EP3114198A1 - Détergent mis à l'avance sous forme de portions comprenant au moins deux formulations liquides séparées - Google Patents

Détergent mis à l'avance sous forme de portions comprenant au moins deux formulations liquides séparées

Info

Publication number
EP3114198A1
EP3114198A1 EP15708188.6A EP15708188A EP3114198A1 EP 3114198 A1 EP3114198 A1 EP 3114198A1 EP 15708188 A EP15708188 A EP 15708188A EP 3114198 A1 EP3114198 A1 EP 3114198A1
Authority
EP
European Patent Office
Prior art keywords
liquid preparation
cleaning agent
acid
agent according
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15708188.6A
Other languages
German (de)
English (en)
Other versions
EP3114198B1 (fr
Inventor
Ulrich Pegelow
Noelle Wrubbel
Volker Blank
Matthias Sunder
Martina Hutmacher
Klaus Dorra
Britta Strauss
Oliver Kurth
von den Karl-Josef DRIESCH
Friedhelm Siepmann
Mario Sturm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL15708188T priority Critical patent/PL3114198T3/pl
Publication of EP3114198A1 publication Critical patent/EP3114198A1/fr
Application granted granted Critical
Publication of EP3114198B1 publication Critical patent/EP3114198B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • Pre-portioned detergents comprising at least two separate liquid preparations
  • the invention relates to pre-portioned detergent, preferably machine dishwashing detergent, in a water-soluble packaging having at least two compartments comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation alkali metal carbonate, preferably sodium carbonate, in an amount of 20 to 60 wt. % (based on the total weight of the first liquid preparation).
  • first liquid preparation alkali metal carbonate, preferably sodium carbonate
  • compositions to provide in a pre-portioned form offers the use of water-soluble films in the form of bags. Disposable portions, especially water-soluble bags enjoy the consumer not only therefore
  • Ingredients can be at least partially attacked. This results in unwanted leaks or leaks in the water-soluble packaging.
  • Ortho-silicates in larger quantities are also undesirable because they lead to strong deposits on the items to be washed.
  • the object of the invention was thus to provide liquid pre-portioned machine dishwashing detergents which have an improved cleaning performance and are simultaneously storage-stable.
  • the object is achieved by providing a pre-portioned detergent, preferably dishwasher detergent, in a water-soluble packaging with at least two compartments, comprising at least a first and a second liquid preparation, characterized in that the first liquid preparation alkali metal carbonate, preferably
  • Sodium carbonate in an amount of 20 to 60 wt .-% (based on the total weight of the first liquid preparation).
  • Liquid as used herein in reference to the cleaning agent of the present invention includes all flowable compositions and more particularly includes gels and pastes
  • compositions which also includes non-Newtonian fluids having a yield point.
  • Pre-portioned detergents are generally present in a water-soluble packaging, for example a film containing a disposable portion.
  • the pre-portioned detergent is in a water-soluble packaging.
  • the cleaning agent in particular machine dishwashing detergent, can be made up in such a way that disposable portions are each packed separately.
  • the water-soluble packaging allows a portioning of the cleaning agent. The amount of total detergent in the
  • Portion pack is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g, in particular 17 to 23 g.
  • the water-soluble packaging in this case has at least two or more spatially separated compartments (chambers) into which spatially separated at least a first liquid and a second liquid preparation are filled.
  • composition understood that in combination with the other preparations / phases, a detergent, especially a machine dishwashing detergent results.
  • Detergent contains in addition to the two mentioned preparations one or two further preparations in other separate compartments.
  • two liquid and one solid preparation, two liquid and two solid preparations, three or four liquid preparations may be present in a corresponding number of separate compartments.
  • a packaging according to the invention with two compartments can be present, wherein the first and the second liquid preparation separated from each other in each one of
  • Preferred may be pre-portioned detergents in which the water-soluble package contains, in addition to two or more liquid preparations, one, two or more chambers with solid preparations.
