EP4077610B1 - Procédés de nettoyage et de soin pour lave-vaisselle automatique - Google Patents

Procédés de nettoyage et de soin pour lave-vaisselle automatique Download PDF

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Publication number
EP4077610B1
EP4077610B1 EP20839267.0A EP20839267A EP4077610B1 EP 4077610 B1 EP4077610 B1 EP 4077610B1 EP 20839267 A EP20839267 A EP 20839267A EP 4077610 B1 EP4077610 B1 EP 4077610B1
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EP
European Patent Office
Prior art keywords
acid
weight
amount
maintenance agent
care product
Prior art date
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Active
Application number
EP20839267.0A
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German (de)
English (en)
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EP4077610A1 (fr
Inventor
Thomas Doering
Michael Kreis
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP4077610A1 publication Critical patent/EP4077610A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • A47L15/0018—Controlling processes, i.e. processes to control the operation of the machine characterised by the purpose or target of the control
    • A47L15/0057—Cleaning of machines parts, e.g. removal of deposits like lime scale or proteins from piping or tub
    • 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
    • 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
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the present invention relates to a method for cleaning and/or maintaining automatic dishwashers, which removes deposits in an automatic dishwasher and can be carried out together with a machine dishwashing detergent in a normal dishwashing cycle.
  • WO 2007/068920 discloses a method for cleaning a dishwasher in which a machine cleaner containing an acid or a builder is dosed into the machine, followed by a conventional dishwashing detergent.
  • the care product is used together with a machine dishwashing detergent in a normal cleaning cycle to clean dirty dishes, i.e. in the presence of dishes (or crockery) to be cleaned.
  • a machine dishwashing detergent in a normal cleaning cycle to clean dirty dishes, i.e. in the presence of dishes (or crockery) to be cleaned.
  • This has the advantage that the machine does not have to run idle at high water temperatures. Energy and water are therefore not wasted.
  • the consumer does not have to completely empty the machine during daily use, but can clean the machine at the same time as the dishes. Due to this minimal effort for the consumer, regular cleaning of the machine is made easier. In such a case, stubborn dirt that can only be removed under harsh conditions does not accumulate in the dishwasher.
  • the simultaneous use of the care product in the usual dishwashing cycle with dishes saves time, water and energy. Food residues and dirt, especially in the dishwasher sieve, which represent a breeding ground for unwanted germs, are also significantly reduced and thus contribute to improving the microbiological condition of the machine.
  • Normal cleaning cycle refers to a program for cleaning dishes of an automatic dishwasher. Such a cleaning cycle may include one or more pre-wash cycles, one or more main wash cycles and one or more final rinse cycles. Such a cleaning cycle involves the automatic cleaning/rinsing of soiled dishes.
  • At least one includes, but is not limited to, 1, 2, 3, 4, 5, 6, and more.
  • At least two includes, but is not limited to, 2, 3, 4, 5, 6, and more.
  • the data in % by weight given in this application refer to the active ingredient content in g based on the weight of the total composition in g.
  • the care products described here for use in methods according to the invention contain pH regulators in the form of at least one acid and/or at least one buffer system that contains at least one acid and at least one base.
  • polycarboxylic acids are suitable as acids, whereby polycarboxylic acids are understood to be carboxylic acids that have more than one acid function. Examples of these are oxalic acid, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • Corresponding buffer systems can contain one or more of the acids mentioned as well as the respective corresponding base(s) and other bases. Citric acid or a buffer system made up of citric acid and citrate is preferably used.
  • aminocarboxylic acids include aspartic acid, methylglycinediacetic acid (MGDA) and glutamic diacetic acid (GLDA) or ethylenediamine diacetic acid. Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). However, it is preferred that the acids used are not aminocarboxylic acids.
  • Suitable bases are all bases known in the art for dishwashing detergents. However, it is preferred that the base corresponding to the acid is used in the buffer system of acid and base, ie for example citrate if citric acid is used as the acid. Organic acids and their corresponding bases are therefore preferably used. Bases that can be used additionally are in particular carbonates and silicates, which are described further under the additional builders that can be used; the use of acetates is also possible.
  • the acids and possibly also bases used are preferably solid under standard conditions (temperature 25°C, pressure 1013 mbar) and can preferably be used in the form of a powder, fine crystalline or in the form of granules.
  • the care product is such that (i) the at least one acid is an organic acid, in particular citric acid, and/or (ii) the buffer system contains at least one organic acid, in particular citric acid, and the corresponding base, in particular citrate.
  • a preferred subject matter is therefore a method in which the care product is such that (i) the at least one acid is an organic acid, in particular citric acid, and/or (ii) the buffer system contains at least one organic acid, in particular citric acid, and the corresponding base, in particular citrate.
  • At least one non-ionic surfactant is contained in the care product of the method according to the invention. It is preferred that a mixture of two or more non-ionic surfactants is used in the care product of the method according to the invention.
  • a care product that can be used in the processes described here can contain any of the non-ionic surfactants known to those skilled in the art. In preferred embodiments, however, non-ionic surfactants from the group of alkoxylated alcohols are used in the care product.
  • a class of preferably usable non-ionic surfactants that can be used either as the sole non-ionic surfactant or in combination with other non-ionic surfactants in the care product are therefore alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty alcohols.
  • suitable ethoxylated fatty alcohols include Dehydol LS 6, Emulan AT 9, Lutensol AO 7 and Plurafac 220 and 221 from BASF.
  • a care agent is used in the process in which at least one of the surfactants from iii) is a rinse aid surfactant, preferably an alkoxylated fatty alcohol.
