter Temperatur, aufweisen, um eine temperaturunabhängige Freisetzung der Aktivsubstanzen möglichst weitgehend zu vermeiden. Die Freisetzung der Aktivsubstanz erfolgt auf diese Weise bei Erreichen des Schmelz- oder Erweichungspunkts. Ein weiteres bevorzugtes Vorgehen zur Erlangung einer kontrollierten Freisetzung von Inhaltsstoffen, insbesondere der erfindungsgemäßen Kombination von Zinksalz und Schichtsilikat, aus mehrphasigen Tabletten ist die Kompaktierung der zwei oder mehr Einzelphasen mit unterschiedlichen Drucken. Da die Zerfalls- und Auflöseeigenschaften von Tabletten bzw. Tablettenphasen bekanntlich u.a. auch von dem bei der Tablettierung auf die Tablettenphase ausgeübten Kompaktierungsdruck abhängig ist, können allein durch den Einsatz unterschiedlicher Kompaktierungsdrucke Tablettenphasen mit unterschiedlichen Zerfalls- und Auflöseeigenschaften hergestellt werden. Dabei kann es erfindungsgemäß bevorzugt sein, daß sich die erfindungsgemäße Kombination von Zinksalz und Schichtsilikat gemeinsam in der Phase befinden, welche dem vergleichsweise höheren Tablettierdruck ausgesetzt war und daher später zerfällt. Es kann aber, je nach Zusammensetzung des Reinigungsmittels auch vorteilhaft sein, Zinksalz und Schichtsilikat gemeinsam in der Tablettenphase zu konfektionieren, welche mit der vergleichsweise niedrigeren Druck tablettiert wurde. Schließlich ist es auch bevorzugt Zinksalz und Schichtsilikat in unterschiedlichen Tablettenphasen zu konfektionieren, wobei sich das Zinksalz in einer vorteilhaften Ausführungsform in der vergleichsweise stark kompaktierten Tablettenphase befindet, während es in einer anderen bevorzugten Ausführungsform in der vergleichsweise geringer kompaktierten Tablettenphase befindet.The phases of such multiphase moldings can additionally be distinguished by a different dissolving behavior in the aqueous phase. Such moldings are suitable for the time-controlled release of certain ingredients (controlled release), for example in certain rinses of the machine wash program. In a preferred embodiment, one of the phases of the shaped body as the main constituent has meltable or softenable substances from the group of waxes, paraffins and / or polyalkylene glycols. Furthermore, it has proved to be advantageous if the melted or softenable substances contained molded body or molded body component is at least largely water insoluble. The solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l. In such cases, however, the meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances. The release of the active substance takes place in this way upon reaching the melting or softening point. A further preferred procedure for obtaining a controlled release of ingredients, in particular the combination of zinc salt and sheet silicate according to the invention, from multiphase tablets is the compaction of the two or more individual phases with different pressures. Since the disintegration and dissolution properties of tablets or tablet phases are known to depend inter alia on the compaction pressure exerted on the tablet phase during tabletting, tablet phases having different disintegration and dissolution properties can be prepared solely by using different compaction pressures. It may be preferred according to the invention that the combination of zinc salt and layered silicate according to the invention are together in the phase which was exposed to the comparatively higher tabletting pressure and therefore decomposes later. However, it may also be advantageous, depending on the composition of the cleaning agent, to prepare zinc salt and layered silicate together in the tablet phase, which was tabletted with the comparatively lower pressure. Finally, it is also preferred to formulate zinc salt and phyllosilicate in different tablet phases, wherein the zinc salt is in an advantageous embodiment in the comparatively highly compacted tablet phase, while in another preferred embodiment is in the comparatively less compacted tablet phase.
Als maschinelle Geschirrspülhilfsmittel werden im Rahmen der vorliegenden Anmeldung solche Mittel bezeichnet, die zusätzlich zu einem handelsüblichen Reinigungsmittel, beispielsweise in Form eines speziellen Glasschutzmittels zudosiert werden. Eine derartige Dosierung kann dabei sowohl vor dem Beginn jedes Spülprogramms als auch in Form eines Depotproduktes, das eine kontinuierliche Freisetzung des erfindungsgemäßen Mittels bewirkt, erfolgen.In the context of the present application, automatic dishwashing assistants are those which are added in addition to a commercial detergent, for example in the form of a special glass preservative. Such a dosage can take place both before the beginning of each rinsing program and in the form of a depot product which causes a continuous release of the agent according to the invention.
Bevorzugte feste erfindungsgemäße Mittel liegen in Form einer für einen Reinigungsgang ausreichenden Dosiereinheit vor. Ein Beispiel für derartige Konfektionsformen sind Geschirrspül(hilfs)mitteltabletten.Preferred solid agents according to the invention are in the form of a dosing unit sufficient for a cleaning cycle. An example of such Konfektionsformen are dishwashing (auxiliary) mitteleltabletten.
Liegen die erfindungsgemäßen Mittel in fester partikulärer Form, jedoch nicht in Form abgeteilter Dosiereinheiten vor, so ergibt sich für diese Mittel das Problem der Entmischung einzelner Bestandteile, wobei es insbesondere die Entmischung der in den erfindungsgemäßen Mitteln enthaltenen Zinksalze und Silikate zu vermeiden gilt. Beispiele für derartige partikulären Angebotsformen sind Pulver oder Granulate. In einer bevorzugten Ausführungsform der vorliegenden Erfindung liegt/liegen das/die in den maschinellen Geschirrspülmittel oder maschinellen Geschirrspülhilfsmittel enthaltene(n) Zinksalz(e) und/oder das/die enthaltene(n) kristalline(n) schichtförmige(n) Silikat(e) mit einer oder mehreren weiteren Aktiv- und/oder Gerüstsubstanz(en) konfektioniert, in partikulärer Form, als Compound vor.If the agents according to the invention are in solid particulate form, but not in the form of separate metering units, the problem of segregation of individual constituents arises for these agents, and the segregation of the zinc salts and silicates contained in the agents according to the invention must be avoided. Examples of such particulate forms of supply are powders or granules. In a preferred embodiment of the present invention, the zinc salt (s) contained in the automatic dishwashing detergent or automatic dishwashing auxiliary and / or the contained crystalline layered silicate (s) with one or more further active and / or builder substance (s) pre-formed, in particulate form, as a compound before.
Da die Zinksalze und kristallinen schichtförmigen Silikate nur einen geringen Gewichtsanteil bevorzugter maschineller Geschirrspülmittel ausmachen, vereinfacht eine Compoundierung auf Grund ihres "Verdünnungseffektes" die Dosierung dieser Salze bei der Herstellung erfindungsgemäßer maschineller Geschirrspülmittel. Aber auch in dem Falle, daß ein erfindungsgemäßes Mittel in Form eines Spezialproduktes zum Glaskorrosionsschutz einem handelsüblichen Reinigungsmittel erst durch den Verbraucher zugesetzt wird, wird die Dosierung durch die Compoundierung erleichtert. Die Vorteile der Compoundierung ergeben sich dabei völlig unabhängig davon, ob das maschinelle Geschirrspülmittel, welchem die entsprechenden Compounds zudosiert werden, fest, flüssig oder gelförmig ist.Since the zinc salts and crystalline layered silicates make up only a small proportion by weight of preferred automatic dishwashing detergents, compounding on the basis of their "dilution effect" simplifies the metering of these salts in the preparation of automatic dishwasher detergents according to the invention. But even in the event that an inventive agent in the form of a special product for glass corrosion protection a commercial cleaning agent is added only by the consumer, the dosage is facilitated by the compounding. The advantages of compounding are completely independent of whether the automatic dishwashing agent, to which the corresponding compounds are added, is solid, liquid or gel-like.
Bevorzugte feste Angebotsformen des erfindungsgemäßen maschinellen Geschirrspülmittels enthalten beispielsweise fein- bis grobkörnige Pulver, wie sie zum Beispiel durch Sprühtrocknung oder Granulation erhalten werden. Derartige Pulver können als Handelsprodukt vermarktet oder als Vorgemisch zur Kompaktierung, beispielsweise für die Tablettierung, eingesetzt werden und weisen in der Regel eine Partikelgröße im Bereich von 0,1 bis 10 mm auf. Um eine Entmischung dieser Pulver von den zudosierten Silikat- und/oder Zinksalzcompounds zu verhindern, ist es bevorzugt, daß diese Compounds eine den Pulvern vergleichbare Partikelgröße aufweisen.Preferred solid forms of the machine dishwashing detergent according to the invention contain, for example, fine to coarse-grained powders, as obtained, for example, by spray-drying or granulation. Such powders can be marketed as a commercial product or used as a premix for compaction, for example for tableting, and generally have a particle size in the range from 0.1 to 10 mm. In order to prevent segregation of these powders from the dosed silicate and / or zinc salt compounds, it is preferred that these compounds have a particle size comparable to the powders.
Ein bevorzugter Gegenstand der vorliegenden Anmeldung ist daher ein maschinelles Geschirrspülmittel, dadurch gekennzeichnet, daß die Partikelgröße der mit einem oder mehreren Aktiv- und/oder Gerüstsubstanzen konfektionierten Zinksalze und/oder kristallinen schichtförmigen Silikate 0,1 und 10 mm, vorzugsweise 0,2 und 8 mm und insbesondere 0,5 und 5 mm beträgt, wobei bevorzugte partikuläre Compounds zur Vermeidung von Entmischungsvorgängen zusätzlich eine Dichte von 0,1 bis 2,0 g/cm3, vorzugsweise von 0,2 bis 1,6 g/cm3 und insbesondere von 0,4 bis 1,2 g/cm3 aufweisen.A preferred subject matter of the present application is therefore a machine dishwashing detergent, characterized in that the particle size of the zinc salts and / or crystalline layered silicates compounded with one or more active and / or builder substances is 0.1 and 10 mm, preferably 0.2 and 8 mm and in particular 0.5 and 5 mm, wherein preferred particulate compounds to avoid segregation additionally a density of 0.1 to 2.0 g / cm 3 , preferably from 0.2 to 1.6 g / cm 3 and in particular from 0.4 to 1.2 g / cm 3 .
Erfindungsgemäß bevorzugte maschinelle Geschirrspülmittel sind insbesondere dadurch gekennzeichnet, daß die Partikel der mit einem oder mehreren Aktiv- und/oder Gerüstsubstanzen konfektionierten Zinksalze und/oder kristallinen schichtförmigen Silikate einen Gewichtsanteil der Zinksalze oder kristallinen schichtförmigen Silikate von 0,1 bis 80 Gew.-%, besonders bevorzugt von 0,2 bis 70 Gew-% und insbesondere bevorzugt von 0,5 bis 60 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Partikel, aufweisen.Automated dishwashing agents preferred according to the invention are characterized in particular by the particles of the zinc salts and / or crystalline layered silicates synthesized with one or more active and / or builder substances containing from 0.1 to 80% by weight of the zinc salts or crystalline layered silicates, particularly preferably from 0.2 to 70% by weight and particularly preferably from 0.5 to 60% by weight, in each case based on the total weight of the particles.
Die vorgenannten partikulären Compounds werden erfindungsgemäß bevorzugt durch Sprühtrocknung und/oder Granulation und/oder Extrusion und/oder Walzenkompaktierung und/oder Tablettierung und/oder Erstarrung und/oder Kristallisation, insbesondere jedoch durch Sprühtrocknung und/oder Granulation, erhalten.The abovementioned particulate compounds are obtained according to the invention preferably by spray drying and / or granulation and / or extrusion and / or roller compaction and / or tabletting and / or solidification and / or crystallization, but in particular by spray drying and / or granulation.
Bei der Sprühtrocknung wird in einem ersten Schritt des Verfahrens eine wässrige Aufschlämmung ("Slurry") hergestellt, die neben den erfindungsgemäßen Zinksalzen weitere thermisch stabile Aktiv- und/oder Gerüstsubstanzen enthalten kann, welche sich unter den Bedingungen der Sprühtrocknung weder verflüchtigen noch zersetzen und diese anschließend über Pumpen in den Sprühturm befördert und über im Kopf des Turms befindliche Düsen versprüht. Aufsteigende Heißluft trocknet den Slurry und verdampft das anhaftende Wasser, so daß die Waschmittel-Bestandteile am Auslaß des Turms als feine Pulver erhalten werden. Diesen können bei Bedarf weitere Tempertur-labile Bestandteile, wie z. B. Bleichmittel oder Duftstoffe, zugemischt werden.In spray drying, an aqueous slurry ("slurry") is prepared in a first step of the process, which may contain other thermally stable active and / or builders in addition to the zinc salts according to the invention, which neither volatilize nor decompose under the conditions of spray drying and this then transported via pumps in the spray tower and sprayed via located in the head of the tower nozzles. Ascending hot air dries the slurry and evaporates the adhering water so that the detergent ingredients at the outlet of the tower are obtained as fine powders. These may, if necessary, further Tempertur labile ingredients such. As bleaching agents or perfumes, are admixed.
Die Konfektionierung erfindungsgemäßer Mittel kann außer durch die zuvor beschriebene Sprühtrocknung auch durch ein Granulationsverfahren erfolgen, wobei ein Wirbelschichtverfahren besonders bevorzugt wird, in welchem auf waagerechten, perforierten Böden lagerndes feinkörniges Schüttgut, welches neben den erfindungsgemäßen Zinksalzen weitere Aktiv- und/oder Gerüstsubstanzen enthalten kann, von unten von Gasen (z.B. Heißluft) durchströmt wird. Unter bestimmten Strömungsbedingungen stellt sich dabei ein Zustand ein, der dem einer kochenden Flüssigkeit ähnelt; die Schicht wirft Blasen auf, und die Teilchen des Schüttgutes befinden sich innerhalb der Schicht in einer ständigen, wirbelnden Auf- und Abbewegung und bleiben so gewissermaßen in der Schwebe. Die große Oberfläche des Wirbelgutes ermöglicht dann beispielsweise die Umsetzung mit weiteren Substanzen wie Lösungsmitteln, Lösungen von Aktiv- und/oder Gerüstsubstanzen, flüssigen Aktivsubstanzen oder aber weiteren Inhaltsstoffen, die bei Raumtemperatur als Feststoff vorliegen, durch Temperaturerhöhung und/oder Zusatz sehr begrenzter Mengen an flüssigen Zusatzstoffen aber wenigstens oberflächlich erweichen und/oder unter Temperatureinwirkung eine Kleb- und Haftfestigkeit ausbilden. Typische Beispiele der vorgenannten Substanzen sind Wasser sowie wässrige Lösungen, wobei beispielsweise auch wässrige Lösungen der erfindungsgemäßen Zinksalze eingesetzt werden können, bei Raumtemperatur flüssige oder feste Tensidverbindungen, insbesondere Niotenside, oder aber Polymerverbindungen synthetischen und/oder natürlichen Ursprungs, beispielsweise (co)-polymere Carboxylate.The preparation of compositions according to the invention can be carried out not only by the spray drying described above but also by a fluidized bed process in which fine granular bulk material stored on horizontal, perforated trays, which besides the zinc salts according to the invention can contain further active and / or builder substances, from below by gases (eg hot air) is flowed through. Under certain flow conditions, this creates a state that is similar to that of a boiling liquid; the layer causes bubbles, and the particles of the bulk material are within the layer in a constant, swirling up and down movement and remain so to speak in the balance. The large surface of the fluidized material then allows, for example, the reaction with other substances such as solvents, solutions of active and / or builders, liquid active substances or other ingredients that are present as solid at room temperature, by increasing the temperature and / or addition of very limited amounts of liquid But soften additives at least superficially and / or form an adhesive and adhesive strength under the influence of temperature. Typical examples of the aforementioned substances are water and aqueous solutions, for example, aqueous solutions of zinc salts according to the invention can be used at room temperature liquid or solid surfactant compounds, especially nonionic surfactants, or polymer compounds of synthetic and / or natural origin, for example (co) -polymere carboxylates ,
Eine weitere für die Granulation bevorzugte Vorgehensweise ist der Einsatz von Mischern/Verdichtern, wie sie zu diesem Zwecke neben anderen Anbietern beispielsweise auch durch die Firma Lödige bereitgestellt werden und welche in besonderer Weise für die Herstellung erfindungsgemäß konfektionierter Partikel geeignet sind, da sie dem Anwender durch Variation verschiedener Verfahrensparameter wie der Umdrehungszahl des Mischers, der Verweildauer der Einzelkomponenten, des Dosierzeitpunkts einzelner Komponenten während des Mischvorgangs, der Geometrie der eingesetzten Mischelemente oder des Energieeintrags die Möglichkeit der gezielten Steuerung der Produkteigenschaften der erhaltenen Granulate bieten. Auch die Korngröße und/oder Dichte von Granulaten kann auf diese Weise gezielt beeinflußt werden, und die Konfektionierung von erfindungsgemäßen Zinksalzen mit einer oder mehreren weiteren Aktiv- und/oder Gerüstsubstanz(en) in den vorgenannten Mischern/Verdichtern ist daher im Rahmen der vorliegenden Erfindung besonders bevorzugt.Another preferred procedure for the granulation is the use of mixers / compressors, as they are provided for this purpose, among other providers, for example, by the company Lödige and which are particularly suitable for the production of preformed particles according to the invention, as by the user Variation of different process parameters such as the number of revolutions of the mixer, the residence time of the individual components, the dosing of individual components during the mixing process, the geometry of the mixing elements used or the energy input offer the possibility of targeted control of the product properties of the resulting granules. The grain size and / or density of granules can be influenced in this way, and the assembly of zinc salts according to the invention with one or more further active and / or builder substance (s) in the aforementioned mixers / compressors is therefore within the scope of the present invention particularly preferred.
Schließlich besteht die Möglichkeit, die erfindungsgemäßen Zinksalze und/oder Silikate mit weiteren Einzelkomponenten zu vermischen, die sich in ihren Schüttdichten nur geringfügig von denen der genannten Salze unterscheiden. Derartige Mischungen weisen nur geringe Entmischungstendenzen der Komponenten bei Lagerung, Transport und Verarbeitung auf und sind daher ebenfalls in besonderer Weise für die angestrebte sichere und zuverlässige Dosierung der erfindungsgemäßen Silikate und/oder Zinksalze geeignet. Bevorzugt im Rahmen der vorliegenden Erfindung sind daher Mischungen von Silikaten und/oder Zinksalzen mit weiteren Aktiv- und/oder Gerüstsubstanzen, dadurch gekennzeichnet, daß sich die Schüttgewichte der miteinander vermischten Einzelkomponenten um maximal 200 g/l, vorzugsweise um maximal 150 g/l, bevorzugt um maximal 100 g/l und insbesondere um maximal 50 g/l unterscheiden.Finally, it is possible to mix the zinc salts and / or silicates according to the invention with further individual components which differ only slightly in their bulk densities from those of the salts mentioned. Such mixtures have only slight separation tendencies of the components during storage, transport and processing and are therefore also particularly suitable for the desired safe and reliable dosing of the silicates and / or zinc salts according to the invention. Preferred in the context of the present invention are therefore mixtures of silicates and / or zinc salts with further active and / or builders, characterized in that the bulk densities of the individual components mixed with one another by a maximum of 200 g / l, preferably by a maximum of 150 g / l, preferably differ by a maximum of 100 g / l and in particular by a maximum of 50 g / l.
Die Gerüst- und/oder Aktivsubstanzen, welche bei der zuvor beschriebenen Konfektionierung bevorzugter erfindungsgemäßer maschinelle Geschirrspülmittel eingesetzt werden können, umfassen neben anderen üblichen Bestandteilen von Reinigungsmitteln beispielsweise Gerüststoffe (Builder, Cobuilder), Tenside, Bleichmittel, Bleichaktivatoren, Enzyme, Farbstoffe, Duftstoffe, Korrosionschutzmittel oder Polymere.The scaffolding and / or active substances which can be used in the above-described formulation of preferred automatic dishwashing compositions according to the invention include, among other conventional ingredients of detergents, for example builders, co-builders, surfactants, bleaches, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors or polymers.
Während als Aktiv- und/oder Gerüsfsubstanzen für die Konfektionierung erfindungsgemäßer Zinksalze generell alle genannten Substanzen geeignet sind, sind im Rahmen der vorliegenden Erfindung jedoch solche maschinellen Geschirrspülmittel oder maschinellen Geschirrspülhilfsmittel besonders bevorzugt, in welchen die mit einem oder mehreren Aktiv- und/oder Gerüstsubstanzen konfektionierten Zinksalzcompounds, Aktiv- und/oder Gerüstsubstanzen aus der Gruppe der Phosphate, Carbonate, Hydrogencarbonate, Sulfate, Silikate, Citrate, Citronensäure, Acetate, vorzugsweise in Mengen von 20 bis 99 Gew.%, besonders bevorzugt von 30 bis 98 Gew.-% und insbesondere bevorzugt von 40 bis 95 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Partikel, enthalten.Whilst all the substances mentioned are generally suitable as active and / or greasy substances for the formulation of zinc salts according to the invention, those automatic dishwashing or machine dishwashing auxiliaries are particularly preferred in the context of the present invention in which they are compounded with one or more active and / or builder substances Zinc salt compounds, active and / or builders from the group of phosphates, carbonates, bicarbonates, sulfates, silicates, citrates, citric acid, acetates, preferably in amounts of 20 to 99 wt.%, Particularly preferably from 30 to 98 wt .-% and particularly preferably from 40 to 95 wt .-%, each based on the total weight of the particles.
Weitere für die Konfektionierung der Zinksalze im Rahmen der vorliegenden Erfindung besonders bevorzugte Aktiv- und/oder Gerüstsubstanzen sind die Tenside, vorzugsweise die Niotenside, und/oder die polymeren Carboxylate, insbesondere die Polysulfocarboxylate.Other active and / or builder substances which are particularly preferred for the preparation of the zinc salts in the context of the present invention are the surfactants, preferably the nonionic surfactants, and / or the polymeric carboxylates, in particular the polysulfocarboxylates.
Zur weiteren Beschreibung besonders bevorzugter Tenside oder polymerer Carboxylate sowie der Polysulfocarboxylate sei zur Vermeidung von Wiederholungen auf die nachfolgenden Ausführungen verwiesen.For further description of particularly preferred surfactants or polymeric carboxylates and polysulfocarboxylates, reference is made to the following statements to avoid repetition.