  • two or more solid preparations it is preferred that they be of different composition and / or have a different solid form
  • the cleaning agent according to the invention in particular machine dishwashing detergent, can also be present in a water-soluble packaging, which in particular contains more than two, so for example, three, four, five or six compartments.
  • the package contains two, three or more chambers, wherein two, three or more of these chambers are filled with liquid preparations, which are preferably different from each other (for example in the weight proportions of individual components), and in particular one or more different from each other
  • At least one as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more.
  • At least two as used herein means 2 or more, respectively,
  • the first liquid preparation contains 20 to 60 wt .-% alkali metal carbonate, in particular sodium carbonate (a2C03).
  • alkali metal carbonates are not alkali metal hydrogencarbonates, such as, for example, Sodium bicarbonate, or
  • Alkali metal sesquicarbonates to be construed.
  • the alkali metal carbonates depending on their amount and the water content of the first preparation in solution or as a dispersion available. Due to a lower tendency to separate into dispersions, it may be preferable to use sodium carbonate, in particular in the case of relatively high amounts of alkali metal carbonate in the first preparation or in the case of small amounts of water in the first preparation. It is particularly advantageous when using sodium carbonate, that the incorporation of the alkali reserve in the form of sodium carbonate (soda) is stable in the liquid preparation.
  • alkali metal carbonates e.g. Sodium carbonate and potassium carbonate, or sodium carbonate and lithium carbonate are used.
  • the amounts stated below then apply to the total amount of alkali metal carbonates used in the first liquid preparation. It is preferred to use a single alkali metal carbonate,
  • alkali metal carbonate preferably sodium carbonate (soda)
  • the second liquid preparation (and optionally in further preparations) alkali metal carbonate, but it is preferred that the second liquid
  • Preparation (or if any other preparations (ie all preparations contained in the pre-portioned detergent except the first preparation) is substantially free of alkali metal carbonate.
  • Substantially free of alkali metal carbonate means that the second (and possibly the other, separated from the first preparation) preparations, less than 10 wt .-%, in particular less than 5 wt .-%, preferably less than 1 wt .-%, in particular less than 0.5 wt .-%, alkali metal carbonate (in each case based on the weight of the individual preparation).
  • alkali metal carbonate preferably sodium carbonate (soda)
  • alkali metal carbonate preferably sodium carbonate (soda)
  • the said total amount of 1 to 3 g of alkali metal carbonate, in particular sodium carbonate (soda), may also be the
  • Total amount per job ie the total amount of detergent used in a complete dishwasher cleaning program.
  • the ratio of alkali metal carbonate to water in the first liquid preparation is based in each case on the total amount of the first liquid Preparation preferably between 7: 1 and 1: 1, in particular between 6: 1 and 2: 1, particularly preferably between 5: 1 and 3: 1. This ratio applies in particular to the weight ratio of sodium carbonate (soda) to water.
  • the first liquid preparation is preferably low in water.
  • Low-water as used herein means that the first liquid preparation contains less than 20% by weight of water, more preferably less than 15% by weight of water, most preferably less than 13% by weight of water (based on the total weight of water)
  • the water content as defined herein refers to the water content determined by the Karl Fischer titration.
  • the low-water first liquid preparation preferably contains from 5 to 12% by weight of water (based on the total weight of the first liquid phase).
  • Alkali metal carbonate in particular sodium carbonate (soda)
  • sodium carbonate sodium carbonate
  • the weight ratio of alkali metal carbonate in particular
  • Sodium carbonate (soda) to water between 7: 1 and 2: 1, in particular between 6: 1 and 2.5: 1, more preferably between 5: 1 and 3: 1.
  • a phyllosilicate in particular magnesium-containing phyllosilicate, preferably sodium-magnesium-containing phyllosilicates, very particularly a Li-Na-Mg phyllosilicate, are furthermore contained in the first liquid preparation.
  • phyllosilicates in particular magnesium-containing phyllosilicate, preferably sodium-magnesium-containing phyllosilicates, preferably prepared synthetically, are suitable for the formation of a stable and storage-stable dispersion of the large
  • Alkalimetallcarbonatmenge reach without segregation during storage of the agent takes place.