  • a further preferred subject matter is therefore a process wherein at least one of the surfactants from iii) is a rinse aid surfactant, preferably an alkoxylated fatty alcohol.
  • a fatty alcohol alkoxylate in particular a fatty alcohol ethoxylate, is therefore used.
  • non-end-capped fatty alcohol alkoxylates are preferred.
  • the fatty alcohol ethoxylate has the formula R 1 -O-(EO) m -H, where R 1 is a linear or branched, substituted or unsubstituted alkyl group having 12 to 24, in particular 14 to 20, in particular 16 to 18 C atoms; EO is an ethylene oxide unit; and m is 10 to 50, in particular 20 to 30, preferably 22 to 27, in particular 25.
  • the fatty alcohol ethoxylate has the formula R 1 -O-(EO) m -H , where R 1 is a linear or branched, substituted or unsubstituted alkyl group having 16 to 18 C atoms; EO is an ethylene oxide unit; and m is 20 to 30, preferably 22 to 27, in particular 25.
  • the alkyl group R 1 is a linear, preferably unsubstituted, alkyl group having 16 to 18 C atoms.
  • the fatty alcohol alkoxylate preferably the fatty alcohol ethoxylate, in particular the fatty alcohol ethoxylate of the formulas mentioned can be contained in the care product in an amount of 0.1 to 20% by weight, preferably 1 to 13% by weight, particularly preferably 3 to 9% by weight, based on the care product. Such amounts are preferred in order to ensure sufficient fat dissolution and removal.
  • a nonionic surfactant that can be used in the care products described herein for the methods according to the invention is contained in the care products in an absolute amount of 0.1 to 4 g/job, preferably 1 to 3 g/job, in particular 1.2 to 2.2 g/job, for example 1.5 g/job or 2.0 g/job.
  • a fatty alcohol ethoxylate of the formula R 1 -O-(EO) m -H where R 1 is a linear or branched, substituted or unsubstituted alkyl group having 12 to 24, in particular 14 to 20, in particular 16 to 18 C atoms; EO is an ethylene oxide unit; and m is 10 to 50, in particular 20 to 30, preferably 22 to 27, in particular 25; is contained in the care products in an absolute amount of 0.1 to 4 g/job, preferably 1 to 3 g/job, in particular 1.2 to 2.2 g/job, for example 1.5 g/job or 2.0 g/job.
  • a fatty alcohol ethoxylate of the formula R 1 -O-(EO) m -H where R 1 is a linear or branched, substituted or unsubstituted alkyl group having 16 to 18 C atoms; EO is an ethylene oxide unit; and m is 20 to 30, preferably 22 to 27, in particular 25; is contained in the care products in an absolute amount of 0.1 to 4 g/job, preferably 1 to 3 g/job, in particular 1.2 to 2.2 g/job, for example 1.5 g/job or 2.0 g/job.
  • the nonionic surfactant is preferably a fatty alcohol ethoxylate which is solid under standard conditions (temperature 25°C, pressure 1013 mbar) and can preferably be used in the form of a powder or granules.
  • a fatty alcohol alkoxylate of the formula R 2 -(AO) w -R 3 where R 2 represents a linear or branched, substituted or unsubstituted alkyl group having 8 to 16 carbon atoms; R 3 represents H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; each A independently represents a radical selected from the group consisting of -CH 2 CH 2 - and - CH 2 -CH(CH 3 )-, CH 2 - CH 2 -CH 2 -, CH 2 - CH 2 - CH 2 -CH 2 -, -CH 2 - CH(CH 2 -CH 3 )-, -CH 2 - C(CH 3 ) 2 - or - CH 2 - CH 2 -CH(CH 3 )-, wherein at least one A is -CH 2 CH 2 - and at least one A is -CH 2 -CH(CH 3 )-, CH 2 - CH 2 -CH 2 -, CH 2 -CH
  • the ratio of the ethylene oxide units and the higher alkylene oxide units in the fatty alcohol alkoxylate of the formula is 12:1 to 1:1, preferably 10:1 to 2:1, in particular 6:1 to 3:1.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO(G) x , in which R corresponds to a primary linear or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • non-ionic surfactants that can be used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Non-ionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides may also be suitable.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of that.
  • Suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • a care agent is used in the process which contains non-ionic surfactant in an amount of 0.1 to 20 wt. %, particularly preferably in an amount of 2 to 15 wt. %, especially preferably in an amount of 4 to 10 wt. %, based on the total amount of care agent.
  • a further preferred subject matter is therefore a process wherein the care product contains nonionic surfactant in an amount of 0.1 to 20% by weight, particularly preferably in an amount of 2 to 15% by weight, particularly preferably in an amount of 4 to 10% by weight, based on the total amount of care product.
  • a care product is used in the process in which non-ionic surfactant is contained in part A in a proportion of 2 to 50% by weight, preferably in a proportion of 5 to 40% by weight, very particularly preferably in a proportion of 10 to 35% by weight, based on the total amount of non-ionic surfactant in the care product.
  • a further preferred subject matter is therefore a process wherein nonionic surfactant is contained in portion A in a proportion of 2 to 50% by weight, preferably in a proportion of 5 to 40% by weight, very particularly preferably in a proportion of 10 to 35% by weight, based on the total amount of nonionic surfactant in the care product.
  • a care product is used in the process which contains non-ionic surfactant in an amount of 0.1 to 20 wt. %, particularly preferably in an amount of 2 to 15 wt. %, especially preferably in an amount of 4 to 10 wt. %, based on the total amount of care product, wherein the non-ionic surfactant is at least partially an alkoxylated, preferably ethoxylated, alcohol.