Auch die in den erfindungsgemäßen maschinellen Geschirrspülmitteln oder maschinellen Geschirrspülhilfsmitteln enthaltenen Silikate liegen in diesen Mitteln bevorzugt mit anderen Aktiv- oder Gerüststubstanzen konfektioniert vor, wobei hier insbesondere Aktiv- oder Gerüstsubstanzen aus der Gruppe der organischen Mono- oder Polycarbonsäuren, der Hydroxypolycarbonsäuren und der Phosphonsäuren eingesetzt werden.The silicates present in the machine dishwashing detergents or dishwashing auxiliaries according to the invention are also preferably packaged with other active ingredients or builders in these compositions, active substances or builders from the group of organic monocarboxylic or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids being used here ,
Ein weiterer bevorzugter Gegenstand der vorliegenden Anmeldung sind daher maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, dadurch gekennzeichnet, daß das/die kristalline(n) schichtförmige(n) Silikat(e) der allgemeinen Formel (Ia) mit einer oder mehreren weiteren Aktiv- und/oder Gerüstsubstanz(en), vorzugsweise mit einer oder mehreren weiteren Aktiv- und/oder Gerüstsubstanzen aus der Gruppe der organischen Mono- oder Polycarbonsäuren, der Hydroxypolycarbonsäuren und der Phosphonsäuren konfektioniert, in partikulärer Form, als Compound vorliegt/vorliegen.A further preferred subject matter of the present application is therefore dishwasher detergents or automatic dishwasher detergents, characterized in that the crystalline layered silicate (s) of the general formula (Ia) with one or more further active and / or Framework substance (s), preferably with one or more further active and / or builders from the group of organic mono- or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids, in particulate form, as a compound.
Die partikulär vorliegenden, mit einem oder mehreren Aktiv- und/oder Gerüstsubstanzen konfektionierten Zinksalze und/oder kristallinen schichtförmigen Silikate können zum Schutz von Umwelteinflüssen und damit zur Verbesserung ihrer Lagerstabilität oder zur Beeinflussung des Auflöseverhaltens mit einer Beschichtung (Coating) versehen sein. Beschichtungsmaterialien sowie Verfahren zur Beschichtung partikulärer Mittel sind in der Literatur breit beschrieben und sollen nachfolgend nur bezüglich besonders bevorzugter Ausführungsformen erläutert werden.The particulate present, with one or more active and / or builders formulated zinc salts and / or crystalline layered silicates may be provided to protect environmental influences and thus to improve their storage stability or to influence the dissolution behavior with a coating (coating). Coating materials and methods for coating particulate agents are widely described in the literature and will be explained below only with respect to particularly preferred embodiments.
Besonders bevorzugt ist die Verwendung von schmelzbaren oder erweichbaren Substanzen als Beschichtungsmaterial. (Die Bezeichnung "Beschichtung" meint im Rahmen der vorliegenden Erfindung neben der Beschichtung einzelner oder mehrerer Seiten oder Oberflächen eines partikulären, erfindungsgemäß konfektionierten Mittels auch die eine vollständige Beschichtung, also die Umhüllung dieses partikulären Gegenstandes.) Erfindungsgemäß bevorzugte schmelzbare Substanzen weisen dabei einen Schmelzpunkt oberhalb 30°C auf. Sollen die konfektionierten Zinksalze und/oder kristallinen schichtförmigen Silikate zu unterschiedlichen Zeiten beispielsweise während der verschiedenen Spülgänge eines Reinigungsprozesses freigesetzt werden, so kann dies beispielsweise durch den Einsatz verschiedener schmelzbarer Beschichtungen erfolgen, die sich bezüglich ihres Schmelzpunktes unterscheiden, wobei die Schmelzpunkte dieser Substanzen vorzugsweise an den Temperaturverlauf dieses Reinigungsprozesses angepaßt sind und die Differenz der Schmelzpunkte ausreicht, um das gesonderte Auflösen der einzelnen Matrizes oder Beschichtungen zu gewährleisten. Ist es beispielsweise vorgesehen, Zinksalze und kristalline schichtförmige Silikate zeitlich getrennt freizusetzten, so sind solche Substanzen für die unterschiedliche Beschichtungen bevorzugt, die sich bezüglich ihres Schmelzpunktes um mindestens 5°C, vorzugsweise um 10°C, besonders bevorzugt um 15°C und insbesondere um mindestens 20°C unterscheiden, wobei es weiterhin bevorzugt ist, daß der Schmelzpunkt mindestens einer der schmelzbaren Substanzen, die eine Beschichtung bilden unterhalb 30°C liegt, während der Schmelzpunkt mindestens einer weiteren Substanz, die eine weitere Matrix oder Beschichtung bilden, oberhalb 30°C liegt.Particularly preferred is the use of fusible or softenable substances as coating material. (The term "coating" means in the context of the present invention, in addition to the coating of single or multiple sides or surfaces of a particulate, inventively prepared agent also a complete coating, so the envelope of this particulate article.) According to the invention preferred fusible substances have a melting point above 30 ° C on. If the ready-made zinc salts and / or crystalline layered silicates are to be released at different times, for example during the various rinses of a cleaning process, this can be done, for example, by the use of different fusible coatings which differ in their melting point, the melting points of these substances preferably being on the Adjusted temperature course of this cleaning process and the difference of the melting points is sufficient to ensure the separate dissolution of the individual matrices or coatings. If, for example, it is envisaged to release zinc salts and crystalline layer-form silicates at separate times, then such substances are preferred for the different coatings which, with respect to their melting point, are at least 5 ° C., preferably around 10 ° C., more preferably around 15 ° C. and in particular around at least 20 ° C, wherein it is further preferred that the melting point of at least one of the fusible substances forming a coating is below 30 ° C, while the melting point of at least one further substance forming another matrix or coating, above 30 ° C is.
Derartige Beschichtungen können beispielsweise durch Tauchen, Besprühen oder Umwälzen in einem Trommelcoater oder Dragierkessel aufgebracht werden. Besonders bevorzugt werden als schmelz- oder erweichbare Substanzen für die Beschichtungen Wachse, Paraffine, Polyalkylenglycole usw. eingesetzt.Such coatings can be applied, for example, by dipping, spraying or tumbling in a drum coater or coating pan. Particular preference is given to using waxes, paraffins, polyalkylene glycols, etc., as the meltable or softenable substances for the coatings.
Es hat sich als vorteilhaft erwiesen, wenn die schmelz- oder erweichbaren Substanzen keinen scharf definierten Schmelzpunkt zeigt, wie er üblicherweise bei reinen, kristallinen Substanzen auftritt, sondern einen unter Umständen mehrere Grad Celsius umfassenden Schmelzbereich aufweisen. Die schmelz- oder erweichbaren Substanzen weisen vorzugsweise einen Schmelzbereich auf, der zwischen etwa 45°C und etwa 75°C liegt. Das heißt im vorliegenden Fall, daß der Schmelzbereich innerhalb des angegebenen Temperaturintervalls auftritt und bezeichnet nicht die Breite des Schmelzbereichs. Vorzugsweise beträgt die Breite des Schmelzbereichs wenigstens 1 °C, vorzugsweise etwa 2 bis etwa 3°C.It has proved to be advantageous if the meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius. The meltable or softenable substances preferably have a melting range of between about 45 ° C and about 75 ° C. That is, in the present case, that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Preferably, the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.
Die oben genannten Eigenschaften werden in der Regel von sogenannten Wachsen erfüllt. Unter "Wachsen" wird eine Reihe natürlicher oder künstlich gewonnener Stoffe verstanden, die in der Regel über 40°C ohne Zersetzung schmelzen und schon wenig oberhalb des Schmelzpunktes verhältnismäßig niedrigviskos und nicht fadenziehend sind. Sie weisen eine stark temperaturabhängige Konsistenz und Löslichkeit auf.The above properties are usually met by so-called waxes. "Waxing" is understood to mean a series of naturally or artificially produced substances which generally melt above 40 ° C. without decomposition and are already relatively low-viscosity and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility.
Nach ihrer Herkunft teilt man die Wachse in drei Gruppen ein, die natürlichen Wachse, chemisch modifizierte Wachse und die synthetischen Wachse.According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
Zu den natürlichen Wachsen zählen beispielsweise pflanzliche Wachse wie Candelillawachs, Carnaubawachs, Japanwachs, Espartograswachs, Korkwachs, Guarumawachs, Reiskeimölwachs, Zuckerrohrwachs, Ouricurywachs, oder Montanwachs, tierische Wachse wie Bienenwachs, Schellackwachs, Walrat, Lanolin (Wollwachs), oder Bürzelfett, Mineralwachse wie Ceresin oder Ozokerit (Erdwachs), oder petrochemische Wachse wie Petrolatum, Paraffinwachse oder Mikrowachse.The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe fat, mineral waxes such as ceresin or ozokerite (groundwax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
Zu den chemisch modifizierten Wachsen zählen beispielsweise Hartwachse wie Montanesterwachse, Sassolwachse oder hydrierte Jojobawachse.The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
Unter synthetischen Wachsen werden in der Regel Polyalkylenwachse oder Polyalkylenglycolwachse verstanden. Als schmelz- oder erweichbaren Substanzen für die durch Abkühlung aushärtenden Massen einsetzbar sind auch Verbindungen aus anderen Stoffklassen, die die genannten Erfordernisse hinsichtlich des Erweichungspunkts erfüllen. Als geeignete synthetische Verbindungen haben sich beispielsweise höhere Ester der Phthalsäure, insbesondere Dicyclohexylphthalat, das kommerziell unter dem Namen Unimoll® 66 (Bayer AG) erhältlich ist, erwiesen. Geeignet sind auch synthetisch hergestellte Wachse aus niederen Carbonsäuren und Fettalkoholen, beispielsweise Dimyristyl Tartrat, das unter dem Namen Cosmacol® ETLP (Condea) erhältlich ist. Umgekehrt sind auch synthetische oder teilsynthetische Ester aus niederen Alkoholen mit Fettsäuren aus nativen Quellen einsetzbar. In diese Stoffklasse fällt beispielsweise das Tegin® 90 (Goldschmidt), ein Glycerinmonostearat-palmitat. Auch Schellack, beispielsweise Schellack-KPS-Dreiring-SP (Kalkhoff GmbH) ist als schmelz- oder erweichbaren Substanzen einsetzbar.Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances for the compositions which cure by cooling, and compounds from other substance classes which meet the stated requirements with regard to the softening point. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, commercially available under the name Unimoll 66 ® (Bayer AG) is available, proven. Also suitable are synthetic waxes made of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea) is available. Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can also be used as meltable or softenable substances.
Ebenfalls zu den Wachsen im Rahmen der vorliegenden Erfindung werden beispielsweise die sogenannten Wachsalkohole gerechnet. Wachsalkohole sind höhermolekulare, wasserunlösliche Fettalkohole mit in der Regel etwa 22 bis 40 Kohlenstoffatomen. Die Wachsalkohole kommen beispielsweise in Form von Wachsestem höhermolekularer Fettsäuren (Wachssäuren) als Hauptbestandteil vieler natürlicher Wachse vor. Beispiele für Wachsalkohole sind Lignocerylalkohol (1-Tetracosanol), Cetylalkohol, Myristylalkohol oder Melis sylalkohol. Die Umhüllung der konfektionierten Zinksalze oder kristallinen schichtförmigen Silikate kann gegebenenfalls auch Wollwachsalkohole enthalten, worunter man Triterpenoid- und Steroidalkohole, beispielsweise Lanolin, versteht, das beispielsweise unter der Handelsbezeichnung Argowax® (Pamentier & Co) erhältlich ist. Ebenfalls zumindest anteilig als Bestandteil der schmelz- oder erweichbaren Substanzen einsetzbar sind im Rahmen der vorliegenden Erfindung Fettsäureglycerinester oder Fettsäurealkanolamide aber gegebenenfalls auch wasserunlösliche oder nur wenig wasserlösliche Polyalkylenglycolverbindungen.Likewise to the waxes in the context of the present invention, for example, the so-called wax alcohols are calculated. Wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols are present, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melisyl alcohol. The enclosure of the assembled zinc salts or crystalline layered silicates can optionally also contain wool wax alcohols which are understood to be understood triterpenoid and steroid alcohols, for example lanolin, available, for example, under the trade designation Argowax ® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds may likewise be used as part of the meltable or softenable substances.
Besonders bevorzugte schmelz- oder erweichbaren Substanzen sind solche aus der Gruppe der Polyethylenglycole (PEG) und/oder Polypropylenglycole (PPG) enthält, wobei Polyethylenglycole mit Molmassen zwischen 1500 und 36.000 bevorzugt, solche mit Molmassen von 2000 bis 6000 besonders bevorzugt und solche mit Molmassen von 3000 bis 5000 insbesondere bevorzugt sind. Auch entsprechende Verfahren, die dadurch gekennzeichnet sind, daß die die plastisch verformbare(n) Masse(n) mindestens einen Stoff aus der Gruppe der Polyethylenglycole (PEG) und/oder Polypropylenglycole (PPG) enthält/enthalten, sind bevorzugt.Particularly preferred meltable or softenable substances are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains, with polyethylene glycols having molecular weights between 1500 and 36,000 are preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred. Also, corresponding processes, which are characterized in that the plastically deformable mass (s) at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains / are preferred.
Hierbei sind Beschichtungsmittel bevorzugt, die als einzige schmelz- oder erweichbaren Substanzen Propylenglycole (PPG) und/oder Polyethylenglycole (PEG) enthalten. Erfindungsgemäß einsetzbare Polypropylenglycole (Kurzzeichen PPG) sind Polymere des Propylenglycols, die der nachfolgenden allgemeinen Formel
Erfindungsgemäß bevorzugt einsetzbare Polyethylenglycole (Kurzzeichen PEG) sind dabei Polymere des Ethylenglycols, die der allgemeinen Formel
H-(O-CH2-CH2)n-OH
genügen, wobei n Werte zwischen 20 und ca. 1000 annehmen kann. Die vorstehend genannten bevorzugten Molekulargewichtsbereiche entsprechen dabei bevorzugten Bereichen des Wertes n in Formel IV von ca. 30 bis ca. 820 (genau: von 34 bis 818), besonders bevorzugt von ca. 40 bis ca. 150 (genau: von 45 bis 136) und insbesondere von ca. 70 bis ca. 120 (genau: von 68 bis 113).Polyethylene glycols (abbreviated to PEG) which can preferably be used according to the invention are polymers of ethylene glycol, those of the general formula
H- (O-CH 2 -CH 2 ) n -OH
satisfy, where n can take values between 20 and about 1000. The abovementioned preferred molecular weight ranges correspond to preferred ranges of the value n in formula IV of about 30 to about 820 (exactly: from 34 to 818), more preferably from about 40 to about 150 (exactly: from 45 to 136). and especially from about 70 to about 120 (exactly: from 68 to 113).
In einer weiteren bevorzugten Ausführungsform enthalten die Beschichtungsmaterialien Paraffinwachs.In a further preferred embodiment, the coating materials contain paraffin wax.
Paraffinwachse weisen gegenüber den anderen genannten, natürlichen Wachsen im Rahmen der vorliegenden Erfindung den Vorteil auf, daß in einer alkalischen Reinigungsmittelumgebung keine Hydrolyse der Wachse stattfindet (wie sie beispielsweise bei den Wachsestern zu erwarten ist), da Paraffinwachs keine hydrolisierbaren Gruppen enthält.In the context of the present invention, paraffin waxes have the advantage over the other natural waxes mentioned that no hydrolysis of the waxes takes place in an alkaline detergent environment (as is to be expected, for example, in the case of wax esters), since paraffin wax contains no hydrolyzable groups.
Paraffinwachse bestehen hauptsächlich aus Alkanen, sowie niedrigen Anteilen an Iso- und Cycloalkanen. Das erfindungsgemäß einzusetzende Paraffin weist bevorzugt im wesentlichen keine Bestandteile mit einem Schmelzpunkt von mehr als 70°C, besonders bevorzugt von mehr als 60°C auf. Anteile hochschmelzender Alkane im Paraffin können bei Unterschreitung dieser Schmelztemperatur in der Reinigungsmittelflotte nicht erwünschte Wachsrückstände auf den zu reinigenden Oberflächen oder dem zu reinigenden Gut hinterlassen. Solche Wachsrückstände führen in der Regel zu einem unschönen Aussehen der gereinigten Oberfläche und sollten daher vermieden werden.Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent leaving unwanted wax residue on the surfaces to be cleaned or the property to be cleaned. Such wax residues usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided.
Bevorzugt zu verarbeitende schmelz- oder erweichbaren Substanzen enthalten mindestens ein Paraffinwachs mit einem Schmelzbereich von 50°C bis 60°C, wobei bevorzugte Beschichtungsmaterialien dadurch gekennzeichnet sind, daß sie ein Paraffinwachs mit einem Schmelzbereich von 50°C bis 55°C enthalten.Preferably melt or softenable substances to be processed contain at least one paraffin wax with a melting range of 50 ° C to 60 ° C, preferred coating materials being characterized in that they contain a paraffin wax having a melting range of 50 ° C to 55 ° C.
Vorzugsweise ist der Gehalt des eingesetzten Paraffinwachses an bei Umgebungstemperatur (in der Regel etwa 10 bis etwa 30°C) festen Alkanen, Isoalkanen und Cycloalkanen möglichst hoch. Je mehr feste Wachsbestandteile in einem Wachs bei Raumtemperatur vorhanden sind, desto brauchbarer ist es im Rahmen der vorliegenden Erfindung. Mit zunehmenden Anteil an festen Wachsbestandteilen steigt die Belastbarkeit der Verfahrensendprodukte gegenüber Stößen oder Reibung an anderen Oberflächen an, was zu einem länger anhaltenden Schutz führt. Hohe Anteile an Ölen oder flüssigen Wachsbestandteilen können zu einer Schwächung der Beschichtung führen, wodurch Poren geöffnet werden und die Aktivstoffe den Umgebungseinflüssen ausgesetzt werden.Preferably, the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax constituents in a wax at room temperature, the more useful it is within the scope of the present invention. As the proportion of solid wax constituents increases, the end-of-processability of the process end products increases against impacts or friction on other surfaces, resulting in longer-lasting protection. High levels of oils or liquid wax components can weaken the coating, opening pores and exposing the active ingredients to environmental conditions.
Die schmelz- oder erweichbaren Substanzen können neben Paraffin als Hauptbestandteil noch eine oder mehrere der oben genannten Wachse oder wachsartigen Substanzen enthalten. In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung sollte das die schmelz- oder erweichbaren Substanzen bildende Gemisch so beschaffen sein, daß die Masse und die daraus gebildete Beschichtung wenigstens weitgehend wasserunlöslich sind. Die Löslich keit in Wasser sollte bei einer Temperatur von etwa 30°C etwa 10 mg/l nicht übersteigen und vorzugsweise unterhalb 5 mg/l liegen.The meltable or softenable substances may contain, in addition to paraffin as the main constituent, one or more of the abovementioned waxes or waxy substances. In a In another preferred embodiment of the present invention, the mixture forming the meltable or softenable substances should be such that the composition and the coating formed therefrom are at least substantially insoluble in water. The solubility in water at a temperature of about 30 ° C should not exceed about 10 mg / l and preferably be below 5 mg / l.
In solchen Fällen sollten die schmelz- oder erweichbaren Substanzen jedoch eine möglichst geringe Wasserlöslichkeit, auch in Wasser mit erhöhter Temperatur, aufweisen, um eine temperaturunabhängige Freisetzung der Aktivsubstanzen möglichst weitgehend zu vermeiden.In such cases, however, the meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances.
Bevorzugte erfindungsgemäß zu verarbeitende Beschichtungsmaterialien sind dadurch gekennzeichnet, daß sie als schmelz- oder erweichbaren Substanzen ein oder mehrere Stoffe mit einem Schmelzbereich von 40°C bis 75 °C in Mengen von 6 bis 30 Gew.-%, vorzugsweise von 7,5 bis 25 Gew.% und insbesondere von 10 bis 20 Gew.-%, jeweils bezogen auf das Gewicht des Beschichtungsmaterials, enthalten.Preferred coating materials to be processed according to the invention are characterized in that they contain, as meltable or softenable substances, one or more substances having a melting range from 40 ° C. to 75 ° C. in amounts of from 6 to 30% by weight, preferably from 7.5 to 25 Wt.% And in particular from 10 to 20 wt .-%, each based on the weight of the coating material.
Außer durch die Wahl einer geeigneten Beschichtung kann das Auflöseverhalten der Zinksalz oder Silikatcompounds auch durch die oben erwähnten Kompaktierungsverfahren beeinflußt werden. Hierbei ist neben der Höhe des eingesetzten Druckes und dem Einsatz von Hilfsmitteln, wie beispielsweise von Bindemitteln, insbesondere die Wahl des/der co-konfektionierten Aktivund/oder Gerüstsubstanzen von großer Bedeutung. So eignen sich insbesondere kompaktierte Silikate, insbesondere Disilikate, und/oder Poylcarboxylate und/oder Mischungen verschiedener Polycarboxylate auf Grund ihrer verzögerten Lösung/Dispersion bzw. auf Grund auftretender Vergelung dieser Substanzen oder Substanzgemische in wässriger Flotte als "Depotsubstanzen" für die Zinksalze oder kristallinen schichtförmigen Silikate.Apart from the choice of a suitable coating, the dissolution behavior of the zinc salt or silicate compounds can also be influenced by the abovementioned compaction methods. Here, in addition to the amount of pressure used and the use of aids, such as binders, in particular the choice of / the co-assembled active and / or builders of great importance. For example, compacted silicates, in particular disilicates, and / or polycarboxylates and / or mixtures of various polycarboxylates are suitable as "depot substances" for the zinc salts or crystalline layered form due to their delayed solution / dispersion or due to gelling of these substances or substance mixtures in aqueous liquor silicates.
Eine weitere im Rahmen der vorliegenden Anmeldung besonders bevorzugte Form der Konfektionierung erfindungsgemäßer maschineller Geschirrspülmittel oder maschineller Geschirrspülhilfsmittel sind Polymermatrizes. Derartige Polymermatrizes sind universell in verschiedenen Programmgängen einsetzbar, zeichnen sich dabei durch eine einfache und kostengünstige Herstellungsweise aus und können variierende Mengen an aktivem Agens enthalten.Another particularly preferred form of compounding machine dishwashing or automatic dishwashing auxiliaries according to the present invention is polymer matrices. Such polymer matrices are universally applicable in various programs, are characterized by a simple and cost-effective method of preparation and may contain varying amounts of active agent.