  • These phyllosilicates in particular the lithium-magnesium-sodium phyllosilicates, have the effect that no separation of different liquid phases or sedimentation of solid constituents takes place in the first liquid preparation.
  • These include, for example, available under the trade name Laponite ® magnesium or sodium magnesium phyllosilicates BYK Additives GmbH, in particular the Laponite ® RD or Laponite ® RDS, or the Optigel ® SH.
  • Particularly preferred phyllosilicates are lithium-magnesium-sodium phyllosilicates, for example available under the trade name Laponite® RD, which are particularly suitable for ensuring the stability of the dispersion of the alkali metal carbonates in the first liquid preparation over an extended period of time, during storage.
  • the phyllosilicates can also serve to thicken or to adjust the viscosity of the first liquid preparation.
  • the phyllosilicate in the first liquid preparation is from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, in particular from 0.3 to 5% by weight, very particularly preferably from 0.6 to 3 wt .-% (active substance, in each case based on the total weight of the first liquid
  • the detergents prepared according to the invention preferably further comprise at least one nonionic surfactant.
  • one or more nonionic surfactants may be present in the first and / or in the second (and further liquid) preparations. Preference is given to using at least one nonionic surfactant which is a rinse aid surfactant which produces the rinse aid result (after the end of the
  • Dishwasher cleaning program positively influenced.
  • first and / or the second liquid preparation can be used in the first and / or the second liquid preparation. It may be preferable to use a nonionic surfactant other than the second liquid preparation in the first liquid preparation.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of alkoxylated alcohols which constitute an important group of rinse-action nonionic surfactants (i.e., rinse aid surfactants).
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants have been low foaming nonionic surfactants which contain alternating ethylene oxide (EO) and
  • Alkylene oxide units have. These surfactants show a good effect as rinse aid surfactants. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R is -O- (CH 2 -CH (R 2 ) -O) w- (CH 2 -CH (R 3 ) -O) x- (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH ( R 5 ) -0) z R 6 wherein R is selected from straight-chain or branched, saturated C 6-24 -alkyl radicals; R 2 and R 4 are -H, R 3 and R 5 are -CH 3 ,
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • indices w, x, y, z are independently integers from 1 to 6.
  • nonionic surfactants having a C9-alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units, followed by 1 to 4
  • Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH20- (AO) w- (AO) x- (A "0) y- (A '" 0) zR 2 , in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24-alkyl or alkenyl radical
  • R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, ⁇ ', A "and A'" independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, - CH 2 -CH (CH 2 -CH 3 ),
  • w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • nonionic surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) w- (AO) x- (A "0) y- (A '" 0) zR 2 , hereinafter also referred to as "hydroxy mixed ether "
  • the performance, in particular the rinsing performance, according to the invention prepared compared to surfactant-free system as well as compared to systems containing only alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • Such surfactants are therefore also to be understood as rinse aid surfactants in the context of the invention. It may be preferable, in addition to nonionic surfactants from the group of polyakoxylated fatty alcohols, to use the previously mentioned hydroxy mixed ethers.
  • surfactants of the formula RO [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is one linear or branched
  • Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands.
  • nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] kCH (OH) [CH 2 ] jOR 2 where R and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic
  • Hydrocarbon radicals having 1 to 30 carbon atoms R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is Values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • k and j are values between 1 and 12, preferably between 1 and 5.
  • R and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22
  • Carbon atoms, with radicals having 8 to 18 carbon atoms are particularly preferred.
  • R 3 H, -Ch or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • R 0 [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 CO 2 simplified.
  • R 1 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactants of the general formula R -CH (OH) CH 2 O- (AO) wR 2 have proven to be particularly effective, in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24-alkyl or alkenyl radical
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26
  • A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3 ), preferably CH 2 CH 2 , and
  • non-ionic surfactants include, for example C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular, the Cs-i2 fatty alcohol - (EO) 22 -2-C4 hydroxydecylether and 22 fatty alcohol (EO) 4o-8o-2-hydroxyalkyl ether.