  • the care product contains nonionic surfactant in an amount of 0.1 to 20 wt. %, particularly preferably in an amount of 2 to 15 wt. %, particularly preferably in an amount of 4 to 10 wt. %, based on the total amount of care product, and wherein the nonionic surfactant is at least partially an alkoxylated, preferably ethoxylated, alcohol.
  • the nonionic surfactant is at least partially a fatty alcohol ethoxylate of the formula R 1 -O-(EO) m -H, where R 1 is a linear or branched, substituted or unsubstituted alkyl group having 16 to 18 C atoms; EO is an ethylene oxide unit; and m is 20 to 30, preferably 22 to 27, in particular 25.
  • a further preferred subject matter is therefore a process in which the care product contains nonionic surfactant in an amount of 0.1 to 20 wt. %, particularly preferably in an amount of 5 to 17 wt. %, particularly preferably in an amount of 7 to 15 wt. %, based on the total amount of care product, wherein the nonionic surfactant is at least partially a fatty alcohol ethoxylate of the formula R 1 -O-(EO) m -H, where R 1 is a linear or branched, substituted or unsubstituted alkyl group having 16 to 18 C atoms; EO is an ethylene oxide unit; and m is 20 to 30, preferably 22 to 27, in particular 25.
  • At least 50% by weight of the non-ionic surfactant, based on the total mass of non-ionic surfactant contained, is at least one alkoxylated alcohol, preferably ethoxylated alcohol and/or ethoxylated and otherwise alkoxylated alcohol, particularly preferably at least 60% by weight, in particular at least 75% by weight.
  • the nonionic surfactant is a mixture of different nonionic surfactants. These can be, for example, mixtures of different alkoxylated alcohols and/or mixtures of one or more alkoxylated alcohols with another type of nonionic surfactant.
  • a care product is used in the process which has at least two different non-ionic surfactants, preferably a first non-ionic surfactant is contained in portion A and in portion B and a second non-ionic surfactant is contained in portion A and not in portion B.
  • a further preferred subject matter is therefore a process wherein at least two different non-ionic surfactants are contained in the care product, preferably a first non-ionic surfactant is contained in portion A and in portion B and/or a second non-ionic surfactant is contained in portion A and not in portion B.
  • a care product is used in the process which has at least two different non-ionic surfactants, preferably a first non-ionic surfactant is contained in portion A and in portion B and a second non-ionic surfactant is contained in portion A and not in portion B, wherein the second non-ionic surfactant Surfactant is a fatty alcohol alkoxylate, preferably a fatty alcohol alkoxylate containing ethoxy and propoxy groups and/or containing ethoxy and butoxy groups.
  • the fatty alcohol alkoxylates mentioned can be end-capped and/or non-end-capped, preferably they are non-end-capped.
  • Another particularly preferred subject matter is therefore a process wherein at least two different non-ionic surfactants are contained in the care product, preferably a first non-ionic surfactant is contained in portion A and in portion B and/or a second non-ionic surfactant is contained in portion A and not in portion B, wherein the second non-ionic surfactant is a fatty alcohol alkoxylate, preferably a fatty alcohol alkoxylate containing ethoxy and propoxy groups and/or containing ethoxy and butoxy groups.
  • the aforementioned at least two different components A and B are formulated in such a way that they are released into the washing solution at different times during the cleaning cycle. This enables the ingredients contained in components A and B to act on the parts to be cleaned or cared for at different times during the cleaning cycle in an automatic dishwasher.
  • portion B is released into the rinsing water in the pre-rinse phase of the cleaning cycle and portion A is released into the rinsing water in the final rinse phase of the cleaning cycle.
  • a method according to the invention is defined in which the care agent used has at least two different proportions A and B, and wherein proportion B is released into the rinsing water in the pre-rinse phase of the cleaning cycle and wherein proportion A is released into the rinsing water in the final rinse phase of the cleaning cycle.
  • part A should be composed so that the ingredients are released in the rinse cycle.
  • the composition of part A is in the form of one or more compressed tablets.
  • the active ingredient composition of part A is embedded in a wax.
  • the active ingredient composition of part A is embedded in a polymer.
  • non-compressed means that the composition of portion B has not been compressed under increased pressure.
  • non-compressed forms include, but are not limited to, powders, granules, gels and liquids.
  • the care product is such that the composition of portion A is in the form of one or more compressed tablets and/or the active substance composition of portion A is embedded in a wax and/or embedded in a polymer and/or that the composition of portion B is non-compressed.
  • a preferred subject matter is therefore a process in which the care product is such that the composition of portion A is in the form of one or more compressed tablets and/or the active ingredient composition of portion A is embedded in a wax and/or embedded in a polymer and/or that the composition of portion B is non-compressed.
  • the composition of portion A is in the form of one or more compressed tablets, the tablet having a breaking hardness of at least 150 N, preferably at least 170 N, particularly preferably at least 200 N after 24 hours of storage at room temperature. It is also preferred according to the invention that such a tablet has a breaking hardness of at least 100 N, preferably at least 110 N, particularly preferably at least 120 N, directly after production. Breaking hardness can be determined using special equipment, for example using a "MultiTest 50" from Pharmatron.
  • the active ingredient composition of portion A is embedded in a wax, the wax having a melting point of at least 50 °C, preferably at least 55 °C.