Bevorzugter Gegenstand der vorliegenden Anmeldung sind daher weiterhin maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, in welchen das/die Zinksalz(e) und/oder das/die kristalline(n) schichtförmige(n) Silikat(e) in einer Polymermatrix konfektioniert vorliegen.The preferred subject matter of the present application is therefore furthermore dishwasher detergents or dishwashing auxiliaries in which the zinc salt (s) and / or the crystalline layered silicate (s) are packaged in a polymer matrix.
Die wirkstoffhaltigen Polymermatrizes lassen sich günstig und in hoher Formvielfalt hergestellen. Durch die Auswahl wasserlöslicher oder wasserunlöslicher Polymere kann die erfindungsgemäße Zusammensetzung sogar als Verpackung von maschinellen Geschirrspülmitteln oder als Körbchen, in das die Mittel eingebracht werden, formuliert werden. Es ist auch möglich, beide Arten der Einbringung miteinander zu kombinieren, indem beispielsweise ein Trägerkörbchen aus wasserunlöslicher, wirkstoffhaltiger Polymermatrix einen Polymerkörper aus wasserlöslicher, wirkstoffhaltiger Polymermatrix enthält. Solche Produkte können aus den verschiedenen Matrizes die aktiven Agentien zu unterschiedlichen Zeitpunkten unterschiedlich stark freisetzen, was zu einer optimalen Konzentration an Aktivsubstanz zu jedem Zeitpunkt des Reinigungsprogramms führt.The active ingredient-containing polymer matrices can be produced cheaply and in a high variety of forms. By selecting water-soluble or water-insoluble polymers, the composition of the present invention can even be formulated as a package of automatic dishwashing detergents or as a basket into which the compositions are incorporated. It is also possible to combine both types of incorporation by, for example, a carrier basket of water-insoluble, active ingredient-containing polymer matrix containing a polymer body of water-soluble, active ingredient-containing polymer matrix. Such products can release different levels of active agents from the various matrices at different times, resulting in an optimal concentration of active ingredient at each point in the cleansing program.
Liegen in erfindungsgemäß bevorzugten Mitteln sowohl das Zinksalz als auch das Silikate in einer Polymermatrix konfektioniert vor, so kann diese Konfektionierung in bevorzugten Ausgestaltungsformen der vorliegenden Erfindung sowohl in der gleichen Polymermatrix als auch in unterschiedlichen Matrizes erfolgen, das heitß, daß das Zinksalz beispielsweise in Polymer A konfektioniert vorliegt, während das Silikat in einem Polymer B konfektioniert wurde. Schließlich können Zinksalz und Silikat auch mittels des gleichen Polymers, jedoch in voneinander getrennten Matrizes konfektioniert werden.If, in accordance with the invention, both the zinc salt and the silicates are packaged in a polymer matrix, this preparation in preferred embodiments of the present invention can take place both in the same polymer matrix and in different matrices, which means that the zinc salt can be converted, for example, into polymer A pre-assembled, while the silicate was formulated in a polymer B. Finally, zinc salt and silicate can also be formulated by means of the same polymer, but in separate matrices.
Die erfindungsgemäßen Mittel lassen sich demnach sowohl mit wasserunlöslichen als auch mit wasserlöslichen Polymeren oder Mischungen daraus realisieren. Bevorzugte maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel sind dadurch gekennzeichnet, daß die Polymermatrix ein oder mehrere wasserlösliche(s) Polymer(e) umfaßt.The compositions of the invention can therefore be realized both with water-insoluble and with water-soluble polymers or mixtures thereof. Preferred automatic dishwashing or machine dishwashing aids are characterized in that the polymer matrix comprises one or more water-soluble polymer (s).
Die erfindungsgemäßen Polymermatrizes können dabei universell formuliert werden. So ist es beispielsweise möglich, erfindungsgemäße Vorweichmittel, Vorspülmittel, Reinigungsmittel für den Hauptspülgang oder Klarspülmittel bereitzustellen. Daneben können erfindungsgemäße Zusammensetzungen auch Kombinationsprodukte sein, die zwei oder mehrere der vorgenannten Mittel in sich vereinen. Auch die Formulierung erfindungsgemäßer Zusammensetzungen als Additionsprodukt, das beispielsweise in die Geschirrspülmaschine eingehängt wird, ist problemlos möglich. Die wirkstoffhaltige Polymermatrix kann teilchenförmig in die erfindungsgemäßen Zusammensetzungen eingearbeitet werden, sie kann aber auch ein kompakter Formkörper sein, der beispielsweise entweder ein Kern ist, welcher eine Mulde einer Reinigungsmitteltablette füllt, oder ein Formkörper, der als Additionsprodukt gleich einem Deo-Hänger in die Spülmaschine eingebracht wird. Auch Körbchen, welche für die Aufnahme von Reinigungsmitteltabletten geeignet sind, lassen sich aus der wirkstoffhaltigen Polymermatrix herstellen. Nicht zuletzt kann die wirkstoffhaltige Polymermatrix auch als Verpackung für maschinelle Geschirrspülmittel genutzt werden. Dies ist insbesondere bei vollständig wasserlöslichen wirkstoffhaltigen Polymermatrizes attraktiv, da der Verbraucher das Produkt nicht auspacken muß, den direkten Kontakt mit dem Produkt, der als unerwünscht empfunden wird, vermeidet und zudem andere Verpackungsmaterialien eingespart werden.The polymer matrices according to the invention can be formulated universally. For example, it is possible to provide pre-softeners, pre-rinsing agents, cleaning agents for the main rinse or rinse aid according to the invention. In addition, compositions according to the invention may also be combination products which combine two or more of the aforementioned agents. Also, the formulation of inventive compositions as an addition product, which is hung for example in the dishwasher, is easily possible. The active ingredient-containing polymer matrix can be particulate incorporated into the compositions of the invention, but it can also be a compact molded body, for example, either a core which fills a trough of a detergent tablet, or a shaped product, which as an addition product equal to a deodorant hanger in the dishwasher is introduced. Also, baskets which are suitable for receiving detergent tablets, can be prepared from the active ingredient-containing polymer matrix. Last but not least, the active ingredient-containing polymer matrix can also be used as a packaging for automatic dishwasher detergents. This is especially true for completely water-soluble active substance-containing polymer matrices attractive, since the consumer does not have to unpack the product, the direct contact with the product, which is perceived as undesirable, avoids and other packaging materials are saved.
Besonders bevorzugt erfindungsgemäße Mittel sind dadurch gekennzeichnet, daß die Polymermatrix
- a) 5 bis 99,5 Gew.-% eines oder mehrerer Polymere,
- b) mindestens ein Zinksalz sowie mindestens ein kristallines schichtförmiges Silikat der allgemeinen Formel (la)
NaMSixO2x+1 · yH2O (Ia),
worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, ist und y für eine Zahl von 0 bis 33 steht, enthält, wobei die Summe der Gewichtsanteile des/der Zinksalze(s) und des/der kristallinen Silikate(s) 0,5 bis 95 Gew.-% beträgt, - c) 0 bis 30 Gew.-% weiterer Wirk- und/oder Hilfsstoffe
umfaßt, wobei sich die Gewichtsangaben jeweils auf das Gesamtgewicht der wirkstoffhaltigen Polymermatrix beziehen.
- a) 5 to 99.5% by weight of one or more polymers,
- b) at least one zinc salt and at least one crystalline layered silicate of the general formula (Ia)
NaMSi × O 2x + 1 × yH 2 O (Ia),
wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33, wherein the sum of the weight proportions of the zinc salt (s ) and of the crystalline silicate (s) is from 0.5 to 95% by weight, - c) 0 to 30 wt .-% of other active ingredients and / or adjuvants
includes, wherein the weights are each based on the total weight of the active ingredient-containing polymer matrix.
Die Polymermatrix der erfindungsgemäß bevorzugten Mittel umfaßt 5 bis 99,5 Gew.-% eines oder mehrerer Polymere. Der Begriff "Polymere" kennzeichnet im Rahmen der folgenden Anmeldung in Anlehnung an die IUPAC-Definition Substanzen, die sich aus einem Kollektiv chemisch einheitlich aufgebauter, sich in der Regel aber hinsichtlich Polymerisationsgrad, Molmasse und Ketten-Länge unterscheidender Makromoleküle zusammensetzt. Nach dieser die Entstehungsweise des Begriffs nicht berücksichtigenden IUPAC-Definition ist ein Polymer "eine Substanz, die aus einer Vielzahl von Molekülen aufgebaut ist, in denen eine Art oder mehrere Arten von Atomen oder Atom-Gruppierungen (sogenannte konstitutive Einheiten, Grundbausteine oder Wiederholungseinheiten) wiederholt aneinander gereiht sind". Die unterschiedlich großen Makromoleküle eines Polymers sind aus so vielen gleichen oder ähnlichen niedermolekularen Bausteinen (Monomeren) aufgebaut, daß sich die physikalischen Eigenschaften der Substanz, besonders die Viskoelastizität, bei geringfügiger Erhöhung oder Reduzierung der Anzahl der Bausteine nicht mehr merklich ändern. Die Größe der Makromoleküle bedingt, daß sich die Endgruppen relativ wenig auf die Eigenschaften der Polymere auswirken, so daß auf ihre explizite Angabe in den nachstehend angegebenen Strukturformeln meist verzichtet wird.The polymer matrix of the agents preferred according to the invention comprises from 5 to 99.5% by weight of one or more polymers. The term "polymers" in the context of the following application, based on the IUPAC definition, denotes substances which are composed of a collective of chemically uniformly structured, but generally differing in terms of degree of polymerization, molecular weight and chain length macromolecules. According to this IUPAC definition, which does not take into account the concept of the term, a polymer "is a substance composed of a plurality of molecules in which one or more types of atoms or atomic groups (so-called constituent units, basic building blocks or repeating units) are repeated are strung together ". The different sized macromolecules of a polymer are composed of so many identical or similar low molecular weight building blocks (monomers) that the physical properties of the substance, especially the viscoelasticity, do not change noticeably with a slight increase or decrease in the number of building blocks. The size of the macromolecules implies that the end groups have relatively little effect on the properties of the polymers, so that their explicit specification in the structural formulas given below is usually dispensed with.
Die die Matrix bildenden Polymere der erfindungsgemäßen Zusammensetzungen können dabei sowohl natürlichen als auch synthetischen Ursprungs sein. Bevorzugte erfindungsgemäße Mittel sind dadurch gekennzeichnet, daß die Polymermatrix 7,5 bis 95 Gew.-%, vorzugsweise 10 bis 90 Gew.-%, besonders bevorzugt 12,5 bis 85 Gew.-%, weiter bevorzugt 15 bis 82,5 Gew.-% und insbesondere 20 bis 80 Gew.-% eines oder mehrerer Polymere umfaßt, wobei die Gewichtsangaben sich auf die wirkstoffhaltige Polymermatrix beziehen.The matrix-forming polymers of the compositions according to the invention may be of natural or synthetic origin. Preferred agents according to the invention are characterized in that the polymer matrix from 7.5 to 95 wt .-%, preferably 10 to 90 wt .-%, particularly preferably 12.5 to 85 wt .-%, more preferably 15 to 82.5 wt .-% and in particular 20 to 80 wt .-% of one or more polymers, wherein the weights are based on the active ingredient-containing polymer matrix.
Die mittlere Molmasse der in den bevorzugten erfindungsgemäßen Mittel enthaltenen Polymere liegt vorzugsweise bei mindestens 5000 g/mol, besonders bevorzugt bei mindestens 10.000 g/mol und insbesondere bei mindestens 12.000 g/mol.The average molar mass of the polymers contained in the preferred agents according to the invention is preferably at least 5000 g / mol, particularly preferably at least 10,000 g / mol and in particular at least 12,000 g / mol.
Wie bereits erwähnt, können die erfindungsgemäß bevorzugten Mittel sowohl wasserunlösliche als auch wasserlösliche Polymere sowie Mischungen dieser Polymere enthalten. Erfindungsgemäß bevorzugte Zusammensetzungen auf der Basis wasserunlöslicher Polymermatrizes sind dadurch gekennzeichnet, daß die Polymermatrix ein oder mehrere wasserunlösliche Polymere aus der Gruppe Polyethylen, Polypropylen, Polytetrafluorethylen, Polystyrol, Polyethylenterphthalat, Polycarbonat, Polyvinylchlorid, der Polyurethane, der Polyamide sowie deren Mischungen umfaßt.As already mentioned, the agents preferred according to the invention may contain both water-insoluble and water-soluble polymers and mixtures of these polymers. According to preferred compositions based on water-insoluble polymer matrices are characterized in that the polymer matrix comprises one or more water-insoluble polymers from the group polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polyurethanes, polyamides and mixtures thereof.
Anstelle von wasserunslöslichen Polymeren oder in Mischung mit ihnen können auch wasserlösliche Polymere natürlichen oder synthetischen Ursprungs die Polymermatrix bilden. Weiter bevorzugte erfindungsgemäße Mittel sind dadurch gekennzeichnet, daß die Polymermatrix ein oder mehrere wasserlösliche Polymere umfaßt, wobei das bzw. die wasserlösliche(n) Polymer(e) vorzugsweise ausgewählt ist/sind aus:
- i) Polyacrylsäuren und deren Salzen
- ii) Polymethacrylsäuren und deren Salzen
- iii) Polyvinylpyrrolidon,
- iv) Vinylpyrrolidon/Vinylester-Copolymeren,
- v) Celluloseethern
- vi) Polyvinylacetaten, Polyvinylalkoholen und ihren Copolymeren
- vii) Pfropfcopolymeren aus Polyethylenglykolen und Vinylacetat
- viii) Alkylacrylamid/Acrylsäure-Copolymeren und deren Salzen
- ix) Alkylacrylamid/Methacrylsäure-Copolymeren und deren Salzen
- x) Alkylacrylamid/Methylmethacrylsäure-Copolymeren und deren Salzen
- xi) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymeren und deren Salzen
- xii) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymeren und deren Salzen
- xiii) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
- xiv) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymeren und deren Salzen
- xv) Copolymeren aus
- xv-i) ungesättigten Carbonsäuren und deren Salzen
- xv-ii) kationisch derivatisierten ungesättigten Carbonsäuren und deren Salzen
- xvi) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkaliund Ammoniumsalze
- xvii) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
- xviii) Methacroylethylbetain/Methacrylat-Copolymere
- xix) Vinylacetat/Crotonsäure-Copolymere
- xx) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
- xxi) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglykolen
- xxii) gepropften Copolymere aus der Copolymerisation von
- xxii-i) mindesten einem Monomeren vom nicht-ionischen Typ,
- xxii-ii) mindestens einem Monomeren vom ionischen Typ,
- xxiii) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
- xxiii-i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
- xxiii-i) ungesättigte Carbonsäuren,
- xxiii-iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C8-18-Alkohols.
- i) polyacrylic acids and their salts
- ii) polymethacrylic acids and their salts
- iii) polyvinylpyrrolidone,
- iv) vinyl pyrrolidone / vinyl ester copolymers,
- v) cellulose ethers
- vi) polyvinyl acetates, polyvinyl alcohols and their copolymers
- vii) graft copolymers of polyethylene glycols and vinyl acetate
- viii) alkylacrylamide / acrylic acid copolymers and their salts
- ix) alkylacrylamide / methacrylic acid copolymers and their salts
- x) alkylacrylamide / methylmethacrylic acid copolymers and their salts
- xi) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
- xii) alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
- xiii) alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
- xiv) alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and their salts
- xv) copolymers
- xv-i) unsaturated carboxylic acids and their salts
- xv-ii) cationically derivatized unsaturated carboxylic acids and their salts
- xvi) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts
- xvii) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts
- xviii) Methacroylethylbetaine / methacrylate copolymers
- xix) vinyl acetate / crotonic acid copolymers
- xx) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
- xxi) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
- xxii) grafted copolymers from the copolymerization of
- xxii-i) at least one nonionic type monomer,
- xxii-ii) at least one ionic type monomer,
- xxiii) copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
- xxiii-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
- xxiii-i) unsaturated carboxylic acids,
- xxiii-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C 8-18 -alcohols.
Die wirkstoffhaltige Polymermatrix weist neben dem oder den Polymer(en) einen Gehalt an mindestens einem Zinksalz und/oder mindestens einem kristallinen schichtförmigen Silikat der allgemeinen Formel (I) bzw. der allgemeinen Formel (Ia) auf, welche aus der Matrix freigesetzt werden könnnen. Erfindungsgemäß bevorzugte Mittel sind dadurch gekennzeichnet, daß sie mindestens ein Zinksalz sowie mindestens ein kristallines schichtförmiges Silikat der allgemeinen Formel (I) bzw. der allgemeinen Formel (Ia) enthalten, wobei die Summe der Gewichtsanteile dieser Bestandteile 1 bis 90 Gew.-%, vorzugsweise 1,5 bis 80 Gew.-%, besonders bevorzugt 2 bis 70 Gew.-%, weiter bevorzugt 2,5 bis 60 Gew.-% und insbesondere 3 bis 50 Gew.-%, jeweils bezogen auf das Gesamtgewicht der wirkstoffhaltigen Polymermatrix, beträgt.The active ingredient-containing polymer matrix has, in addition to the polymer (s), a content of at least one zinc salt and / or at least one crystalline layered silicate of the general formula (I) or of the general formula (Ia) which can be liberated from the matrix. Agents preferred according to the invention are characterized in that they comprise at least one zinc salt and at least one crystalline layered silicate of the general formula (I) or the general formula (Ia), the sum of the proportions by weight of these constituents being from 1 to 90% by weight, preferably 1.5 to 80 wt .-%, particularly preferably 2 to 70 wt .-%, more preferably 2.5 to 60 wt .-% and in particular 3 to 50 wt .-%, each based on the total weight of the active ingredient-containing polymer matrix is.
Die erfindungsgemäßen maschinellen Geschirrspülmittel oder maschinellen Geschirrspülhilfsmittel können die wirkstoffhaltige Polymermatrix in unterschiedlichen Mengen enthalten. Je nachdem, ob die wirkstoffhaltige Polymermatrix in den Zusammensetzungen beispielsweise als feinteiliges Pulver oder Granulat enthalten ist, als Teil eines Formkörpers ausgebildet ist, oder ob sie die Zusammensetzung als Verpackung umschließt, können die Mengenanteile der wirkstoffhaltigen Polymermatrix an der Gesamtzusammensetzung variieren. Hier sind erfindungsgemäße Zusammensetzungen bevorzugt, die, bezogen auf die Gesamtmasse der Zusammensetzung, 1 bis 40 Gew.-%, vorzugsweise 1,5 bis 35 Gew.-%, besonders bevorzugt 2 bis 30 Gew.-% und insbesondere 2,5 bis 20 Gew.-% der wirkstoffhaltigen Polymermatrix enthalten.The automatic dishwasher detergents or automatic dishwashing auxiliaries according to the invention can contain the active ingredient-containing polymer matrix in different amounts. Depending on whether the active ingredient-containing polymer matrix is contained in the compositions, for example as a finely divided powder or granules, as part of a shaped body, or whether it encloses the composition as packaging, the proportions of the active ingredient-containing polymer matrix can vary in the overall composition. Preferred compositions according to the invention are those which, based on the total mass of the composition, are 1 to 40% by weight, preferably 1.5 to 35% by weight, more preferably 2 to 30% by weight and in particular 2.5 to 20 Wt .-% of the active ingredient-containing polymer matrix included.
Besonders bevorzugte Polymermatrizes enthalten mindestens ein Zinksalz in solchen Mengen, daß die Zusammensetzung Zink in oxidierter Form in Gewichtsanteilen von 0,01 bis 1 Gew.-%, vorzugsweise von 0,02 bis 0,5 Gew.-% und insbesondere von 0,04 bis 0,2 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Polymermatrix, enthält.Particularly preferred polymer matrices contain at least one zinc salt in such amounts that the composition comprises zinc in oxidized form in proportions by weight of from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2 wt .-%, each based on the total weight of the polymer matrix contains.
Wie eingangs erwähnt, bedingt die Einarbeitung erfindungsgemäß bevorzugter wirkstoffhaltiger Polymermatrizes in die erfindungsgemäßen Zusammensetzungen keine Einschränkung bezüglich der Anbietungsformen oder der Rezepturen dieser Zusammensetzungen. So können neben üblichen maschinellen Geschirrspülmitteln auch Vorweich- oder Vorspülprodukte, Klarspüler, Maschinenpfleger oder Zusatzprodukte als erfindungsgemäße Zusammensetzung bereitgestellt werden. Eine bevorzugte Ausführungsform der erfindungsgemäßen Zusammensetzung sieht vor, daß die Polymermatrix als separat in die Geschirrspülmaschine einzubringendes Formteil bereitgestellt wird, das über mehrere Spülgänge hinweg die Agentien aus der Polymermatrix freisetzt. Dieses Formteil kann entweder ein Dosierkörbchen für andere Produkte, wie beispielsweise den Reiniger, sein, es kann aber auch als separates und eigenständiges Formteil den Zusatznutzen der Glasschonung verkörpern. Mögliche Formen sind beispielsweise an die bekannten Spülmaschinen-Dodorantien angelehnt. Optisch reizvoll ist die Ausgestaltung des Kunststoffteils in transluzenter, opaleszenter oder vollständig klarer Form, beispielsweise in Form eines stilisierten Diamanten. Durch solche Produktausgestaltungen läßt sich der durch die Glasschonung resultierende Glanz verbrauchernah visualisieren.As mentioned at the beginning, incorporation of preferred active ingredient-containing polymer matrices into the compositions according to the invention does not entail any restriction with regard to the forms of preparation or the formulations of these compositions. Thus, in addition to conventional automatic dishwashing agents, pre-soaking or pre-rinsing products, rinse aid, machine care or additional products can be provided as a composition according to the invention. A preferred embodiment of the composition of the invention provides that the polymer matrix is provided as a separate part to be introduced into the dishwasher, which releases the agents from the polymer matrix over several rinse cycles. This molding can either be a Dosierkörbchen for other products, such as the cleaner, but it can also embody the added benefit of glass preservation as a separate and independent molding. Possible shapes are based, for example, on the known dishwasher Dodorantien. Visually attractive is the design of the plastic part in translucent, opalescent or completely clear form, for example in the form of a stylized diamond. By such product designs, the gloss resulting from the glass preservation can be visualized close to the consumer.
