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
  • C11D17/0034—Fixed on a solid conventional detergent ingredient
• • 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
  • 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
  • C11D1/721—End blocked ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • C11D17/0091—Dishwashing tablets
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0073—Anticorrosion compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase

Definitions

• the present invention relates to dishwasher detergents comprising one or more surfactants on magnesium carbonate carrier Z1), one or more enzymes Z2), and optionally Z3) one or more glass corrosion inhibitors, to a method for cleaning dishware in dishwashers with aqueous alkaline compositions comprising a dishwasher detergent of the invention, and also to the use of the dishwasher detergents of the invention or the surfactants on magnesium carbonate carrier Z1) contained in these dishwasher detergents as rinse agents in machine dishwashing, for improving the wettability of dishware, for reducing the spotting and filming on dishware, for reducing, minimizing or preventing fatty residues in the machine department of an automatic dishwashing machine, for improving the rinse performance of a dishwasher detergent, or for improving the drying performance of a dishwasher detergent.
• the dishwasher detergents of the invention comprehend not only dishwasher detergents in the conventional sense but also rinse agents.
• rinse aids have been successfully used for improved rinse performance in rinse agents and dishwasher detergents, in order to obtain spotless, streak-free, and residue-free dishware.
• the rinse aid is dispensed automatically from a metering tank into the interior of the dishwasher in the rinse cycle of the cleaning program.
• the rinse aid is integrated into the dishwasher detergent itself.
• Conventional rinse aids are liquid mixtures of low-foaming nonionic surfactants, organic acids such as, for example, citric acid, scale-inhibiting polymers, solvents such as, for example, ethanol, and other additives such as hydrotropes, thickeners and/or foam inhibitors.
• the object of the present invention was to provide dishwasher detergents which at least display an advantageous rinse performance and an advantageous drying performance.
• dishwasher detergents comprising
• An aspect of the present invention relates to a dishwasher detergent comprising
• the dishwasher detergent comprises:
• Carrier materials for surfactants are already known in the prior art.
• magnesium carbonate can be used in home care formulations.
• US 4,303,542 refers to a powdered detergent suitable for use in home laundry machines.
• EP 3 517 502 A1 describes a magnesium carbonate carrier material for the release of one or more active agent(s) in a home care formulation, a delivery system for the release of one or more active agent(s) in a home care formulation, a home care formulation comprising the delivery system for the release of one or more active agent(s), a method for preparing the delivery system for the release of one or more active agent(s) in a home care formulation as well as the use of the delivery system for the release of one or more active agent(s) in a home care formulation.
• the poster " Disruptive carrier acts as sequestrant by enhancing performance and sustainability profile in ADW” (Ivanov and Keller, Sepawa Conference October 28-30, 2020 ), describes precipitated hydromagnesite as a material with high porosity which can release ingredients such as automatic dishwashing (ADW) surfactants and allows scavenging calcium ions and may reduce hardness of water.
• ADW automatic dishwashing
• An advantage of the present invention is that the dishwasher detergents of the invention can be prepared with high surfactant concentrations, in particular in solid automatic dishwashing product formats like tablets.
• the dishwasher detergents of the invention display, in addition to their cleaning performance, good dishware wettability, low spotting and filming on dishware, an advantageous rinse performance with no carrier residues, an advantageous drying performance, and less fatty residues, in particular in the machine department of automatic dishwashing machines and specifically on plastic parts of the machine department of the automatic dishwashing machines.
• Surfactants are often wax-like or highly viscous and therefore their use in solid product formats, in particular in tablets, is limited up to a certain concentration. If the amount of wax-like or highly viscous surfactants is too high, the tablet itself tends to be sticky.
• Using surfactants on carrier material allows to incorporate more surfactants into the solid product formats, in particular into tablets, in comparison to the sole use of surfactants which are not present on a carrier. It is thereby possible to obtain non-sticky solid product formats with high surfactant amount. For example, in a solid product format the surfactants which are not present on a carrier could be used in their usual amounts and the total amount of the surfactants could be increased by additionally using surfactants on a carrier.
• -C 2 H 4 - preferably is a linear alkylene residue -CH 2 -CH 2 -.
• -C 3 H 6 - may preferably be -CH 2 -CH 2 -CH 2 - or -CH(CH 3 )-CH 2 - or -CH 2 -CH(CH 3 )-.
• -C 3 H 6 - is -CH 2 -CH(CH 3 )-.
• -C 2 H 4 -O- preferably is a linear alkylene residue -CH 2 -CH 2 -O-.
• -C 3 H 6 -O- may preferably be -CH 2 -CH 2 -CH 2 -O- or -CH(CH 3 )-CH 2 -O- or -CH 2 -CH(CH 3 )-O-.
• a further advantage of the invention is that the handling of surfactants on magnesium carbonate carrier is easier compared to the handling of highly viscous or wax-like surfactants.
• the surfactants on magnesium carbonate carrier of component Z1) can be employed both in conventional and multifunctional combination products or can be employed with broad variability in the dishwasher detergents of the invention and develop their advantageous properties independently of their preparation form.
• the surfactants on magnesium carbonate carrier of component Z1) do not contribute to increased foaming, and accordingly the dishwasher detergents of the invention are low-foaming detergents.
• the dishwasher detergents of the invention are automatic dishwashing (detergent) compositions or automatic dishwashing (detergent) formulations.
• one or more surfactants of formula (XI) comprised in a dishwasher detergent of the present invention are selected from the group consisting of nonionic and cationic surfactants.
• nonionic and cationic surfactants are preferred.
• one or more surfactants comprised in a dishwasher detergent of the present invention are selected from the group consisting of fatty alcohol alkoxylates, end-capped fatty alcohol alkoxylates, ethyleneoxide-propyleneoxide-blockcopolymers, N-acylglucamines / N-acylglucamides, gylcerol triester alkoxylates, esterquats, and mixtures thereof.
• one or more surfactants comprised in a dishwasher detergent of the present invention are selected from the group consisting of end-capped fatty alcohol alkoxylates, preferably end-capped fatty alcohol ethoxylates, N-acylglucamines / N-acylglucamides, gylcerol triester alkoxylates, preferably glycerol triester ethoxylates, and mixtures thereof.
• alkyl and alkenyl groups R a in the formula (XI) are, for example, the alkyl and alkenyl groups of the following alcohols R a -OH: 1-octanol (caprylyl alcohol), 2-ethylhexanol, 1-nonanol (pelargon alcohol), 1-decanol (caprinyl alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol), 9E-octadecen-1
• R a in formula (XI) is preferably a linear or branched saturated alkyl group having 8 to 22 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 22 carbon atoms, more preferably a linear or branched saturated alkyl group having 8 to 20 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 20 carbon atoms, and especially preferably a linear or branched saturated alkyl group having 8 to 18 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms.
• the groups R a in formula (XI) are saturated alkyl groups.
• x is preferably a number from 1 to 50, more preferably a number from 1 to 25, especially preferably a number from 5 to 25 and particularly preferably a number from 15 to 25.
• Examples of the linear or branched saturated alkyl groups Y and R b in the compounds of the formula (XI) include the examples specified above for the saturated alkyl group R a in the compound of the formula (XI). Further examples are the alkyl groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl (2-pentyl), 3-pentyl, 2-methylbutyl, isopentyl (3-methylbutyl), 3-methylbut-2-yl, 2-methylbut-2-yl, neopentyl (2,2-dimethylpropyl), 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl
• Y in formula (XI) is a linear or branched saturated alkyl group
• the saturated alkyl group in question preferably has 1 to 22 carbon atoms.
• R b preferably is a linear or branched saturated alkyl group having 8 to 22 and more preferably 8 to 20 carbon atoms.
• the group -(AO) x - consists of one or more -C 2 H 4 -O- groups and contains no -C 3 H 6 -O- groups.
• the group -(AO) x - comprises one or more -C 2 H 4 -O- groups and one or more -C 3 H 6 -O- groups.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x - is preferably less than 50%, more preferably 45% or less than 45%, especially preferably 40% or less than 40%, and particularly preferably 33% or less than 33%.
• Y in formula (XI) is H.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x - is preferably 20 to less than 50%, more preferably 33 to 45%, and especially preferably 33 to 40%.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x -, is preferably 20% or less than 20% and more preferably 10% or less than 10%.
• Y in formula (XI) is a saturated alkyl group with 1 to 4 carbon atoms.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x -, is preferably 20% or less than 20% and more preferably 10% or less than 10%.
• Y in formula (XI) is the group -CH 2 -CH(OH)-R b , in which R b is a linear or branched saturated alkyl group having 8 to 22 and preferably 8 to 20 carbon atoms.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x - is preferably 20% or less than 20% and more preferably 10% or less than 10%.
• the group -(AO) x - especially preferably consists of one or more -C 2 H 4 -O- groups and contains no -C 3 H 6 -O- groups.
• the group -(AO) x - in formula (XI) comprises on molar average 8 -C 2 H 4 -O- groups and 4 -C 3 H 6 -O-groups and R a is a linear or branched saturated alkyl group having 12 to 15 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 12 to 15 carbon atoms.
• variable "x" in the one or more compounds of the formula (XI) preferably represents molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (XI) having different degrees of alkoxylation.
• dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants on magnesium carbonate carrier of component Z1) of the dishwasher detergents of the invention are selected from the group consisting of the end-capped fatty alcohol ethoxylates of the formula (XI-a) R a O-(AO) x -Y (XI-a) in which
• alkyl and alkenyl groups R a in the formula (XI-a) are, for example, the alkyl and alkenyl groups of the following alcohols R a -OH: 1-octanol (caprylyl alcohol), 2-ethylhexanol, 1-nonanol (pelargon alcohol), 1-decanol (caprinyl alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol), 9E-octadec
• R a in formula (XI-a) is preferably a linear or branched saturated alkyl group having 8 to 18 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms.
• the groups R a in formula (XI-a) are saturated alkyl groups.
• x is preferably a number from 16 to 24 and more preferably from 19 to 23.