  • the wax is contained in the composition of portion A. This can ensure that the ingredients of portion A are not released in the pre-wash cycle and/or main wash cycle.
  • Naturafin 59/62°C from Reseda Binder AG is suitable as an example. If the active ingredient composition of portion A is embedded in such a wax, the wax is contained in the composition of portion A and the proportion of this wax in the overall composition of portion A is preferably 10 to 80% by weight.
  • the active substance composition of portion A is embedded in a polymer, wherein the polymer is completely soluble in 1L of water at a water temperature of 60 °C within 1 to 5 minutes.
  • This can certainly ensure that the ingredients of component A are not released during the pre-rinse cycle.
  • Solublon EF from Aicello Chemical Europe GmbH is a suitable example. The solubility of a polymer can be tested using simple means. 1 litre of water at the desired temperature is kept ready in a beaker.
  • a film (thickness of 30 ⁇ m to 100 ⁇ m, area 2 cm ⁇ 2 cm to 3 cm ⁇ 3 cm) of the polymer to be tested is clamped onto two opposite sides of the piece of film in such a way that it is neither wrinkled nor torn.
  • the film is immersed in the water parallel to the bottom of the beaker so that it is approximately halfway between the bottom of the beaker and the water surface.
  • the water is stirred at 700 rpm using a magnetic stirrer/magnetic stirrer bar. According to the definition of this method, complete dissolution is achieved as soon as no polymer particles are visible to the naked eye. If the active substance composition of portion A is embedded in such a polymer, the polymer is contained in the composition of portion A and the proportion of this polymer in the total composition of portion A is preferably 10 to 80 wt.%.
  • the care product is such that the composition of portion A is in the form of one or more pressed tablets, the tablet having a fracture hardness of at least 150 N, preferably at least 170 N, particularly preferably at least 200 N after 24 hours of storage at room temperature, and/or that the active substance composition of portion A is embedded in a wax, the wax having a melting point of at least 50 °C, preferably at least 55 °C, and/or that the active substance composition of portion A is embedded in a polymer, the polymer being completely soluble in 1L of water at a water temperature of 60 °C within 1 to 5 minutes.
  • a preferred subject matter is therefore a process in which the care product is such that the composition of portion A is in the form of one or more compressed tablets, the tablet having a fracture hardness of at least 150 N, preferably at least 170 N, particularly preferably at least 200 N after 24 hours of storage at room temperature, and/or that the active substance composition of portion A is embedded in a wax, the wax having a melting point of at least 50 °C, preferably at least 55 °C, and/or that the active substance composition of portion A is embedded in a polymer, the polymer being completely soluble in 1L of water at a water temperature of 60 °C within 1 to 5 minutes.
  • composition and active ingredient composition used in this application and in particular in the preceding paragraphs differ in that active ingredient composition comprises the ingredients which have a direct effect in the cleaning and/or maintenance of an automatic dishwasher, including for example, and incompletely listed, include acids, bases, enzymes and/or surfactants.
  • active ingredient composition does not include waxes and/or polymers of the type mentioned in the preceding paragraphs and in which the active ingredient compositions can be embedded as described above.
  • composition is more comprehensive and includes all ingredients belonging to the respective portion or the respective agent.
  • the care product is used in the process according to the invention in pre-portioned form.
  • This can be any possible form of packaging that complies with the conditions mentioned.
  • Preference is given to compositions that are in the form of a multi-phase tablet or a multi-phase pouch, for example.
  • the different phases can be present either on top of one another or next to one another, or simultaneously on top of and next to one another.
  • the care agent is used in an amount of 10 to 30 g/job, preferably 13 to 23 g/job, in particular 15 to 21 g/job.
  • the care product used in the process is phosphate- and/or phosphonate-free.
  • “Phosphate-free” and “phosphonate-free” as used herein means that the composition in question is essentially free of phosphates or phosphonates, i.e. in particular contains phosphates or phosphonates in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the total care product. It is preferred that a total amount of phosphorus in the care product does not exceed 0.3 g/job, preferably 0.03 g/job.
  • a preferred subject matter is therefore a process in which the care product is phosphate and/or phosphonate-free.
  • the care product is preferably in a water-soluble casing.
  • the water-soluble packaging is a film containing polyvinyl alcohol.
  • the water-soluble casing contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble casings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers can additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating.
  • a preferred additional polymer is polylactic acid.
  • Preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers in addition to vinyl alcohol. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
  • the film material contains further additives.
  • the film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol or mixtures thereof.
  • Other additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films with the designation Solublon ® PT, Solublon ® GA, Solublon ® KC or Solublon ® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.
  • the care product can be formulated in such a way that the at least one component A and the at least one component B are present in a weight ratio of 3:1 to 1:10, preferably in a weight ratio of 1:1 to 1:8, in particular of 1:3 to 1:7, for example of 1:4 to 1:6, based on the respective amounts of components A and B, respectively, in the care product.
  • a preferred subject matter is therefore a method in which the care product is such that the at least one portion A and the at least one portion B are present in a weight ratio of 3:1 to 1:10, preferably in a weight ratio of 1:1 to 1:8, in particular from 1:3 to 1:7, for example from 1:4 to 1:6, based on the respective amounts of the portions A and B, respectively, in the care product.
  • the amount of acid from i and/or ii) is present in an amount that is suitable for reducing or eliminating limescale in the dishwasher. It is therefore preferred that the care product contains the at least one acid from i) and/or ii) in an amount of 1 to 80% by weight, preferably in an amount of 5 to 60% by weight, particularly preferably in an amount of 20 to 35% by weight or in an amount of 25 to 45% by weight, based on the total amount of care product, and/or the absolute amount of the at least one acid from i) and/or ii) in the care product is 0.2 to 16 g/job, preferably 3 to 11 g/job, particularly preferably 4 to 10 g/job, for example 7 to 9 g/job.