Der Vielfalt der Formgebung sind aufgrund der Möglichkeiten der Kunststoffverarbeitung keinerlei Grenzen gesetzt. Die wirkstoffhaltigen Polymermatrizes können problemlos mit den gängigen Methoden umgeformt werden.There are no limits to the variety of shape due to the possibilities of plastics processing. The active ingredient-containing polymer matrices can be easily converted by conventional methods.
Die formgebende Verarbeitung erfolgt nach den in der kunststoffverarbeitenden Industrie üblichen Verfahren, wobei insbesondere die Folienherstellung und -weiterverarbeitung, das Blasformen und das Spritzgießen bevorzugt sind. Allen Verfahren ist gemeinsam, daß ein Kunststoffgranulat mit Hilfe eines Extruders aufgeschmolzen und formgebenden Werkzeugen zugeführt wird. Dabei kann das Kunststoffgranulat die Agentien zur Glaskorrosionsinhibierung bereits enthalten, diese können aber auch während des Aufschmelzens im Extruder zugegeben werden, was eine besonders kostengünstige Herstellung der erfindungsgemäß bevorzugzten wirkstoffhaltigen Polymermatrizes ermöglicht.The shaping processing takes place according to the usual in the plastics processing industry process, in particular, the film production and processing, blow molding and injection molding are preferred. All methods have in common that a plastic granules are melted by means of an extruder and fed to forming tools. In this case, the plastic granules may already contain the agents for glass corrosion inhibition, but these can also be added during the melting in the extruder, which allows a particularly cost-effective production of inventively preferred active ingredient-containing polymer matrices.
In einer zusätzlichen bevorzugten Ausführungsform werden die erfindungsgemäßen maschinellen Geschirrspülmittel oder maschinellen Geschirrspülhilfsmittel in einer Art konfektioniert, die es ermöglicht, die in diesen Mitteln enthaltenen Aktivsubstanzen gezielt zu applizieren und zu dosieren. Für dieses Zwecke eignen sich im Rahmen der vorliegenden Anmeldung insbesondere stiftförmige Angebotsform, die, ähnlich einem Klebestift, bei Lagerung und Transport ihre räumlich-geometrische Form nicht verändern, diese jedoch, wird die Angebotsform unter Einwirkung eines Druckes über eine Oberfläche bewegt, in ihrem Kontaktbereich mit der Oberfläche aufgrund der dort auftretenden Scherkräfte verliert. Das Mittel wird als eine Folge der einwirkenden Scherkräfte auf der Oberfläche verschmiert und verbleibt dort nach Beendigung des Einwirkens der Scherkräfte in seiner neuen räumlich-geometrischen Form, ist also wiederum formstabil. Mit Hilfe einer derartigen bevorzugten Konfektionierung lassen sich erfindungsgemäße Mittel gezielt applizieren und dosieren.In an additional preferred embodiment, the automatic dishwasher detergents or automatic dishwashing auxiliaries according to the invention are packaged in a manner which makes it possible to selectively apply and meter the active substances contained in these agents. For this purpose are in the context of the present application, in particular pen-shaped offer form, similar to a glue stick, do not change their spatial-geometric shape during storage and transport, but these, the offer form is moved under the influence of pressure over a surface, in their contact area loses with the surface due to the shear forces occurring there. The agent is smeared as a result of the shearing forces acting on the surface and remains there after the end of the action of the shear forces in its new spatial-geometric shape, so in turn is dimensionally stable. With the aid of such a preferred assembly, compositions according to the invention can be applied and metered in a targeted manner.
Derartige formstabile maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, die sich aufgrund ihrer Materialbeschaffenheit bei Einwirkung einer Scherkraft auf einer Oberfläche verstreichen lassen, ohne Einwirkung einer Scherkraft jedoch in seiner Raumform verharren, lassen sich vorteilhafterweise durch ihre Penetrationszahlen charakterisieren. Als Penetrationszahl wird im Rahmen der vorliegenden Erfindung der Zahlenwert bezeichnet, der sich bei Bestimmung der Härte der erfindungsgemäßen Mittel mittels eines Texture Analyzers, Modell TA-XT2-I der Firma Stable Micro Systems ergibt. Zur Durchführung dieser Messung werden die folgenden Test-Parameter eingestellt:
Die Penetrationszahl wird bestimmt, indem ein bestimmtes Messwerkzeug (TA-15 45°-Kegel aus Edelstahl) mit einer definierten Vorschubgeschwindigkeit (0,5 mm/s) bis zu einer definierten Eindringtiefe (5,0 mm) in das Testmaterial gepresst und anschließend mit einer definierten Geschwindigkeit (0,2 mm/s) aus diesem Material herausgezogen wird. Die untersuchten Testmaterialien hatten eine Temperatur von 23°C, die Messungen wurden bei 20°C Raumtemperatur durchgeführt. Das Meßgerät ermittelte ausgehend von dem beschriebenen Versuchsaufbau einen Zahlenwert in der Einheit Gramm [g]. Dieser Zahlenwert wird im Rahmen der vorliegenden Anmeldung als Penetrationszahl bezeichnet. Die Messungen nach der beschriebenen Methode ergaben nun, daß die bevorzugten formstabilen maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel Penetrationszahlen von 200 bis 1000 g, vorzugsweise von 250 bis 900 g, besonders bevorzugt von 300 bis 800 g und insbesondere von 350 bis 700 g aufweisen.The penetration rate is determined by pressing a specific measuring tool (TA-15 45 ° cone made of stainless steel) at a defined feed rate (0.5 mm / s) to a defined penetration depth (5.0 mm) into the test material and then with a defined speed (0.2 mm / s) is pulled out of this material. The tested test materials had a temperature of 23 ° C, the measurements were carried out at 20 ° C room temperature. Based on the test setup described above, the measuring instrument determined a numerical value in units of grams [g]. This numerical value is referred to in the context of the present application as a penetration number. The measurements according to the described method have now shown that the preferred dimensionally stable automatic dishwashing or machine dishwashing auxiliary penetration numbers of 200 to 1000 g, preferably from 250 to 900 g, more preferably from 300 to 800 g and in particular from 350 to 700 g.
Ein weiterer bevorzugter Gegenstand der vorliegenden Erfindung sind daher erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, die formstabil sind und eine Penetrationszahl von 200 bis 1000 g vorzugsweise von 250 bis 900 g, besonders bevorzugt von 300 bis 800 g und insbesondere von 350 bis 700 g aufweisen.Another preferred subject of the present invention are therefore automatic dishwashing detergents or dishwashing auxiliaries according to the invention which are dimensionally stable and have a penetration number of from 200 to 1000 g, preferably from 250 to 900 g, more preferably from 300 to 800 g and in particular from 350 to 700 g.
Der Begriff "formstabil" bezeichnet im Rahmen der vorliegenden Erfindung maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, die eine Eigen-Formstabilität aufweisen, die sie befähigt, unter üblichen Bedingungen der Herstellung, der Lagerung, des Transports und der Handhabung durch den Verbraucher eine gegen Bruch stabile, nicht desintegrierende Raumform zu haben, die sich auch unter den genannten Bedingungen über längere Zeit nicht verändert, das heißt unter den üblichen Bedingungen der Herstellung, der Lagerung, des Transports und der Handhabung durch den Verbraucher in der durch die Herstellung bedingten räumlich-geometrischen Form verharrt, das heißt, beispielsweise nicht zerfließt.The term "dimensionally stable" in the context of the present invention denotes automatic dishwashing detergents or dishwashing auxiliaries which have an intrinsic dimensional stability which enables them, under normal conditions of manufacture, storage, transport and handling by the consumer, to be stable against breakage, to have non-disintegrating spatial form, which does not change even under the conditions mentioned for a long time, that is under the usual conditions of manufacture, storage, transport and handling by the consumer persists in the caused by the production spatial-geometric shape that is, for example, does not melt.
Die für bevorzugte erfindungsgemäße Mittel kennzeichnende Penetrationszahl von 200 bis 1000 g läßt sich nicht durch Aktivsubstanzen wie Zinksalze oder schichtförmige Silikate in ihrer Reinform realisieren. Es ist daher notwendig ein Trägermaterial oder Matrixmaterial für diese Aktivsubstanzen bereitzustellen, das den genannten physikalischen Anforderungen an ein erfindungsgemäßes Mittel entspricht. Ein solche Matrix sollte zudem mit in ihr enthaltenen aktiven Agentien kompatibel sein, das heißt insbesondere nicht mit diesen reagieren, sondern diese stabilisieren. Weiterhin sollen die Trägermaterialien auch den angestrebten Reinigungsvorgang nicht in Frage stellen, also auch mit allen weiteren während des Reinigungs- und/oder Pflegevorgangs eingesetzten Substanzen verträglich sein. Schließlich sollte das Matrixmaterial vorzugsweise wasserlöslich bzw. wasserdispergierbar sein, um das Auftreten von Rückständen nach der Anwendung des erfindungsgemäßen Mittels zu vermeiden. Besonders bevorzugt sind Trägermaterialien, die neben der Funktion als Matrix für die Aktivsubstanz gleichzeitig eine reinigende oder pflegende Funktion aufweisen. Aus der großen Zahl möglicher Trägermaterialien haben sich im Rahmen der vorliegenden Erfindung eine Reihe von Stoffgruppen als besonders vorteilhaft erwiesen. Auf diese Substanzen soll in der Folge näher eingegangen werden.The penetration number of 200 to 1000 g, which is characteristic for preferred agents according to the invention, can not be realized in their pure form by active substances such as zinc salts or layered silicates. It is therefore necessary to provide a carrier material or matrix material for these active substances, which corresponds to the stated physical requirements for an agent according to the invention. In addition, such a matrix should be compatible with active agents contained in it, ie in particular should not react with them, but stabilize them. In addition, the carrier materials should not jeopardize the intended cleaning process, ie they should also be compatible with all other substances used during the cleaning and / or maintenance process. Finally, the matrix material should preferably be water-soluble or water-dispersible in order to prevent the occurrence of residues to avoid after the application of the agent according to the invention. Particular preference is given to support materials which, in addition to the function as matrix for the active substance, simultaneously have a cleaning or care function. From the large number of possible carrier materials, a number of substance groups have proven to be particularly advantageous in the context of the present invention. These substances will be discussed in more detail below.
Bevorzugt formstabile, erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, sind im Rahmen der vorliegenden Anmeldung daher dadurch gekennzeichnet, daß sie Polyvinylpyrrolidon(e) und/oder Polyvinylalkohol(e) und/oder Polyvinylacetat(e) und/oder Polyacrylat(e) und/oder Polyalkylenglycol(e) und/oder Fett(e) und/oder Fettsäure(n) und/oder Fettsäureester und/oder Fettsäureamid(e) und/oder Fettalkohole und/oder Wachs(e) und/oder Parrafin(e) und/oder Wachsalkohole und/oder Tensid(e), vorzugsweise nichtionische(s) Tensid(e), und/oder Dextrin(e) und/oder Stärkeether enthalten, wobei der Gewichtsanteil dieses Bestandteils/dieser Bestandteile am Gesamtgewicht des formstabilen maschinellen Geschirrspül- und/oder Geschirrspülhilfsmittels vorzugsweise zwischen 30 und 99 Gew.%, besonders bevorzugt zwischen 40 und 95 Gew.-% und insbesondere zwischen 50 und 95 Gew.-% beträgt.In the context of the present application, preferably dimensionally stable dishwashing detergents or dishwashing auxiliaries according to the invention are characterized in that they contain polyvinylpyrrolidone (s) and / or polyvinyl alcohol (s) and / or polyvinyl acetate (s) and / or polyacrylate (s) and / or Polyalkylene glycol (s) and / or fat (s) and / or fatty acid (s) and / or fatty acid esters and / or fatty acid amide (s) and / or fatty alcohols and / or wax (s) and / or parrafin (s) and / or Wax alcohols and / or surfactant (s), preferably nonionic (s) surfactant (s), and / or dextrin (s) and / or starch ethers, wherein the proportion by weight of this component / these components in the total weight of dimensionally stable machine dishwashing and / or Dishwashing auxiliary preferably between 30 and 99 wt.%, Particularly preferably between 40 and 95 wt .-% and in particular between 50 and 95 wt .-% is.
Erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel können außer in den beschriebenen festen bzw. formstabilen Formen auch in Form flüssiger bzw. fließfähiger Mittel konfektioniert werden. In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung weisen die maschinellen Geschirrspülmittel oder maschinellen Geschirrspülhilfsmittel daher eine Viskosität von 500 bis 500.000 mPas, vorzugsweise von 900 bis 200.000 mPas und insbesondere von 1300 bis 100.000 mPas auf. Die Viskosität der erfindungsgemäßen Mittel wird mit üblichen Standardmethoden (beispielsweise Brookfield-Viskosimeter LVT-II bei 20 U/min und 20°C, Spindel 3) gemessen. Der Ausdruck "flüssige oder fließfähige Mittel" wird in der Folge für Mittel verwandt, welche eine Viskosität von 500 bis 500.000 mPas, vorzugsweise von 900 bis 200.000 mPas und insbesondere von 1300 bis 100.000 mPas aufweisen.Automatic dishwashing detergents or automatic dishwashing auxiliaries according to the invention can also be formulated in the form of liquid or flowable agents, in addition to the solid or dimensionally stable forms described. In a further preferred embodiment of the present invention, the automatic dishwashing or machine dishwashing aids therefore have a viscosity of from 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and in particular from 1300 to 100,000 mPas. The viscosity of the compositions according to the invention is measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3). The term "liquid or flowable agents" will be used hereafter for agents which have a viscosity of from 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and especially from 1300 to 100,000 mPas.
Als einen bevorzugten Inhaltsstoff enthalten derartige bevorzugte erfindungsgemäße flüssige oder fließfähige Mittel ein oder mehrere nichtwässrige Lösungsmittel. Diese stammen beispielsweise aus den Gruppen der Mono-Alkohole, Diole, Triole bzw. Polyole, der Ether, Ester und/oder Amide. Besonders bevorzugt sind dabei nichtwässrige Lösungsmittel, die wasserlöslich sind, wobei "wasserlösliche" Lösungsmittel im Sinne der vorliegenden Anmeldung Lösungsmittel sind, die bei Raumtemperatur mit Wasser vollständig, d.h. ohne Mischungslücke, mischbar sind.As a preferred ingredient, such preferred liquid or flowable compositions of the invention contain one or more non-aqueous solvents. These are derived, for example, from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides. Particular preference is given to nonaqueous solvents which are water-soluble, "water-soluble" solvents in the sense of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.
Geeignete nichtwässrige Lösungsmittel stammen vorzugsweise aus der Gruppe ein- oder mehrwertigen Alkohole, Alkanolamine oder Glycolether, sofern sie im angegebenen Konzentrationsbereich mit Wasser mischbar sind. Vorzugsweise werden die Lösungsmittel ausgewählt aus Ethanol, n- oder i-Propanol, Butanolen, Glykol, Propan- oder Butandiol, Glycerin, Diglykol, Propyl- oder Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Etheylenglykolmono-n-butylether, Diethylenglykol-methylether, Diethylenglykolethylether, Propylenglykolmethyl-, -ethyl- oder - propyl-ether, Dipropylenglykolmethyl-, oder-ethylether, Methoxy-, Ethoxy- oder Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen-glykol-t-butylether sowie Mischungen dieser Lösungsmittel.Suitable nonaqueous solvents are preferably from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the given concentration range. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.
Auch bei Raumtemperatur flüssige nichtionische Tenside sind im Rahmen der Anmeldung bevorzugte nichtwässrige Lösungsmittel.Nonionic surfactants which are liquid at room temperature are also preferred nonaqueous solvents in the context of the application.
Ein im Rahmen der vorliegenden Erfindung besonders bevorzugtes flüssiges oder fließfähiges maschinelles Geschirrspülmittel oder maschinelles Geschirrspülhilfsmittel ist dadurch gekennzeichnet, daß es nichtwässrige(s) Lösungsmittel enthält, wobei das/die Lösungsmittel vorzugsweise ausgewählt ist/sind aus der Gruppe der Polyethylenglycole und Polypropylenglycole, Glycerin, Glycerincarbonat, Triacetin, Ethylenglycol, Propylengylcol, Propylencarbonat, Hexylenglycol, Ethanol sowie n-Propanol u nd/oder iso-Propanol.A liquid or free-flowing machine dishwashing detergent or machine dishwashing auxiliary which is particularly preferred in the context of the present invention is characterized in that it contains nonaqueous solvents, the solvent (s) preferably being selected from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate , Triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol, and n-propanol and / or iso-propanol.
Erfindungsgemäß bevorzugt einsetzbare Polyethylenglycole (Kurzzeichen PEG) sind bei Raumtemperatur flüssig. PEG sind Polymere des Ethylenglycols, die der allgemeinen Formel (II)
H-(O-CH2-CH2)n-OH (II)
genügen, wobei n Werte zwischen 1 (Ethylenglycol, siehe unten) und ca. 16 annehmen kann. Für Polyethylenglycole existieren verschiedene Nomenklaturen, die zu Verwirrungen führen können. Technisch gebräuchlich ist die Angabe des mittleren relativen Molgewichts im Anschluß an die Angabe "PEG", so daß "PEG 200" ein Polyethylenglycol mit einer relativen Molmasse von ca. 190 bis ca. 210 charakterisiert. Nach dieser Nomenklatur sind im Rahmen der vorliegenden Erfindung die technisch gebräuchlichen Polyethylenglycole PEG 200, PEG 300, PEG 400 und PEG 600 einsetzbar.Polyethylene glycols (abbreviated to PEG) which can preferably be used according to the invention are liquid at room temperature. PEG are polymers of ethylene glycol which are of the general formula (II)
H- (O-CH 2 -CH 2 ) n -OH (II)
n, where n can assume values between 1 (ethylene glycol, see below) and about 16. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. According to this nomenclature, the commercially available polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.
Für kosmetische Inhaltsstoffe wird eine andere Nomenklatur verwendet, in der das Kurzzeichen PEG mit einem Bindestrich versehen wird und direkt an den Bindestrich eine Zahl folgt, die der Zahl n in der oben genannten Formel entspricht. Nach dieser Nomenklatur (sogenannte
Kommerziell erhältlich sind Polyethylenglycole beispielsweise unter den Handelnamen Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone-Poulenc), Lutrol® E300 (BASF) sowie den entsprechenden Handelnamen mit höheren Zahlen.Commercially available polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone -Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
Erfindungsgemäß einsetzbare Polypropylenglycole (Kurzzeichen PPG) sind Polymere des Propylenglycols, die der allgemeinen Formel (III)
Glycerin ist eine farblose, klare, schwerbewegliche, geruchlose süß schmeckende hygroskopische Flüssigkeit der Dichte 1,261, die bei 18,2°C erstarrt. Glycerin war ursprünglich nur ein Nebenprodukt der Fettverseifung, wird heute aber in großen Mengen technisch synthetisiert. Die meisten technischen Verfahren gehen von Propen aus, das über die Zwischenstufen Allylchlorid, Epichlorhydrin zu Glycerin verarbeitet wird. Ein weiteres technisches Verfahren ist die Hydroxylierung von Allylalkohol mit Wasserstoffperoxid am WO3-Kontakt über die Stufe des Glycids.Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C. Glycerol was originally a by-product of fat saponification but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO 3 contact via the step of the glycide.
Glycerincarbonat ist durch Umesterung von Ethylencarbonat oder Dimethylcarbonat mit Glycerin zugänglich, wobei als Nebenprodukte Ethylenglycol bzw. Methanol anfallen. Ein weiterer Syntheseweg geht von Glycidol (2,3-Epoxy-1-propanol) aus, das unter Druck in Gegenwart von Katalysatoren mit CO2 zu Glycerincarbonat umgesetzt wird. Glycerincarbonat ist eine klare, leichtbewegliche Flüssigkeit mit einer Dichte von 1,398 gcm-3, die bei 125-130°C (0,15 mbar) siedet.Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO 2 to glycerol carbonate. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm -3 , which boils at 125-130 ° C (0.15 mbar).
Ethylenglycol (1,2-Ethandiol, "Glykol") ist eine farblose, viskose, süß schmeckende, stark hygroskopische Flüssigkeit, die mit Wasser, Alkoholen und Aceton mischbar ist und eine Dichte von 1,113 aufweist. Der Erstarrungspunkt von Ethylenglycol liegt bei -11,5°C, die Flüssigkeit siedet bei 198°C. Technisch wird Ethylenglycol aus Ethylenoxid durch Erhitzen mit Wasser unter Druck gewonnen. Aussichtsreiche Herstellungsverfahren lassen sich auch auf der Acetoxylierung von Ethylen und nachfolgender Hydrolyse oder auf Synthesegas-Reaktionen aufbauen.Ethylene Glycol (1,2-Ethanediol, "Glycol") is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113. The solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.
Vom Propylengylcol existieren zwei Isomere, das 1,3-Propandiol und das 1,2-Propandiol. 1,3-Propandiol (Trimethylenglykol) ist eine neutrale, farb- und geruchlose, süß schmeckende Flüssigkeit der Dichte 1,0597, die bei -32°C erstarrt und bei 214°C siedet. Die Herstellung von 1,3-Propandiol gelingt aus Acrolein und Wasser unter anschließender katalytischer Hydrierung.There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3-Propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet-tasting liquid of density 1,0597, which solidifies at -32 ° C and boils at 214 ° C. The preparation of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation.
Technisch weitaus bedeutender ist 1,2-Propandiol (Propylenglykol), das eine ölige, farblose, fast geruchlose Flüssigkeit, der Dichte 1,0381 darstellt, die bei -60°C erstarrt und bei 188°C siedet. 1,2-Propandiol wird aus Propylenoxid durch Wasseranlagerung hergestellt.Technically much more significant is 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-Propanediol is prepared from propylene oxide by water addition.
Propylencarbonat ist eine wasserhelle, leichtbewegliche Flüssigkeit, mit einer Dichte von 1,21 gcm-3, der Schmelzpunkt liegt bei -49°C, der Siedepunkt bei 242°C. Auch Propylencarbonat ist großtechnisch durch Reaktion von Propylenoxid und CO2 bei 200°C und 80 bar zugänglich.Propylene carbonate is a water-bright, easily mobile liquid, with a density of 1.21 gcm -3 , the melting point is -49 ° C, the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO 2 at 200 ° C and 80 bar.