• Examples of the linear or branched saturated alkyl groups R b in the compounds of the formula (XI-a) include the examples specified above for the saturated alkyl group R a in the compound of the formula (XI-a). Further examples are the alkyl groups heneicosyl and behenyl.
• variable "x" in the one or more compounds of the formula (XI-a) preferably represents molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (XI-a) having different degrees of alkoxylation.
• dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants on magnesium carbonate carrier of component Z1) are selected from the group consisting of zwitterionic surfactants and anionic surfactants.
• component Z1 comprises the one or more surfactants in an amount ranging from 10 to 300 wt.-%, preferably from 40 to 250 wt.-%, more preferably from 50 to 200 wt.-%, especially preferably from 60 to 170 wt.-%, and particularly preferably from 70 to 150 wt.-%, based on the total weight of the magnesium carbonate carrier.
• the dishwasher detergents of the invention preferably comprise the one or more surfactants on magnesium carbonate carrier of component Z1) in amounts from 0.5 to 30 wt.-% and more preferably in amounts from 3 to 25 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
• the term "the one or more surfactants on magnesium carbonate carrier” may be understood as the combination of the magnesium carbonate carrier with the one or more surfactants thereon, i.e., as component Z1) as a whole. Accordingly, in other words, in a preferred embodiment of the present invention, the dishwasher detergents of the invention comprise component Z1) in amounts from 0.5 to 30 wt.-% and more preferably in amounts from 3 to 25 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
• the carrier material of component Z1) of the dishwasher detergent of the invention consists of magnesium carbonate, preferably having a specific surface area of ⁇ 25 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:2010.
• magnesium carbonate refers to a material that comprises at least 80 wt.-% magnesium carbonate, e.g. at least 85 wt.-%, preferably between 85 and 100 wt.-%, more preferably between 90 and 99.95 wt.-%, based on the total dry weight of the material.
• the magnesium carbonate may further comprise impurities typically associated with the type of material used.
• the magnesium carbonate may further comprise impurities such as magnesium hydroxide, calcium hydroxide, calcium carbonate and mixtures thereof.
• impurities are present in amounts of less than 20 wt.-%, preferably less than 15 wt.-% and more preferably from 0.05 to 10 wt.-%, based on the total dry weight of the material.
• the magnesium carbonate can be a naturally occurring or synthetic magnesium carbonate.
• the magnesium carbonate encompasses naturally occurring or synthetic magnesium carbonate selected from the group comprising magnesite (MgCO 3 ), hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 4H 2 O), artinite (Mg2(CO3)(OH)2 ⁇ 3H 2 O), dypingite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 5H 2 O), giorgiosite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 5H 2 O), pokrovskite (Mg 2 (CO 3 )(OH) 2 ⁇ 0.5H 2 O), barringtonite (MgCO 3 ⁇ 2H 2 O, lansfordite (MgCO 3 ⁇ 5H 2 O), nesquehonite (MgCO 3 ⁇ 3H 2 O) and mixtures thereof.
• MgCO 3 magnesite
• hydromagnesite Mg 5 (CO 3
• the magnesium carbonate encompasses synthetic magnesium carbonate selected from the group comprising magnesite (MgCO 3 ), hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 4H 2 O), artinite (Mg2(CO3)(OH)2 ⁇ 3H 2 O), dypingite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 5H 2 O), giorgiosite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 5H 2 O), pokrovskite (Mg 2 (CO 3 )(OH) 2 ⁇ 0.5H 2 O), barringtonite (MgCO 3 2H 2 O, lansfordite (MgCO 3 ⁇ 5H 2 O), nesquehonite (MgCO 3 ⁇ 3H 2 O) and mixtures thereof.
• synthetic magnesium carbonate selected from the group comprising magnesite (MgCO 3 ), hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 4H 2
• the magnesium carbonate comprises the synthetic magnesium carbonate selected from the group comprising magnesite (MgCO 3 ), hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 4H 2 O), artinite (Mg2(CO3)(OH)2 ⁇ 3H 2 O), dypingite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 5H 2 O), giorgiosite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 5H 2 O), pokrovskite (Mg 2 (CO 3 )(OH) 2 ⁇ 0.5H 2 O), barringtonite (MgCO 3 ⁇ 2H 2 O, lansfordite (MgCO 3 ⁇ 5H 2 O), nesquehonite (MgCO 3 ⁇ 3H 2 O) and mixtures thereof in an amount of at least 80 wt.-%, preferably at least 85 wt.-%, more preferably between 85 and 100 wt.-%, and especially preferably
• the magnesium carbonate comprises synthetic hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 4H 2 O).
• the magnesium carbonate comprises synthetic hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ⁇ 4H 2 O) in an amount of at least 80 wt.-%, more preferably at least 85 wt.-%, especially preferably between 85 and 100 wt.-%, and particularly preferably between 90 and 99.95 wt.-%, based on the total dry weight of the material.
• a carrier material having a specific surface area of ⁇ 25 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:2010 has a high loading capacity for surfactant(s) together with a high release efficiency when loaded with surfactant(s). Accordingly, such carrier material is specifically suitable as delivery system for the release of one or more surfactants in dishwasher detergents of the invention.
• the magnesium carbonate has a specific surface area of ⁇ 25 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:2010. It is preferred that the magnesium carbonate has a specific surface area in the range from 25 to 150 m 2 /g, more preferably from 35 to 120 m 2 /g, and especially preferably from 35 to 100 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:2010.
• the magnesium carbonate has a high intra-particle intruded specific pore volume.
• the magnesium carbonate has an intra-particle intruded specific pore volume in the range from 0.9 to 2.3 cm 3 /g, calculated from mercury intrusion porosimetry.
• the magnesium carbonate has an intra-particle intruded specific pore volume in the range from 1.1 to 2.1 cm 3 /g, and most preferably from 1.2 to 2.0 cm 3 /g, calculated from mercury intrusion porosimetry.
• the magnesium carbonate has
• the magnesium carbonate has a specific surface area in the range from 35 to 100 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:2010, and an intra-particle intruded specific pore volume in the range from 1.2 to 2.0 cm 3 /g, calculated from mercury porosimetry measurement.
• the magnesium carbonate is in the form of a particulate material and may have a particle size distribution as conventionally employed for the material(s) involved in the type of product to be produced.
• the magnesium carbonate has a d 50 (vol) in the range from 1 to 75 ⁇ m, as determined by laser diffraction.
• the magnesium carbonate has a d 50 (vol) in the range from 1.2 to 50 ⁇ m, more preferably from 1.5 to 30 ⁇ m, especially preferably from 1.7 to 15 ⁇ m and particularly preferably from 1.9 to 10 ⁇ m, as determined by laser diffraction.
• the magnesium carbonate has a d 98 (vol) in the range from 2 to 150 ⁇ m, as determined by laser diffraction.
• the magnesium carbonate has a d 98 (vol) in the range from 4 to 100 ⁇ m, more preferably from 6 to 80 ⁇ m, especially preferably from 8 to 60 ⁇ m and particularly preferably from 10 to 40 ⁇ m, as determined by laser diffraction.
• the magnesium carbonate preferably has a
• the magnesium carbonate has a d 50 (vol) in the range from 1.9 to 10 ⁇ m, as determined by laser diffraction, and a d 98 (vol) in the range from 10 to 40 ⁇ m, as determined by laser diffraction.
• magnesium carbonate has
• the magnesium carbonate has
• the magnesium carbonate has
• the carrier material consists of magnesium carbonate. That is to say, the carrier material contains the magnesium carbonate in an amount of at least 96.0 wt.-%, preferably between 96.0 and 100 wt.-%, more preferably between 99.0 and 99.99 wt.-%, and especially preferably between 99.3 and 99.8 wt.-%, based on the total dry weight of the carrier material.
• the magnesium carbonate contains up to 15 000 ppm Ca 2+ ions.
• the magnesium carbonate contains up to 10 000 ppm, more preferably up to 5 000 ppm and especially preferably up to 2 000 ppm Ca 2+ ions.
• the magnesium carbonate preferably has a residual total moisture content of from 0.01 to 20 wt.-%, more preferably from 0.01 to 15 wt.-%, especially preferably from 0.02 to 12 wt.-% and particularly preferably from 0.04 to 10 wt.-%, based on the total dry weight of the magnesium carbonate. It is appreciated that the total moisture content includes crystal water as well as free water.
• Component Z1) of the dishwasher detergents of the invention is a delivery system for the release of one or more surfactants in the dishwasher detergents of the invention, i.e. in automatic dishwashing formulations. It is required that the delivery system comprises the carrier material as defined herein, i.e. the magnesium carbonate carrier, and one or more surfactant(s) which is/are loaded on the carrier material.
• the carrier material as defined herein, i.e. the magnesium carbonate carrier, and one or more surfactant(s) which is/are loaded on the carrier material.
• the delivery system for the release of one or more surfactant(s) in an automatic dishwashing formulation of the invention thus comprises
• one requirement of the present invention is that one or more surfactant(s) is/are loaded on the carrier material.
• the one or more surfactant(s) can be one kind of surfactant.
• the one or more surfactant(s) can be a mixture of two or more kinds of surfactants.
• the one or more surfactant(s) is/are loaded on the carrier material as defined herein.
• the loading is preferably an adsorption onto the surface of the carrier material, be it the outer or the inner surface of the material or an absorption into the carrier material, which is possible due to its porosity.
• this material is a superior carrier material to release previously loaded surfactant(s) over time relative to common carrier materials having lower specific surface areas and/or intra-particle intruded specific pore volume.
• the one or more surfactant(s) is/are adsorbed onto and/or adsorbed and/or absorbed into the carrier material.
• the delivery system comprises the carrier material as defined herein and one or more surfactant(s) which is/are loaded on the carrier material.
• the amount of the one or more surfactant(s) which is/are loaded on the carrier material depends on the surfactant(s) and the intended use.
• the delivery system comprises the one or more surfactant(s) in an amount ranging from 10 to 300 wt.-%, based on the total weight of the carrier material.