  • a preferred subject matter is therefore a process in which the care product is such that the care product contains the at least one acid from i) and/or ii) in an amount of 1 to 80 wt.%, preferably in an amount of 5 to 60 wt.%, particularly preferably in an amount of 20 to 35 wt.% or in an amount of 25 to 45 wt.%, based on the total amount of care product, and/or the absolute amount of the at least one acid from i) and/or ii) in the care product is 0.2 to 16 g/job, preferably 3 to 11 g/job, particularly preferably 4 to 10 g/job, for example 7 to 9 g/job.
  • the active ingredients in the composition required to dissolve the limescale are dissolved as quickly as possible so that they can take effect before the automatic dishwashing detergent is added.
  • the care agent is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the dishwasher detergent.
  • the subject matter of the invention is therefore a method in which the care agent is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwashing detergent.
  • Dosing or adding to the interior of the dishwasher means that the care product or the automatic dishwashing detergent enters the interior of the dishwasher, for example by manually inserting it, by opening the dosing flap (possibly program-controlled) and/or by automatically adding it from an automatic dosing device. It is possible that the portion of cleaning agent or the automatic dishwashing detergent is available in the washing liquor for cleaning and/or care purposes immediately or only after a period of time. This depends on the dissolving speed and therefore on the type, composition and nature of the respective agent or composition. According to the definition given here, the dissolving process is not part of dosing or adding. The dissolving process of any water-soluble wrapping that may be present, for example a film, is also not part of dosing or adding the care product or the automatic dishwashing detergent.
  • Dosing the care product at the beginning of the cleaning cycle can enable the care product to contribute to cleaning and/or maintaining the dishwasher during the pre-wash cycle and/or at the beginning of the main wash cycle. Dosing a machine dishwashing detergent at a later stage can help to maintain the conditions necessary for cleaning and/or maintaining the dishwasher.
  • the base corresponding to the acid is used. It goes without saying that the total amounts of acid and base in the buffer system must be selected so that the desired pH range is achieved. This applies both to the pH range achieved by dissolving the acid and to the pH range achieved by dissolving the buffer system, as well as to the pH range obtained by dissolving the entire composition of the care product. It is preferred for the further course of the cleaning cycle and its effect if a pH value of 3.0 to 7.0, particularly preferably 3.5 to 6.5, very particularly preferably 4.0 to 6.0, is achieved in the existing rinsing liquor by completely dissolving the claimed composition.
  • a preferred subject matter is a method in which the rinsing liquor of the cleaning cycle reaches a pH value of 3.0 to 7.0, preferably 3.5 to 6.5, very particularly preferably 4.0 to 6.0, by at least partially dissolving the care agent, preferably before the automatic dishwashing detergent is dosed into the interior of the machine.
  • the acid is released as quickly as possible in order to obtain an acidic rinsing solution. It is particularly preferred that the time until the acid is completely released from a pre-portioned care product with a mass of 20 g in 1 L of water at room temperature while stirring (in a 2-liter beaker with a diameter of 12 cm with a propeller stirrer with a diameter of 6 cm (blade of the stirrer at a height of 3 cm above the bottom of the beaker) at 200 rpm) is 0.1 to 15 minutes, preferably 0.3 to 5 minutes, particularly preferably 0.5 to 2 minutes.
  • a further preferred subject matter is therefore a method in which a care product is used which is such that the time until the acid is completely released from 20 g of pre-portioned care product in 1 L of water at room temperature while stirring (in a 2 liter beaker with a diameter of 12 cm with a propeller stirrer with a diameter of 6 cm (blade of the stirrer at a height of 3 cm above the bottom of the beaker) at 200 rpm) is 0.1 to 15 minutes, preferably 0.3 to 5 minutes, particularly preferably 0.5 to 2 minutes.
  • the care product dissolves in a 100-fold amount of water, based on the mass of the care product used, in such a way that after 1 minute of stirring (in a 3-liter beaker with a diameter of 13.5 cm with a propeller stirrer with a diameter of 7 cm (blade of the stirrer at a height of 3.5 cm above the bottom of the beaker) at 200 rpm) at room temperature, a solution with a pH of 3.0 to 6.5, preferably 4.0 to 6.0, is obtained.
  • a further preferred subject matter is therefore a process in which a care product is used which is such that the care product dissolves in 100 times the amount of water, based on the mass of the care product used, in such a way that after 1 minute of stirring (in a 3 liter beaker with a diameter of 13.5 cm with a propeller stirrer with a diameter of 7 cm (blade of the stirrer at a height of 3.5 cm above the bottom of the beaker) at 200 rpm) at room temperature, a solution with a pH of 3.0 to 6.5, preferably 4.0 to 6.0, is obtained.
  • the acid from i) or ii) is available as quickly as possible for cleaning and maintaining the dishwasher.
  • the acid from i) and/or ii) is contained for the most part in portion B. Therefore, it is preferred that the acid from i) and/or ii) is contained in portion B in an amount of 80 to 100 wt.%, preferably in an amount of 95 to 100 wt.%, particularly preferably in an amount of at least 99 wt.%, based on the total amount of acid in the care product.