In bevorzugten erfindungsgemäßen flüssigen oder fließfähigen maschinellen Geschirrspülmitteln oder maschinellen Geschirrspülhilfsmitteln ist/sind das/die nichtwässrige(n) Lösungsmittel in Mengen von 0,1 bis 70 Gew.-%, vorzugsweise von 0,5 bis 60 Gew.-%, besonders bevorzugt von 1 bis 50 Gew.-%, ganz besonders bevorzugt von 2 bis 40 Gew.-% und insbesondere von 2,5 bis 30 Gew.-%, jeweils bezogen auf das gesamte Mittel, enthalten.In preferred liquid or flowable automatic dishwashing or machine dishwashing auxiliaries according to the invention, the nonaqueous solvent (s) is / are in amounts of from 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, more preferably from 1 to 50 wt .-%, most preferably from 2 to 40 wt .-% and in particular from 2.5 to 30 wt .-%, each based on the total agent included.
Dabei ist im Rahmen dieser Erfindung unter "nichtwässrig" ein Zustand zu verstehen, bei dem der Gehalt an freiem Wasser in den Mitteln deutlich unter 5 Gew.-%, bezogen auf das Mittel, liegt. Es ist bevorzugt, daß der Gehalt der erfindungsgemäßen maschinellen Geschirrspülmittel oder maschinellen Geschirrspülhilfsmittel an freiem, d.h. nicht in Form von Hydratwasser und/oder Konstitutionswasser vorliegendem Wasser unter 10 Gew.-%, vorzugsweise unter 8 Gew.-% und insbesondere sogar unter 6 Gew.-%, jeweils bezogen auf das Mittel, liegt. Wasser kann dementsprechend im wesentlichen nur in chemisch und/oder physikalisch gebundener Form bzw. als Bestandteil der als Feststoff vorliegenden Rohstoffe bzw. Compounds, aber nicht als Flüssigkeit, Lösung oder Dispersion in das Mittel eingebracht werden.In the context of this invention, "non-aqueous" is to be understood as meaning a state in which the content of free water in the agents is significantly below 5% by weight, based on the agent. It is preferred that the level of the automatic dishwashing or machine dishwashing aids of the invention be free, i. not present in the form of water of hydration and / or water of constitution below 10% by weight, preferably below 8% by weight and in particular even below 6% by weight, in each case based on the agent. Accordingly, water can be introduced into the agent substantially only in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as solid, but not as a liquid, solution or dispersion.
Als weiteren bevorzugten Inhaltsstoff enthalten bevorzugte erfindungsgemäße flüssige oder fließfähige maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel ein oder mehrere nichtionische Tenside, kurz Niotenside. Die Mengen, in denen die nichtionischen Tenside eingesetzt werden, liegen erfindungsgemäß bevorzugt zwischen 5 und 30 Gew.-%, wobei erfindungsgemäß solche Mittel besonders bevorzugte sind, die 1 bis 25 Gew.-%, vorzugsweise 2 bis 22,5 Gew.-%, besonders bevorzugt 3 bis 20 Gew.-% und insbesondere 4 bis 17,5 Gew.% nichtionische(s) Tensid(e) enthalten.As a further preferred ingredient, preferred liquid or free-flowing automatic dishwasher detergents or dishwashing auxiliaries according to the invention comprise one or more nonionic surfactants, in short nonionic surfactants. The amounts in which the nonionic surfactants are used are according to the invention preferably between 5 and 30% by weight, whereby according to the invention those agents which are 1 to 25% by weight are particularly preferred, preferably 2 to 22.5% by weight, particularly preferably 3 to 20% by weight and in particular 4 to 17.5% by weight of nonionic surfactant (s).
Für eine ausführliche Beschreibung dieser Niotenside sei zur Vermeidung von Wiederholungen an dieser Stellen auf die nachfolgenden Ausführungen zu den bevorzugten wasch- oder reinigungsaktiven Inhaltsstoffen bevorzugter erfindungsgemäßer Mittel verwiesen.For a detailed description of these nonionic surfactants, reference is made to the following remarks on the preferred washing or cleaning-active ingredients of preferred compositions according to the invention in order to avoid repetitions at these points.
Zur Viskositätsregelung können die erfindungsgemäßen Mittel weitere Inhaltsstoffe enthalten, mit deren Einsatz beispielsweise das Absetzverhalten oder die Gieß- bzw. Fließfähigkeit gezielt gesteuert werden kann. In nichtwässrigen Systemen haben sich dabei insbesondere Kombinationen aus Strukturgebern und Verdickern bewährt.For viscosity control, the compositions according to the invention may comprise further ingredients, the use of which, for example, the settling behavior or the pourability or flowability can be specifically controlled. In non-aqueous systems in particular combinations of structurizers and thickeners have proven to be useful.
Im Rahmen der vorliegenden Erfindung bevorzugte maschinelle Geschirspülmittel enthalten weiterhin
- a) 0,1 bis 1,0 Gew.-% eines oder mehrerer Strukturgeber aus der Gruppe der Bentonite und/oder mindestens teilweise veretherten Sorbitole sowie
- b) 5,0 bis 30 Gew.-% eines oder mehrerer Verdicker aus der Gruppe der Carbonate, Sulfate und amorphen oder kristallinen Disilikate.
- a) 0.1 to 1.0 wt .-% of one or more structurants from the group of bentonites and / or at least partially etherified sorbitol and
- b) 5.0 to 30 wt .-% of one or more thickeners from the group of carbonates, sulfates and amorphous or crystalline disilicates.
Der Strukturgeber a) stammt aus der Gruppe der Bentonite und/oder mindestens teilweise veretherten Sorbitole. Diese Stoffe werden eingesetzt, um die physikalische Stabilität der Mittel zu gewährleisten und die Viskosität einzustellen. Obwohl herkömmliche Verdickungsmittel wie Polyacrylate oder Polyurethane in nichtwässrigen Medien versagen, gelingt die Viskositätsregelung mit den genannten Substanzen im nichtwässrigen System.The structurant a) comes from the group of bentonites and / or at least partially etherified sorbitols. These substances are used to ensure the physical stability of the agents and to adjust the viscosity. Although conventional thickeners such as polyacrylates or polyurethanes fail in non-aqueous media, the viscosity control with the substances mentioned succeeds in the non-aqueous system.
Bentonite sind verunreinigte Tone, die durch Verwitterung vulkanischer Tuffe entstanden sind. Aufgrund ihres hohen Gehalts an Montmorillonit besitzen Bentonite wertvolle Eigenschaften wie Quellfähigkeit, Ionenaustauschvermögen und Thixotropie. Es ist dabei möglich, die Eigenschaften der Bentonite dem Verwendungszweck entsprechend zu modifizieren. Bentonite sind als Tonbestandteil in tropischen Böden häufig und werden als Natrium-Bentonit z.B. in Wyoming/USA abgebaut. Natrium-Bentonit weist die günstigsten anwendungstechnischen Eiegenschaften (Quellfähigkeit) auf, so daß seine Verwendung im Rahmen der vorliegenden Erfindung bevorzugt ist. Natürlich vorkommende Calcium-Bentonite stammen beispielsweise aus Mississippi/USA oder Texas/USA bzw. aus Landshut/D. Die natürlich gewonnenen Ca-Bentonite werden künstlich durch Austausch von Ca gegen Na in die quellfähigeren Na-Bentonite umgewandelt.Bentonites are contaminated clays caused by the weathering of volcanic tuffs. Due to their high content of montmorillonite, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonite according to the intended use. Bentonites are common as clay constituents in tropical soils and are used as sodium bentonite, e.g. mined in Wyoming / USA. Sodium bentonite has the most favorable application properties (swelling capacity), so that its use is preferred in the context of the present invention. Naturally occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. The naturally obtained Ca-bentonites are artificially converted by exchange of Ca for Na in the more swellable Na-bentonites.
Den Hauptbestandteile der Bentonite bilden sogenannte Montmorillonite, die im Rahmen der vorliegenden Erfindung auch in reiner Form eingesetzt werden können. Montmorillonite sind zu den Phyllosilicaten und hier zu den dioktaedrischen Smektiten gehörende Tonminerale, die monoklin-pseudohexagonal kristallisieren. Montmorillonite bilden überwiegend weiße, grauweiße bis gelbliche, völlig amorph erscheinende, leicht zerreibliche, im Wasser quellende, aber nicht plastisch werdende Massen, die durch die allgemeinen Formeln
Al2[(OH)2/Si4O10]·nH2O bzw.
Al2O3·4SiO2·H2O·nH2O bzw.
Al2[(OH)2/Si4O10] (bei 150° getrocknet)
beschrieben werden können.The main constituents of the bentonites form so-called montmorillonites, which can also be used in their pure form in the context of the present invention. Montmorillonites are too the clay silicates and here to the dioctahedral smectites belonging clay minerals, which crystallize monoclinic pseudohexagonal. Montmorillonite form predominantly white, grayish-white to yellowish, completely amorphous appearing, easily friable, in the water swelling, but not plasticizing masses, by the general formulas
Al 2 [(OH) 2 / Si 4 O 10 ] .nH 2 O or
Al 2 O 3 · 4SiO 2 · H 2 O · nH 2 O or
Al 2 [(OH) 2 / Si 4 O 10 ] (dried at 150 °)
can be described.
Bevorzugte maschinelle Geschirspülmittel oder maschinelle Geschirrspülhilfsmittel sind dadurch gekennzeichnet, daß als Strukturgeber Montmorillonite eingesetzt werden. Montmorillonite besitzen eine Dreischicht-Struktur, die aus zwei Tetraeder-Schichten besteht, die über die Kationen einer Oktaeder-Zwischenschicht elektrostatisch vernetzt sind. Die Schichten sind nicht starr verbunden, sondern können durch reversible Einlagerung von Wasser (in der 2-7fachen Menge) und anderen Substanzen wie z.B. Alkoholen, Glykolen, Pyridin, □-Picolin, AmmoniumVerbindungen, Hydroxy-Aluminosilicat-Ionen usw. aufquellen. Die oben angegebenen. Formeln stellen nur angenäherte Formeln dar, da Montmorillonite ein großes lonenaustausch-Vermögen besitzen. So kann Al gegen Mg, Fe2+, Fe3+, Zn, Cr, Cu und andere Ionen ausgetauscht werden. Als Folge einer solchen Substitution resultiert eine negative Ladung der Schichten, die durch andere Kationen, bes. Na+ und Ca2+ ausgeglichen wird.Preferred automatic dishwashing detergents or dishwashing auxiliaries are characterized in that montmorillonites are used as structurants. Montmorillonites have a three-layer structure consisting of two tetrahedral layers, which are electrostatically crosslinked via the cations of an octahedral intermediate layer. The layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, □ -picolin, ammonium compounds, hydroxy-aluminosilicate ions, etc. The above. Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity. Thus Al can be exchanged for Mg, Fe 2+ , Fe 3+ , Zn, Cr, Cu and other ions. As a result of such substitution, a negative charge of the layers results, which is balanced by other cations, especially Na + and Ca 2+ .
In Kombination mit den Bentoniten oder als Ersatz für sie, wenn ihre Verwendung nicht gewünscht wird, können mindestens teilweise veretherte Sorbitole als Strukturgeber eingesetzt werden.In combination with the bentonites or as a substitute for them, if their use is not desired, at least partially etherified sorbitols can be used as structurants.
Sorbitol ist ein zu den Hexiten gehörender 6-wertiger Alkohol (Zuckeralkohol), der intramolekular relativ leicht ein oder zwei Mol Wasser abspaltet und cyclische Ether bildet (beispielsweise Sorbitan und Sorbid). Die Abspaltung von Wasser ist auch intermolekular möglich, wobei sich nichtcyclische Ether aus Sorbitol und den betreffenden Alkoholen bilden. Auch hier ist die Ausbildung von Mono-Ethern und Bis-Ethern möglich, wobei auch höhere Veretherungsgrade wie 3 und 4 auftreten können. Im Rahmen der vorliegenden Erfindung bevorzugt einzusetzende mindestens teilweise veretherte Sorbitole sind zweifach veretherte Sorbitole, von denen das Dibenzylidensorbitol besonders bevorzugt ist. Hier sind maschinelle Geschirspülmittel bevorzugt, die als Strukturgeber zweifach veretherte Sorbitole, insbesondere Dibenzylidensorbitol, enthalten.Sorbitol is a hexavalent 6-valent alcohol (sugar alcohol) that is relatively easy to split one or two moles of water intramolecularly and forms cyclic ethers (eg, sorbitan and sorbide). The removal of water is also possible intermolecularly, forming noncyclic ethers of sorbitol and the alcohols in question. Again, the formation of mono-ethers and bis-ethers is possible, with higher degrees of etherification such as 3 and 4 may occur. At least partially etherified sorbitols to be used in the context of the present invention are doubly etherified sorbitols, of which the dibenzylidenesorbitol is particularly preferred. Here, automatic dishwashing detergents which contain twice etherified sorbitols, in particular dibenzylidenesorbitol, as structurants are preferred.
Die bevorzugten erfindungsgemäßen flüssigen oder fließfähigen Mittel können die Strukturgeber in Mengen von 0,1 bis 1,0 Gew.-%, bezogen auf das gesamte Mittel und auf die Aktivsubstanz der Strukturgeber enthalten. Bevorzugte Mittel enthalten den Strukturgeber in Mengen von 0,2 bis 0,9 Gew.-%, vorzugsweise in Mengen von 0,25 bis 0,75 Gew.-% und insbesondere in Mengen von 0,3 bis 0,5 Gew.-%, jeweils bezogen auf das gesamte Mittel.The preferred liquid or flowable compositions according to the invention may contain the structurants in amounts of from 0.1 to 1.0% by weight, based on the total agent and on the active substance of the structurizer. Preferred agents contain the modifier in amounts of from 0.2 to 0.9% by weight, preferably in amounts of from 0.25 to 0.75% by weight and in particular in amounts of from 0.3 to 0.5% by weight. %, in each case based on the total mean.
Als Verdicker können die bevorzugten erfindungsgemäßen flüssigen oder fließfähigen Mittel anorganische Salze aus der Gruppe der Carbonate, Sulfate und amorphen oder kristallinen Disilikate enthalten. Prinzipiell können hierbei die genannten Salze aller Metalle eingesetzt werden, wobei die Alkalimetallsalze bevorzugt sind. Besonders bevorzugt werden im Rahmen der vorliegenden Erfindung als Verdicker Alkalicarbonat(e), Alkalisulfat(e) und/oder amorphe(s) und/oder kristalline(s) Alkalidisilikat(e), vorzugsweise Natriumcarbonat, Natriumsulfat und/oder amorphes oder kristallines Natriumdisilikat eingesetzt.As thickeners, the preferred liquid or flowable agents according to the invention may contain inorganic salts from the group of carbonates, sulfates and amorphous or crystalline disilicates. In principle, the said salts of all metals can be used, the alkali metal salts being preferred. Alkaline carbonate (s), alkali metal sulphate (s) and / or amorphous (s) and / or crystalline alkali metal disilicate (s), preferably sodium carbonate, sodium sulphate and / or amorphous or crystalline sodium disilicate, are particularly preferably used in the context of the present invention as thickener ,
Die bevorzugten erfindungsgemäßen flüssigen oder fließfähigen Mittel enthalten die Verdicker in Mengen von 5 bis 30 Gew.-%, bezogen auf das gesamte Mittel. Besonders bevorzugte Mittel enthalten den oder die Verdicker in Mengen von 7,5 bis 28 Gew.-%, vorzugsweise in Mengen von 10 bis 26 Gew.% und insbesondere in Mengen von 12,5 bis 25 Gew.-%, jeweils bezogen auf das gesamte Mittel.The preferred liquid or flowable compositions according to the invention contain the thickeners in amounts of from 5 to 30% by weight, based on the total agent. Particularly preferred compositions contain the thickener (s) in amounts of 7.5 to 28 wt .-%, preferably in amounts of 10 to 26 wt.% And in particular in amounts of 12.5 to 25 wt .-%, each based on the entire means.
Im Hinblick auf eine erhöhte Absetzstabilität ist es bevorzugt, daß die in den erfindungsgemäßen Mitteln enthaltenen Feststoffe möglichst feinteilig eingesetzt werden. Dies ist insbesondere bei den anorganischen Verdickern und bei den Bleichmitteln von Vorteil. Hier sind erfindungsgemäße maschinelle Geschirspülmittel bevorzugt, bei denen die mittlere Teilchengröße der Bleichmittel und Verdicker sowie der optional einzusesetzenden Builder weniger als 75 µm, vorzugsweise weniger als 50 µm und insbesondere weniger als 25 µm beträgt.With regard to an increased settling stability, it is preferred that the solids present in the agents according to the invention are used as finely divided as possible. This is particularly advantageous in the case of inorganic thickeners and bleaching agents. Here, automatic dishwashing detergents according to the invention are preferred in which the average particle size of the bleaching agents and thickeners as well as the optionally use builder is less than 75 μm, preferably less than 50 μm and in particular less than 25 μm.
Die erfindungsgemäßen flüssigen maschinellen Geschirrspülmittel können zur Einstellung einer eventuell gewünschten höheren Viskosität auch andere Viskositätsregler bzw. Verdickungsmittel enthalten. Hierbei sind sämtliche bekannten Verdickungsmittel einsetzbar, also solche auf der Basis natürlicher oder synthetischer Polymere.The liquid automatic dishwashing compositions according to the invention may also contain other viscosity regulators or thickeners for adjusting a possibly desired higher viscosity. In this case, all known thickening agents can be used, ie those based on natural or synthetic polymers.
Aus der Natur stammende Polymere, die als Verdickungsmittel Verwendung finden, sind beispielsweise Agar-Agar, Carrageen, Tragant, Gummi arabicum, Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Gelatine und Casein.Naturally derived polymers which are used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.
Abgewandelte Naturstoffe stammen vor allem aus der Gruppe der modifizierten Stärken und Cellulosen, beispielhaft seien hier Carboxymethylcellulose und andere Celluloseether, Hydroxyethyl- und -propylcellulose sowie Kernmehlether genannt.Modified natural products come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers.
Im Rahmen der vorliegenden Erfindung bevorzugte flüssige oder fließfähige maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel enthalten als Verdickungsmittel Hydroxyethylcellulose und/oder Hydroxypropylcellulose, vorzugsweise in Mengen von 0,01 bis 4,0 Gew.-%, besonders bevorzugt in Mengen von 0,01 bis 3,0 Gew.-% und insbesondere in Mengen von 0,01 bis 2,0 Gew.%, jeweils bezogen auf das gesamte Mittel.In the context of the present invention, preferred liquid or free-flowing automatic dishwashing or machine dishwashing aids comprise, as thickening agents, hydroxyethylcellulose and / or hydroxypropylcellulose, preferably in amounts of from 0.01 to 4.0% by weight, more preferably in amounts of from 0.01 to 3, 0 wt .-% and in particular in amounts of 0.01 to 2.0 wt.%, Each based on the total agent.
Eine große Gruppe von Verdickungsmitteln, die breite Verwendung in den unterschiedlichsten Anwendungsgebieten finden, sind die vollsynthetischen Polymere wie Polyacryl- und Polymethacryl-Verbindungen, Vinylpolymere, Polycarbonsäuren, Polyether, Polyimine, Polyamide und Polyurethane.A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
Verdickungsmittel aus den genannten Substanzklassen sind kommerziell breit erhältlich und werden beispielsweise unter den Handelsnamen Acusol®-820 (Methacrylsäure(stearylalkohol-20-EO)ester-Acrylsäure-Copolymer, 30%ig in Wasser, Rohm & Haas), Dapral®-GT-282-S (Alkylpolyglykolether, Akzo), Deuterol®-Polymer-11 (Dicarbonsäure-Copolymer, Schöner GmbH), Deuteron®-XG (anionisches Heteropolysaccharid auf Basis von β-D-Glucose, D-Manose, D-Glucuronsäure, Schöner GmbH), Deuteron®-XN (nichtionogenes Polysaccharid, Schöner GmbH), Dicrylan®-Verdicker-O (Ethylenoxid-Addukt, 50%ig in Wasser/Isopropanol, Pfersse Chemie), EMA®-81 und EMA®-91 (Ethylen-Maleinsäureanhydrid-Copolymer, Monsanto), Verdicker-QR-1001 (Polyurethan Emulsion, 19-21 %ig in Wasser/Diglykolether, Rohm & Haas), Mirox®-AM (anionische Acrylsäure-Acrylsäureester-Copolymer-Dispersion, 25%ig in Wasser, Stockhausen), SER-AD-FX-1100 (hydrophobes Urethanpolymer, Servo Delden), Shellflo®-S (hochmolekulares Polysaccharid, mit Formaldehyd stabilisiert, Shell) sowie Shellflo®-XA (Xanthan-Biopolymer, mit Formaldehyd stabilisiert, Shell) erhältlich.Thickeners from said substance classes are widely available commercially and are sold for example under the trade name Acusol ® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ® -GT- 282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ® -xg (anionic heteropolysaccharide based on β-D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH ) deuteron ® -XN (nonionic polysaccharide Schoner GmbH), DICRYLAN ® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® -91 (ethylene-maleic anhydride copolymer, Monsanto), thickener QR-1001 (polyurethane emulsion, 19-21% in water / diglyme, Rohm & Haas), Mirox ® -AM (anionic acrylic acid-acrylate copolymer dispersion, 25% in water, Stockhausen), SER-AD FX 1100 (hydrophobic urethane polymer, servo Delden), Shellflo ® -S (hochmole kulares polysaccharide, stabilized with formaldehyde, Shell), and Shellflo XA ® (xanthan biopolymer, stabilized with formaldehyde, Shell).