• the delivery system comprises the one or more surfactant(s) in an amount preferably ranging from 40 to 250 wt.-%, more preferably from 50 to 200 wt.-%, especially preferably from 60 to 170 wt.-% and particularly preferably from 70 to 150 wt.-%, based on the total weight of the carrier material.
• the delivery system can be provided in any form that is conventionally employed for the material(s) involved in the type of product to be produced. It is appreciated that the carrier material is in the form of a particulate material.
• the term "particulate" in the meaning of the present application refers to a material which is composed of a plurality of particles.
• the delivery system is preferably in the form of a powder, a tablet, a pellet, or granules. More preferably, the delivery system is in the form of a powder.
• Such forms and methods for their preparation are well known in the art and do not need to be described in more detail in the present application.
• the method for preparing a delivery system for the release of one or more surfactant(s) in a dishwasher detergent of the invention comprises the steps of
• the magnesium carbonate may be provided in any suitable liquid or dry form in step a).
• the magnesium carbonate may be in form of a powder and/or a suspension.
• the suspension can be obtained by mixing the magnesium carbonate with a solvent, preferably water.
• the magnesium carbonate to be mixed with a solvent, and preferably water, may be provided in any form, for example, as suspension, slurry, dispersion, paste, powder, a moist filter cake or in pressed or granulated form.
• the magnesium carbonate is preferably provided in dry from, i.e. as a powder.
• the moisture content of the magnesium carbonate can be between 0.01 and 20 wt.-%, based on the total weight of the magnesium carbonate.
• the moisture content of the magnesium carbonate can be, for example, in the range from 0.01 to 15 wt.-%, based on the total weight of the magnesium carbonate, preferably in the range from 0.02 to 12 wt.-%, and more preferably in the range from 0.04 to 10 wt.-%.
• the one or more surfactant(s) is/are provided in the form of a liquid or dissolved in a solvent.
• the one or more surfactant(s) is/are in the form of a liquid.
• liquid with regard to the one or more surfactant(s) refers to non-gaseous fluid surfactant(s), which is/are readily flowable at the pressure conditions and temperature of use, i.e. the pressure and temperature at which the method, preferably method step c), is carried out.
• the one or more surfactant(s) can be liquid in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C.
• the one or more surfactant(s) can be liquid in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C at ambient pressure conditions, i.e. at atmospheric pressure.
• the one or more surfactant(s) can be liquid in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C at reduced pressure conditions, e.g. a pressure of from 100 to 700 mbar.
• the one or more surfactant(s) is/are dissolved in a solvent. That is to say, the one or more surfactant(s) and the solvent form a system in which no discrete solid particles are observed in the solvent and thus form a "solution".
• the solvent is selected from the group comprising water, methanol, ethanol, n-butanol, isopropanol, n-propanol, acetone, dimethylsulphoxide, dimethylformamide, tetrahydrofurane, vegetable oils and the derivatives thereof, animal oils and the derivatives thereof, molten fats and waxes, and mixtures thereof.
• the solvent is selected from water, alkanes, esters, ethers, alcohols, such as ethanol, ethylene glycol and glycerol, and/or ketones, such as acetone. More preferably, the solvent is water.
• the contacting of the magnesium carbonate of step a) with the one or more surfactant(s) of step b) may be carried out in any manner known by the skilled person.
• the contacting is preferably carried out under mixing.
• the mixing may be carried out under conventional mixing conditions.
• the skilled person will adapt these mixing conditions (such as the configuration of mixing pallets and mixing speed) according to his process equipment. It is appreciated that any mixing method which would be suitable to form the delivery system may be used.
• step a) is loaded with the one or more surfactant(s) of step b) by contacting step c) to form the delivery system.
• the loading may be achieved by adding the one or more surfactant(s) to the dry magnesium carbonate.
• the magnesium carbonate is defined to be loaded, if the specific surface area is at least partially covered and/or the intra-particle pore volume of same is at least partially filled by the one or more surfactant(s), and if present, the solvent in which the one or more surfactant(s) is/are dissolved.
• the magnesium carbonate is loaded, if the specific surface area is at least partially covered and/or the intra-particle pore volume of same is at least partially filled preferably by at least 10 wt.-%, more preferably at least 40 wt.-%, especially preferably at least 50 wt.-%, particularly preferably at least 60 wt.-%, and exceptionally preferably at least 70 wt.-%, based on the total weight of the magnesium carbonate, with the one or more surfactant(s), and if present, the solvent in which the one or more surfactant(s) is/are dissolved.
• the magnesium carbonate is loaded, if the specific surface area is at least partially covered and/or the intra-particle pore volume of same is at least partially filled by 10 to 300 wt.-%, more preferably from 40 to 250 wt.-%, especially preferably from 50 to 200 wt.-%, particularly preferably from 60 to 170 wt.-%, and exceptionally preferably from 70 to 150 wt.-%, based on the total weight of the magnesium carbonate, with the one or more surfactant(s), and if present, the solvent in which the one or more surfactant(s) is/are dissolved.
• method step c) can be carried out over a broad temperature and/or pressure range, provided that the one or more surfactant(s) is/are in liquid form.
• method step c) is carried out in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C at ambient pressure conditions, i.e. at atmospheric pressure.
• method step c) is carried out in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C at reduced pressure conditions, e.g. a pressure of from 100 to 700 mbar.
• method step c) is carried out at ambient temperature and pressure conditions, e.g., at room temperature, such as from about 5 to 35°C, preferably from 10 to 30°C and more preferably from 15 to 25°C, and at atmospheric pressure.
• room temperature such as from about 5 to 35°C, preferably from 10 to 30°C and more preferably from 15 to 25°C, and at atmospheric pressure.
• This embodiment preferably applies in case the one or more surfactant(s) is/are liquid at room temperature or are dissolved in a solvent.
• the solvent is preferably removed after method step c), e.g. by evaporation.
• the method thus preferably comprises a further step of separating the prepared delivery system from the excess solvent.
• the solvent is preferably removed by means of separating the solvent from the loaded magnesium carbonate. This is preferably achieved by drying by means selected from the group comprising drying in a rotational oven, jet-drying, fluidized bed drying, freeze drying, flash drying, spray drying and temperature-controlled high or low shear mixer.
• the delivery system according to the present invention may thus be produced by a method comprising the following steps:
• the method may further comprise an optional step e) of granulating the mixture obtained in step c) or optional step d) for obtaining tablets, pellets or granules of the desired form and size.
• the granulation equipment may be selected from the conventionally used ones for granulation purposes.
• the granulation device may be selected from the group comprising Eirich mixers, fluidized bed dryers/granulators, plate granulators, table granulators, drum granulators, disc granulators, dish granulators, ploughshare mixer, vertical or horizontal mixers, high or low shear mixer, high speed blenders, roller compactor and rapid mixer granulators.
• the use of a fluidized bed mixer for granulation appears to provide a more uniform granule size distribution than the Lödige mixer, whereas the Lödige mixer gives a wider size distribution.
• multiple size ranges may be provided.
• the method for preparing a delivery system for the release of one or more surfactant(s) in an automatic dishwashing formulation of the invention comprises the steps of
• the carrier material has a high loading capacity for surfactant(s) together with a high release efficiency when loaded with surfactant(s).
• release efficiency 100 * m surfactant released m surfactant loaded of ⁇ 50%.
• the delivery system provides a release efficiency for the one or more surfactant (s) represented by the formula (I) of ⁇ 72%, and more preferably ⁇ 80%.
• the release efficiency is attained within a time period of 15 min, preferably within 5 min and more preferably within 1 min.
• volume determined median particle size d 50 (vol) and the volume determined top cut particle size d 98 (vol) is evaluated using a Malvern Mastersizer 3000 Laser Diffraction System (Malvern Instruments Pic., Great Britain) equipped with a Hydro LV system.
• the d 50 (vol) or d 98 (vol) value indicates a diameter value such that 50% or 98% by volume, respectively, of the particles have a diameter of less than this value.
• the powders are suspended in 0.1 wt.-% Na 4 O 7 P 2 solution.
• SSA Specific surface area
• the specific surface area is measured via the BET method according to ISO 9277:201 using nitrogen as adsorbing gas on a Micromeritics ASAP 2460 instrument from Micromeritics.
• the samples are pretreated in vacuum (10 -5 bar) by heating at 100°C for a period of 120 min prior to measurement.
• the specific pore volume is measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter having a maximum applied pressure of mercury 414 MPa (60 000 psi), equivalent to a Laplace throat diameter of 0.004 ⁇ m ( ⁇ nm).
• the equilibration time used at each pressure step is 20 seconds.
• the sample material is sealed in a 3 cm 3 chamber powder penetrometer for analysis.
• the data are corrected for mercury compression, penetrometer expansion and sample material compression using the software Pore-Camp ( Gane, P.A.C., Kettle, J.P., Matthews, G.P. and Ridgway, C.J., "Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations", Industrial and Engineering Chemistry Research, 35(5), 1996, p1753-1764 .).
• the total pore volume seen in the cumulative intrusion data can be separated into two regions with the intrusion data from 208 ⁇ m down to about 1 - 4 ⁇ m showing the coarse packing of the sample between any agglomerate structures contributing strongly. Below these diameters lies the fine inter-particle packing of the particles themselves. If they also have intra-particle pores, then this region appears bi-modal, and by taking the specific pore volume intruded by mercury into pores finer than the modal turning point, i.e. finer than the bi-modal point of inflection, the specific intra-particle pore volume is defined. The sum of these three regions gives the total overall pore volume of the powder, but depends strongly on the original sample compaction/settling of the powder at the coarse pore end of the distribution.
• COD chemical oxygen demand
• suspensions are filtered (Chromafil ® Xtra RC-20/25 syringe filter) and adequately diluted for the analysis.
• Active concentrations are determined using a cell test (according to ISO 15705; Spectroquant ® for non-Merck photometers; 0-1500 mg L -1 ) in an Aqualytics COD250 varia photometer. For each sample, 5 readings are taken and the result averaged. The concentration of the samples is calculated based on a calibration curve with previously prepared standard solutions.
