EP3884021A1 - Mehrkomponentiges reinigungssystem - Google Patents
Mehrkomponentiges reinigungssystemInfo
- Publication number
- EP3884021A1 EP3884021A1 EP19812717.7A EP19812717A EP3884021A1 EP 3884021 A1 EP3884021 A1 EP 3884021A1 EP 19812717 A EP19812717 A EP 19812717A EP 3884021 A1 EP3884021 A1 EP 3884021A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- weight
- detergent
- cleaning agent
- cartridge
- 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.)
- Pending
Links
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- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008261 styrofoam Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 description 1
- 108010031354 thermitase Proteins 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 108010068608 xanthan lyase Proteins 0.000 description 1
- 108010083879 xyloglucan endo(1-4)-beta-D-glucanase Proteins 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940006174 zinc valerate Drugs 0.000 description 1
- MXODCLTZTIFYDV-JHZYRPMRSA-L zinc;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O MXODCLTZTIFYDV-JHZYRPMRSA-L 0.000 description 1
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- BUDAIZWUWHWZPQ-UHFFFAOYSA-L zinc;pentanoate Chemical compound [Zn+2].CCCCC([O-])=O.CCCCC([O-])=O BUDAIZWUWHWZPQ-UHFFFAOYSA-L 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/045—Multi-compartment
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L15/00—Washing or rinsing machines for crockery or tableware
- A47L15/42—Details
- A47L15/44—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants
- A47L15/4418—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants in the form of liquids
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L15/00—Washing or rinsing machines for crockery or tableware
- A47L15/42—Details
- A47L15/44—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants
- A47L15/4463—Multi-dose dispensing arrangements
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L15/00—Washing or rinsing machines for crockery or tableware
- A47L15/42—Details
- A47L15/44—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants
- A47L15/4472—Blister packaging or refill cartridges
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0068—Deodorant 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
- C11D3/08—Silicates
-
- 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
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/2079—Monocarboxylic 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
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38618—Protease or amylase in liquid compositions only
-
- 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
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the invention relates to a cleaning agent which contains, separately from one another in a packaging means, at least one enzyme-containing and at least one builder-containing preparation and an active substance composition which comprises at least one carrier material, preferably a water-insoluble carrier material and at least one active substance.
- devices for multiple dosing of cleaning agents are from
- Devices can be differentiated between metering containers integrated in the dishwasher on the one hand and independent devices independent of the dishwasher on the other. By means of these devices, the multiple of those necessary for carrying out a cleaning process
- Containing amount of detergent, detergent portions are metered into the interior of the cleaning machine in an automatic or semi-automatic manner in the course of several successive cleaning processes. For the consumer, this eliminates the need to dose the detergent before the start of each individual cleaning cycle. Examples of such devices are described in European patent application EP 1 759 624 A2 (Reckitt Benckiser) or in German patent application DE 10 2005 062 479 A1 (BSH Bosch and Siemens Hausmaschine GmbH).
- dishwashers that are loaded with dishes for several days and in which the soiled items remain uncleaned for some time inside the dishwasher before a washing cycle is carried out have the problem that unpleasant smells, e.g. develop through acidifying milk, etc.
- temperatures are the first approximation of the water temperatures used to carry out the cleaning processes. These temperatures can amount to up to 95 ° C, whereby usually only temperatures between 50 and 75 ° C are reached in the area of machine dishwashing.
- a cleaning agent contained in a device provided for multiple dosing is accordingly repeatedly heated in the course of several cleaning processes to temperatures significantly above the temperatures customary for transport and storage, in particular temperature-sensitive ones
- Fragrance scavengers and / or fragrances that are contained in liquid formulations can mask these odors for a short time due to the release in each rinse cycle, but this is not sufficient in particular in the case of rinsing cycles that are often several days apart in order to significantly reduce the odor load that arises in the meantime.
- These fragrance scavengers and / or fragrances cannot escape between the cycles from the appropriately packaged liquid formulations, since this is prevented by the closed construction and the control of the multiple dosing systems.
- fragrances in the liquid formulations are also those mentioned above.
- the object of the present application was therefore to provide a
- a first subject of the present application is therefore a cleaning agent supply form, comprising
- a preferred subject of the present application is therefore one
- Active substance composition is located, which contains at least one carrier material, preferably a water-insoluble carrier material and at least one active substance.
- the provision of the active ingredient composition in the packaging means that the scent or the control of the bad odors lasts longer or also during longer rinsing breaks than if these active ingredients were contained in one or more of the liquid preparations.
- the active ingredient composition is accommodated in the packaging means such that the washing liquor can flow through it during the washing process and / or air can also flow between the washing steps.
- the at least one active ingredient C is released into the washing liquor and / or the air and can thus develop its effect.
- the subject of this application are corresponding forms of detergent which are obtained by combining two liquid detergent preparations A and B with the active substance composition, comprising at least one carrier material, preferably a water-insoluble carrier material, and at least one active substance C.
- the liquid detergent preparations A and B and the active ingredient composition are obtained by combining two liquid detergent preparations A and B with the active substance composition, comprising at least one carrier material, preferably a water-insoluble carrier material, and at least one active substance C.
- Detergent preparations are phosphate-free, i.e. that they contain less than 1% by weight of phosphate, preferably less than 0.5% by weight of phosphate, particularly preferably less than 0.1% by weight of phosphate and in particular no phosphate.
- the cleaning agent preparation A contains one or more builders as the first essential component.
- the builders include in particular carbonates, organic cobuilders and silicates.
- Forms of cleaning agent according to the invention are preferably characterized in that the builder a1) is selected from the group of carbonates, bicarbonates, citrates, silicates, polymeric carboxylates and polymers containing sulfonic acid groups or mixtures thereof.
- Preferred forms of detergent supply comprise a detergent preparation A which, based on its total weight, 2 to 50% by weight, preferably 6 to 45% by weight and
- builders a1) from the group of the carbonates and / or hydrogen carbonates, preferably alkali carbonates, is particularly preferred
- Sodium carbonate in amounts of 2 to 30% by weight, preferably 3 to 20% by weight and in particular 4 to 15% by weight, in each case based on the weight of the
- Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, (poly) aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
- Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
- these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,
- polycarboxylic acids to understand non-polymeric polycarboxylates.
- Such polymeric polycarboxylates have a larger number, preferably 4 and more carboxylic acid-containing monomers.
- the free acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH of
- Citric acid Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
- Particularly preferred cleaning agent preparations A according to the invention contain citrate as one of their essential builders.
- Forms of detergent characterized in that the detergent preparation A, based on their total weight, contains 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight of citrate, are preferred according to the invention.
- Citrate or citric acid have in particular in combination with phosphonate, in particular 1-hydroxyethane-1, 1-diphosphonic acid, and / or
- Polymers containing sulfonic acid groups have proven to be the most effective builders in terms of cleaning performance, such as rinse aid performance and in particular scale inhibition.
- Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
- Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
- Copolymers of polycarboxylates are also suitable, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
- Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
- the amount of (co) polymeric polycarboxylates in the dishwasher detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
- Automatic dishwashing agents can use crystalline layered silicates of the general formula NaMSix0 2x + i y H2O, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x 2, 3 or 4, and y represents a number from 0 to 33, preferably from 0 to 20.
- Amorphous sodium silicates with a module Na2Ü: S1O2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferred, can also be used
- the silicate content based on the total weight of the automatic dishwashing agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
- Particularly preferred automatic dishwashing agents according to the invention are silicate-free.
- dishwashing detergents are characterized in that the dishwashing detergent contains at least two builders from the group of the carbonates and citrates, and the polymers containing sulfonic acid groups, the proportion by weight of these
- Builders based on its total weight of the automatic dishwashing detergent, is preferably 2 to 50% by weight, preferably 5 to 45% by weight and in particular 10 to 40% by weight.
- the combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
- a sulfopolymer preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfone group-containing polymer.
- the copolymers can have two, three, four or more different monomer units.
- Preferred copolymers polysulfonates contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.
- unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, a-chloroacrylic acid, a-cyanoacrylic acid, crotonic acid, a-phenyl-acrylic acid, maleic acid,
- H 2 C CH-X-S0 3 H
- H 2 C C (CH 3 ) -X-S0 3 H or H0 3
- SX- (R 6 ) C C (R 7 ) -X-S0 3 H
- a cleaning agent preparation preferably contains
- Detergent preparation A such a polymer comprising, as a monomer containing sulfonic acid groups, acrylamidopropane sulfonic acids, methacrylamidomethyl propane sulfonic acids or acrylamidomethyl propane sulfonic acid.
- Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenlsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
- the polymers the
- All or part of the sulfonic acid groups are present in neutralized form, that is to say that the acidic hydrogen atom of the sulfonic acid group is present in some or all of the sulfonic acid groups
- Metal ions preferably alkali metal ions and especially sodium ions, can be replaced.
- the use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
- the monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in each case in copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight % and the share of
- Monomers containing carboxylic acid groups from 10 to 50% by weight the monomers here being preferably selected from the abovementioned.
- the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
- Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 g mol -1 , preferably from 4000 to 25,000 g mol -1 and in particular from 5000 to 15,000 g mol -1 .
- the copolymers also comprise
- Monomer containing carboxyl groups and monomer containing sulfonic acid groups furthermore at least one nonionic, preferably hydrophobic monomer.
- the detergent preparations particularly preferably comprise, in particular
- Detergent preparation A comprising a copolymer
- Preferred nonionic monomers are monomers of the general formula
- nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethyl- hexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, a-olefins with 10 or more
- Carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-a-olefin, 2-styrene, a-methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2 Ethyl 4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate,
- AMPS 2-acrylamido-2-methylpropanesulfonic acid
- the cleaning agent preparation A contains a complexing agent which is different from the builders mentioned above.
- the weight fraction of the complexing agent in the total weight of the cleaning agent preparation A is preferably 2 to 60% by weight, preferably 3 to 55% by weight, preferably 4 to 55% by weight and in particular 8 to 50% by weight.
- the phosphonates form a first group of preferred complexing agents.
- the complex-forming phosphonates comprise a number
- DTPMP diethylenetriaminepenta- (methylenephosphonic acid)
- hydroxyalkane or aminoalkanephosphonates are of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the
- Tetrasodium salt reacts alkaline (pH 9).
- Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP.
- the class becomes the class becomes the
- Phosphonates preferably used HEDP.
- the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
- a cleaning agent preparation A preferred in the context of this application contains one or more phosphonate (s) from the group
- ATMP aminotrimethylenephosphonic acid
- ETMP ethylenediaminetetra (methylenephosphonic acid)
- DTPMP Diethylenetriaminepenta (methylenephosphonic acid)
- HDTMP hexamethylenediaminetetra (methylenephosphonic acid)
- NTMP Nitrilotri (methylenephosphonic acid)
- Detergent preparations A which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.
- HEDP 1-hydroxyethane-1,1-diphosphonic acid
- DTPMP diethylenetriaminepenta
- phosphonates are particularly preferred.
- the automatic dishwashing agents according to the invention can of course contain two or more different phosphonates.
- the total weight of cleaning agent preparations A according to the invention is preferably 1 to 8% by weight, preferably 1.2 to 6% by weight, preferably 1.3 to 5% by weight, particularly preferably 1.4 to 4.5% by weight and in particular 1.5 to 4% by weight.
- the complexing agent a2) is selected from the group of hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glutamic acid diacetic acid, especially L-glutamic acid - / ⁇ /, / ⁇ / - diesiacetic acid, iminodisuccinic acid, hydroxynacetic acid, pa rag i nsä u red iessig acid, hydroxyethane-1, 1-diphosphonic acid or diethylenetriaminepenta (methylenephosphonic acid) and their salts or mixtures thereof, preferably L-glutamic acid - / ⁇ /, / ⁇ / - diesiacetic acid and / or
- Methylglycinediacetic acid and its salts include not only the free acids but also their salts, for example their sodium or potassium salts.
- the cleaning agent preparations A according to the invention can in particular L-glutamic acid - / ⁇ /, / ⁇ / - diacetic acid and / or the corresponding alkali salt (GLDA), preferably the tetrasodium salt, and / or methylglycinediacetic acid and / or the corresponding alkali salt, preferably that Trisodium salt.
- GLDA alkali salt
- MGDA methylglycinediacetic acid
- MGDA methylglycinediacetic acid
- preferred detergent preparations A being characterized in that they are based on the total weight of the
- the cleaning agent preparation A contains the complexing agents selected from phosphonates, in particular HEDP, provided that
- the builders then include citrate and carbonate and / or hydrogen carbonate.
- the detergent preparation A based on its total weight, contains MGDA and / or its salts in amounts of 5 to 30% by weight, in particular 8 to 25% by weight, for example 10 to 15% by weight .-%, citrate in amounts of 3 to 20% by weight, in particular 4 to 15% by weight, and carbonate in amounts of 5 to 30% by weight, in particular 7 to 20% by weight.
- citrate amounts of 3 to 20% by weight, in particular 4 to 15% by weight, and carbonate in amounts of 5 to 30% by weight, in particular 7 to 20% by weight, are also preferred, provided this is for regulatory reasons is permissible to contain phosphonate and / or its salt in amounts of 1.2 to 6% by weight, particularly preferably 1.4 to 4.5% by weight, in particular 1.5 to 4% by weight.
- one of the cleaning agent preparation preferably cleaning agent preparation B, furthermore contains at least one surfactant, in particular selected from anionic, nonionic, zwitterionic and amphoteric surfactants.
- the surfactants can also be contained in a cleaning agent preparation different from the cleaning agent preparations A and B. If used in a cleaning agent preparation B according to the invention, surfactants are preferably used in an amount of up to 40% by weight, in particular 2 to 40% by weight or 4 to 40% by weight, particularly preferably in an amount of 5 to 35% by weight .-%, in particular 10 to 30 wt .-%, contain.
- Detergent preparation A preferably contains less than 2% by weight of surfactant, preferably less than 1% by weight of surfactant, particularly preferably less than 1% by weight of surfactant, in particular no surfactant, in each case based on the total weight of detergent preparation A.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C12-14- Alcohols with 3 EO, 4 EO or 7 EO, C9-n-alcohol with 7 EO, C-s-alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-is-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -i 4 alcohol with 3 EO and Ci2-is alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO,
- Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
- block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
- mixed alkoxylated nonionic surfactants can also be used, in which the EO and PO units are not distributed in blocks, but are statistically distributed. Such products can be obtained from the simultaneous action of ethylene and propylene oxide on fatty alcohols.
- the content of nonionic surfactants in the cleaning preparation B is 5 to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by weight, based on the total amount of the cleaning preparation B.
- the cleaning preparation B can also contain anionic surfactants.
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably C9-i3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from Ci2-is monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates which are obtained from Ci2-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- the esters of a-sulfofatty acids (ester sulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- the anionic surfactants, including the soaps can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the anionic surfactant content of the cleaning preparation B is 0.1 to 30% by weight, preferably 2 to 20% by weight, based on the
- a preferred pH value of cleaning preparations A according to the invention is between 9 and 14, in particular 9 and 12.
- the pH can be adjusted if necessary
- pH adjusting agents in particular sodium or potassium hydroxide, are carried out.
- the cleaning agent preparations B according to the invention contain at least one cleaning-active enzyme as their first essential constituent.
- the weight fraction of the cleaning-active enzyme preparation in the total weight of the cleaning agent preparation B is preferably 5 and 80% by weight, preferably 5 and 60% by weight, particularly preferably 10 and 50% by weight and in particular 10 and 30% by weight.
- the enzyme preparations used in this way each contain from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight and particularly preferably from 0.4 to 20% by weight and in particular from 0.8 up to 10% by weight of active enzyme protein.
- the enzymes used with particular preference include proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred.
- Detergents preferably contain enzymes in total amounts of 1 x 10 6 to 5 wt .-% based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.
- Detergent preparations B characterized in that they contain at least one cleaning-active enzyme from the group of amylases and / or proteases and / or cellulases and / or mannanases, in particular from the group of amylases and / or proteases.