Ein bevorzugt einzusetzendes polymeres Verdickungsmittel ist Xanthan, ein mikrobielles anionisches Heteropolysaccharid, das von Xanthomonas campestris und einigen anderen Species unter aeroben Bedingungen produziert wird und eine Molmasse von 2 bis 15 Millionen Dalton aufweist. Xanthan wird aus einer Kette mit β-1,4-gebundener Glucose (Cellulose) mit Seitenketten gebildet. Die Struktur der Untergruppen besteht aus Glucose, Mannose, Glucuronsäure, Acetat und Pyruvat, wobei die Anzahl der Pyruvat-Einheiten die Viskosität des Xanthan bestimmt.A preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
Im Rahmen der vorliegenden Erfindung ebenfalls bevorzugt einzusetzende Verdickungsmittel sind Polyurethane oder modifizierte Polyacrylate, die, bezogen auf das gesamte Mittel, beispielsweise in Mengen von 0,1 bis 5 Gew.-% eingesetzt werden können.Also preferably used in the context of the present invention thickeners are polyurethanes or modified polyacrylates, which, based on the total agent, for example, in amounts of 0.1 to 5 wt .-% can be used.
Polyurethane (PUR) werden durch Polyaddition aus zwei- und höherwertigen Alkoholen und Isocyanaten hergestellt und lassen sich durch die allgemeine Formel IV beschreiben
Technisch wichtige PUR werden aus Polyester- und/oder Polyetherdiolen und beispielsweise z.B. aus 2,4- bzw. 2,6-Toluoldiisocyanat (TDI, R2 = C6H3-CH3), 4,4'-Methylendi(phenylisocyanat) (MDI, R2 = C6H4-CH2-C6H4) oder Hexamethylendiisocyanat [HMDI, R2 = (CH2)6] hergestellt.Technically important PU are from polyester and / or polyether diols and, for example, from 2,4- and 2,6-toluene diisocyanate (TDI, R 2 = C 6 H 3 -CH 3 ), 4,4'-methylenedi (phenyl isocyanate) (MDI, R 2 = C 6 H 4 -CH 2 -C 6 H 4 ) or hexamethylene diisocyanate [HMDI, R 2 = (CH 2 ) 6 ].
Handelsübliche Verdickungsmittel auf Polyurethan-Basis sind beispielsweise unter den Namen Acrysol®PM 12 V (Gemisch aus 3-5% modifizierter Stärke und 14-16% PUR-Harz in Wasser, Rohm&Haas), Borchigel® L75-N (nichtionogene PUR-Dispersion, 50%ig in Wasser, Borchers), Coatex® BR-100-P (PUR-Dispersion, 50%ig in Wasser /Butylglycol, Dimed), Nopco® DSX-1514 (PUR-Dispersion, 40%ig in Wasser/Butyltrigylcol,Henkel-Nopco), Verdicker QR 1001 (20%ige PUR-Emulsion in Wasser/Digylcolether, Rohm&Haas) und Rilanit® VPW-3116 (PUR-Dispersion, 43%ig in Wasser, Henkel) erhältlich. Für die Zwecke der vorliegenden Erfindung ist bei der Verwendung wässriger Dispersionen darauf zu achten, daß der Wassergehalt der erfindungsgemäßen Mittel innerhalb der vorstehend genannten Grenzen bleibt. Falls der Einsatz der wässrigen Dispersionen aus diesen Gründen nicht möglich ist, können Dispersionen in anderen Lösungsmitteln, oder auch die Feststoffe eingesetzt werden.Commercially available thickener based on polyurethane are, for example, under the names Acrysol ® PM 12 V (mixture of 3-5% modified starch and 14-16% polyurethane resin in water, Rohm & Haas), Borchigel ® L75-N (non-ionic polyurethane dispersion, 50% in water, Borchers), Coatex ® BR-100-P (PUR-dispersion, 50% in water / butyl glycol, Dimed), Nopco ® DSX-1514 (polyurethane dispersion, 40% in water / Butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% polyurethane emulsion in water / Digylcolether, Rohm & Haas) and Rilanit ® VPW-3116 (polyurethane dispersion, 43% in water, Henkel) available. For the purposes of the present invention, when using aqueous dispersions, care must be taken that the water content of the agents according to the invention remains within the abovementioned limits. If the use of the aqueous dispersions for these reasons is not possible, dispersions in other solvents, or even the solids can be used.
Modifizierte Polyacrylate, die im Rahmen der vorliegenden Erfindung eingesetzt werden können, leiten sich beispielsweise von der Acrylsäure bzw. der Methacrylsäure ab und lassen sich durch die allgemeine Formel V beschreiben
Da es sich bei den einsetzbaren Polymeren um technische Verbindungen handelt, stellt die Bezeichnung der an X gebundenen Reste einen statistischen Mittelwert dar, der im Einzelfall hinsichtlich Kettenlänge bzw. Alkoxylierungsgrad variieren kann. Die Formel V gibt dabei lediglich Formeln für idealisierte Homopolymere an. Einsetzbar sind im Rahmen der vorliegenden Erfindung aber auch Copolymere, in denen der Anteil von Monomereinheiten, die der Formel V genügen, mindestens 30 Gew.-% beträgt. So sind beispielsweise auch Copolymere aus modifizierten Polyacrylaten und Acrylsäure bzw. deren Salzen einsetzbar, die noch acide H-Atome oder basische -COO--Gruppen besitzen.Since the polymers which can be used are technical compounds, the designation of the radicals bound to X represents a statistical mean value which, in individual cases, can vary with regard to chain length or degree of alkoxylation. The formula V indicates only formulas for idealized homopolymers. In the context of the present invention, however, it is also possible to use copolymers in which the proportion of monomer units which satisfy the formula V is at least 30% by weight. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO - groups.
Im Rahmen der vorliegenden Erfindung bevorzugt einzusetzende modifizierte Polyacrylate sind Polyacrylat-Polymethacrylat-Copolymerisate, die der Formel Va genügen
Produkte der Formel Va sind kommerziell beispielsweise unter dem Namen Acusol® 820 (Rohm&Haas) in Form 30 Gew.-%iger Dispersionen in Wasser erhältlich. Bei dem genannten Handelsprodukt steht R4 für einen Stearylrest, R6 ist ein Wasserstoffatom, R7 ist H oder CH3 und der Ethoxylierungsgrad a ist 20. Auch bei dieser Dispersion gilt das zum Wassergehalt der Mitttel vorstehend Gesagte.Products of formula Va are commercially available for example under the name Acusol ® 820 (Rohm & Haas) in the form of 30 wt .-% strength dispersion in water available. In the commercial product mentioned, R 4 is a stearyl, R 6 is a hydrogen atom, R 7 is H or CH 3 and the degree of ethoxylation a is 20. In this dispersion, the above water content of the Mitttel said applies.
Im Rahmen der vorliegenden Erfindung bevorzugte flüssige oder fließfähige maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel sind dadurch gekennzeichnet, daß sie zusätzlich 0,01 bis 5 Gew.-%, vorzugsweise 0,02 bis 4 Gew.-%, besonders bevorzugt 0,05 bis 3 Gew.-% und insbesondere 0,1 bis 1,5 Gew.-%, eines polymeren Verdickungsmittels, vorzugsweise aus der Gruppe der Polyurethane oder der modifizierten Polyacrylate unter besonderer Bevorzugung von Verdickungsmitteln der Formel VI
Die erfindungsgemäßen festen bzw. formstabilen und flüssigen bzw. fließfähigen maschinellen Geschirrspülmittel oder Geschirrspülhilfsmittel können dem Verbraucher in herkömmlichen Behältern, beispielsweise Flaschen, Schraubgläsern, Kanistern, Ballons, Bechern oder Spritzgefäßen angeboten werden, aus denen er diese zur Anwendung dosiert. Höherviskose Produkte können auch in Tuben oder Dosierspendern wie sie von Zahnpasta oder Dichtungsmassen bekannt sind, angeboten werden. Solche Behälter werden heute üblicherweise aus nicht wasserlöslichen Polymeren gefertigt und können beispielsweise aus allen üblichen wasserunlöslichen Verpackungsmaterialien bestehen, die dem Fachmann auf diesem Gebiet wohlbekannt sind. Als bevorzugte Polymere sind dabei insbesondere Kunststoffe auf Kohlenwasserstoff-Basis zu nennen. Zu den besonders bevorzugten Polymeren gehören Polyethylen, Polypropylen (weiter bevorzugt orientiertes Polypropylen) und Polymer-Mischungen wie beispielsweise Mischungen der genannten Polymere mit Polyethylenterephthalat. Weiter kommen auch eines oder mehrere Polymere aus der Gruppe Polyvinylchlorid, Polysulfone, Polyacetale, wasserunlösliche Cellulosederivate, Celluloseacetat, Cellulosepropionat, Celluloseacetobutyrat sowie Mischungen der genannten Polymere oder die genannten Polymere umfassende Copolymere in frage.The solid or dimensionally stable and liquid or free-flowing automatic dishwashing or dishwashing auxiliaries according to the invention can be offered to the consumer in conventional containers, for example bottles, screw jars, canisters, balloons, cups or spray vessels, from which they are dosed for use. Higher viscosity products can also be offered in tubes or dispensers as known from toothpaste or sealants. Such containers are today usually made of non-water-soluble polymers and may for example consist of all common water-insoluble packaging materials, which are well known to those skilled in the art. In particular, polymers based on hydrocarbons may be mentioned as preferred polymers. Particularly preferred polymers include polyethylene, polypropylene (more preferably oriented polypropylene) and polymer blends such as blends of said polymers with polyethylene terephthalate. Also suitable are one or more polymers from the group consisting of polyvinyl chloride, polysulfones, polyacetals, water-insoluble cellulose derivatives, cellulose acetate, cellulose propionate, cellulose acetobutyrate and mixtures of said polymers or copolymers comprising said polymers.
Eine besonders bevorzugte Ausführungsform der vorliegenden Erfindung bezweckt jedoch, dem Verbraucher vorportionierte erfindungsgemäße Mittel an die Hand zu geben, damit er die ihm von der Angebotsform "Tablette" her bekannten Dosiervorteile nutzen und mit der schnellen Löse- und Freisetzungsgeschwindigkeit sowie den Leistungsvorteilen der erfindungsgemäßen Mittel kombinieren kann. Solche vorportionierten erfindungsgemäßen Mittel können ebenfalls in wasserunlöslichen Verpackungen vorliegen, so daß der Verbraucher diese vor der Benutzung in geeigneter Weise öffnen muß. Es ist aber auch möglich und bevorzugt, portionierte erfindungsgemäße Mittel so zu verpacken, daß der Verbraucher sie ohne weitere Handhabungsschritte direkt, d.h. mitsamt der Verpackung, in die Geschirrspülmaschine geben kann. Solche Verpackungen umfassen wasserlösliche oder -zersetzbare Verpackungen wie Beutel aus wasserlöslicher Folie (sogenannte Pouches), Beutel oder andere Verpackungen aus wasserlöslichen oder -zersetzbaren Vliesen oder auch flexible oder starre Körper aus wasserlöslichen Polymeren, vorzugsweise in Form befüllter Hohlkörper, welche beispielsweise durch Tiefziehen, Spritzgießen, Blasformen, Kalandrieren usw. hergestellt werden können.A particularly preferred embodiment of the present invention, however, aims to provide the consumer with pre-portioned means according to the invention so that he can use the dosing advantages known to him from the "tablet" offering and combine them with the rapid dissolution and release rates and the performance advantages of the agents according to the invention can. Such pre-portioned agents according to the invention may also be present in water-insoluble packaging, so that the consumer must open them before use in a suitable manner. However, it is also possible and preferred to package portioned compositions according to the invention so that the consumer can give them without further handling steps directly, ie together with the packaging, into the dishwasher. Such packages include water-soluble or decomposable packages such as bags of water-soluble film (so-called pouches), bags or other packaging of water-soluble or decomposable nonwovens or flexible or rigid bodies of water-soluble polymers, preferably in the form of filled hollow body, which for example by deep drawing, injection molding , Blow molding, calendering, etc. can be made.
Ein bevorzugter Gegenstand der vorliegenden Erfindung sind daher erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, die portioniert in einer wasserlöslichen Umhüllung verpackt sind.A preferred subject matter of the present invention are therefore automatic dishwashing detergents or dishwashing auxiliaries according to the invention, which are packaged in portions in a water-soluble casing.
Bevorzugt umfassen erfindungsgemäße maschinelle Geschirrspülmittel oder Geschirrspülhilfsmittel eine ganz oder teilweise in Wasser lösliche Umhüllung. Die Form der Umhüllung ist nicht auf bestimmte Formen beschränkt. Grundsätzlich kommen alle archimedischen und platonischen Körper, also dreidimensionale Formkörper, als Formen der Umhüllung infrage. Beispiele für die Form der Umhüllung sind Kapseln, Würfel, Kugeln, eiförmige Formkörper, Quader, Kegel, Stäbe oder Beutel. Auch Hohlkörper mit einem oder mehreren Kompartimenten sind als Umhüllung für die Geschirreinigungsmittel geeignet. In bevorzugten Ausführungsformen der Erfindung haben die Umhüllungen die Form von Kapseln, wie sie beispielsweise auch in der Pharmazie zur Verabreichung von Arzneimitteln verwendet werden, von Kugeln oder von Beuteln. Letztere sind vorzugsweise an zumindest einer Seite verschweißt oder verklebt, wobei als Kleber in besonders bevorzugten Ausführungsformen der Erfindung ein Kleber verwendet wird, der wasserlöslich ist.Dishwasher detergents or dishwashing auxiliaries according to the invention preferably comprise a completely or partially water-soluble coating. The shape of the wrapper is not limited to specific shapes. Basically, all Archimedean and Platonic bodies, ie three-dimensional shaped bodies, come into question as forms of envelopment. Examples of the shape of the wrapper are capsules, cubes, spheres, ovoid moldings, cuboids, cones, rods or bags. Also hollow body with one or more compartments are suitable as a sheath for the Geschirreinigungsmittel. In preferred embodiments of the invention, the wrappers are in the form of capsules, such as those used in pharmacy for the administration of drugs, spheres or bags. The latter are preferably welded or glued on at least one side, wherein the adhesive used in particularly preferred embodiments of the invention is an adhesive that is water-soluble.
Nach einer bevorzugten Ausführungsform der Erfindung ist das das maschinelle Geschirrspülmittel oder Geschirrspülhilfsmittel teilweise oder vollständig umgebende wasserlösliche Polymer-Material eine wasserlösliche Verpackung. Darunter wird ein flächig ausgebildetes Teil verstanden, das das Geschirreinigungsmittel teilweise oder vollständig umgibt. Die exakte Form einer derartigen Verpackung ist nicht kritisch und kann den Gebrauchsgegebenheiten weitgehend angepaßt werden. Es kommen beispielsweise zu verschiedenen Formen (wie Schläuchen, Kissen, Zylindern, Flaschen, Scheiben o.ä.) gearbeitete verarbeitete Kunststoff-Folien oder -Platten, Kapseln und andere denkbare Formen in Frage. Erfindungsgemäß besonders bevorzugt sind Folien, die beispielsweise zu Verpackungen wie Schläuchen, Kissen o. ä. verklebt und/oder versiegelt werden können, nachdem sie mit Teilportionen der erfindungsgemäßen Reinigungsmittel oder mit den erfindungsgemäßen Reinigungsmitteln selbst befüllt wurden.According to a preferred embodiment of the invention, the water-soluble polymer material which partially or completely surrounds the automatic dishwashing or dishwashing auxiliary is a water-soluble packaging. This is understood to mean a flat part which partially or completely surrounds the dishwashing detergent. The exact form of such packaging is not critical and can be largely adapted to the conditions of use. For example, processed plastic foils or sheets, capsules and other conceivable forms come into consideration for various forms (such as hoses, cushions, cylinders, bottles, disks or the like). Particularly preferred according to the invention are films which, for example, can be bonded and / or sealed to packagings such as hoses, cushions or the like, after they have been filled with partial portions of the cleaning agents according to the invention or with the cleaning agents according to the invention.
Weiter bevorzugt sind erfindungsgemäß aufgrund der ausgezeichnet den gewünschten physikalischen Bedingungen anpaßbaren Eigenschaften Kunststoff-Folienverpackungen aus wasserlöslichen Polymer-Materialien. Derartige Folien sind grundsätzlich aus dem Stand der Technik bekannt.Further preferred are, according to the invention, due to the excellent adaptable to the desired physical conditions properties plastic film packaging of water-soluble polymer materials. Such films are basically known from the prior art.
Zusammenfassend sind sowohl Hohlkörper beliebiger Gestalt, die durch Spritzgießen, Flaschenblasen, Tiefziehen usw. hergestellt werden können, als auch Hohlkörper aus Folien, insbesondere Beutel (sogenannte Pouches) als Verpackungen für portionierte erfindungsgemäße Mittel bevorzugt. Bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel sind somit dadurch gekennzeichnet, daß die wasserlösliche Umhüllung einen Beutel aus wasserlöslicher Folie und/oder ein Spritzgußteil und/oder ein Blasformteil und/oder ein Tiefziehteil umfaßt.In summary, both hollow body of any shape, which can be produced by injection molding, bottle blowing, deep drawing, etc., as well as hollow body of films, in particular bags (so-called pouches) as packages for portioned inventive Medium preferred. Preferred automatic dishwasher detergents or dishwashing auxiliaries according to the invention are thus characterized in that the water-soluble casing comprises a bag of water-soluble film and / or an injection-molded part and / or a blow-molded part and / or a deep-drawn part.
Erfindungsgemäß ist es bevorzugt, daß die eine oder mehreren Umfassung(en) abgeschlossen ist/sind. Dies bringt den Vorteil mit sich, daß die Geschirreinigungsmittel optimal gegen Einflüsse der Umwelt, insbesondere gegen Feuchtigkeit geschützt sind. Außerdem läßt sich mit diesen abgeschlossenen Umfassungen die Erfindung dahingehend weiterentwickeln, daß die Reinigungsmittel zum Schutz des Inhalts der Umfassung(en) vor Feuchtigkeit wenigstens ein Gas enthalten, siehe unten.According to the invention, it is preferred that the one or more enclosures are / are completed. This has the advantage that the Geschirreinigungsmittel are optimally protected against the effects of the environment, especially against moisture. In addition, with these closed enclosures, the invention can be further developed such that the detergents contain at least one gas to protect the contents of the enclosure (s) from moisture, see below.
Als Materialien für die ganz oder teilweise wasserlösliche Umhüllung kommen grundsätzlich alle Materialien infrage, die sich unter den gegebenen Bedingungen eines Waschvorgangs, Spülvorgangs oder Reinigungsvorgangs (Temperatur, pH-Wert, Konzentration an waschaktiven Komponenten) in wässriger Phase vollständig oder teilweise lösen können. Die Polymer-Materialien können besonders bevorzugt den Gruppen (gegebenenfalls teilweise acetalisierter) Polyvinylalkohol, Polyvinylpyrrolidon, Poly-ethylenoxid, Gelatine, Cellulose und deren Derivate, Stärke und deren Derivate, insbesondere modifizierte Stärken, und Mischungen (Polymerblends, Verbünde, Koextrudate etc.) der genannten Materialien zugehören. Besonders bevorzugt sind Gelatine und Polyvinylalkohole sowie die genannten beiden Materialien jeweils im Verbund mit Stärke oder modifizierter Stärke. Es kommen auch anorganische Salze und Mischungen daraus als Materialien für die zumindest teilweise wasserlösliche Umhüllung infrage.Suitable materials for the completely or partially water-soluble coating are in principle all materials in question, which can completely or partially dissolve in the aqueous phase under the given conditions of a washing process, rinsing or cleaning process (temperature, pH, concentration of detergent components). The polymer materials may particularly preferably the groups (optionally partially acetalized) polyvinyl alcohol, polyvinylpyrrolidone, poly-ethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, in particular modified starches, and mixtures (polymer blends, composites, coextrudates, etc.) of belong to the materials mentioned. Particularly preferred are gelatin and polyvinyl alcohols and the two materials mentioned in each case in combination with starch or modified starch. There are also inorganic salts and mixtures thereof as materials for the at least partially water-soluble envelope in question.
Bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel sind dadurch gekennzeichnet, daß die Umhüllung ein oder mehrere Materialien aus der Gruppe Acrylsäure-haltige Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester und Polyether und deren Mischungen umfaßt.Preferred automatic dishwasher detergents or dishwashing auxiliaries according to the invention are characterized in that the coating comprises one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.
Besonders bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel sind dadurch gekennzeichnet, daß die Umhüllung ein oder mehrere wasserlösliche(s) Polymer(e), vorzugsweise ein Material aus der Gruppe (gegebenenfalls acetalisierter) Polyvinylalkohol (PVAL), Polyvinylpyrrolidon, Polyethylenoxid, Gelatine, Cellulose, und deren Derivate und deren Mischungen, weiter bevorzugt (gegebenenfalls acetalisierter) Polyvinylalkohol (PVAL), umfaßt.Particularly preferred automatic dishwasher detergents or dishwashing auxiliaries according to the invention are characterized in that the coating comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalised) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
"Polyvinylalkohole" (Kurzzeichen PVAL, gelegentlich auch PVOH) ist dabei die Bezeichnung für Polymere der allgemeinen Struktur
Handelsübliche 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) angeboten werden, haben Hydrolysegrade von 98-99 bzw. 87-89 Mol-%, enthalten also noch einen Restgehalt an Acetyl-Gruppen. Charakterisiert werden die Polyvinylalkohole von Seiten der Hersteller durch Angabe des Polymerisationsgrades des Ausgangspolymeren, des Hydrolysegrades, der Verseifungszahl bzw. der Lösungsviskosität.Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
Polyvinylalkohole sind abhängig vom Hydrolysegrad löslich in Wasser und wenigen stark polaren organischen Lösungsmitteln (Formamid, Dimethylformamid, Dimethylsulfoxid); von (chlorierten) Kohlenwasserstoffen, Estern, Fetten und Ölen werden sie nicht angegriffen. Polyvinylalkohole werden als toxikologisch unbedenklich eingestuft und sind biologisch zumindest teilweise abbaubar. Die Wasserlöslichkeit kann man durch Nachbehandlung mit Aldehyden (Acetalisierung), durch Komplexierung mit Ni- oder Cu-Salzen oder durch Behandlung mit Dichromaten, Borsäure od. Borax verringern. Die Beschichtungen aus Polyvinylalkohol sind weitgehend undurchdringlich für Gase wie Sauerstoff, Stickstoff, Helium, Wasserstoff, Kohlendioxid, lassen jedoch Wasserdampf hindurchtreten.Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
Im Rahmen der vorliegenden Erfindung ist es bevorzugt, daß die 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-% beträgt.In the context of the present invention it is preferred that the 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% ,
Vorzugsweise werden als Materialien für die Umhüllung Polyvinylalkohole eines bestimmten Molekulargewichtsbereichs eingesetzt, wobei erfindungsgemäß bevorzugt ist, daß die Umhüllung einen Polyvinylalkohol umfaßt, dessen Molekulargewicht im Bereich von 10.000 bis 100.000 gmol- 1, vorzugsweise von 11.000 bis 90.000 gmol-1, besonders bevorzugt von 12.000 bis 80.000 gmol-1 und insbesondere von 13.000 bis 70.000 gmol-1 liegt.Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the coating, it being preferred according to the invention for the coating to comprise a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol . 1 , preferably from 11,000 to 90,000 gmol -1 , more preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
Der Polymerisationsgrad solcher bevorzugten Polyvinylalkohole liegt zwischen ungefähr 200 bis ungefähr 2100, vorzugsweise zwischen ungefähr 220 bis ungefähr 1890, besonders bevorzugt zwischen ungefähr 240 bis ungefähr 1680 und insbesondere zwischen ungefähr 260 bis ungefähr 1500.The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
Die vorstehend beschriebenen Polyvinylalkohole sind kommerziell breit verfügbar, beispielsweise unter dem Warenzeichen Mowiol® (Clariant). Im Rahmen der vorliegenden Erfindung besonders geeignete Polyvinylalkohole sind beispielsweise Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 sowie Mowiol® 8-88.The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
Weitere als Material für die Hohlkörper besonders geeignete Polyvinylalkohole sind der nachstehenden Tabelle zu entnehmen:
Weitere als Material für die Hohlform geeignete Polyvinylalkohole sind ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (Warenzeichen der Du Pont), ALCOTEX® 72.5, 78, B72, F80/40, F88/4, F88/26, F88/40, F88/47 (Warenzeichen der Harlow Chemical Co.), Gohsenol® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Warenzeichen der Nippon Gohsei K.K.).Other suitable as a material for the mold, polyvinyl alcohols are ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).