• the one or more enzymes of component Z2) of the dishwasher detergents of the invention are selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, oxidoreductases, and mixtures thereof. These enzymes are typically of natural origin. Improved variants based on the natural molecules are obtainable for use in dishwasher detergents and accordingly are preferred.
• subtilisin type preference is given to those of the subtilisin type.
• subtilisins BPN' and Carlsberg and also the further-developed forms thereof, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and subtilases.
• amylases which can be used in accordance with the invention are the ⁇ -amylases from Bacillus licheniformis, from B . amyloliquefaciens, from B . stearothermophilus, from Aspergillus niger and A. oryzae, and also the further-developed forms of the aforesaid amylases that have been improved for use in dishwasher detergents. Further deserving of emphasis for this purpose are the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
• lipases or cutinases are lipases or cutinases, particularly on the basis of their triglyceride-cleaving activities, but also for generating peracids in situ from suitable precursors. They include, for example, the lipases obtainable originally from Humicola lanuginosa ( Thermomyces lanuginosus ) and/or further developments thereof, particularly those with the amino acid replacement D96L. Further of possible use, for example, are the cutinases isolated originally from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, and/or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocma and Fusarium solanii.
• oxidoreductases examples being oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, or bromo-peroxidases, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases).
• peroxidases such as halo-, chloro-, or bromo-peroxidases
• lignin such as halo-, chloro-, or bromo-peroxidases
• lignin such as halo-, chloro-, or bromo-peroxidases
• lignin such as halo-, chloro-, or bromo-peroxidases
• lignin such as halo-, chloro-, or bromo-peroxidases
• lignin such as halo-, chloro-, or bromo-peroxidases
• lignin such as halo
• the enzymes can be used in any form established according to the prior art. These forms include, for example, the solid preparations obtained by granulation, extrusion or lyophilization, or else - particularly in the case of liquid or gel compositions - solutions of the enzymes, advantageously in very highly concentrated form, of low water content and/or with stabilizers added.
• the enzymes for both the solid and the liquid presentation forms, may be encapsulated, by spray drying or extrusion of the enzyme solution, for example, together with a preferably natural polymer, or in the form of capsules, examples being those wherein the enzymes are included as in a solidified gel, or in those of the core-shell type, for which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and/or chemicals.
• a protective layer which is impermeable to water, air and/or chemicals.
• additional-on layers there may additionally be further active ingredients applied, examples being stabilizers, emulsifiers, pigments, bleaches or dyes.
• Capsules of these kinds are applied by techniques that are known per se, as for example by agitated granulation or roll granulation or in fluid-bed operations.
• such granules as a result of application of polymeric film-formers, for example, are low in dust and stable in storage by virtue of the coating.
• Dishwasher detergents of the invention comprise the one or more enzymes of component Z2) preferably in amounts from 1 x 10 -6 to 5 wt.-%, more preferably in amounts from 1 x 10 -5 to 3 wt.-%, and especially preferably in amounts from 1 x 10 -4 to 2 wt.-%, based in each case on the total weight of the dishwasher detergents of the invention.
• the amount of the one or more enzymes of component Z2) of the dishwasher detergents of the invention is also based on active protein.
• the protein concentration may be determined by known techniques, such as by the BCA method or the biuret method, for example.
• Glass corrosion inhibitors may be ingredients of the dishwasher detergents of the present invention. Glass corrosion inhibitors may prevent the appearance of clouding, streaks and scratches, but may also prevent the surface of machine-cleaned glassware becoming iridescent.
• a glass corrosion inhibitor may be any glass corrosion inhibitor known in the art.
• Preferred glass corrosion inhibitors may include one or more salts selected from the group consisting of magnesium (which different from the magnesium carbonate carrier of component Z1), cobalt, bismuth, and zinc, and also complexes of one or more of magnesium (which different from the magnesium carbonate carrier of component Z1), cobalt, bismuth, and/or zinc.
• the one or more glass corrosion inhibitors of component Z3) are selected from the group consisting of, preferably water-soluble, salts or complexes of one or more cations selected from the group consisting of zinc, magnesium, cobalt, bismuth, and combinations of two or more thereof.
• the one or more glass corrosion inhibitors of component Z3) are, preferably water-soluble, salts comprising one or more anions selected from the group consisting of sulfate, nitrate, acetate, oxide, sulfate, phosphate, halide, carbonate or carboxylate salt.
• the one or more glass corrosion inhibitors may be selected from the group consisting of zinc sulfate, zinc nitrate, zinc acetate, zinc phosphate, zinc a zinc halide (e.g., zinc chloride), zinc carbonate, magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium phosphate, magnesium, a magnesium halide (e.g., magnesium chloride), magnesium carbonate, cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt phosphate, cobalt, a cobalt halide (e.g., cobalt chloride), cobalt carbonate, bismuth sulfate, bismuth nitrate, bismuth acetate, bismuth phosphate, bismuth, a bismuth halide (e.g., bismuth chloride), bismuth carbonate, and combinations of two or more thereof or complexes comprising one or more of these salts.
• the dishwasher detergent according to the present invention comprises component Z3) in an amount from 0.01 to 10 wt.-%, more preferably in an amount from 0.1 to 5 wt.-%, even more preferably in an amount from 0.2 to 4 wt.-%, and especially preferably in an amount from 0.4 to 3 wt.-%, from 0.5 to 2 wt.-% or from 0.2 to 1 wt.-%, based in each case on the total weight of the dishwasher detergent.
• component Z3 in an amount from 0.01 to 10 wt.-%, more preferably in an amount from 0.1 to 5 wt.-%, even more preferably in an amount from 0.2 to 4 wt.-%, and especially preferably in an amount from 0.4 to 3 wt.-%, from 0.5 to 2 wt.-% or from 0.2 to 1 wt.-%, based in each case on the total weight of the dishwasher detergent.
• the dishwasher detergents of the invention may optionally additionally comprise one or more further substances.
• these further substances optionally present in the dishwasher detergents of the invention are selected from the components Z4), Z5), Z6), Z7), and/or Z8):
• the one or more surfactants other than those of component Z1) of component Z5) are selected from the group consisting of fatty alcohol alkoxylates, end-capped fatty alcohol alkoxylates, ethyleneoxide-propylenoxide-blockcopolymers, N-acylglucamines, N-acylglucamides, gylcerol triester alkoxylates, esterquats, and mixtures thereof, preferably wherein the one or more surfactants of component Z5) are on the magnesium carbonate carrier,
• the pH of the dishwasher detergents of the invention at 20°C is preferably from 8 to 14, more preferably from 9 to 11.5, and especially preferably from 9.5 to 11.5, measured as a 10 wt.-% solution of the solid or liquid dishwasher detergent of the invention in water.
• the dishwasher detergents of the invention may also comprise a bleaching system.
• the bleaching system of the dishwasher detergents of the invention comprises preferably one or more substances from the group consisting of bleaches, bleach activators, and bleaching catalysts.
• the dishwasher detergents of the invention may comprise an oxygen bleach.
• oxygen bleaches which in water yield H 2 O 2 , particular importance is possessed by sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate.
• other useful bleaches are peroxypyrophosphates, citrate perhydrates, and also H 2 O 2 -donating peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
• Organic bleaches can also be used. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Further typical organic bleaches are the peroxy acids, such as alkylperoxy acids and the arylperoxy acids.
• the dishwasher detergents of the invention preferably comprise one or more bleaches from the group consisting of oxygen bleaches, peroxypyrophosphates, citrate perhydrates, H 2 O 2 -donating peracid salts or peracids, and organic bleaches.
• the dishwasher detergents of the invention comprise 1.0 to 20 wt.-%, preferably 4.0 to 18 wt.-%, and more preferably 8 to 15 wt.-%, of an oxygen bleach, preferably sodium carbonate, based in each case on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergents of the invention may additionally comprise one or more bleach activators.
• the bleach activator or bleach activators are preferably selected from the group consisting of compounds which under perhydrolysis conditions furnish aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid.
• Suitable substances are those which carry O- and/or N-acyl groups with the stated number of carbon atoms, and/or optionally substituted benzoyl groups.
• Preferred are polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
• Bleach activators especially TAED are used preferably in amounts of up to 10 wt.-%, more preferably in amounts of 0.1 to 8 wt.-%, especially preferably in amounts of 2 to 8 wt.-%, and particularly preferably in amounts of 2 to 6 wt.-%, based in each case on the total weight of the bleach activator-containing dishwasher detergent of the invention.
• bleaching catalysts are bleach-boosting transition metal salts or transition metal complexes such as, for example, Mn-, Fe-, Co-, Ru- or Mo-salen complexes or -carbonyl complexes. Also possible for use as bleaching catalysts are Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes with nitrogen-containing tripod ligands, and also Co-, Fe-, Cu-, and Ru-amine complexes.
• complexes of manganese in the II, III, IV or V oxidation state preferably containing one or more macrocyclic ligands with N, NR, PR, O and/or S donor functions.
• Preferred ligands are those having nitrogen donor functions.
• bleaching catalyst(s) comprising as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN) and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN).
• Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
• TACN 1,4,7-triazacyclononane
• TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
• Me-TACD 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane
• Me/TACN 2-methyl-1,4,7-triazacyclononane
• the dishwasher detergents of the invention comprise one or more bleaching catalysts from the group of the bleach-boosting transition metal salts and transition metal complexes, preferably from the group of the manganese complexes with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN) and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), since by means of these bleaching catalysts it is possible to pose significant improvements in the cleaning outcome.
• the bleach-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
• Me 4 -TACN 1,2,4,7-tetramethyl-1,4,7-triazacyclononane
• the bleaching system preferably comprises one or more bleaches and one or more substances from the group of the bleach activators and bleaching catalysts.
• the bleaching system comprises one or more bleaches, one or more bleach activators, and one or more bleaching catalysts.