- proteases those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
- Liquid detergent preparations B preferred according to the invention contain, based on the total weight of the detergent preparation, 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight of protease preparations. Detergent preparations B which contain 15 to 25% by weight of protease preparations, based on their total weight, are particularly preferred.
- amylases which can be used according to the invention are the a-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens
- Liquid detergent preparations B preferred according to the invention contain, based on the total weight of the detergent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of amylase preparations.
- Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of cellulase preparations.
- Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of mannanase preparations.
- Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, those originally from Humicola lanuginosa
- Thermomyces lanuginosus available or further developed lipases, especially those with the amino acid exchange D96L. Furthermore, the cutinases can be used, for example, which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases or cutinases, their
- Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of lipase preparations.
- enzymes can be used, which are called hemicellulases
- oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenol oxidases) can be used according to the invention.
- organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to reduce the redox potential between the oxidizing enzymes and the enzymes
- Cleaning-active enzymes in particular proteases and amylases, are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
- These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers or other auxiliaries.
- the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type in which an enzyme-containing core with a water, air and / or
- Chemical-impermeable protective layer is coated. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by granular or roll granulation or in fluid-bed processes. Such granules are advantageously polymeric, for example by applying them
- enzyme preparations preferably used according to the invention contain from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight, particularly preferably from 0.4 to 20% by weight and in particular from 0.8 to 10% by weight of the enzyme protein.
- Liquid detergent preparations B which are particularly preferred according to the invention therefore contain, based on the total weight of the detergent preparation, 7 to 40% by weight, in particular 10 to 30% by weight of protease preparations and 2 to 20% by weight, in particular 4.0 to 16 Wt .-% amylase preparations used, each 0.4 to 20 wt .-%,
- active protein contains in particular from 0.8 to 10% by weight of active protein.
- enzymes and / or enzyme preparations preferably liquid protease preparations and / or amylase preparations, and optionally cellulase preparations and / or mannanase preparations are preferably used.
- a preferred pH value of detergent preparations B according to the invention is between 6 and 9.
- the cleaning agent preparations B of the cleaning agent dosage forms according to the invention preferably contain less than 2.5% by weight of complexing agents. They preferably contain less than 2.5% by weight of complexing agents and / or builders. The lowering of the
- detergent preparation B contains less than 2.0% by weight of complexing agent, preferably less than 1.0% by weight of complexing agent, particularly preferably less than 0.5% by weight of complexing agent and in particular none Contains complexing agents.
- the total amount of complexing agent and / or builders contained in the detergent preparation B is preferably less than 10% by weight, preferably less than 6% by weight, particularly preferably less than 2% by weight and in particular 0% by weight.
- organic solvents come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers.
- the solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, monoethanolamine, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy
- Preferred solvents are preferably selected from glycerol, 1, 2-propylene glycol, 1, 3-propylene glycol, dipropylene glycol and polyethylene glycols, in particular those polyethylene glycols which have an average molecular weight between 100 and 800, preferably 200 and 600 g / mol. The proportion by weight of these organic solvents in the total weight of each
- Detergent preparations according to the invention are preferably 5 to 80% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight.
- a particularly preferred organic solvent which is particularly effective in terms of stabilizing the cleaning agent preparation, in particular cleaning agent preparation B, is 1,2-propylene glycol.
- the proportion by weight of 1,2-propylene glycol in the total weight of the detergent preparations B according to the invention can vary within wide limits, but such preparations have proven to be particularly stable, based on the
- Total weight of the respective detergent preparation B 5 to 80 wt .-%, preferably 10 to 60 wt .-% and in particular 20 to 50 wt .-% 1, 2-propylene glycol. Corresponding preparations are therefore preferred according to the invention.
- boric acid or a boric acid derivative is a boric acid or a boric acid derivative.
- the boronic acids or their salts or esters are preferably used, in particular derivatives with aromatic groups, for example ortho, meta- or para-substituted phenylboronic acids, in particular 4-formylphenyl-boronic acid (4-FPBA), or the Salts or esters of the compounds mentioned.
- 4-FPBA 4-formylphenyl-boronic acid
- the total weight of detergent preparations B according to the invention is preferably 0.001 to 10% by weight, preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight.
- a particularly preferred boric acid derivative which is particularly effective in terms of stabilizing the cleaning agent preparation is 4-formylphenyl-boronic acid.
- the proportion by weight of 4-formylphenyl boronic acid in the total weight of the cleaning agent preparations according to the invention can vary within wide limits, but such preparations have proven to be particularly stable based on the total weight of the cleaning agent preparation B, 0.001 to 10% by weight, preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight. Corresponding preparations are therefore preferred according to the invention.
- Another optional component of the cleaning agent preparations according to the invention is a Ca or Mg ion source.
- the weight fraction of the Ca or Mg ion source in the total weight of cleaning agent preparations B according to the invention is preferably 0.01 to 10% by weight, preferably 0.2 to 8% by weight and in particular 0.5 to 5% by weight.
- the organic calcium salts have proven to be particularly preferred and particularly effective in terms of stabilizing the cleaning agent preparation B.
- the proportion by weight of the organic calcium salts in the total weight of the cleaning agent preparations according to the invention can vary within wide limits, but those preparations which, based on the total weight of the cleaning agent preparations according to the invention can vary within wide limits, but those preparations which, based on the total weight of the cleaning agent preparations according to the invention.
- Detergent preparation 0.01 to 10 wt .-%, preferably 0.2 to 8 wt .-% and in particular 0.5 to 5 wt .-% contain. Corresponding preparations are therefore preferred according to the invention.
- detergent preparations B according to the invention may also contain polyols, in particular sorbitol.
- the liquid cleaning agent preparations B preferably contain 30% by weight and less, preferably 25% by weight and less, in particular 15% by weight and less.
- the detergent preparations B contain, based on their total weight, 0.5 to 30% by weight, preferably 1.0 to 25% by weight and in particular 1.5 to 30% by weight of water.
- the packaging means also contains at least one, preferably of the cleaning agent preparations, in particular of the
- Detergent preparations A and B separately present active ingredient composition, which contains at least one carrier material, preferably a water-insoluble carrier material, and at least one active ingredient C.
- the detergent supply form can contain one or more active substance compositions, which are preferably separate from the detergent preparations, for example two, three, four, five or more active substance compositions which differ from one another in at least one of their ingredients can be present. These different Active substance compositions can be present both separately from one another and mixed with one another.
- the packaging means preferably the part of the packaging means in which the at least one active substance composition is separate from the cleaning agent preparations A and B (for example the chamber) is provided with a plurality of openings, the size of which is dimensioned such that the small particles pass through the openings cannot escape.
- the openings are dimensioned such that the active ingredient, preferably the fragrances and / or the fragrance scavenger, can be emitted to the outside, starting from the receiving space of the packaging means.
- the chamber has a plurality of openings, in particular adjacent to one another, preferably each having a size of less than 20 mm, preferably less than 10 mm, in particular less than 5 mm, very particularly preferably less than 2.5 mm.
- the part of the packaging means preferably the chamber, in which the at least one active substance composition comprising at least one active substance C and a carrier material, preferably a water-insoluble carrier material, is designed in such a way that the chamber contains between 5 and 95% of the volume, preferably 10 to 90 % of the volume is filled, preferably filled with the at least one active ingredient composition, so that the rinsing liquor and / or air can optimally flow through the chamber.
- the form of cleaning agent is suitable for
- these active substances are preferably released over a period of time which is a multiple of the period of a cleaning process.
- it is suitable for metering one or more active ingredients in 4 to 50, preferably 10 to 40 and in particular 15 to 35 cleaning cycles of a dishwasher.
- Such a long-lasting release of the active ingredients can be achieved, for example, by the active ingredients used being delayed in solution by appropriate packaging, in particular the choice of the carrier material and the processing of
- Carrier material and active ingredient for the ultimate active ingredient composition are Carrier material and active ingredient for the ultimate active ingredient composition
- Affect release kinetics of the active substance is based on the spatial design of the container.