Die Wasserlöslichkeit von PVAL kann durch Nachbehandlung mit Aldehyden (Acetalisierung) oder Ketonen (Ketalisierung) verändert werden. 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 PVAL und Stärke.The water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility. To use extremely advantageous are the reaction products of PVAL and starch.
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. Folien aus PVAL sind weitgehend undurchdringlich für Gase wie Sauerstoff, Stickstoff, Helium, Wasserstoff, Kohlendioxid, lassen jedoch Wasserdampf hindurchtreten.Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values. Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
Beispiele geeigneter wasserlöslicher PVAL-Folien sind die unter Bezeichnung "SOLUBLON®" von der Firma Syntana Handelsgesellschaft E. Harke GmbH & Co. erhältlichen PVAL-Folien. Deren Löslichkeit in Wasser läßt sich Grad-genau einstellen, und es sind Folien dieser Produktreihe erhältlich, die in allen für die Anwendung relevanten Temperaturbereichen in wässriger Phase löslich sind.Examples of suitable water PVAL films under the name "SOLUBLON® ®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. available PVAL films. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.
Polyvinylpyrrolidone, kurz als PVP bezeichnet, lassen sich durch die folgende allgemeine Formel beschreiben:
PVP werden durch radikalische Polymerisation von 1-Vinylpyrrolidon hergestellt. Handelsübliche PVP haben Molmassen im Bereich von ca. 2.500 bis 750.000 g/mol und werden als weiße, hygroskopische Pulver oder als wässrige Lösungen angeboten.PVP are prepared by radical polymerization of 1-vinylpyrrolidone. Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
Polyethylenoxide, kurz PEOX, sind Polyalkylenglykole der allgemeinen Formel
H-[O-CH2-CH2]n-OH
die technisch durch basisch katalysierte Polyaddition von Ethylenoxid (Oxiran) in meist geringe Mengen Wasser enthaltenden Systemen mit Ethylenglykol als Startmolekül hergestellt werden. Sie haben Molmassen im Bereich von ca. 200 bis 5.000.000 g/mol, entsprechend Polymerisationsgraden n von ca. 5 bis >100.000. Polyethylenoxide besitzen eine äußerst niedrige Konzentration an reaktiven Hydroxy-Endgruppen und zeigen nur noch schwache Glykol-Eigenschaften.Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
H- [O-CH 2 -CH 2 ] n -OH
the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
Gelatine ist ein Polypeptid (Molmasse: ca. 15.000 bis >250.000 g/mol), das vornehmlich durch Hydrolyse des in Haut und Knochen von Tieren enthaltenen Kollagens unter sauren oder alkalischen Bedingungen gewonnen wird. Die Aminosäuren-Zusammensetzung der Gelatine entspricht weitgehend der des Kollagens, aus dem sie gewonnen wurde, und variiert in Abhängigkeit von dessen Provenienz. Die Verwendung von Gelatine als wasserlösliches Hüllmaterial ist insbesondere in der Pharmazie in Form von Hart- oder Weichgelatinekapseln äußerst weit verbreitet. In Form von Folien findet Gelatine wegen ihres im Vergleich zu den vorstehend genannten Polymeren hohen Preises nur geringe Verwendung.Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as the water-soluble shell material is especially in pharmacy in the form of hard or soft gelatin capsules extremely widespread. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.
Bevorzugt sind im Rahmen der vorliegenden Erfindung auch Geschirreinigungsmittel, deren Verpackung aus zumindest zum Teil wasserlöslicher Folie aus mindestens einem Polymer aus der Gruppe Stärke und Stärkederivate, Cellulose und Cellulosederivate, insbesondere Methylcellulose und Mischungen hieraus besteht.Also preferred in the context of the present invention are dishwashing detergents whose packaging consists of at least partially water-soluble film of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and mixtures thereof.
Stärke ist ein Homoglykan, wobei die Glucose-Einheiten a-glykosidisch verknüpft sind. Stärke ist aus zwei Komponenten unterschiedlichen Molekulargewichts aufgebaut: aus ca. 20 bis 30% geradkettiger Amylose (MG. ca. 50.000 bis 150.000) und 70 bis 80% verzweigtkettigem Amylopektin (MG. ca. 300.000 bis 2.000.000). Daneben sind noch geringe Mengen Lipide, Phosphorsäure und Kationen enthalten. Während die Amylose infolge der Bindung in 1,4-Stellung lange, schraubenförmige, verschlungene Ketten mit etwa 300 bis 1.200 Glucose-Molekülen bildet, verzweigt sich die Kette beim Amylopektin nach durchschnittlich 25 Glucose-Bausteinen durch 1,6-Bindung zu einem astähnlichen Gebilde mit etwa 1.500 bis 12.000 Molekülen Glucose. Neben reiner Stärke sind zur Herstellung wasserlöslicher Umhüllungen der Waschmittel-, Spülmittel- und Reinigungsmittel-Portionen im Rahmen der vorliegenden Erfindung auch Stärke-Derivate geeignet, die durch polymeranaloge Reaktionen aus Stärke erhältlich sind. Solche chemisch modifizierten Stärken umfassen dabei beispielsweise Produkte aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert wurden. Aber auch Stärken, in denen die Hydroxy-Gruppen gegen funktionelle Gruppen, die nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Stärke-Derivate einsetzen. In die Gruppe der Stärke-Derivate fallen beispielsweise Alkalistärken, Carboxymethylstärke (CMS), Stärkeester und -ether sowie Aminostärken.Starch is a homoglycan, wherein the glucose units are linked a-glycosidically. Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000). In addition, small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
Reine Cellulose weist die formale Bruttozusammensetzung (C6H10O5)n auf und stellt formal betrachtet ein β-1,4-Polyacetal von Cellobiose dar, die ihrerseits aus zwei Molekülen Glucose aufgebaut ist. Geeignete Cellulosen bestehen dabei aus ca. 500 bis 5.000 Glucose-Einheiten und haben demzufolge durchschnittliche Molmassen von 50.000 bis 500.000. Als Desintegrationsmittel auf Cellulosebasis verwendbar sind im Rahmen der vorliegenden Erfindung auch Cellulose-Derivate, die durch polymeranaloge Reaktionen aus Cellulose erhältlich sind. Solche chemisch modifizierten Cellulosen umfassen dabei beispielsweise Produkte aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert wurden. Aber auch Cellulosen, in denen die Hydroxy-Gruppen gegen funktionelle Gruppen, die nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Cellulose-Derivate einsetzen.Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
In die Gruppe der Cellulose-Derivate fallen beispielsweise Alkalicellulosen, Carboxymethylcellulose (CMC), Celluloseester und -ether sowie Aminocellulosen.The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
Bevorzugte Umhüllungen aus zumindest partiell wasserlöslicher Folie enthalten mindestens ein Polymer mit einer Molmasse zwischen 5.000 und 500.000 g/Mol, vorzugsweise zwischen 7.500 und 250.000 g/Mol und insbesondere zwischen 10.000 und 100.000 g/Mol. Die Umhüllung weist je nach Herstellungsverfahren unterschiedliche Materialstärken auf, wobei erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel bevorzugt sind, bei denen die Wandstärke der Umhüllung 10 bis 5000 µm, vorzugsweise 20 bis 3000 µm, besonders bevorzugt 25 bis 2000 µm und insbesondere 100 bis 1500 µm beträgt.Preferred casings of at least partially water-soluble film comprise at least one polymer having a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol. Depending on the production method, the casing has different material thicknesses, automatic dishwashing agents or automatic dishwashing auxiliaries according to the invention being preferred in which the wall thickness of the casing is 10 to 5000 μm, preferably 20 to 3000 μm, particularly preferably 25 to 2000 μm and in particular 100 to 1500 μm ,
Werden Folienbeutel (sogenannte Pouches) als Verpackung gewählt, so weist die wasserlösliche Folie, die die Umhüllung bildet, vorzugsweise eine Dicke von 1 bis 300 µm, vorzugsweise von 2 bis 200 µm, besonders bevorzugt von 5 bis 150 µm und insbesondere von 10 bis 100 µm, auf.If film pouches (so-called pouches) are selected as the packaging, then the water-soluble film forming the coating preferably has a thickness of 1 to 300 μm, preferably 2 to 200 μm, more preferably 5 to 150 μm and in particular 10 to 100 μm, up.
Diese wasserlöslichen Folien können nach verschiedenen Herstellverfahren hergestellt werden. Hier sind prinzipiell Blas-, Kalandrier- und Gießverfahren zu nennen. Bei einem bevorzugten Verfahren werden die Folien dabei ausgehend von einer Schmelze mit Luft über einen Blasdorn zu einem Schlauch geblasen. Bei dem Kalandrierverfahren, das ebenfalls zu den bevorzugt eingesetzten Herstellverfahren gehört, werden die durch geeignete Zusätze plastifizierten Rohstoffe zur Ausformung der Folien verdüst. Hier kann es insbesondere erforderlich sein, an die Verdüsungen eine Trocknung anzuschließen. Bei dem Gießverfahren, das ebenfalls zu den bevorzugten Herstellverfahren gehört, wird eine wässrige Polymerzubereitung auf eine beheizbare Trockenwalze gegeben, nach dem Verdampfen des Wassers wird optional gekühlt und die Folie als Film abgezogen. Gegebenenfalls wird dieser Film vor oder während des Abziehens zusätzlich abgepudert.These water-soluble films can be produced by various production methods. Blow molding, calendering and casting processes should be mentioned here in principle. In a preferred method, the films are blown starting from a melt with air through a mandrel to a hose. In the case of the calendering process, which is likewise one of the preferred production processes, the raw materials plasticized by suitable additives are atomized to form the films. In particular, it may be necessary to attach drying to the atomizations. In the casting process, which is also one of the preferred production methods, an aqueous polymer preparation is placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film is peeled off as a film. Optionally, this film is additionally powdered before or during the removal.
Erfindungsgemäß bevorzugt ist eine Ausführungsform, gemäß der die Umhüllung als ganzes wasserlöslich ist, d. h. sich bei bestimmungsgemäßem Gebrauch beim maschinellen Reinigen, vollständig auflöst, wenn die für das Lösen vorgesehenen Bedingungen erreicht sind. Besonders bevorzugt als ganz wasserlösliche Umhüllungen sind z. B. Kapseln aus Gelatine, mit Vorteil aus Weichgelatine, oder Beutel aus (gegebenenfalls teilweise acetalisiertem) PVAL oder Kugeln aus Gelatine oder (gegebenenfalls teilweise acetalisiertem) PVAL oder aus einem oder mehreren organischen und/oder anorganischen Salzen, vorzugsweise Kugeln aus Weichgelatine. Wesentlicher Vorteil dieser Ausführungsform ist, daß sich die Umhüllung innerhalb einer praktisch relevant kurzen Zeit - als nicht begrenzendes Beispiel lassen sich wenige Sekunden bis 5 min - unter genau definierten Bedingungen in der Reinigungsflotte zumindest partiell löst und damit entsprechend den Anforderungen den umhüllten Inhalt, d. h. das reinigungsaktive Material oder mehrere Materialien, in die Flotte einbringt.According to the invention, an embodiment is preferred in accordance with which the coating is water-soluble as a whole, ie, dissolves completely under normal use during mechanical cleaning when the conditions for release are reached. Particularly preferred as completely water-soluble coatings z. B. gelatin capsules, advantageously of soft gelatin, or bags of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably spheres of soft gelatin. The essential advantage of this embodiment is that the sheath within a practically relevant short time - as a non-limiting example can be a few seconds to 5 min - at least partially dissolves under precisely defined conditions in the cleaning liquor and thus according to the requirements, the coated content, ie the cleaning-active material or several materials in the fleet brings.
In einer anderen, ebenfalls aufgrund vorteilhafter Eigenschaften bevorzugten Ausführungsform der Erfindung umfaßt die wasserlösliche Umhüllung weniger gut oder gar nicht wasserlösliche oder erst bei höherer Temperatur wasserlösliche Bereiche und gut wasserlösliche oder bei niedriger Temperatur wasserlösliche Bereiche. Mit anderen Worten: Die Umhüllung besteht nicht aus einem einheitlichen, in allen Bereichen die gleiche Wasserlöslichkeit aufweisenden Material, sondern aus Materialien unterschiedlicher Wasserlöslichkeit. Dabei sind Bereiche guter Wasserlöslichkeit einerseits zu unterscheiden von Bereichen mit weniger guter Wasserlöslichkeit, mit schlechter oder gar fehlender Wasserlöslichkeit oder von Bereichen, in denen die Wasserlöslichkeit erst bei höherer Temperatur oder erst bei einem anderen pH-Wert oder erst bei einer geänderten Elektrolytkonzentration den gewünschten Wert erreicht, andererseits. Dies kann dazu führen, daß sich bei bestimmungsgemäßem Gebrauch unter einstellbaren Bedingungen bestimmte Bereiche der Umhüllung lösen, während andere Bereiche intakt bleiben. So bildet sich eine mit Poren oder Löchern versehene Umhüllung, in die Wasser und/oder Flotte eindringen, waschaktive, spülaktive oder reinigungsaktive Inhaltsstoffe lösen und aus der Umhüllung ausschleusen kann. In gleicher Weise können auch Umhüllungssysteme in Form von Mehrkammer-Beuteln oder in Form von ineinander angeordneten Hohlkörpern (z. B. Kugeln: "Zwiebelsystem") vorgesehen werden. So lassen sich Systeme mit kontrollierter Freisetzung der waschaktiven, spülaktiven oder reinigungsaktiven Inhaltsstoffe herstellen.In another embodiment of the invention, which is also preferred because of its advantageous properties, the water-soluble coating comprises regions which are less soluble or not water-soluble or only water-soluble at relatively high temperatures and regions which are readily soluble in water or soluble in water at low temperature. In other words, the coating does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility. On the one hand, areas of good water solubility are to be distinguished from areas with less good water solubility, with poor or even absent water solubility or areas in which the water solubility reaches the desired value only at a higher temperature or only at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand. This may result in certain areas of the enclosure becoming disengaged under normal conditions of use, while other areas remain intact. Thus, an envelope provided with pores or holes is formed, into which water and / or liquor can penetrate, which can dissolve washing-active, rinse-active or cleaning-active ingredients and remove them from the casing. In the same way, wrapping systems in the form of multi-chamber bags or in the form of nested hollow bodies (eg balls: "onion system") can also be provided. Thus, controlled release systems of the detergent-active, rinse-active or cleaning-active ingredients can be produced.
Zur Ausbildung derartiger Systeme unterliegt die Erfindung keinen Beschränkungen. So können Umhüllungen vorgesehen werden, in denen ein einheitliches Polymer-Material kleine Bereiche eingearbeiteter Verbindungen (beispielsweise von Salzen) umfaßt, die schneller wasserlöslich sind als das Polymer-Material. Andererseits können auch mehrere Polymer-Materialien mit unterschiedlicher Wasserlöslichkeit gemischt werden (Polymer-Blend), so daß das schneller lösliche Polymer-Material unter definierten Bedingungen durch Wasser oder die Flotte schneller desintegriert wird als das langsamer lösliche.To form such systems, the invention is not limited. Thus, wraps can be provided in which a uniform polymeric material comprises small areas of incorporated compounds (for example, salts) which are more rapidly soluble in water than the polymeric material. On the other hand, several polymer materials with different water solubility can be mixed (polymer blend), so that the faster soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the slower soluble.
Es entspricht einer besonders bevorzugten Ausführungsform der Erfindung, daß die weniger gut wasserlöslichen Bereiche oder gar nicht wasserlöslichen Bereiche oder erst bei höherer Temperatur wasserlöslichen Bereiche der Umhüllung Bereiche aus einem Material sind, das chemisch im wesentlichen demjenigen der gut wasserlöslichen Bereiche oder bei niedrigerer Temperatur wasserlöslichen Bereiche entspricht, jedoch eine höhere Schichtdicke aufweist und/oder einen geänderten Polymerisationsgrad desselben Polymers aufweist und/oder einen höheren Vernetzungsgrad derselben Polymerstruktur aufweist und/oder einen höheren Acetalisierungsgrad (bei PVAL, beispielsweise mit Sacchariden, Polysacchariden, wie Stärke) aufweist und/oder einen Gehalt an wasserunlöslichen Salzkomponenten aufweist und/oder einen Gehalt an einem wasserunlöslichen Polymeren aufweist. Selbst unter Berücksichtigung der Tatsache, daß sich die Umhüllung nicht vollständig löst, können so Reinigungsmittel-Portionen gemäß der Erfindung bereitgestellt werden, die vorteilhafte Eigenschaften bei der Freisetzung der Geschirreinigungsmittel in die jeweilige Flotte aufweisen.It is in accordance with a particularly preferred embodiment of the invention that the less readily water-soluble or water-insoluble areas or areas of the enclosure which are water-soluble at higher temperatures are areas of a material chemically substantially that of the water-soluble or water-soluble areas but has a higher layer thickness and / or has a modified degree of polymerization of the same polymer and / or has a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer. Even taking into account the fact that the enclosure does not dissolve completely, it is thus possible to provide detergent portions according to the invention which have advantageous properties in the release of the dishwashing detergent into the respective liquor.
Das wasserlösliche Hüllmaterial ist vorzugsweise transparent. Unter Transparenz ist im Sinne dieser Erfindung zu verstehen, daß die Durchlässigkeit innerhalb des sichtbaren Spektrums des Lichts (410 bis 800 nm) größer als 20%, vorzugsweise größer als 30%, äußerst bevorzugt größer als 40% und insbesondere größer als 50% ist. Sobald somit eine Wellenlänge des sichtbaren Spektrums des Lichtes eine Durchlässigkeit größer als 20% aufweist, ist es im Sinne der Erfindung als transparent zu betrachten.The water-soluble shell material is preferably transparent. For the purposes of this invention, transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%. Thus, once a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.
Erfindungsgemäße Geschirreinigungsmittel, die in transparenten Umhüllungen bzw. Behältnissen verpackt sind, können als wesentlichen Bestandteil ein Stabilisierungsmittel enthalten. Stabilisierungsmittel im Sinne der Erfindung sind Materialien, welche die Reinigungsmittelbestandteile in ihren wasserlöslichen, transparenten Umhüllungen vor Zersetzung oder Desaktivierung durch Lichteinstrahlung schützen. Als besonders geeignet haben sich hier Antioxidantien, UV-Absorber und Fluoreszensfarbstoffe erwiesen.Dishwashing detergents according to the invention, which are packaged in transparent envelopes or containers, can contain a stabilizing agent as an essential constituent. Stabilizing agents in the context of the invention are materials which protect the detergent components in their water-soluble, transparent sheaths from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
Besonders geeignete Stabilisierungsmittel im Sinne der Erfindung sind die Antioxidantien. Um unerwünschte, durch Lichteinstrahlung und damit radikalischer Zersetzung verursachte Veränderungen an den Formulierungen zu verhindern, können die Formulierungen Antioxidantien enthalten. Als Antioxidantien können dabei beispielsweise durch sterisch gehinderte Gruppen substituierte Phenole, Bisphenole und Thiobisphenole verwendet werden. Weitere Beispiele sind Propylgallat, Butylhydroxytoluol (BHT), Butylhydroxyanisol (BHA), t-Butylhydrochinon (TBHQ), Tocopherol und die langkettigen (C8-C22) Ester der Gallussäure, wie Dodecylgallat. Andere Substanzklassen sind aromatische Amine, bevorzugt sekundäre aromatische Amine und substituierte p-Phenylendiamine, Phosphorverbindungen mit dreiwertigem Phosphor wie Phosphine, Phosphite und Phosphonite, Zitronensäuren und Zitronensäurederivate, wie Isopropylcitrat, Endiol-Gruppen enthaltende Verbindungen, sogenannte Reduktone, wie die Ascorbinsäure und ihre Derivate, wie Ascorbinsäurepalmitat, Organoschwefelverbindungen, wie die Ester der 3,3'-Thiodipropionsäure mit C1-8-Alkanolen, insbesondere C10-18-Alkanolen, Metallionen-Desaktivatoren, die in der Lage sind, die Autooxidation katalysierende Me-tallionen, wie z.B. Kupfer, zu komplexieren, wie Nitrilotriessigsäure und deren Abkömmlinge und ihre Mischungen. Antioxidantien können in den Formulierungen in Mengen bis 35 Gew.-%, vorzugsweise bis 25 Gew.-%, besonders bevorzugt von 0,01 bis 20 und insbesondere von 0,03 bis 20 Gew.-% enthalten sein.Particularly suitable stabilizing agents in the context of the invention are the antioxidants. In order to prevent undesirable changes in the formulations caused by light irradiation and thus radical decomposition, the formulations may contain antioxidants. Examples of antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic palmitate, organosulfur compounds such as the esters of 3,3'-thiodipropionic acid with C 1-8 alkanols, especially C 10-18 alkanols, metal ion deactivators capable of auto-oxidation catalyzing metal ions such as Copper, such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.