• the dishwasher detergents of the invention comprise the bleaching system of component Z4) preferably in amounts of 1 to 40 wt.-%, more preferably in amounts of 0.5 to 30 wt.-%, and especially preferably in amounts of 3 to 25 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
• Preferred dishwasher detergents of the invention further comprise one or more surfactants of component Z5), the group of the surfactants including the nonionic, the anionic, the cationic, and the amphoteric surfactants.
• these surfactants of component Z5) are not present on a carrier material and in this preferred embodiment the surfactants themselves may be optionally the same as those used in component Z1).
• the surfactants of component Z5) can be on magnesium carbonate carrier and in this other preferred embodiment the surfactants themselves are different from those used in component Z1).
• At least one surfactant of the one or more surfactants, and more preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the nonionic surfactants and more preferably of the low-foaming nonionic surfactants.
• Nonionic surfactants which can be used in the context of the present invention are all nonionic surfactants known to the skilled person.
• At least one surfactant of the one or more surfactants, and even more preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group of nonionic surfactants consisting of fatty alcohol alkoxylates, endgroup-capped fatty alcohol alkoxylates, preferably end-capped fatty alcohol ethoxylates, e.g.
• epoxy-capped poly(alkoxylated) fatty alcohols preferably epoxy-capped poly(ethoxylated) fatty alcohols, ethyleneoxide-propyleneoxide-blockcopolymers, N-acylglucamines / N-acylglucamides, glycerol triester alkoxylates, preferably glycerol triester ethoxylates, and mixtures thereof.
• dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the fatty alcohol alkoxylates and end-capped fatty alcohol alkoxylates of the formula (XI-b) RaO-(AO)x-Y (XI-b), in which
• alkyl and alkenyl groups R a in the formula (XI-b) are, for example, the alkyl and alkenyl groups of the following alcohols R a -OH: 1-octanol (caprylyl alcohol), 2-ethylhexanol, 1-nonanol (pelargon alcohol), 1-decanol (caprinyl alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol), 9E-octadec
• R a in formula (XI-b) is preferably a linear or branched saturated alkyl group having 8 to 22 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 22 carbon atoms, more preferably a linear or branched saturated alkyl group having 8 to 20 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 20 carbon atoms, and especially preferably a linear or branched saturated alkyl group having 8 to 18 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms.
• the groups R a in formula (XI-b) are saturated alkyl groups.
• x is preferably a number from 1 to 50, more preferably a number from 1 to 25, especially preferably a number from 5 to 25 and particularly preferably a number from 15 to 25.
• Examples of the linear or branched saturated alkyl groups Y and R b in the compounds of the formula (XI-b) include the examples specified above for the saturated alkyl group R a in the compound of the formula (XI-b). Further examples are the alkyl groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl (2-pentyl), 3-pentyl, 2-methylbutyl, isopentyl (3-methylbutyl), 3-methylbut-2-yl, 2-methylbut-2-yl, neopentyl (2,2-dimethylpropyl), 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-penty
• Y in formula (XI-b) is a linear or branched saturated alkyl group
• the saturated alkyl group in question preferably has 1 to 22 carbon atoms.
• R b preferably is a linear or branched saturated alkyl group having 8 to 22 and more preferably 8 to 20 carbon atoms.
• the group -(AO) x - consists of one or more -C 2 H 4 -O- groups and contains no -C 3 H 6 -O- groups.
• the group -(AO) x - comprises one or more -C 2 H 4 -O- groups and one or more -C 3 H 6 -O- groups.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x - is preferably less than 50%, more preferably 45% or less than 45%, especially preferably 40% or less than 40%, and particularly preferably 33% or less than 33%.
• Y in formula (XI-b) is H.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x - is preferably 20 to less than 50%, more preferably 33 to 45%, and especially preferably 33 to 40%.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x -, is preferably 20% or less than 20% and more preferably 10% or less than 10%.
• Y in formula (XI-b) is a saturated alkyl group with 1 to 4 carbon atoms.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x -, is preferably 20% or less than 20% and more preferably 10% or less than 10%.
• Y in formula (XI-b) is the group -CH 2 -CH(OH)-R b , in which R b is a linear or branched saturated alkyl group having 8 to 22 and preferably 8 to 20 carbon atoms.
• the molar amount of the -C 3 H 6 -O- groups in the group -(AO) x -, based on the total amount of -C 2 H 4 -O- and -C 3 H 6 -O- groups in the group -(AO) x - is preferably 20% or less than 20% and more preferably 10% or less than 10%.
• the group -(AO) x - especially preferably consists of one or more -C 2 H 4 -O- groups and contains no -C 3 H 6 -O- groups.
• the group -(AO) x - in formula (XI-b) comprises on molar average 8 -C 2 H 4 -O- groups and 4 -C 3 H 6 -O-groups and R a is a linear or branched saturated alkyl group having 12 to 15 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 12 to 15 carbon atoms.
• the one or more nonionic surfactants of component Z5) of the dishwasher detergents of the invention have with particular preference a cloud point of 40 to 60°C.
• variable "x" in the one or more compounds of the formula (XI-b) preferably represents molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (XI-b) having different degrees of alkoxylation.
• dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the end-capped fatty alcohol ethoxylates of the formula (XI-c) R a O-(AO) x -Y (XI-c) in which
• alkyl and alkenyl groups R a in the formula (XI-c) are, for example, the alkyl and alkenyl groups of the following alcohols R a -OH: 1-octanol (caprylyl alcohol), 2-ethylhexanol, 1-nonanol (pelargon alcohol), 1-decanol (caprinyl alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol), 9E-octadec
• R a in formula (XI-c) is preferably a linear or branched saturated alkyl group having 8 to 18 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms.
• the groups R a in formula (XI-c) are saturated alkyl groups.
• x is preferably a number from 16 to 24 and more preferably from 19 to 23.
• Examples of the linear or branched saturated alkyl groups R b in the compounds of the formula (XI-c) include the examples specified above for the saturated alkyl group R a in the compound of the formula (XI-c). Further examples are the alkyl groups heneicosyl and behenyl.
• variable "x" in the one or more compounds of the formula (XI-c) preferably represents molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (XI-c) having different degrees of alkoxylation.
• the dishwasher detergent of the invention further comprises one or more further surfactants as component Z5), which optionally may also be on a magnesium carbonate carrier (optionally the magnesium carbonate carrier of component Z1)).
• Such optional further surfactants are preferably selected from the group consisting of the N-acylglucamides, which are also known as N-1-deoxysorbityl-fatty acid amides or glucamides, of the formula (XII) in which
• Rc is more preferably a methyl group.
• Rb is preferably a linear or branched saturated alkyl group having 11 to 17 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 11 to 17 carbon atoms.
• Rb is more preferably a linear or branched saturated alkyl group having 15 to 17 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 15 to 17 carbon atoms.
• 50 wt.-% or more, preferably 60 to 99 wt.-%, and more preferably 70 to 98 wt.-%, of the groups Rb in the one or more N-acylglucamides of the formula (XII) are linear or branched saturated alkyl groups having 17 carbon atoms.
• 0.1 to 50 wt.-%, preferably 0.5 to 40 wt.-%, and more preferably 1.0 to 30 wt.-% of the groups Rb in the one or more N-acylglucamides of the formula (XII) are linear or branched saturated alkyl groups having 15 carbon atoms.
• 50 wt.-% or more of the groups Rb in the one or more N-acylglucamides of the formula (XII) are linear or branched unsaturated alkenyl groups having one or more double bonds.
• 50 wt.-% or more, preferably 80 wt.-% or more and more preferably 90 wt.-% or more of the groups Rb in the one or more N-acylglucamides of the formula (XII) are linear or branched unsaturated alkenyl groups having one or more double bonds and 17 carbon atoms.
• Rb preferably is a linear group.
• RbCO in the one or more N-acylglucamides of the formula (XII) derives from lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid, preferably from stearic acid, oleic acid, linoleic acid or linolenic acid, more preferably from oleic acid, linoleic acid or linolenic acid, and especially preferably from oleic acid.
• surfactants which may optionally be comprised in a dishwasher detergent of the present invention as component Z5) (optionally also on a magnesium carbonate carrier such as, e.g., that of component Z1)) may preferably be selected from the group consisting of the glycerol triester ethoxylates of formula (I) wherein R 1 , R 2 and R 3 are equal or different and are independently selected from linear or branched saturated alkyl groups having 7 to 25 carbon atoms or linear or branched unsaturated alkenyl groups having one or more double bonds and 7 to 25 carbon atoms; m, n and o are equal or different and are each independently a number from 1 to 200, preferably from 1 to 80, more preferably from 2 to 70, with the proviso that the number-average of the sum of m + n + o is greater than 5, preferably from 20 to 70, more preferably from 30 to 60.
• R 1 , R 2 and R 3 are equal or different and are independently selected from linear or branched saturated al
• dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the glycerol triester ethoxylates of formula (I) prepared from ethylene oxide and one or more triglycerides of formula (II) in the presence of a calcium catalyst (C), wherein R 1 , R 2 and R 3 in formulae (I) and (II) are equal or different and are independently selected from linear or branched saturated alkyl groups having 7 to 25 carbon atoms or linear or branched unsaturated alkenyl groups having one or more double bonds and 7 to 25 carbon atoms; m, n and o in formula (I) are equal or different and are each independently a number from 1 to 200, preferably from 1 to 80, more preferably from 2 to 70, with the proviso that the number-average of the sum of m + n + o is
• variables "m”, “n” and “o” in the one or more compounds of the formula (I) preferably represent molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (I) having different degrees of ethoxylation.