  • a preferred subject matter is therefore a process in which the care product is such that the acid from i) and/or ii) is contained in portion B in an amount of 80 to 100% by weight, preferably in an amount of 95 to 100% by weight, particularly preferably in an amount of at least 99% by weight, based on the total amount of acid in the care product.
  • the care products used in the process according to the invention can contain further components, preferably at least one further component, preferably selected from the group consisting of further builders, further surfactants, polymers, enzymes, corrosion inhibitors, glass corrosion inhibitors, thickeners, foam inhibitors, dyes, disintegration aids, fragrances and/or perfume carriers and/or odor neutralizers, preferably one or more polymers and/or enzymes.
  • further components preferably at least one further component, preferably selected from the group consisting of further builders, further surfactants, polymers, enzymes, corrosion inhibitors, glass corrosion inhibitors, thickeners, foam inhibitors, dyes, disintegration aids, fragrances and/or perfume carriers and/or odor neutralizers, preferably one or more polymers and/or enzymes.
  • Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates.
  • fatty acid cyanamides sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-alkyl esters with 8 to 18 carbon atoms, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates as well as ⁇ -sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • sulfosuccinates sulfosuccinic acid esters
  • sulfosuccinic acid mono- and di-alkyl esters with 8 to 18 carbon atoms sulfosuccinamates,
  • the anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, as well as in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, and in the case of sulfonates also in the form of their corresponding acid, e.g. dodecylbenzenesulfonic acid.
  • the additional builders that can be used include in particular carbonates, organic cobuilders and silicates.
  • carbonates organic cobuilders and silicates.
  • carbonate(s) and/or hydrogen carbonate(s), preferably alkali carbonate(s), particularly preferably sodium carbonate, is possible.
  • alkali carbonates, in particular sodium carbonate can be contained in the care product in an amount of 1 to 40% by weight, preferably 2 to 30% by weight, based on the total weight of the care product.
  • Organic cobuilders include polycarboxylates/polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins.
  • Useful organic builders include, for example, the free acid and/or its sodium salts usable polycarboxylic acids, whereby polycarboxylic acids are understood to be carboxylic acids that have more than one acid function. Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • NTA nitrilotriacetic acid
  • 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 mass of 500 to 70,000 g/mol.
  • Suitable polymers are in particular polyacrylates and/or copolymers and/or terpolymers containing acrylate monomers, which preferably have a molecular weight of 1000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular weights of 1000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, can be preferred.
  • the polycarboxylate used is preferably a copolymeric polyacrylate, preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers can have two, three, four or more different monomer units.
  • Preferred copolymeric 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, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, Cinnamic acid or mixtures thereof.
  • Unsaturated dicarboxylic acids can of course also be used.
  • H 2 C CH-X-SO 3 H
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 and -CH(CH 3 ) 2
  • the care product can contain a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as a monomer containing sulfonic acid groups.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-
  • the sulfonic acid groups can be present in completely or partially neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized copolymers containing sulfonic acid groups in the care product is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention is for copolymers containing only carboxylic acid group-containing monomers and sulfonic acid group-containing Monomers contain, preferably in each case, 5 to 95% by weight, particularly preferably the proportion of monomer containing sulfonic acid groups is 50 to 90% by weight and the proportion of monomer containing carboxylic acid groups is 10 to 50% by weight, the monomers are preferably selected from those mentioned above.
  • the molecular weight 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 care products are characterized in that the copolymers have molecular weights of 2000 to 200,000 g ⁇ mol -1 , preferably of 4000 to 25,000 g ⁇ mol -1 and in particular of 5000 to 15,000 g ⁇ mol -1 .
  • the copolymers in the care product comprise, in addition to carboxyl group-containing monomer and sulfonic acid group-containing monomer, at least one non-ionic, preferably hydrophobic monomer.
  • 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-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22- ⁇
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • Polyacrylate-containing polymers can be present in the care product in the process according to the invention in amounts of 0.5 to 15% by weight, preferably 0.6 to 10% by weight, particularly preferably in amounts of 0.8 to 3% by weight or 1 to 5% by weight, based on the total weight of the care product. Mixtures of different polymers can also be used.
  • the agents can also contain crystalline layered silicates of the general formula NaMSixO 2x+1 ⁇ y H 2 O as a builder, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a NazO:SiOz modulus of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which preferably have delayed dissolution and secondary washing properties, can also be used.
  • the content of silicates, based on the total weight of the care agent is limited to amounts below 10% by weight, preferably below 7% by weight and in particular below 5% by weight.
  • Care products used in particularly preferred processes contain silicate as a builder.
  • Care products used in very particularly preferred processes contain silicate in the specified amount range in portion A, based on the total weight of the care product. It is also preferred that the amount of silicate, based on the mass of portion A, is between 5 and 50 wt.%, preferably between 10 and 30 wt.%, very particularly preferably between 15 and 25 wt.%.
  • fragrance compounds e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type
  • perfume oils or fragrances can be used in the care product as perfume oils or fragrances.
  • mixtures of different fragrances are preferably used in the care product, which together produce an appealing scent.
  • perfume oils can also contain natural fragrance mixtures, such as those available from plant sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the care product in the process according to the invention can contain bleach or be bleach-free. It is a preferred embodiment if a bleach is contained in the care product.
  • a preferred bleach is an alkali metal percarbonate, preferably sodium percarbonate.
  • a bleaching agent, preferably sodium percarbonate can be contained in the care product in an amount of 1 to 15 wt.%, preferably 2 to 10 wt.% or 3 to 12 wt.%, based on the total weight of the care product.
  • the care product may also contain one or more enzymes.