- Textile materials or polymers are used with particular preference as water-insoluble carrier materials.
- a dosing device characterized in that the container a water-insoluble material, preferably made of a textile material or a polymer or a polymer mixture, is preferred according to the invention.
- Synthetic polymers are preferably used as polymers, in particular water-insoluble polymers.
- Active substance compositions characterized in that at least one of the carrier materials is a polymeric material, preferably a substance from the group comprising ethylene / vinyl acetate copolymers, low or high density polyethylene (LDPE, HDPE) or mixtures thereof, polypropylene, polyethylene / Polypropylene copolymers, polyether / polyamide block copolymers, styrene / butadiene (block) copolymers, styrene / isoprene (block) copolymers, styrene / ethylene / butylene copolymers, acrylonitrile / butadiene / styrene copolymers, acrylonitrile / butadiene Copolymers, polyether esters, polyisobutene, polyisoprene, ethylene / ethyl acrylate copolymers, poly
- Polyethylene is a collective name for polymers belonging to the polyolefins with groups of the type CH2-CH2 as a characteristic basic unit of the polymer chain.
- Polypropylene is the name for thermoplastic polymers of propylene with the general formula - (CH 2 -CH [CH3]) n -.
- Polyether is a general term in the field of macromolecular chemistry for polymers whose organic repeating units are held together by ether functionalities (C-O-C). According to this definition, a large number of structurally very different polymers belong to the polyethers, e.g. B. the polyalkylene glycols (polyethylene glycols, polypropylene glycols and polyepichlorohydrins) as polymers of 1, 2-epoxides, epoxy resins, polytetrahydrofurans (polytetramethylene glycols), polyoxetanes, polyphenylene ethers (see.
- polyalkylene glycols polyethylene glycols, polypropylene glycols and polyepichlorohydrins
- polymers of 1, 2-epoxides epoxy resins
- polytetrahydrofurans polytetramethylene glycols
- polyoxetanes polyphenylene ethers
- Polyaryl ethers or polyether ether ketones (see polyether ketones). Polymers with pendant ether groups are not counted among the polyethers, as u. a. the cellulose ethers, starch ethers and vinyl ether polymers.
- the group of polyethers also includes functionalized polyethers, i.e. H. Compounds with a polyether backbone that have other functional groups attached to their main chains, such as. B. carboxy, epoxy, allyl or amino groups, etc.
- Block copolymers of polyethers and polyamides are very versatile.
- PA Polyamides
- polypeptides and proteins e.g. protein, wool, silk.
- the synthetic polyamides are thermoplastic, chain-shaped polymers. In addition to homopolyamides, some copolyamides have also become important. It is usual with these a qualitative and quantitative indication of the composition z.
- PA 66/6 80:20 for polyamides prepared from 1, 6-hexanediamine, adipic acid and e-caprolactam in a molar ratio of 80:80:20. Because of their special properties, polyamides that contain only aromatic residues (e.g. those made from p-phenylenediamine and terephthalic acid) are classified under the generic name. Aramids or polyaramides combined (example: Nomex®).
- Polyamides from building blocks with side chains or copolyamides from widely different components that are largely amorphous. In contrast to the generally milky-opaque, partially crystalline polyamides, these are almost crystal-clear.
- the most common homo-polyamides are between 200 and 260 ° C (PA 6: 215-220 ° C, PA 66: 255-260 ° C).
- Polyester is the collective name for polymers whose basic building blocks are held together by ester bonds (-CO-0-). According to their chemical structure, the so-called homopolyesters can be divided into two groups, the hydroxycarboxylic acid types (AB polyester) and the dihydroxy dicarboxylic acid types (AA-BB polyester). The former are made from only a single monomer by e.g. B. polycondensation of a w-hydroxycarboxylic acid 1 or by ring-opening polymerization of cyclic esters (lactones) 2.
- Polyesters generally include polycarbonates (carbonic acid polyesters).
- AB-type polyesters (I) include a. Polyglycolic acids, polylactic acids, polyhydroxybutyric acid [poly (3-hydroxybutyric acid), poly (8-caprolactone) e and polyhydroxybenzoic acids.
- Purely aliphatic AA-BB type polyesters (II) are polycondensates of aliphatic diols and dicarboxylic acids, which u. a. are used as products with terminal hydroxyl groups (as polydiols) for the production of polyester polyurethanes [e.g. B. Polytetramethylene adipate].
- AA-BB-type polyesters made from aliphatic diols and aromatic dicarboxylic acids, in particular the polyalkylene terephthalates, with polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and poly (1,4-cyclohexanedimethylene terephthalate) e (PCDT) as the most important representatives .
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PCDT poly (1,4-cyclohexanedimethylene terephthalate) e
- These types of polyesters can be made by using other aromatic dicarboxylic acids (e.g. isophthalic acid) or by using diol mixtures in polycondensation, their properties can be varied widely and adapted to different areas of application.
- polyesters are the polyarylates, to which u. a. which include poly (4-hydroxybenzoic acid).
- unsaturated polyesters can also be prepared from unsaturated dicarboxylic acids which have gained technical importance as polyester resins, in particular as unsaturated polyester resins (UP resins).
- Polymers are referred to as polyurethanes (PUR) in their macromolecules
- Polyurethanes are generally made from poly or polyhydric alcohols and polyaddition
- polyurethanes are created with very different mechanical properties, which are used as components of adhesives and varnishes (polyurethane resins), as ionomers, as thermoplastic materials for bearing parts, rollers, tires, rollers and as more or less hard elastomers in fiber form (elasto fibers, short PUE for these elastane or spandex fibers) or as polyether or polyester urethane rubber (EU or AU)
- adhesives and varnishes polyurethane resins
- ionomers as thermoplastic materials for bearing parts, rollers, tires, rollers and as more or less hard elastomers in fiber form (elasto fibers, short PUE for these elastane or spandex fibers) or as polyether or polyester urethane rubber (EU or AU)
- the polymeric carrier material of the particles consists at least in part of ethylene / vinyl acetate copolymer. Another preferred subject of the present application is therefore one
- a polymeric carrier material contains at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 70% by weight of ethylene / vinyl acetate copolymer, preferably entirely of ethylene / vinyl acetate copolymer is made.
- Ethylene / vinyl acetate copolymers is the name for copolymers of ethylene and vinyl acetate. This polymer is generally produced in a process comparable to the production of low density polyethylene (LDPE). With a
- the crystallinity of the polyethylene is interrupted and in this way the melting and softening points or the hardness of the resulting products are reduced.
- the vinyl acetate also makes the copolymer more polar and thus improves its adhesion to polar substrates.
- ethylene / vinyl acetate copolymers described above are widely available commercially, for example under the tradename Elvax ® (Dupont).
- Elvax ® Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example Elvax ® 265, Elvax ® 240, Elvax ® 205 W, Elvax ® 200 W and Elvax ® 360.
- Other suitable products are, for example, products available under the trademark Evatane® (Arkema).
- active substance compositions are particularly preferred in which ethylene / vinyl acetate copolymer is used as the polymeric carrier material and this copolymer contains 5 to 50% by weight of vinyl acetate, preferably 10 to 40% by weight .-% vinyl acetate and in particular 20 to 30 wt .-% vinyl acetate, each based on the total weight of the copolymer contains.
- Active ingredient compositions contain a polyether ester amide polymer (PEEA polymer) of the general formula H0 [C (0) -PA-C (0) -0-PE-0] n H.
- Objects of the application according to the invention characterized in that at least one of the active substance compositions is a polyether-ester-amide polymer (PEEA polymer) of the general formula H0 [C (0) -PA-C (0) -0-PE- 0] n H contains, in which PA stands for a polyamide group, PE stands for a polyether group and n stands for an integer, are particularly preferred.
- Corresponding PEEA polymers are, for example, by copolymerization of the polyamide of a dicarboxylic acid, which has a terminal acid group and has an average molecular weight between 300 and 15,000, with a linear or branched aliphatic polyalkylene glycol, which carries a terminal hydrxoyl group and has an average molecular weight between 200 and 6000 , available.