Eine weitere Klasse bevorzugt einsetzbarer Stabilisierungsmittel sind die UV-Absorber. UV-Absorber können die Lichtbeständigkeit der Rezepturbestandteile verbessern. Darunter sind organische Substanzen (Lichtschutzfilter) zu verstehen, die in der Lage sind, ultraviolette Strahlen zu absorbieren und die aufgenommene Energie in Form längerwelliger Strahlung, z.B. Wärme wieder abzugeben. Verbindungen, die diese gewünschten Eigenschaften aufweisen, sind beispielsweise die durch strahlungslose Desaktivierung wirksamen Verbindungen und Derivate des Benzophenons mit Substituenten in 2- und/oder 4-Stellung. Weiterhin sind auch substituierte Benzotriazole, wie beispielsweise das wasserlösliche Benzolsulfonsäure-3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(methylpropyl)-mononatriumsalz (Cibafast® H), in 3-Stellung Phenylsubstituierte Acrylate (Zimtsäurederivate), gegebenenfalls mit Cyanogruppen in 2-Stellung, Salicylate, organische Ni-Komplexe sowie Naturstoffe wie Umbelliferon und die körpereigene Urocansäure geeignet. Besondere Bedeutung haben Biphenyl- und vor allem Stilbenderivate, die kommerziell als Tinosorb® FD oder Tinosorb® FR ex Ciba erhältlich sind. Als UV-B-Absorber sind zu nennen 3-Benzylidencampher bzw. 3-Benzylidennorcampher und dessen Derivate, z.B. 3-(4-Methylbenzyliden)campher; 4-Aminobenzoesäurederivate, vorzugsweise 4-(Dimethylamino)benzoesäure-2-ethylhexylester, 4-(Dimethylamino)benzoesäure-2-octylester und 4-(Dimethylamino)benzoesäureamylester; Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure-2-ethylhexylester, 4-Methoxyzimtsäurepropylester, 4-Methoxyzimtsäureisoamylester, 2-Cyano-3,3-phenylzimtsäure-2-ethylhexylester (Octocrylene); Ester der Salicylsäure, vorzugsweise Salicylsäure-2-ethylhexylester, Salicylsäure-4-isopropylbenzylester, Salicylsäurehomomenthylester; Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon; Ester der Benzalmalonsäure, vorzugsweise 4-Methoxy-benzmalonsäuredi-2-ethylhexylester, Triazinderivate, wie z.B. 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazin und Octyl Triazon oder Dioctyl Butamido Triazone (Uvasorb® HEB); Propan-1,3-dione, wie z.B. 1-(4-tert.Butylphenyl)-3-(4'methoxyphenyl)propan-1,3-dion; Ketotricyclo(5.2.1.0)decan-Derivate. Weiterhin geeignet sind 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium- und Glucammoniumsalze; Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und ihre Salze; Sulfonsäurederivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bornylidenmethyl)benzol-sulfonsäure und 2-Methyl-5-(2-oxo-3-bornyliden)sulfonsäure und deren Salze.Another class of preferably usable stabilizers are the UV absorbers. UV absorbers can improve the light stability of the formulation ingredients. These are understood to be organic substances (light protection filters) which are able to absorb ultraviolet rays and to release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ® Fast H), phenyl-substituted in the 3-position acrylates (cinnamic acid derivatives) , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's urocanic acid suitable. The biphenyl and especially stilbene derivatives which are available commercially as Tinosorb ® FD or Tinosorb ® FR available ex Ciba. 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate, triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
Als typische UV-A-Filter kommen insbesondere Derivate des Benzoylmethans in Frage, wie beispielsweise 1-(4'-tert.Butylphenyl)-3-(4'-methoxyphenyl)propan-1,3-dion, 4-tert.-Butyl-4'-meth-oxydibenzoylmethan (Parsol 1789), 1-Phenyl-3-(4'-isopropylphenyl)-propan-1,3-dion sowie Enaminverbindungen. Die UV-A und UV-B-Filter können selbstverständlich auch in Mischungen eingesetzt werden. Neben den genannten löslichen Stoffen kommen für diesen Zweck auch unlösliche Lichtschutzpigmente, nämlich feindisperse, vorzugsweise nanoisierte Metalloxide bzw. Salze in Frage. Beispiele für geeignete Metalloxide sind insbesondere Zinkoxid und Titandioxid und daneben Oxide des Eisens, Zirkoniums, Siliciums, Mangans, Aluminiums und Cers sowie deren Gemische. Als Salze können Silicate (Talk), Bariumsulfat oder Zinkstearat eingesetzt werden. Die Oxide und Salze werden in Form der Pigmente bereits für hautpflegende und hautschützende Emulsionen und dekorative Kosmetik verwendet. Die Partikel sollten dabei einen mittleren Durchmesser von weniger als 100 nm, vorzugsweise zwischen 5 und 50 nm und insbesondere zwischen 15 und 30 nm aufweisen. Sie können eine sphärische Form aufweisen, es können jedoch auch solche Partikel zum Einsatz kommen, die eine ellipsoide oder in sonstiger Weise von der sphärischen Gestalt abweichende Form besitzen. Die Pigmente können auch oberflächenbehandelt, d.h. hydrophilisiert oder hydrophobiert vorliegen. Typische Beispiele sind gecoatete Titandioxide, wie z.B. Titandioxid T 805 (Degussa) oder Eusolex® T2000 (Merck). Als hydrophobe Coatingmittel kommen dabei vor allem Silicone und dabei speziell Trialkoxyoctylsilane oder Simethicone in Frage. Vorzugsweise wird mikronisiertes Zinkoxid verwendet.As a typical UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds. Of course, the UV-A and UV-B filters can also be used in mixtures be used. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used.
UV-Absorber können in den Geschirreinigungsmitteln in Mengen bis 5 Gew.-%, vorzugsweise bis 3 Gew.-%, besonders bevorzugt von 0,01 bis 2,0 und insbesondere von 0,03 bis 1 Gew.-% enthalten sein.UV absorbers may be present in the dishwashing detergents in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight.
Eine weitere bevorzugt einzusetzende Klasse von Stabilisierungsmitteln sind die Fluoreszenzfarbstoffe. Zu ihnen zählen die 4,4'-Diamino-2,2'-stilbendisulfonsäuren (Flavonsäuren), 4,4'-Distyrylbiphenylen, Methyl-umbelliferone, Cumarine, Dihydrochinolinone, 1,3-Diarylpyrazoline, Naphthalsäureimide, Benzoxazol-, Benzisoxazol- und Benzimidazol-Systeme sowie der durch Hetero-cyclen substituierten Pyrenderivate. Von besonderer Bedeutung sind dabei die Sulfonsäuresalze der Diaminostilben-Derivate, sowie polymere Fluoreszenzstoffe, wie sie in der
Fluoreszenzstoffe können in den Formulierungen in Mengen bis 5 Gew.-%, vorzugsweise bis 1 Gew.-%, besonders bevorzugt von 0,01 bis 0,5 und insbesondere von 0,03 bis 0,1 Gew.-% enthalten sein.Fluorescent substances can be present in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.
In einer bevorzugten Ausführungsform werden die vorgenannten Stabilisierungsmittel in beliebigen Mischungen eingesetzt. Die Stabilisierungsmittel werden in Mengen bis 40 Gew.-%, vorzugsweise bis 30 Gew.-%, besonders bevorzugt von 0,01 bis 20 Gew.-%, insbesondere von 0,02 bis 5 Gew.-% eingesetzt.In a preferred embodiment, the abovementioned stabilizers are used in any mixtures. The stabilizers are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.
Bevorzugte maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel enthalten unabhängig von der Art ihrer Konfektionierung mindestens eine wasch- oder reinigungsaktive Substanz aus der Gruppe der Bleichmittel, Bleichaktivatoren, Polymere, Gerüststoffe, Tenside, Enzyme, Elektrolyte, pH-Stellmittel, Duftstoffe, Parfümtrager, Farbstoffe, Hydrotrope, Schauminhibitoren, antimikrobiellen Wirkstoffe, Germizide, Fungizide, Korrosionsinhibitoren, nichtwässrigen Lösungsmittel.Irrespective of the nature of their preparation, preferred automatic dishwashing or machine dishwashing aids comprise at least one washing or cleaning substance from the group of bleaches, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, hydrotropes, Foam inhibitors, antimicrobial agents, germicides, fungicides, corrosion inhibitors, non-aqueous solvents.
Ein weiterer Gegenstand der vorliegenden Anmeldung ist die Verwendung eines erfindungsgemäßen maschinellen Geschirrspülmittels oder maschinellen Geschirrspülhilfsmittel zur Verringerung der Glaskorrosion beim maschinellen Geschirrspülen.A further subject of the present application is the use of a machine dishwashing detergent or automatic dishwashing auxiliary according to the invention for reducing the glass corrosion in automatic dishwashing.
Nicht angeschmutzte Gläser wurden in einer kontinuierlich betriebenen Geschirrspülmaschine mit einem handelsüblichen Maschinengeschirrspülmittel bei einer Wasserhärte von 0-1°dH gespült. Im Vergleichsbeispiel V1 wurden für jeden Reinigungsgang lediglich 24,5 g eines handelsüblichen Maschinengeschirrspülmittel eindosiert. In den Vergleichsbeispielen V2 bzw. V3 wurden gleichzeitig mit den 24,5 g des handelsüblichen Maschinengeschirrspülmittels 250 mg Zinkacetat bzw. 400 mg des kristallinen schichtförmigen Silikats Na-SKS-6 (δ-Na2Si2O5) eindosiert. Im erfindungsgemäßen Beispiel E1 wurden schließlich außer dem Maschinengeschirrspülmittel zusätzlich 250 mg Zinkacetat und 400 mg Na-SKS-6 eindosiert. Der Spülvorgang wurde unter den vorstehend beschriebenen Bedingungen 50 mal wiederholt. Das Gesamterscheinungsbild des Spülgutes wurde anhand der unten aufgeführten Bewertungsskala beurteilt.Uncleaned glasses were rinsed in a continuously operated dishwasher with a commercial machine dishwashing detergent at a water hardness of 0-1 ° dH. In Comparative Example C1, only 24.5 g of a commercially available machine dishwashing detergent were metered in for each cleaning cycle. In Comparative Examples C2 and V3, respectively, 250 mg of zinc acetate or 400 mg of the crystalline layered silicate Na-SKS-6 (δ-Na 2 Si 2 O 5 ) were metered in simultaneously with the 24.5 g of the commercial machine dishwashing detergent. In the inventive example E1, in addition to the machine dishwashing detergent, 250 mg zinc acetate and 400 mg Na-SKS-6 were additionally metered in. The rinse was repeated 50 times under the conditions described above. The overall appearance of the items to be washed was assessed on the basis of the rating scale listed below.
Die Ergebnisse sind in der nachstehenden Tabelle angegeben
Die Tabelle zeigt, daß das erfindungsgemäße maschinelle Gechirrspülmittel, welches die Kombination eines Zinksalzes und eines kristallinen schichtförmigen Silikats enthält, unter den genannten Bedingungen deutlich bessere Galskorrosionseigenschaften aufweist als Geschirrspülmittel, die nur Zinksalz bzw. nur Silikat enthalten. Der korrosionsinhibierende Effekt der Wirkstoffkombination aus Zinksalz und Silikat liegt dabei deutlich oberhalb der Summe der für die Einzelsubstanzen beobachteten Effekte.The table shows that the machine dishwashing detergent according to the invention, which contains the combination of a zinc salt and a crystalline layered silicate, under the conditions mentioned significantly better Galskorrosionseigenschaften than dishwashing detergents containing only zinc salt or only silicate. The corrosion-inhibiting effect of the active ingredient combination of zinc salt and silicate is significantly above the sum of the effects observed for the individual substances.
Claims (12)
- Automatic dishwashing agent or automatic dishwashing agent auxiliary, comprising at least one soluble zinc salt as well as, relative to the total weight of said agent, 0.1 to 20 wt % crystalline layered silicate(s) of the general Formula (Ia)
NaMSixO2x+1 • y H2O (Ia),
in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, and y stands for a number from 0 to 33, characterised in that it comprises the zinc salt(s) as well as the crystalline layered silicate(s) of the general Formula (Ia) in the ratio 3:1 to 1:10 and wherein a "soluble zinc salt" is understood to mean a zinc salt with a solubility in water of greater than 100 mg/L (solubility at 20° C water temperature). - Automatic dishwashing agent or automatic dishwashing agent auxiliary according to claim 1, characterised in that it comprises at least one zinc salt selected from the group of the soluble inorganic zinc salts, in particular from the group zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
- Automatic dishwashing agent or automatic dishwashing agent auxiliary according to claim 1, characterised in that it comprises at least one zinc salt selected from the group of the soluble organic zinc salts, particularly preferably from the group of the soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluene sulfonate.
- Automatic dishwashing agent according to one of claims 1 to 3, characterised in that the weight fraction of the zinc salt relative to the total weight of said agent is 0.1 to 10 wt %, preferably 0.2 to 7 wt % and in particular 0.4 to 4 wt %.
- Automatic dishwashing agent according to one of claims 1 to 4, characterised in that the weight fraction of the crystalline layered silicate of the general Formula (Ia) relative to the total weight of said agent is 0.2 to 15 wt % and in particular 0.4 to 10 wt %.
- Automatic dishwashing agent or automatic dishwashing agent auxiliary according to one of claims 1 to 5, characterised in that the comprised zinc salt(s) and/or the comprised crystalline layered silicate(s) converted with one or more additional active substances and/or builders, is/are present in particulate form as a compound.
- Automatic dishwashing agent or automatic dishwashing agent auxiliary according to one of claims 1 to 6, characterised in that the crystalline layered silicate(s) of the general Formula (Ia) converted with one or more additional active substances and/or builders, preferably with one or more additional active substances and/or builders from the group of the organic mono or polycarboxylic acids, the hydroxypolycarboxylic acids and the phosphonic acids, is/are present in particulate form as a compound.
- Automatic dishwashing agent or automatic dishwashing agent auxiliary according to one of claims 1 to 7, characterised in that the zinc salt(s) and/or the crystalline layered silicate(s) are present converted in a polymer matrix.
- Automatic dishwashing agent or automatic dishwashing agent auxiliary according to one of claims 1 to 8, characterised in that it is dimensionally stable and has a penetration number of 200 to 1000 g, preferably 250 to 900 g, particularly preferably 300 to 800 g and in particular 350 to 700 g.
- Automatic dishwashing agent or automatic dishwashing agent auxiliary according to one of claims 1 to 9, characterised in that it has a viscosity of 500 to 500 000 mPas, preferably 900 to 200 000 mPas and in particular 1300 to 100 000 mPas.
- Automatic dishwashing agent or automatic dishwashing agent auxiliary according to one of claims 1 to 10, characterised in that it is packaged in portions in a water-soluble encasement.
- Use of an automatic dishwashing agent or automatic dishwashing agent auxiliary according to one of claims 1 to 11 for reducing glass corrosion in automatic dishwashing.
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EP05027033A EP1657295B1 (en) | 2002-06-06 | 2003-05-28 | Compound comprising a zink salt and a crystalline, layered silicate |
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DE10225116 | 2002-06-06 | ||
DE10225116A DE10225116A1 (en) | 2002-06-06 | 2002-06-06 | Automatic dishwashing detergent with improved glass corrosion protection II |
PCT/EP2003/005602 WO2003104370A1 (en) | 2002-06-06 | 2003-05-28 | Automatic dishwashing detergent with improved glass anti-corrosion properties |
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DE10334047A1 (en) | 2003-07-25 | 2005-02-24 | Clariant Gmbh | Adsorbate from phyllosilicate and its use |
US20050119154A1 (en) * | 2003-10-16 | 2005-06-02 | The Procter & Gamble Company | Methods for protecting glassware from surface corrosion in automatic dishwashing appliances |
US7094740B2 (en) * | 2003-10-16 | 2006-08-22 | The Procter & Gamble Company | Zinc corrosion protection agents for treating glassware surfaces |
US7271138B2 (en) | 2003-10-16 | 2007-09-18 | The Procter & Gamble Company | Compositions for protecting glassware from surface corrosion in automatic dishwashing appliances |
US7241726B2 (en) | 2003-10-16 | 2007-07-10 | The Procter & Gamble Company | Complete-cycle methods for protecting glassware from surface corrosion in automatic dishwashing appliances |
US7101833B2 (en) | 2004-10-12 | 2006-09-05 | The Procter & Gamble Company | Methods for treating glassware surfaces using zinc corrosion protection agents |
DE102005025332A1 (en) * | 2005-05-31 | 2006-12-07 | Henkel Kgaa | surfactant compound |
DE102008017796A1 (en) * | 2008-04-08 | 2009-10-15 | Süd-Chemie AG | Phyllosilicate odor adsorbers based on zinc ricinoleates and related compounds |
DE102008020274A1 (en) | 2008-04-22 | 2009-10-29 | Henkel Ag & Co. Kgaa | Preparing a cleaning agent tablet, useful for cleaning or washing e.g. moldings, comprises compressing a particulate premix containing zinc-containing granulates and other ingredients |
DE102008020275A1 (en) | 2008-04-22 | 2009-10-29 | Henkel Ag & Co. Kgaa | Cleaning agent shaped body from pressed particulate material, useful e.g. for cleaning utensils in a household dishwasher, comprises zinc-containing cogranulate comprising zinc compounds and carrier material from group of builders |
EP2216393B1 (en) * | 2009-02-09 | 2024-04-24 | The Procter & Gamble Company | Detergent composition |
DE102011077865A1 (en) * | 2011-06-21 | 2012-12-27 | Henkel Ag & Co. Kgaa | Dishwashing detergent with improved decor protection |
CN103874756B (en) | 2011-10-19 | 2017-04-05 | 巴斯夫欧洲公司 | Preparaton, its as or for preparing purposes and its preparation of dishwasher detergent |
RU2656214C2 (en) | 2013-04-02 | 2018-06-01 | Басф Се | Formulations, their use as or for producing dishwashing detergents and their production |
JP5801941B1 (en) * | 2014-11-21 | 2015-10-28 | 株式会社ニイタカ | Cleaning composition, dishwashing method, liquid cleaning composition kit and cartridge cleaning |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3255117A (en) * | 1963-10-08 | 1966-06-07 | Fmc Corp | Low-foaming dishwashing composition |
DE2539531A1 (en) * | 1975-09-05 | 1977-03-17 | Henkel & Cie Gmbh | Dishwashing compsn. - contains a divalent or trivalent cation additive to reduce corrosion |
US4670617A (en) * | 1985-12-30 | 1987-06-02 | Amoco Corporation | Propylation of toluene with a high surface area, zinc-modified, crystalline silica molecular sieve |
US4917812A (en) * | 1989-02-13 | 1990-04-17 | The Procter & Gamble Company | Granular automatic dishwasher detergent composition providing glassware protection containing insoluble zinc compound |
US4933101A (en) * | 1989-02-13 | 1990-06-12 | The Procter & Gamble Company | Liquid automatic dishwashing compositions compounds providing glassware protection |
US6391839B1 (en) * | 1992-08-01 | 2002-05-21 | The Procter & Gamble Company | Detergent bleach compositions containing layered silicate builder and percarbonate stabilized by EDDS |
DE4437486A1 (en) * | 1994-10-20 | 1996-04-25 | Henkel Kgaa | Crystalline layered silicates in automatic dishwashing detergents |
DE69603226T2 (en) * | 1995-05-25 | 2000-02-03 | Mizusawa Industrial Chemicals, Ltd. | Iodine complex and its use |
DE19819187A1 (en) * | 1998-04-30 | 1999-11-11 | Henkel Kgaa | Solid dishwasher detergent with phosphate and crystalline layered silicates |
DE19943470A1 (en) * | 1999-09-11 | 2001-03-15 | Clariant Gmbh | Crystalline alkali layer silicate |
DE10039100A1 (en) * | 2000-08-07 | 2002-02-28 | Henkel Kgaa | Deodorant textile treatment agent |
DE10140535B4 (en) * | 2001-08-17 | 2006-05-04 | Henkel Kgaa | Machine dishwashing detergent with improved glass corrosion protection |
PL202632B1 (en) * | 2001-08-17 | 2009-07-31 | Henkel Ag & Co Kgaa | Dishwasher detergent with improved protection against glass corrosion n |
-
2002
- 2002-06-06 DE DE10225116A patent/DE10225116A1/en not_active Ceased
-
2003
- 2003-05-28 EP EP05027033A patent/EP1657295B1/en not_active Expired - Lifetime
- 2003-05-28 ES ES05027033T patent/ES2298919T3/en not_active Expired - Lifetime
- 2003-05-28 AU AU2003237704A patent/AU2003237704A1/en not_active Abandoned
- 2003-05-28 DE DE50308871T patent/DE50308871D1/en not_active Expired - Lifetime
- 2003-05-28 EP EP03735481.8A patent/EP1509589B1/en not_active Expired - Lifetime
- 2003-05-28 AT AT05027033T patent/ATE381608T1/en not_active IP Right Cessation
- 2003-05-28 WO PCT/EP2003/005602 patent/WO2003104370A1/en active Application Filing
- 2003-05-28 ES ES03735481.8T patent/ES2527542T3/en not_active Expired - Lifetime
- 2003-05-28 JP JP2004511431A patent/JP2005534728A/en active Pending
Also Published As
Publication number | Publication date |
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EP1657295B1 (en) | 2007-12-19 |
AU2003237704A1 (en) | 2003-12-22 |
DE50308871D1 (en) | 2008-01-31 |
JP2005534728A (en) | 2005-11-17 |
ES2527542T3 (en) | 2015-01-26 |
ES2298919T3 (en) | 2008-05-16 |
WO2003104370A1 (en) | 2003-12-18 |
ATE381608T1 (en) | 2008-01-15 |
DE10225116A1 (en) | 2003-12-24 |
EP1657295A1 (en) | 2006-05-17 |
EP1509589A1 (en) | 2005-03-02 |
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