• surfactants which may optionally be comprised in a dishwasher detergent of the present invention as component Z5) (optionally also on a magnesium carbonate carrier such as, e.g., that of component Z1)) may preferably be selected from the group consisting of the surfactants of formulae (VII), (VIII) and/or (IX) wherein each R 10 group is independently selected from linear or branched, preferably linear, saturated alkyl groups having 1 to 6 carbon atoms, linear or branched, preferably linear, unsaturated alkenyl groups having one or more double bonds and 2 to 6 carbon atoms, and linear or branched, preferably linear, saturated hydroxyalkyl groups having 1 to 6 carbon atoms; each R 11 group is independently selected from linear or branched saturated alkyl groups having 8 to 28 carbon atoms, linear or branched unsaturated alkenyl groups having one or more double bonds and 8 to 28 carbon atoms; R 12 is the same as R 10 or (CH 2 ) n -T-R 11
• surfactants which may optionally be comprised in a dishwasher detergent of the present invention as component Z5) (optionally also on a magnesium carbonate carrier such as, e.g., that of component Z1)) may preferably be selected from the group consisting of the compounds of formula (X) wherein
• dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the compounds formula (X), wherein
• variables "r”, “s” and “t” in the one or more compounds of the formula (X) preferably represent molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (X) having different degrees of ethoxylation.
• dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of the component Z5) of the dishwasher detergents of the invention are selected from the group consisting of zwitterionic surfactants and anionic surfactants.
• the zwitterionic surfactants are preferably selected from the group consisting of C 8 to C 18 (preferably C 12 to C 18 ) amine oxides, sulfobetaines and hydroxylbetaines, such as N-alkyl-N,N-dimethylamino-1-propanesulfonate, where the alkyl group may be C 9 to C 18 , preferably C 10 to C 14 .
• the anionic surfactants are preferably selected from alkyl ethoxysulfates having a degree of ethoxylation of more than 3, more preferably 4 to 10, and especially preferably 6 to 8, and a chain length in the range from C 8 to C 16 and preferably C 11 to C 15 . Also, branched alkyl carboxylates are preferred if the branching occurs in the middle and the average overall chain length is 10 to 18 and preferably 12 to 16 in the case of a side-chain length of 2 to 4 carbon atoms. One example thereof is 2-butyloctanoic acid.
• the anionic surfactant is commonly of a type having good solubility in the presence of calcium.
• Anionic surfactants of this kind are further represented by sulfobetaines, alkyl (polyethoxy)sulfates (AES), short-chain C 6 -C 10 alkyl sulfates and alkylsulfonates. It has emerged that straight-chain fatty acids are ineffective because of their sensitivity toward calcium.
• the dishwasher detergents of the invention comprise the one or more surfactants of component Z5) preferably in amounts of 0 to 15 wt.-%, more preferably in amounts of 0 to 10 wt.-%, especially preferably in amounts of 0.5 to 7 wt.-% and particularly preferably in amounts of 3 to 7 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergents of the invention may comprise further ingredients which are commonly used in dishwasher detergents.
• the dishwasher detergents of the invention comprise one or more substances selected from the group consisting of complexing agents, water, organic solvents, thickeners, foam inhibitors, color particles, silver protectants, agents for preventing the tarnishing of silver, dyes, fillers, microbicides, hydrotropes, antioxidants, enzyme stabilizers, fragrances, solubilizers, carrier materials, processing assistants, pigments, and pH modifiers.
• the dishwasher detergents of the invention may also comprise one or more builders.
• the dishwasher detergents of the invention preferably comprise one or more builders of the group consisting of carbonates, hydrogencarbonates, organic builders, preferably citrate, methylglycinediacetic acid (MGDA), silicates, phosphates, phosphonates, and alkali metal hydroxides.
• MGDA methylglycinediacetic acid
• silicates phosphates, phosphonates, and alkali metal hydroxides.
• These compounds are used preferably in amounts of 2 to 50 wt.-%, more preferably of 10 to 30 wt.-%, and especially preferably of 10 to 25 wt.-%, based on the total weight of the dishwasher detergent of the invention.
• the organic builders include polycarboxylates, polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, and dextrins.
• Useful organic builders include the polycarboxylic acids, which can be used in the form of the free acid and/or the sodium salts thereof, with polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and nitrilotriacetic acid (NTA), and also mixtures thereof.
• the free acids typically also possess the property of an acidifying component, as well as their builder effect, and hence also serve to establish a lower and milder pH for the dishwasher detergents of the invention.
• Preferred in this context are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, tartaric acid, and any desired mixtures thereof.
• customary aminocarboxylic acids which are preferred in the context of the present invention are ethylenediaminetetraacetic acid (EDTA), methylglycinediacetic acid (MGDA), and glutaminediacetic acid (GLDA). Mixtures can also be used.
• EDTA ethylenediaminetetraacetic acid
• MGDA methylglycinediacetic acid
• GLDA glutaminediacetic acid
• polymeric aminodicarboxylic acids are also to be mentioned as further preferred builders. Particular preference is given to using polyaspartic acids, their salts and/or their derivatives.
• dishwasher detergents of the invention which comprise citric acid or a salt of citric acid, in which case the weight fraction of the citric acid or of the salt of citric acid is preferably from 2 to 50 wt.-%, more preferably 5 to 30 wt.-%, and especially preferably 10 to 30 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergents of the invention comprise MGDA as one of their builders.
• Dishwasher detergents of the invention comprise preferably 0.5 to 25 wt.-% and more preferably 2 to 25 wt.-% of MGDA, based on the total weight of the dishwasher detergent of the invention.
• polymeric carboxylates are also suitable as organic builders. These are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, examples being those having a relative molecular mass of 500 to 70 000 g/mol.
• Suitable polymeric carboxylates are, in particular, polyacrylates, preferably having a molecular mass of 2000 to 20 000 g/mol. By virtue of their superior solubility, preference may be given in turn, from this group, to the short-chain polyacrylates having molar masses of 2000 to 10 000 g/mol and more preferably of 3000 to 5000 g/mol.
• Suitable co-monomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid.
• copolymeric carboxylates of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid are particularly suitable.
• copolymers of acrylic acid with maleic acid which contain 50 to 90 wt.-% of acrylic acid and 10 to 50 wt.-% of maleic acid.
• Their relative molecular mass, based on free acids is preferably 2000 to 70 000 g/mol, more preferably 20 000 to 50 000 g/mol, and especially preferably 30 000 to 40 000 g/mol.
• copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C 3 -C 10 monocarboxylic and/or C 4 -C 10 dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, and citraconic acid, with at least one hydrophilically or hydrophobically modified monomer as recited below.
• Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butane, pentene, hexene, and styrene, olefins having 10 or more carbon atoms or mixtures thereof, such as, for example, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, and 1-hexacosene, C 22 ⁇ -olefin, a mixture of C 20 -C 24 ⁇ -olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.
• Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, and also nonionic monomers with hydroxy function or alkylene oxide groups, and optionally further ionic or nonionic monomers.
• hydrophilic monomers examples include allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate, and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate.
• Polyalkylene glycols here may contain 3 to 50, preferably 5 to 40, and more preferably 10 to 30 alkylene oxide units per molecule.
• Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (2-acryloylamino-2-methylpropanesulfonic acid), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, 2-
• Particularly preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.
• amphoteric polymers may also be used as builders.
• the amount of these (co)polymeric carboxylates in the dishwasher detergent of the invention is preferably 0.5 to 20 wt.-% and more particularly 3 to 10 wt.-%, based on the total weight of the dishwasher detergent of the invention.
• Oxydisuccinates and other derivatives of disuccinates are also further preferred organic builders, which are frequently also referred to as cobuilders.
• ethylenediamine-N,N'-disuccinate (EDDS) is used preferably in the form of its sodium or magnesium salts.
• Further preferred as builder or co-builder in this context are also glyceroldisuccinates and glyceroltrisuccinates.
• Dishwasher detergents of the invention may as builders preferably comprise crystalline sheet-like sodium silicates of the formula NaMSi x O 2x+1 ⁇ yH 2 O, 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 0 to 20.
• the dishwasher detergents of the invention comprise preferably a weight fraction of the crystalline sheet-like silicate of the formula NaMSi x O 2x+1 ⁇ yH 2 O of 0.1 to 20 wt.-%, more preferably of 0.2 to 15 wt.-%, and especially preferably of 0.4 to 10 wt.-%, based in each case on the total weight of the dishwasher detergents of the invention.
• amorphous sodium silicates having a Na 2 O:SiO 2 modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8, and more preferably of 1:2 to 1:2.6, which are preferably dissolution-retarded and have secondary cleaning properties.
• Retarded dissolution relative to conventional amorphous sodium silicates may have been brought about in a variety of ways, as for example by surface treatment, compounding, compacting, densification, or by overdrying.
• the term "amorphous" is understood to mean that in x-ray diffraction experiments, the silicates provide none of the sharp x-ray reflections of the kind typical of crystalline substances, but instead invoke at most one or more maxima in the scattered x-radiation, with a latitude of several degree units of the diffraction angle.
• x-ray-amorphous silicates are used, whose silicate particles in electron diffraction experiments yield indistinct or even sharp diffraction maxima. This is to be interpreted to mean that the products have microcrystalline regions of ten to several hundred nm in size, with preference being given to values up to a maximum of 50 nm and more particularly up to a maximum of 20 nm.
• X-ray-amorphous silicates of this kind likewise have retarded dissolution in relation to the conventional waterglasses.
• densified/compacted amorphous silicates, compounded amorphous silicates, and overdried x-ray-amorphous silicates are densified/compacted amorphous silicates, compounded amorphous silicates, and overdried x-ray-amorphous silicates.
• these silicates preferably alkali metal silicates, more preferably crystalline or amorphous alkali metal disilicates, to be present in the dishwasher detergents of the invention in amounts of 3 to 60 wt.-%, preferably of 8 to 50 wt.-%, and more particularly of 20 to 40 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
• the phosphates have proven to be effective builders in relation to the cleaning performance.
• the multiplicity of phosphates available commercially the greatest significance in the detergents industry is possessed by the alkali metal phosphates, especially pentasodium and/or pentapotassium triphosphate (sodium and/or potassium tripolyphosphate).
• Alkali metal phosphates here is the overarching designation for the alkali metal salts (especially sodium and potassium salts) of the various phosphoric acids, among which it is possible to differentiate metaphosphoric acids (HPO 3 ) m and orthophosphoric acid H 3 PO 4 , as well as representatives of higher molecular mass.