- the copolymerization is preferably carried out in a melt at temperatures between 100 and 400 ° C.
- PEEA polymers are commercially available under the name Pebax ® .
- Active ingredient compositions particularly preferred which are able to absorb at least 2.3 times, preferably 5 times their own weight of fragrances.
- Suitable PEEA polymers are, for example, Pebax ® 2533, Pebax ® 3533 or Pebax ® 4033.
- PEEA polymer polyether-ester-amide polymer
- the invention comprises
- Active ingredient composition as carrier material activated carbon is understood to mean black, light, dry, odorless and tasteless powders or granules made from the smallest graphite crystals and amorphous carbon with a porous structure and very large internal surfaces (preferably between 500-1500 m 2 / g).
- powdered activated carbon granular activated carbon and, for example, cylindrical shaped activated carbon.
- Activated carbon can contain up to 25% by weight of mineral components.
- the activated carbon can act as a scent catcher and is therefore both carrier material and active ingredient.
- Other suitable carrier materials are the cyclodextrins.
- inorganic carrier materials are preferably also used. Be particularly preferred
- Forms of cleaning agent characterized in that at least one of the carrier materials is an inorganic carrier material, preferably a silicate, phosphate or borate.
- the silicates, phosphates or borates are preferably in the form of a glass, particularly preferably in the form of a water-soluble glass.
- Particularly preferred glasses are glasses containing zinc and / or bismuth, in particular those containing bismuth phosphate and / or
- the carrier material is water-soluble and already contains in its substance the active ingredient, in particular the glass corrosion inhibitors (zinc and / or bismuth) in the carrier material.
- the detergent dosage forms can contain such zinc or bismuth-containing glasses, particularly preferably zinc phosphate-containing glasses, in addition to a further active ingredient composition comprising a carrier material, preferably a
- water-insoluble carrier material and at least one active ingredient e. These can then be contained in a common chamber or in separate chambers, in particular in one or more chambers which have openings, in particular openings such that the washing liquor and / or the air can flow through them. Those are preferred
- Forms of detergent which contain a glass containing zinc phosphate or bismuth phosphate and furthermore at least one, preferably two, three or more
- Contain active ingredient compositions which comprise one or more fragrances and / or one or more fragrance scavengers as active ingredients.
- Particularly preferred inorganic support materials are, for example, zeolites, preferably acid-modified zeolites.
- the aforementioned carrier materials can be used alone or in combination with others
- Carrier materials are used.
- thermoplastic in particular thermoplastic
- Deformation of the carrier materials in the course of one or more applications will result in a change in the carrier material surface, in particular a change in the size of the
- Dosing devices characterized in that at least one polymeric carrier material has a melting or softening point between 40 and 125 ° C, preferably between 60 and 100 ° C, particularly preferably a melting point of 70 to 90 ° C and in particular between 73 and 80 ° C ( preferred method of determination for the
- Carrier materials are insoluble in water.
- the active substance compositions can in principle assume all physical states and / or spatial forms that can be achieved depending on the chemical and physical properties of the carrier materials. In a further embodiment, at least one of the
- Active ingredient compositions as a gel.
- At least one of the active substance compositions is in the form of a solid. Active ingredient compositions in the form of individual blocks comprising an entire active ingredient composition are used with particular preference.
- the active substance compositions can preferably be in particulate form, the active substance compositions in which the carrier material comprises at least one of the
- Active ingredient compositions are in particle form, these particles preferably being one have average diameters from 0.5 to 20 mm, preferably from 1 to 10 mm and in particular from 3 to 6 mm, are particularly preferred.
- Active ingredient compositions which comprise at least one colored active ingredient composition are particularly preferably used.
- the coloring of at least one of the active ingredient compositions enables an optical differentiation of these compositions to be achieved and the multiple use of these different compositions can be clarified in a simple manner.
- the dyes are also suitable as an indicator, in particular as a consumption indicator for the colored active ingredient compositions.
- Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as glass, ceramics or plastic tableware, to be precise stain.
- the form of cleaning agent is characterized in that the at least one active ingredient C is selected from the group of fragrances, preferably linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate,
- Zinc ricinoleate Dyes, glass corrosion inhibitors, antimicrobial agents, germicides or fungicides and mixtures thereof, preferably mixtures of at least one fragrance scavenger, preferably with one, two, three or more fragrances and / or at least one dye.
- fragrances preferably two, three or more fragrances and at least one dye
- perfume oils or fragrances can be used in the context of the present invention
- Fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. However, are preferred
- perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- a fragrance In order to be perceptible, a fragrance must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role. Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, whereby the odor impressions are described in "top note” (top note), “heart or middle note” (middle note or body ) and “base note” (end note or dry out).
- the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile, i.e. non-stick fragrances.
- more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly.
- fixatives for example, which prevents them from evaporating too quickly.
- the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release.
- Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
- fragrances are linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol and / or eucalyptol and their
- the known ricenolates in particular the zinc ricenoleates, can be used, for example, as scent catchers (or odor neutralizers or scent neutralizers, agents against malodour or bad odors).
- scent catchers or odor neutralizers or scent neutralizers, agents against malodour or bad odors.
- Activated carbon and / or cyclodextrins and / or zeolites, preferably acid-modified zeolites, can also be used with particular preference.
- Zinc ricinoleate alone or in combination with one or more of the above-mentioned fragrances and / or fragrance scavengers is particularly preferred, since it also has a positive effect on the inhibition of glass corrosion during the rinsing process.
- Fragrances and / or fragrance scavengers antimicrobial agents are used.
- bacteriostatics and bactericides fungistatics and fungicides, etc.
- Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and
- Phenol mercuric acetate although these compounds can also be dispensed with entirely.
- the active substances can be contained in the active substance preparations in any amounts.
- dosing devices are particularly preferred in which the proportion by weight of the active ingredient (s) is 1 to 70% by weight, preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight, in particular 30 to 40% by weight, is based in each case on the total weight of the active ingredient composition (s).
- active ingredient compositions can be present separately from one another or next to one another in the packaging means of the detergent form.
- the different active substance compositions can preferably be present next to one another, that is to say in direct contact with one another, in the packaging means of the detergent form.
- the form of detergent supply further comprises a liquid detergent preparation D, the detergent preparation D preferably comprising the detergent preparations A and B and the at least one
- Active ingredient composition is different.
- Detergent preparation D used. When used in a dishwashing process, this detergent preparation D is preferably surfactant and / or acidic, preferably surfactant and acidic.
- this detergent preparation D is preferably surfactant and / or acidic, preferably surfactant and acidic.
- the rinse aid achieved in the dishwashing method according to the invention can be improved. This applies in particular to those preferred processes in which the dosage of the cleaning agent preparations A, B and D takes place with a time delay.
- the nonionic surfactants described above are particularly suitable as surfactant additives for detergent preparation D. However, nonionic surfactants of the general formula R 1 -CH (0H) CH 2 0- (A0) w- (AO) x- (AO) y - (A ”O) zR 2 , in which
- R 1 is a linear or branched, saturated or mono- or polyunsaturated C6 is 24 alkyl or alkenyl radical;
- R 2 represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
- A, A ', A "and A'” independently of one another for a radical from the group -CH2CH2, -CH2CH2-CH2, -CH 2 -CH (CH 3 ), -CH2-CH2-CH2-CH2, -CH2-CH (CH 3 ) -CH 2 -, -CH 2 - CH (CH 2 -CH 3 ),
- w, x, y and z stand for values between 0.5 and 120, where x, y and / or z can also be 0
- non-ionic surfactants of the general formula R 1 -CH (0H) CH 2 0- (A0) wR 2 , in which the
- R 1 for a straight-chain or branched, saturated or single or
- R 2 represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
- A represents a radical from the group CH2CH2, -CH2CH2-CH2, -CH2-CH (CH 3 ), and
- w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.
- the group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C4-22 fatty alcohol (EO) 40 -80-2-hydroxyalkyl ether.
- Detergent preparation D is preferably from 1.0 to 20% by weight, preferably from 2.0 to 18% by weight, particularly preferably from 4.0 to 15% by weight and in particular from 6.0 to 12% by weight.