  • the enzyme or enzymes used may be present in one or more enzyme preparations or enzyme compositions.
  • Suitable enzymes include proteases, amylases, lipases, cellulases and/or pectinases and preferably mixtures thereof.
  • Other enzymes such as hemicellulases other than pectinases, for example ⁇ -glucanases, and/or perhydrolases and/or oxidoreductases, and mixtures thereof, can also be used in combination with at least one of the aforementioned enzymes.
  • These enzymes are in principle of natural origin; based on the natural molecules, improved variants are available for use in dishwashing detergents and are therefore preferably used.
  • proteases are among the most technically important enzymes of all. They break down protein-containing soiling on the items being cleaned, which can also be parts of the dishwasher itself.
  • proteases of the subtilisin type are particularly important; they are serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases and hydrolyze any acid amide bonds that are located inside peptides or proteins. Their pH optimum is usually in the clearly alkaline range.
  • Subtilases are naturally formed by microorganisms. Of particular note are the subtilisins formed and secreted by Bacillus species, which are the most important group within the subtilases.
  • subtilisin-type proteases preferably used in washing and dishwashing detergents or care products are the subtilisins BPN' and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense, as well as variants of the proteases mentioned which have an amino acid sequence that is different from the original protease.
  • Proteases are modified in a targeted or random manner using methods known from the state of the art and are thus optimized for use in washing and dishwashing detergents, for example. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. For most of the proteases known from the state of the art, optimized variants are known.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the Further developments of the aforementioned amylases have been improved for use in dishwashing detergents.
  • Other examples for this purpose include the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Lipases or cutinases can also be used, particularly because of their triglyceride-cleaving activities, but also to produce peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed lipases, particularly those with the amino acid substitution D96L.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect. It is advantageous to also add organic, particularly aromatic, compounds that interact with the enzymes in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons when the redox potentials between the oxidizing enzymes and the soiling differ greatly (mediators).
  • An enzyme can be protected against damage such as inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • damage such as inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Dishwashing detergents or care products for dishwashers can contain stabilizers for this purpose; the use of such agents in the care product represents a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases as well as the other enzymes mentioned are generally not provided in the form of pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, Solutions of the enzymes, preferably as concentrated as possible, low in water and/or containing stabilizers or other additives.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, 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 if in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer that is impermeable to water, air and/or chemicals.
  • active ingredients such as stabilizers, emulsifiers, pigments, bleaching agents or dyes, can be applied in superimposed layers.
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable in storage due to the coating.
  • the enzyme protein only forms a fraction of the total weight of conventional enzyme preparations.
  • Preferably used enzyme preparations contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein.
  • care products which contain, based on their total weight, 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations are preferably used in processes according to the invention.
  • the care products preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5% by weight based on active protein.
  • the protein concentration can be determined using known methods, for example the BCA method or the biuret method.
  • care products are used in the process according to the invention which have a total amount of active enzyme protein of 0.5 to 500 mg/job, preferably 10 to 250 mg/job by weight, particularly preferably 50 to 150 mg/job.
  • compositions described herein may also contain enzyme stabilizers.
  • stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including in particular derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned.
  • Peptide aldehydes i.e. oligopeptides with a reduced C-terminus, especially those made up of 2 to 50 monomers, are also used for this purpose.
  • Peptide reversible protease inhibitors include ovomucoid and leupeptin.
  • Specific, reversible peptide inhibitors for the protease subtilisin as well as fusion proteins made up of proteases and specific peptide inhibitors are also suitable for this purpose.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to the person skilled in the art from the prior art.
  • bleach and enzyme are contained in the care product, it is preferred in processes according to the invention that bleach and enzyme are present in different phases of the care product.

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Claims (12)

  1. Procédé de nettoyage et/ou d'entretien d'un lave-vaisselle automatique, caractérisé en ce que, dans un cycle de nettoyage normal pour le nettoyage de la vaisselle, en particulier de la vaisselle sale, avec un produit de lavage de la vaisselle en machine, on ajoute un produit d'entretien préportionné pour lave-vaisselle automatique, formulé séparément du produit de lavage de la vaisselle, le produit d'entretien
    i. un acide et/ou
    ii. un système tampon composé d'au moins un acide et d'au moins une base, et
    iii. au moins un agent de surface non ionique
    et où le produit de soin présente au moins deux parts A et B différentes, la part B présentant un acide de i) et/ou ii) et au moins un agent tensioactif non ionique de iii) et la part A présentant au moins un agent tensioactif non ionique de iii) et éventuellement au moins une base de ii),
    le produit d'entretien étant dosé à l'intérieur du lave-vaisselle automatique au début du cycle de nettoyage, de préférence avant le produit de lavage de la vaisselle en machine et dans lequel la partie B est libérée dans le bain de rinçage lors de l'étape de prérinçage du cycle de nettoyage et la partie A est libérée dans le bain de rinçage lors de l'étape de rinçage du cycle de nettoyage.
  2. Procédé selon la revendication 1, caractérisé en ce que la composition de la fraction A se présente sous la forme d'un ou plusieurs comprimé(s) compressé(s) et/ou la composition de principe actif de la fraction A est incorporée dans une cire et/ou incorporée dans un polymère et/ou en ce que la composition de la fraction B est non compressée.