• the phosphates here unite a number of advantages: they act as alkali metal carriers, prevent limescale deposits on machine components, and contribute to the cleaning performance.
• Phosphates particularly important technically are pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate) and also the corresponding potassium salt pentapotassium triphosphate K 5 P 3 O 10 (potassium tripolyphosphate). Also used preferably in accordance with the invention are the sodium potassium tripolyphosphates.
• preferred compositions comprise phosphate(s), preferably alkali metal phosphate(s), more preferably pentasodium and/or pentapotassium triphosphate (sodium and/or potassium tripolyphosphate), in amounts of 2 to 50 wt.-%, preferably of 2 to 30 wt.-%, more preferably of 3 to 25 wt.-%, and especially preferably of 3 to 15 wt.-%, based in each case on the weight of the dishwasher detergent of the invention.
• phosphate(s) preferably alkali metal phosphate(s), more preferably pentasodium and/or pentapotassium triphosphate (sodium and/or potassium tripolyphosphate)
• 2 to 50 wt.-% preferably of 2 to 30 wt.-%, more preferably of 3 to 25 wt.-%, and especially preferably of 3 to 15 wt.-%, based in each case on the weight of the dishwasher detergent of the invention.
• dishwasher detergents of the invention may comprise are one or more phosphonates, which are frequently also referred to as cobuilders.
• the weight fraction of phosphonate is preferably 0.5 to 20 wt.-% and more preferably 1.0 to 10 wt.-%.
• the complex-forming phosphonates embrace a series of different compounds such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP). Particularly preferred are hydroxyalkane- and aminoalkanephosphonates.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• DTPMP diethylenetriaminepenta(methylenephosphonic acid)
• hydroxyalkane- and aminoalkanephosphonates particularly preferred.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• It is used preferably as the sodium salt, with the disodium salt giving a neutral reaction and the tetrasodium salt an alkaline reaction (pH 9).
• Suitable aminoalkanephosphonates include ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and also their higher homologs. They are used preferably in the form of the neutrally reacting sodium salts (e.g., as the hexasodium salt of EDTMP and/or as the hepta- and octasodium salt of DTPMP). From the class of the phosphonates, preference is given to using HEDP.
• Dishwasher detergents of the invention may comprise alkali metal hydroxides as further builders. These alkali metal carriers are preferably used only in small amounts, preferably in amounts of 10 wt.-% or less, more preferably 6 wt.-% or less, especially preferably 5 wt.-% or less, particularly preferably 0.1 to 5 wt.-%, and exceptionally preferably 0.5 to 5 wt.-%, based on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergents of the invention comprise one or more builders from the group of the organic builders.
• the dishwasher detergents of the invention comprise one or more builders from the group consisting of citrate, methylglycinediacetic acid (MGDA), and ethylenediamine-N,N'-disuccinate (EDDS).
• the dishwasher detergents of the invention comprise MGDA.
• the dishwasher detergents of the invention may comprise the aforesaid builders either individually or else in the form of mixtures of two, three, four or more builders.
• the dishwasher detergents of the invention comprise no phosphate builders and no phosphate-based builders and preferably are phosphate-free.
• the dishwasher detergents of the invention comprise the one or more builders preferably in amounts of 2 to 50 wt.-%, more preferably in amounts of 10 to 30 wt.-%, and especially preferably in amounts of 10 to 25 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
• a protein and/or enzyme may be protected, particularly during storage, against forms of damage such as inactivation, denaturing or disintegration (as a result, for example, of physical influences, oxidation or proteolytic cleavage).
• the proteins and/or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, especially if the dishwasher detergents of the invention also comprise proteases.
• Dishwasher detergents of the invention may comprise stabilizers for this purpose. The provision of such agents in dishwasher detergents of the invention represents a preferred embodiment of the present invention.
• dishwasher detergents which comprise 0.1 to 12 wt.-%, more preferably 0.2 to 10 wt.-%, and especially preferably 0.5 to 8 wt.-%, of enzyme preparation, based in each case on the total weight of the dishwasher detergent of the invention.
• dishwasher detergents of the invention comprise at least one organic solvent.
• Preferred liquid dishwasher detergents of the invention comprise organic solvent in amounts of 0.2 to 15 wt.-%, more preferably in amounts of 0.5 to 12 wt.-%, and especially preferably in amounts of 1.0 to 10 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
• organic solvents are, for example, monoalcohols, diols, triols, polyols, ethers, esters and/or amides. Particularly preferred here are organic solvents which are water-soluble, with “water-soluble” solvents in the sense of the present specification being solvents which at room temperature are miscible with water completely (i.e., without a miscibility gap).
• the organic solvents from the group of the organic amines and/or the alkanolamines are effective in relation to the cleaning performance and especially in relation to the cleaning performance on bleachable stains, particularly on tea stains.
• the dishwasher detergents of the invention may have thickeners added to them.
• the dishwasher detergents of the invention it is possible to use the thickeners that are typically used in dishwasher detergents.
• the respective dishwasher detergents of the invention advantageously comprise the thickener in amounts which are preferably from 0.1 to 8 wt.-%, more preferably from 0.2 to 6 wt.-%, and especially preferably from 0.4 to 4 wt.-%, based on the total weight of the dishwasher detergent of the invention.
• the foam inhibitors, color particles, silver protectants, agents for preventing the tarnishing of silver may be selected from the corresponding substances which are typically used in dishwasher detergents.
• a tableting aid may be understood in the broadest sense as generally understood in the art.
• a tableting agent supports the formation of a compact and cohesive tablet when formed from the other ingredients.
• the tableting aid is selected from one or more types of polyethylene glycol (PEG), one or more polysaccharides (e.g., cylclodextrine, starch, cellulose) and derivatives thereof (e.g., methyl cellulose, hydroxymethyl cellulose, starch derivatives).
• the tableting aid has a mean molecular weight (e.g., determined by means of size exclusion chromatography) of more than 500 Da, of more than 100 Da, or of more than 5000 Da.
• Suitable polymers of component Z8) include washing or cleaning-active polymers, for example rinse aid polymers and/or polymers which act as softeners.
• the dishwasher detergent of the present invention may include, as polymers of component Z8), nonionic, cationic, anionic and/or amphoteric polymers.
• Cationic polymers in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
• Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylates and methacrylates, vinylpyrrolidone-methoimidazolinium chloride copolymers, quaternized polyvinyl alcohols, or polymers having the INCI names polyquaternium 2, polyquaternium 17, polyquaternium 18 and polyquaternium 27.
• cationic polymers are used in component Z8), they are preferably selected from copolymers comprising polyalkylene oxide groups and quaternary nitrogen atoms. More preferably the cationic polymers of component Z8) are copolymers comprising 0.1 to 99.9 mol-%, preferably 20.0 to 80.0 mol-%, more preferably 22.0 to 77.6 mol-% of one or more cationic structural units (D); and 0.1 to 99.9 mol-%, preferably 0.4 to 20.0 mol-%, more preferably 0.5 to 4.4 mol-% of one or more macromonomeric structural units (E), wherein the one or more cationic structural units (D) are represented by the following general formulae (XI) and/or (XII): wherein R 19 and R 21 are equal or different and are independently selected from hydrogen and/or a methyl group; R 20 , R 22 , R 23 and R 24 are equal or different and are independently selected from the group consisting of hydrogen, an aliphatic hydro
• cationic polymers In these cationic polymers the molar amounts of the structural units (D) and (E) are based on the total weight of the cationic polymer.
• the cationic polymers comprising structural units (D) and E) may preferably also comprise structural units resulting from the polymerization of further monomers such as further nonionic monomers, preferably amides and more preferably N,N-dimethyl acrylamide.
• Amphoteric polymers in the context of the present invention have, alongside positively charged groups, also negatively charged groups or monomeric units in the polymer chain. These negatively charged groups or monomeric units may be derived, e.g. from carboxylic acids, sulfonic acids ot phosphonic acids.
• Preferable amphoteric polymers applicable in component Z8) of the dishwasher detergent of the invention are selected from the group consisting of alkylacrylamide/acrylic acid-copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkyl aminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/alkylmethacrylate/alkylaminoethylmethacrylate/alkylmethacrylate copolymers, and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or not-ionogenic mono
• amphoteric polymers are selected from the group consisting of acrylamidoalkyl-trialkylammonium chloride/acrylic acid copolymers and their alkaline metal or ammonium salts, acrylamidoalkyl-trialkylammonium chloride/methacrylic acid copolymers and their alkaline metal or ammonium salts, and methacroylethylmetaine/methacrylate copolymers.
• the dishwasher detergent of the invention contains cationic and/or amphoteric polymers in component Z8), these polymers are preferably present in amounts of from 0.01 to 10 wt.-%, based on the total weight of the dishwasher detergent of the invention.
• Another group of preferably applicable polymers applicable in component Z8) of the dishwasher detergent of the invention are alkoxylated polyalkyleneimines.
• Alkoxylated polyalkyleneimines have a polyalkyleneimine backbone and alkoxy chains.
• the polyalkyleneimine is polyethyleneimine. More preferably, the alkoxylated polyalkyleneimine is not quaternized.
• the dishwasher detergent comprises alkoxylated polyalkyleneimines in component Z8), it preferably comprises from 1% to 10 wt.-%, more preferably from 1% to 8 wt.-% of alkoxylated polyalkyleneimines, based on the total weight of the dishwasher detergent of the invention.
• the alkoxylated polyalkyleneimine used in component Z8) comprises 0.5 to 40 wt.-%, more preferably 1 to 30 wt.-%, especially preferably 2 to 20 wt.-% of the polyalkyleneimine backbone and 60 to 99 wt.-%, more preferably 60 to 95 wt.-%, especially preferably from 60 to 90 wt.-% of the alkoxy chains.
• the alkoxy chains have an average of from about 1 to about 50, more preferably from about 2 to about 40, especially preferably from about 3 to about 30, particularly preferably from about 3 to about 20, and exceptionally preferably from about 4 to about 15 alkoxy units, which are preferably ethoxy units.