- Detergent preparation in particular at least one detergent preparation further comprising a nonionic surfactant, particularly preferably at least
- Detergent preparation B and / or D at least one hydrotrope (hereinafter also referred to as a solubilizer).
- Preferred hydrotropes are xylene sulfonate, cumene sulfonate, urea and / or / V-methyl acetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, in particular cumene sulfonate. It was found that the use of hydrotropes, in particular cumene sulfonate, enormously improves the phase stability with regard to the temperature fluctuations. This can be observed in particular for preparations which contain at least one nonionic surfactant.
- At least the detergent preparation D in particular the detergent preparations D and B, have at least one hydrotrope, preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, especially cumene sulfonate, preferably in an amount from 2 to 25% by weight, in particular from 4 to 20% by weight and particularly preferably in an amount of 6 to 15, for example from 7 to 12% by weight, based on the total weight of the respective detergent preparation.
- hydrotrope preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, especially cumene sulfonate, preferably in an amount from 2 to 25% by weight, in particular from 4 to 20% by weight and particularly
- the weight ratio of the at least one nonionic surfactant to the at least one hydrotrope preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, in particular cumene sulfonate, is preferred.
- the detergent preparations D according to the invention preferably contain at least one acidifying agent when used in a dishwashing process.
- Acidifying agents can be added to the cleaning agent preparations D according to the invention in order to lower the pH of the liquor in the rinse cycle.
- Both inorganic acids and organic acids are suitable here, provided they are compatible with the other ingredients.
- the solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. Preferred from this group are formic acid, citric acid,
- Tartaric acid succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
- Organic sulfonic acids such as amidosulfonic acid can also be used.
- Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
- Detergent preparations D based on the total weight of the
- Detergent preparation D one or more acidifying agents, preferably mono-, oligo- and polycarboxylic acids, particularly preferably formic acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid and in particular formic acid, acetic acid and / or citric acid in amounts of 0.1 up to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.3 to 8.0% by weight are preferred
- the use of formic acid is preferred because, in addition to the acid function to improve the rinse aid result, it also has a positive influence on the storage stability of the cleaning preparation D has, which due to storage in the interior of the dishwasher, as stated above, is subject to strong temperature fluctuations. Furthermore, it has a disinfectant effect, so that when using formic acid in the rinse cycle, both the number of bacteria is reduced. This applies both to those bacteria that are in the rinse liquor of the rinse cycle and to those that remain in the sump of the dishwasher during and after the rinse cycle as well as the interior of the dishwasher. The number of residual germs on the washed dishes can also be reduced as a result.
- an active ingredient composition C in particular comprising fragrances and / or scent scavengers
- formic acid is used as an acidifying agent in preparation D.
- the formic acid itself has a slightly pungent smell, which is noticeable to sensitive consumers. Due to the separate storage of the
- Active substance composition C and the release of the at least one active substance C is formed neither during the dishwashing process nor in the time between
- the cleaning agent preparations A, B and D described above differ in their composition and are therefore not identical.
- detergent preparations A, B and / or D according to the invention preferably contain at least one glass corrosion inhibitor when used in a dishwashing process.
- Preparation (s) A and / or preparation (s) D particularly preferably contain a corresponding amount of glass corrosion inhibitor (s).
- Glass corrosion inhibitors selected from water-soluble zinc salts, preferably zinc chloride, zinc sulfate and / or zinc acetate, particularly preferably zinc acetate, polyalkyleneimines, in particular polyethyleneimines.
- the preparations according to the invention in particular preparations A and / or D, preferably at least preparation (s) D, contain at least one zinc salt, in particular inorganic or organic, as a further constituent
- the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
- the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
- zinc acetate is used as the zinc salt.
- the zinc salt in cleaning agent preparations according to the invention is preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1% by weight to 2% by weight, based on the total weight of the respective detergent preparation, in particular the respective detergent preparation A or D.
- Polyethyleneimines as are available, for example, under the name Lupasol® (BASF), are preferably used in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight, based on the total weight of the respective preparation Glass corrosion inhibitors are used.
- composition of some exemplary cleaning agent forms according to the invention comprising the cleaning agent preparations A, B and D, can be found in the following tables.
- the combination of cleaning agents described above is made up by means of a packaging agent in which the cleaning agent preparations A and B or A, B and D are present separately from one another.
- This separation can be achieved, for example, by separate receiving chambers, each of these receiving chambers containing one of the cleaning agents combined with one another.
- Examples of such assembly forms are cartridges with two, three, four or more separate receiving chambers, for example two, three, four or multi-chamber bottles.
- the viscosity of all cleaning agent preparations A and B or A, B and C is preferably less than 120 mPas, in particular from 1 to 100 mPas, in particular 10 to 80 mPas, preferably 20 to 60 mPas (measured at 20 ° C. with a Brookfield Instrument LVDV II +, spindle 31, 100 rpm). This has the advantage that the detergent preparations from the
- Packaging material only by opening a valve on the underside of the packaging material (especially the cartridge) based on gravity, preferably without the involvement of electrical or electronic means, such as Pumps etc. can be dosed.
- the chambers are preferably largely completely emptied, i.e. without large residual amounts of the detergent preparations to be dosed. This is advantageous for the consumer and for the environment because only small amounts of the detergent preparations remain unused in the chambers of the packaging means or the cartridge.
- Another object of the present application is a cleaning agent supply form, comprising
- a cleaning agent preparation A according to the invention in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
- At least one further cleaning agent preparation B different from A in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times
- at least one further active ingredient composition different from A and B in an amount sufficient for at least twice, preferably at least four times and in particular at least eight times to carry out an automatic dishwashing process which contains at least one carrier material, preferably a water-insoluble carrier material and at least one active substance C;
- Another object of the present application is a detergent dosing system comprising
- a cleaning agent preparation A according to the invention in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
- the cartridges described above are the
- Such a metering device can be connected to the cartridge, for example, by means of an adhesive, snap-in, snap or plug connection. Filling the cartridge is simplified, for example, by separating the cartridge and the metering device. Alternatively, the detachable
- a particularly preferred subject matter of this application is a detergent dosing system comprising
- a cleaning agent supply form comprising an amount of cleaning agent preparations A, B and C or A, B, C and D sufficient for carrying out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times; b) a dispenser detachably connected to the form of the detergent.
- the present application furthermore relates to a detergent dosing system comprising
- a cleaning agent supply form comprising an amount of cleaning agent preparations A, B and C or A, B, C and D sufficient for carrying out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times; b) a dosing device that is permanently connected to the form of the detergent
- the aforementioned detergent dosing systems comprising the detergent supply form according to the invention (and optionally one or two more, from the one according to the invention)
- Detergent preparations A and B and C different compositions, a cartridge and a dispenser detachably connected to the cartridge are present in a preferred embodiment in a common outer packaging, the filled cartridge and the dispenser being particularly preferably contained separately from one another in the outer packaging.
- the outer packaging is used for storage, transport and presentation of the form of cleaning agent according to the invention and protects it from dirt, shock and impact.
- the outer packaging should be designed to be at least partially transparent.
- the dosing system according to the invention consists of the basic components of a cartridge filled with the cleaning agent according to the invention and a dosing device that can be coupled to the cartridge, which in turn is formed from further assemblies, such as, for example, component carrier, actuator, closure element, sensor, energy source and / or control unit.
- the metering system according to the invention is movable. Movable in the sense of this application means that the metering system is not inextricably linked to a water-carrying device such as a dishwasher or the like, but rather can be removed from a dishwasher by the user or positioned in a dishwasher, i.e. can be handled independently
- the metering device is not releasably connected to a water-carrying device such as a dishwasher or the like for the user and only the cartridge is movable.
- the preparations to be dosed can have a pH between 2 and 14, in particular 2 and 12, depending on the intended use, all components of the dosing system that come into contact with the preparations should have an appropriate acid and / or alkali resistance. Furthermore, these components should be largely chemically inert, for example against nonionic surfactants, enzymes and / or fragrances, through a suitable choice of material.