  3. Procédé selon la revendication 2, caractérisé en ce qu'un comprimé pressé éventuellement présent présente, après 24 h de stockage à température ambiante, une dureté à la rupture d'au moins 150 N, de préférence d'au moins 170 N, de manière particulièrement préférée d'au moins 200 N, et/ou en ce qu'une cire éventuellement présente est contenue dans la composition de la fraction A et présente un point de fusion d'au moins 50°C, de préférence d'au moins 55°C, et/ou en ce qu'un polymère éventuellement présent est contenu dans la composition de la fraction A et est complètement soluble dans 1L d'eau à une température d'eau de 60°C en 1 à 5 minutes.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que le produit de soin contient le au moins un acide de i) et/ou ii) en une quantité de 1 à 80 % en poids, de préférence en une quantité de 5 à 60 % en poids, de manière particulièrement préférée en une quantité de 20 à 35 % en poids, par rapport à la quantité totale de produit de soin.% ou en une quantité de 25 à 45 % en poids, par rapport à la quantité totale de produit de soin, et/ou la quantité absolue d'au moins un acide de i) et/ou ii) dans le produit de soin est de 0,2 à 16 g/job, de préférence de 3 à 11 g/job, de manière particulièrement préférée de 4 à 10 g/job, par exemple de 7 à 9 g/job.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'acide de i) et/ou ii) est contenu dans la fraction B en une quantité de 80 à 100 % en poids, de préférence en une quantité de 95 à 100 % en poids, en particulier de préférence en une quantité d'au moins 99 % en poids, par rapport à la quantité totale d'acide dans le produit de soin.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le bain de lavage du cycle de nettoyage atteint un pH de 3,0 à 7,0, de préférence de 3,5 à 6,5, de manière tout à fait préférée de 4,0 à 6,0, par une dissolution au moins partielle du produit d'entretien, de préférence avant que le produit de lavage de vaisselle en machine ne soit dosé dans l'espace intérieur de la machine.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'au moins deux agents tensioactifs non ioniques différents sont contenus dans le produit de soin, de préférence un premier agent tensioactif non ionique est contenu dans la fraction A et dans la fraction B et/ou un deuxième agent tensioactif non ionique est contenu dans la fraction A et non dans la fraction B.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'un au moins des tensioactifs de iii) est un tensioactif de rinçage, de préférence un alcool gras alcoxylé.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que le produit de soin contient un agent tensioactif non ionique en une quantité de 0,1 à 20 % en poids, de manière particulièrement préférée en une quantité de 2 à 15 % en poids, de manière particulièrement préférée en une quantité de 4 à 10 % en poids, par rapport à la quantité totale de produit de soin.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'agent tensioactif non ionique est contenu dans une proportion de 2 à 50 % en poids, de préférence dans une proportion de 5 à 40 % en poids, de manière tout à fait préférée dans une proportion de 10 à 35 % en poids, par rapport à la quantité totale d'agent tensioactif non ionique dans le produit de soin, dans la proportion A.
  11. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que (i) ledit au moins un acide est un acide organique, en particulier l'acide citrique, et/ou (ii) le système tampon comprend au moins un acide organique, en particulier l'acide citrique, et la base correspondante, en particulier le citrate.
  12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ladite au moins une fraction A et ladite au moins une fraction B sont présentes dans le produit de soin dans un rapport pondéral de 3:1 à 1:10, de préférence dans un rapport pondéral de 1:1 à 1:8, en particulier de 1:3 à 1:7, par exemple de 1:4 à 1:6, par rapport aux quantités respectives des fractions A et B.
EP20839267.0A 2019-12-20 2020-12-17 Procédés de nettoyage et de soin pour lave-vaisselle automatique Active EP4077610B1 (fr)

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DE102019220459.7A DE102019220459A1 (de) 2019-12-20 2019-12-20 Verfahren zur Reinigung und Pflege einer automatischen Geschirrspülmaschine
PCT/EP2020/086628 WO2021122886A1 (fr) 2019-12-20 2020-12-17 Procédés de nettoyage et de soin pour lave-vaisselle automatique

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EP4077610B1 true EP4077610B1 (fr) 2024-08-14

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DE (1) DE102019220459A1 (fr)
ES (1) ES2990119T3 (fr)
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WO (1) WO2021122886A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4401104A1 (de) * 1994-01-17 1995-07-20 Henkel Kgaa Maschinenpflegestift
DE20022229U1 (de) * 2000-07-07 2001-07-12 Henkel KGaA, 40589 Düsseldorf Maschinengeschirrspülmittel mit Zusatznutzen
EP1679363B1 (fr) * 2005-01-10 2008-07-09 The Procter and Gamble Company Composition de nettoyage pour machines de vaisselle ou de lavage
EP1679362A1 (fr) * 2005-01-10 2006-07-12 The Procter & Gamble Company Composition de nettoyage pour machines de vaisselle ou de lavage
GB0525314D0 (en) * 2005-12-13 2006-01-18 Reckitt Benckiser Nv Method and composition
DE102013214780A1 (de) * 2013-07-29 2015-01-29 Henkel Ag & Co. Kgaa Pflegemittel für automatische Geschirrspülmaschinen
DE102015218475A1 (de) * 2015-09-25 2017-03-30 Henkel Ag & Co. Kgaa Verfahren zur Pflege und Reinigung einer automatischen Geschirrspülmaschine
DE102018222240A1 (de) * 2018-12-19 2020-06-25 Henkel Ag & Co. Kgaa Reinigungsmittelportion für automatische Geschirrspülmaschinen

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PL4077610T3 (pl) 2024-11-25
WO2021122886A1 (fr) 2021-06-24
DE102019220459A1 (de) 2021-06-24
ES2990119T3 (es) 2024-11-28

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