• the alkoxy chains have an average of from about 0 to 30, more preferably from about 1 to about 12, especially preferably from about 1 to about 10 and particularly preferably from about 1 to about 8 propoxy units.
• alkoxylated polyethyleneimines wherein the alkoxy chains comprise a combination of ethoxy and propoxy chains, in particular polyethyleneimines comprising chains of from 4 to 20 ethoxy units and from 0 to 6 propoxy units.
• the alkoxylated polyalkyleneimine is obtained from alkoxylation wherein the starting polyalkyleneimine has a weight-average molecular weight of from about 100 to about 60,000, preferably from about 200 to about 40,000, more preferably from about 300 to about 10,000 g/mol.
• a polyethyleneimine with a weight average molecular weight of 600 g/mol ethoxylated with 20 EO groups per NH group is used as the alkoxylated polyalkyleneimine.
• Suitable polyalkyleneimines for applicable in component Z8) of the dishwasher detergent of the invention include compounds having the following general structure: bis((C 2 H 5 O)(C 2 H 4 O) n )(CH 3 )-N + -C 2 H 2x -N + -(CH 3 )-bis((C 2 H 5 O)(C 2 H 40 ) n ), wherein n is a number from 20 to 30, and x is a number from 3 to 8, or sulfated or sulfonated variants thereof.
• the dishwasher detergent of the invention comprises 0.5 to 30 wt.-%, preferably 1 to 25 wt.-%, more preferably 2 to 20 wt.-%, especially preferably 3 to 15 wt.-%, and particularly preferably 5 to 10 wt.-% of component Z1), based in each case on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergent of the invention comprises 7 to 20 wt.-%, preferably 10 to 18 wt.-%, and more preferably 12 to 15 wt.-% of component Z1), based in each case on the total weight of the dishwasher detergent of the invention.
• ratio of surfactant which is on magnesium carbonate to magnesium carbonate is in the range of 0.1 : 10 to 10: 0.1, or in the range of 0.5 : 5 to 5: 0.5, or in the range of 0.7 : 2 to 2: 0.7.
• the dishwasher detergent comprises 0.1 to 20 wt.-%, preferably 0.5 to 15 wt.-%, more preferably 5 to 10 wt.-%, especially preferably 2 to 5 wt.-%, and particularly preferably 3 to 4 wt.-% of surfactant which is comprised on magnesium carbonate in component Z1), based in each case on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergent comprises 1 x 10 -6 to 5 wt.-% of component Z2), based on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergent comprises 0.01 to 10 wt.-%, preferably 0.1 to 5 wt.-%, more preferably 0.2 to 4 wt.-%, even more preferably 0.4 to 3 wt.-%, 0.5 to 2 wt.-% or 0.2 to 1 wt.-%, of component Z3), based in each case on the total weight of the dishwasher detergent of the invention,.
• the dishwasher detergent comprises 0 to 40 wt.-%, preferably 1 to 40 wt.-%, more preferably 2 to 20 wt.-%, even more preferably 5 to 10 wt.-%, of component Z4), based in each case on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergent comprises 0 to 50 wt.-%, preferably 0 to 15 wt.-%, more preferably 0 to 10 wt.-%, even more preferably 0.5 to 7 wt.-%, and especially preferably 3 to 7 wt.-%, of component Z5), based in each case on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergent comprises 0 to 80 wt.-%, preferably 0 to 70 wt.-%, more preferably 0 to 60 wt.-%, of component Z6), based in each case on the total weight of the dishwasher detergent of the invention (e.g., including 2 to 50 wt.-% of one or more builders, based on the total weight of the dishwasher detergent).
• the dishwasher detergent comprises 0 to 50 wt.-%, preferably 0.1 to 40 wt.-%, more preferably 0.5 to 20 wt.-%, even more preferably 1 to 10 wt.-%, of component Z7), based in each case on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergent comprises 0 to 10 wt.-%, of component Z8), based on the total weight of the dishwasher detergent of the invention.
• dishwasher detergents of the invention comprise
• the dishwasher detergents of the invention may be produced in solid form and also as a combination of solid and liquid presentation forms.
• Preferred dishwasher detergents of the invention are those which are solid at 20°C or in which at least one phase is solid.
• Suitable solid presentation forms include, in particular, powders, granules, extrudates or compacts, especially tablets, in single-phase or multiphase form. Tablets are formulated for single-dose applications.
• the solid compositions of the invention preferably comprise 20 wt.-% or less than 20 wt.-% of water, more preferably 0.1 to 20 wt.-% of water, and especially preferably 0.5 to 5 wt.-% of water, based in each case on the total weight of the dishwasher detergent of the invention.
• the dishwasher detergents of the invention are anhydrous.
• the dishwasher detergent of the invention is solid at 20°C and is in the form of a tablet.
• detergent compositions for machine dishwashing according to the invention which comprise dishwasher detergents of the invention and are enclosed in a water-soluble foil, preferably a polyvinyl alcohol containing foil.
• water soluble foil means that the foil comprises a water-soluble polymer, copolymer or mixtures thereof in a weight fraction of at least 90 wt.-%, based on the weight of the foil.
• Water soluble polymers in the context of the present invention are polymers which are soluble in water at 25°C to an amount of more than 2.5 wt.-%, based on the amount of water.
• Preferable materials of the water soluble foil are at least partially composed of a substance selected from the group consisting of polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinylpyrrolidones, gelatine, polyvinyl alcohols substituted with sulfate, carbonate and/or citrate, polyalkylene oxides such as polyethylene oxides, acrylamides, cellulose esters, cellulose ethers, cellulose acetate, polycarboxylic acids and their salts, polyaminoacids or peptides, copolymers of acrylamides and (meth)acrylic acid, polysaccharides such as starch or guar derivatives, and compounds with the INCI names polyquaternium 2, polyquaternium 17, polyquaternium 18 and polyquaternium 27.
• the material of the water-soluble foil comprises polyvinyl alcohol.
• the material of the water-soluble foil comprises mixtures of different substances, such as copolymers. Such mixtures enable the adjustment of the mechanical properties of the foil and the container formed thereof and may affect the degree of water solubility.
• the water-soluble foil contains at least one polyvinyl alcohol and/or at least one polyvinyl alcohol copolymer.
• a further subject of the invention is a method for cleaning dishware in a dishwasher, wherein soiled dishware is treated in a dishwasher with an aqueous alkaline composition comprising a dishwasher detergent of the invention.
• the pH of the aqueous alkaline composition is preferably 8 or more and more preferably 9 or more.
• the dishwasher detergent of the invention or surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention may be advantageously suitable as rinse agent in machine dishwashing, preferably in a method of the invention for cleaning dishware in a dishwasher.
• a further subject of the present invention is therefore the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention may be for use as a rinse agent in machine dishwashing, preferably in a method of the invention for cleaning dishware in a dishwasher.
• the dishwasher detergents of the invention or the one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention are advantageously suitable for improving the wettability of dishware, for reducing the spotting and filming on dishware, for reducing, minimizing or preventing fatty residues in the machine department of an automatic dishwashing machine, for improving the rinse performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, or for improving the drying performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, more preferably in a method of the invention for cleaning dishware in a dishwasher.
• a further subject of the present invention is therefore the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention for improving the wettability of dishware or for reducing spotting and filming on dishware, preferably in a method of the invention for cleaning dishware in a dishwasher.
• a further subject of the present invention is the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention for reducing, minimizing or preventing fatty residues in the machine department of an automatic dishwashing machine, preferably in a method of the invention for cleaning dishware in a dishwasher.
• a further subject of the present invention is the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention for improving the rinse performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, more preferably in a method of the invention for cleaning dishware in a dishwasher.
• a further subject of the present invention is the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention for improving the drying performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, more preferably in a method of the invention for cleaning dishware in a dishwasher.
• the preferred embodiments specified above for the dishwasher detergents of the invention are also valid correspondingly for the method of the invention for cleaning dishware in a dishwasher and also for the inventive use of the dishwasher detergents of the invention or of the one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention as rinse agents in machine dishwashing, for reducing, minimizing or preventing fatty residues in the machine department of an automatic dishwashing machine, for improving the wettability of dishware, for reducing the spotting and filming on dishware, for improving the rinse performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, and for improving the drying performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention.
• Example 1 Drying performance and clean dishwasher interior
• testware was started 30 minutes after the dishwashing cycle was completed. During this time, the dishwasher door was closed. For each test, dishwashing cycles 2 to 4 were evaluated. The assessment was carried out in each case with an illumination of 1000 - 1500 lux.
• composition of the formulation F1 is shown in the following Table A.
• Dishwashing Machine Miele G 1222 SC GSL
• Testware dishes 6 drinking glasses (higher quality) (8 material groups) 6 drinking glasses (lower quality) 3 PP bowls 3 melamine plates 3 butter dishes + 4 knives (stainless steel; lower quality) 4 knives (stainless steel; higher quality) 3 porcelain plates (higher quality) 3 porcelain plates (lower quality)
• composition of the formulation F1 according to the invention is shown in the following table A. The results are also shown in Table A.
• Table A Composition, drying performance, fatty residues and rinse performance of formulation F1
• Component F1 wt.-% *) Trisodium citrate Dihydrate 28.5 Sodium carbonate 19.5 Sodium silicate (Britesil H20 ® (PQ Corp., PA, USA)) 2.0 MGDA-Na 3 (Trilon ® M Max Granules (BASF SE, Germany)) 15.0 Polycarboxylate (Sokalan ® PA 30 CL (BASF SE, Germany)) 10.0 Natriumpercarbonate (Oxyper SCS ® (Solvay, Belgium)) 9.0 TAED (Peractive AC white ® (WeylChem, Germany)) 2.0 HEDP 0.9 Protease (Blaze Evity 100T ® , Novozymes, Denmark) 0.9 Amylase (Stainzyme 120T ® , Novozymes, Denmark)

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• 2021
  • 2021-04-01 EP EP21166655.7A patent/EP4067468A1/fr not_active Withdrawn

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