- a cartridge in the sense of this application is understood to mean a packaging material which is suitable for enveloping or holding together flowable or scatterable preparations and which can be coupled to a metering device for dispensing the preparation.
- a cartridge can also comprise a plurality of chambers which are different from one another
- compositions can be filled. It is also conceivable for a plurality of containers to be arranged to form a cartridge unit.
- the cartridge has at least one outlet opening, which is arranged in such a way that the preparation can be released from the container under the force of gravity in the use position of the metering device.
- At least one second chamber is provided for receiving at least one second flowable or scatterable preparation, the second chamber having at least one outlet opening which is arranged such that a product release caused by gravity from the second chamber in the use position of the dosing device.
- the arrangement of a second chamber is particularly advantageous when preparations are stored in the separate containers, which are usually not stable with one another, such as bleaches and enzymes.
- At least one of the chambers for dispensing active substances) C is one
- Fragrance or in particular an odor neutralizer to the environment, designed so that it has openings through which the washing liquor and / or the air can flow.
- the cartridge is formed in one piece.
- the cartridges can be formed inexpensively in one production step, in particular by means of suitable blow molding processes.
- the chambers of a cartridge can be separated from one another, for example, by webs or material bridges.
- the cartridge can also be formed in several pieces by components that are injection molded and then joined together. Furthermore, it is conceivable that the cartridge is formed in such a way that at least one chamber, preferably all chambers, can be removed individually from the dosing device or inserted into the dosing device. This makes it possible to replace a chamber that has already been emptied if the consumption of a preparation from one chamber varies, while the others, which may still be filled with preparation, remain in the metering device. In this way, a targeted and needs-based refilling of the individual chambers or their preparations can be achieved.
- the chambers of a cartridge can be fixed to one another by suitable connection methods, so that a container unit is formed.
- the chambers can be detachable or non-detachable by means of a suitable positive, non-positive or material connection
- connection types from the group of snap-in connections, Velcro connections, press connections, fusion connections, adhesive connections, welded connections, soldered connections, screw connections,
- the fixation can also be formed by a shrink tube (so-called sleeve), which is pulled over the entire or sections of the cartridge in a heated state and firmly encloses the chambers or the cartridge in the cooled state.
- the bottom of the chambers can be inclined in a funnel shape towards the discharge opening.
- the inner wall of a chamber can be formed by a suitable choice of material and / or surface configuration in such a way that a slight material adhesion of the preparation to the inner one
- Chamber wall is realized. This measure can also further optimize the residual emptiness of a chamber.
- the chambers of a cartridge can have the same or different filling volumes.
- the ratio of the container volumes is preferably 5: 1, in a configuration with three chambers preferably 4: 1: 1, whereby this
- Configurations are particularly suitable for use in dishwashers.
- the cartridge preferably has 3, 4, 5 or 6 chambers.
- the first chamber contains an alkaline cleaning preparation
- the second chamber contains an enzymatic preparation
- the third chamber contains a rinse aid, the volume ratio of the chambers being approximately 4: 1: 1.
- the fourth chamber contains the at least one
- Active ingredient composition comprising the at least one active ingredient C and a carrier material, preferably a water-insoluble carrier material.
- a dosing chamber can be formed in or on a chamber in the direction of flow of the preparation in front of the outlet opening.
- the metering chamber determines the amount of preparation that is to be released into the environment when preparation is released from the chamber. This is particularly advantageous if the closure element of the metering device, which causes the preparation to be dispensed from a chamber into the environment, can only be put into a dispensing and a closure state without checking the dispensing quantity.
- the dosing chamber then ensures that a predefined amount of preparation is released without an immediate feedback of the dispensed preparation amount.
- the metering chambers can be formed in one piece or in several pieces.
- one or more chambers each have a chamber opening that can be closed in a liquid-tight manner in addition to an outlet opening.
- This chamber opening makes it possible, for example, to refill the preparation stored in this chamber.
- ventilation options can be provided in particular in the head region of the cartridge, in order to ensure pressure compensation when the filling level of the chambers falls between the interior of the cartridge chambers and the surroundings.
- These ventilation options can be designed, for example, as a valve, in particular a silicone valve, micro-openings in the cartridge wall or the like.
- cartridge chambers are not to be ventilated directly, but rather via the metering device or no ventilation, e.g. If flexible containers, such as bags, are provided, this has the advantage that when the container is elevated
- the cartridge usually has a filling volume of ⁇ 5,000 ml, in particular ⁇ 1,000 ml, preferably ⁇ 500 ml, particularly preferably ⁇ 250 ml, very particularly preferably ⁇ 50 ml.
- the cartridge can take any shape. For example, it can be cube-shaped, spherical or plate-like.
- the shape of the cartridge and the metering device can in particular be designed in such a way that they ensure as little loss of useful volume as possible, in particular in a dishwasher.
- the dosing device based on the dishes to be cleaned in dishwashers.
- this can be plate-shaped, approximately in the dimensions of a plate.
- the cartridge preferably has a ratio of height: width: depth between 5: 5: 1 and 50: 50: 1, particularly preferably of about 10: 10: 1.
- the “slim” design of the dosing device and the cartridge makes it possible, in particular, to position the device in the lower cutlery basket of a dishwasher in the receptacles provided for plates. This has the advantage that the preparations dispensed from the dosing device go directly into the washing liquor and cannot adhere to other items to be washed.
- the metering system dimensioned the metering system such that positioning of the metering system is only possible in the receptacles provided for the lower basket.
- the width and the height of the metering system can be chosen in particular between 150 mm and 300 mm, particularly preferably between 175 mm and 250 mm.
- the dosing unit in a cup shape with an essentially circular or square base area.
- the cartridge In order to protect heat-sensitive components of a preparation in a cartridge from exposure to heat, it is advantageous to manufacture the cartridge from a material with a low thermal conductivity.
- a further possibility for reducing the influence of heat on a preparation in a chamber of the cartridge is to isolate the chamber by means of suitable measures, e.g. through the use of thermal insulation materials such as styrofoam, which completely or partially enclose the chamber or the cartridge in a suitable manner.
- the cartridge has an RFID label that at least contains information about the contents of the cartridge and that can be read out by the sensor unit.
- This information can be used to select a dosing program stored in the control unit. This can ensure that an optimal dosing program is always used for a specific preparation. It can also be provided that, in the absence of an RFID label or in the case of an RFID label with an incorrect or incorrect identification, no dosing is carried out by the dosing device and instead an optical or acoustic signal is generated that the user is aware of the error points out.
- the cartridges can also have structural elements which correspond to corresponding elements of the metering device according to the
- Control unit are transmitted, whereby a control of the metering device can be carried out which is coordinated with the content of the corresponding container.
- the cartridge is designed in particular for receiving flowable cleaning agents.
- a cartridge particularly preferably has a plurality of chambers for spatially separated accommodation of preparations of a cleaning agent which are in each case different from one another on.
- the cartridge can be designed so that it is detachable or fixed in or on the
- Dishwasher can be arranged.
- control unit The control unit, sensor unit and at least one actuator required for operation are integrated in the dosing device.
- An energy source is preferably also arranged in the metering device.
- the dosing device consists of a splash-proof housing that prevents the ingress of splash water, such as when used in a
- Dishwasher can prevent inside of the dispenser.
- the dosing device comprises at least one first interface, which interacts with a corresponding interface designed in or on a water-carrying device, in particular a water-carrying household appliance, preferably a dishwasher, such that a transmission of electrical energy from the water-carrying device to the dosing device is realized.
- a water-carrying device in particular a water-carrying household appliance, preferably a dishwasher
- the interfaces are formed by plug connectors.
- the interfaces can be designed in such a way that wireless transmission of electrical energy is effected.
- a second interface is provided on the metering device and the water-carrying device, such as a dishwasher
- An adapter can be used to easily couple the dosing system to a water-bearing household appliance.
- the adapter is used for the mechanical and / or electrical connection of the dosing system to the water-bearing household appliance.
- the adapter is, preferably fixed, connected to a water-carrying line of the household appliance. However, it is also conceivable to use the adapter for positioning in or on
- the adapter makes it possible to run a dosing system for both a self-sufficient and a "build-in” version. It is also possible to use the adapter as a kind of charging station for the
- Form dosing system in which, for example, the energy source of the dosing device is charged or data is exchanged between the dosing device and the adapter.
- the adapter can be arranged in a dishwasher on one of the inner walls of the washing chamber, in particular on the inner side of the dishwasher door.
- the adapter as such is positioned so that it is not accessible to the user in the water-conducting household appliance, so that the metering device is inserted into the adapter, for example during assembly of the household device, the adapter, the metering device and the household device being designed in this way that a cartridge can be coupled to the dosing device by the user.
- the cleaning agent supply forms according to the invention are suitable for use in dishwashing, but the use of a cleaning agent according to the invention is nevertheless
- Form of detergent or a detergent dosing system for washing dishes in a machine dishwashing method is preferred.
- the cleaning agents according to the invention are notable for particular physical and chemical stability
- the cleaning agents according to the invention are therefore particularly suitable for metering by means of a metering system located in the interior of a dishwasher.
- a dosing system located in the interior of a dishwasher.
- Such a dosing system which can be immovably integrated into the interior of the dishwasher (machine-integrated dosing device), however
- Movable in the sense of this application means that the dispensing and metering system is not inextricably linked to a device such as a dishwasher or the like, but rather can be removed from a dishwasher or positioned in a dishwasher, for example.
- a movable cartridge of a dosing system provided for positioning in the interior of a dishwasher
- an immovable cartridge is a container integrated immovably into the interior, for example into the side wall or the interior lining of the door of a dishwasher.
- An example of a movable cartridge is a container that the consumer places in the interior of the dishwasher and remains there throughout the course of a cleaning cycle. Such a cartridge can be integrated into the interior, for example by simply inserting it into the cutlery or crockery basket, but can also be removed from the interior of the dishwasher by the consumer.
- the detergent or the detergent combination is dosed from the cartridge into the interior of the dishwasher, as described above, preferably by means of a dosing device that can be detached from the cartridge.
- a dosing device can be connected to the cartridge by means of an adhesive, latching, snap or plug connection.
- Cartridges with an inseparably connected dosing device can of course also be used.
- Detergent reservoir for i) a dosing device immovably integrated into the interior of a dishwasher or ii) one for positioning in the interior of a
- Movable dosing device provided in the dishwasher is preferred.
- Detergent reservoir for a dishwasher is a further subject of the present application.
- a cleaning agent preparation A according to the invention in an amount sufficient to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times;
- Receiving chambers are available as a detergent reservoir for
- a movable metering device provided for positioning in the interior of a dishwasher.
- the cleaning agents and cleaning agent combinations according to the invention are preferably used as automatic dishwashing agents.
- a partial amount a of the detergent preparation A located in the cartridge is metered into the interior of the dishwasher, a remaining amount of the detergent preparation located in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that it
- Residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset a; and a portion b of the detergent preparation B located in the cartridge is metered into the interior of the dishwasher, a remaining amount of the detergent preparation located in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that it
- Residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset b; and a portion c of the active ingredient C in the cartridge is metered into the interior of the dishwasher, a residual amount of the active ingredient in the cartridge remaining in the cartridge until the end of the dishwashing process, characterized in that this residual amount is at least twice, preferably at least corresponds to four times and in particular at least eight times the amount of subset c and
- a partial amount d of the detergent preparation D which may be located in the cartridge, is metered into the interior of the dishwasher, a residual amount of the detergent preparation located in the cartridge remaining in the cartridge until the end of the dishwashing process, thereby
- this residual amount corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset d.
- the invention also relates to a machine
- Dishwashing process in which the active ingredient composition is in the cartridge and through which the washing liquor and / or air flows through openings.
- fragrance (s) are released into the air in the interior of the dishwasher and, in addition to scenting the washing liquor during the dishwashing process, also leads to an odor situation that is pleasant for the consumer when opening and loading the dishwasher .
- the dosage of the cleaning agent preparation A and the cleaning agent preparation B and optionally the cleaning agent preparation D takes place at different times of the cleaning cycle.
- Another preferred subject of this application is therefore a machine dishwashing process using a cleaning agent supply form according to the invention or a cleaning agent metering system according to the invention, in the course thereof
- Dishwashing process remains in the cartridge, which of the at least double,
- Cartridge located in the dishwasher a subset b of the detergent preparation B located in the second cartridge, which is different from the cleaning agent preparation A according to the invention, is metered into the interior of the dishwasher, with a remaining amount of the cleaning agent located in this cartridge until the end of the
- Dishwashing process remains in the cartridge, which is at least double
- Cartridge detergent preparation D different from the detergent preparations A and B according to the invention are located in the interior of the dishwasher is metered, a residual amount of the cleaning agent located in this cartridge remaining in the cartridge until the end of the dishwashing process, which corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of partial amount d.
- the time t2 is at least 1 minute in time, preferably at least 2 minutes and in particular between 3 and 30 minutes, in particular between 3 and 20 minutes , before or after, preferably before time t1.
- a delayed metering of the minute preferably at least 2 minutes and in particular between 3 and 30 minutes, in particular between 3 and 20 minutes, before or after, preferably after the time t1.
- the cleaning preparation B is metered into the interior at a temperature of 20-35 ° C., then the cleaning preparation A at a temperature of 30-60 ° C. and then the cleaning preparation D at a temperature below 20 ° C.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102018220185.4A DE102018220185A1 (de) | 2018-11-23 | 2018-11-23 | Mehrkomponenten-Reinigersystem |
PCT/EP2019/081771 WO2020104445A1 (de) | 2018-11-23 | 2019-11-19 | Mehrkomponentiges reinigungssystem |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3884021A1 true EP3884021A1 (de) | 2021-09-29 |
Family
ID=68731952
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19812717.7A Pending EP3884021A1 (de) | 2018-11-23 | 2019-11-19 | Mehrkomponentiges reinigungssystem |
Country Status (4)
Country | Link |
---|---|
US (1) | US20210324307A1 (de) |
EP (1) | EP3884021A1 (de) |
DE (1) | DE102018220185A1 (de) |
WO (1) | WO2020104445A1 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102019200702A1 (de) * | 2019-01-21 | 2020-07-23 | Henkel Ag & Co. Kgaa | Mehrkomponentiges Reinigungssystem |
KR20210039026A (ko) * | 2019-10-01 | 2021-04-09 | 엘지전자 주식회사 | 인공 지능 식기 세척기 및 그를 이용한 식기 세척 방법 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2386129B (en) | 2002-03-06 | 2004-12-01 | Reckitt Benckiser Nv | Detergent dosing device |
DE10237066A1 (de) * | 2002-08-09 | 2004-02-26 | Henkel Kgaa | Duftabgabesystem |
DE102005062479A1 (de) | 2005-12-27 | 2007-07-05 | BSH Bosch und Siemens Hausgeräte GmbH | Dosiervorrichtung für die Zugabe eines Zuschlagmittels in einen Behandlungsraum und Geschirrspülmaschine mit einer Dosiervorrichtung |
WO2008101810A1 (de) * | 2007-02-20 | 2008-08-28 | Henkel Ag & Co. Kgaa | Verwendung von harnstoff-derivaten in wasch- und reinigungsmitteln |
DE102010030021A1 (de) * | 2010-06-14 | 2011-12-15 | Henkel Ag & Co. Kgaa | Maschinelles Reinigungsverfahren |
-
2018
- 2018-11-23 DE DE102018220185.4A patent/DE102018220185A1/de not_active Withdrawn
-
2019
- 2019-11-19 WO PCT/EP2019/081771 patent/WO2020104445A1/de unknown
- 2019-11-19 EP EP19812717.7A patent/EP3884021A1/de active Pending
-
2021
- 2021-05-24 US US17/328,799 patent/US20210324307A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US20210324307A1 (en) | 2021-10-21 |
DE102018220185A1 (de) | 2020-05-28 |
WO2020104445A1 (de) | 2020-05-28 |
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