  • EO fatty alcohol
  • R 2 is hydrogen and R, R 3 , A, ⁇ ', A ", A" ⁇ w, x, y and z are as defined above.
  • Preferred liquid cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant on
  • Total weight of the total cleaning agent is preferably 0.1 to 10 wt .-%, preferably 0.5 to 8.0 wt .-% and in particular 1, 0 to 4.0 wt .-% is.
  • such hydroxy mixed ethers are contained in the first and / or the second liquid preparation. If further preparation is present in the cleaning agent, these may also contain nonionic surfactants, in particular alkoxylated fatty alcohols and / or hydroxy mixed ethers. It may be particularly preferred if the o.g.
  • the first liquid preparation contains at least one nonionic surfactant, preferably selected from the group of the alkoxylated alcohols, in particular the abovementioned alkoxylated alcohols.
  • the first liquid preparation contains between 1 and 75% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight (based in each case on the total weight of the first liquid preparation) of at least one nonionic surfactant. If several nonionic surfactants are included, the aforementioned amount refers to the sum of all nonionic surfactants in the first liquid preparation.
  • the first liquid preparation contains from 25 to 50% by weight.
  • Alkali metal carbonate, preferably sodium carbonate, and 10 to 50 wt .-% of nonionic surfactant selected from the alkoxylated alcohols, in particular those alkoxylated alcohols of the abovementioned general formula (I) contains (in each case based on the total weight of the first liquid preparation).
  • the quantitative ratios given here are based on the sum of all nonionic surfactants selected from the alkoxylated alcohols in the first liquid preparation.
  • the first liquid preparation contains as a nonionic surfactant a component according to the following formula (I) R-O- (CH 2 -CH (R 2 ) -O) w- (CH 2 -CH (R 3 ) -O) x- (CH 2 -CH (R 4 ) -O) y- (CH 2 -CH (R 5 ) -0) z R ( wherein R is selected from straight-chain or branched, saturated Ce-ie-alkyl radicals;
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 0 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3.
  • nonionic surfactants selected above as preferred have the advantage that they are generally liquid to pasty, and in addition to their action as rinse aid surfactant, they can also serve as liquid matrix component (s) in the first liquid preparation.
  • the first liquid preparation contains from 25 to 50% by weight.
  • Alkali metal carbonate preferably sodium carbonate, and 10 to 50 wt .-% of at least one of the preceding paragraph as particularly preferred according to formula (I) described
  • nonionic surfactants contains nonionic surfactants. If a plurality of nonionic surfactants contain the surfactants mentioned as preferred in the preceding paragraph, then the stated amounts relate in each case to the total amount of the nonionic surfactants falling under the preferred formula.
  • nonionic surfactants mentioned in particular those mentioned as being preferred, may also be present (also in addition) in the second liquid preparation.
  • the liquid preparations each contain one or more solvents, preferably organic solvents.
  • suitable solvents are for example 1, 2 propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, dipropylene glycol, diethylene glycol, alkanolamines, glycerol, and / or mixtures thereof.
  • Alkanolamines such as in particular monoethanolamine and triethanolamine, are likewise suitable, although it is preferred that these be present only in small amounts, in particular up to about 5% by weight. otherwise it may impair the integrity of the enveloping package (especially in PVA-containing films).
  • Particularly preferred solvents are 1, 2 propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, dipropylene glycols (individually or as a mixture), glycerol, and / or a mixture thereof.
  • 1,2-propanediol, glycerol or a mixture of 1,2-propanediol and glycerol are particularly preferred.
  • solvents are suitable which are selected from non-volatile organic solvents.
  • Non-volatile organic solvents for the purposes of the present invention have a volatility (also volatility or
  • Evaporation number mentioned of at least 10, and in particular more than 35, on.
  • the volatility is given as the ratio of the vapor pressure of the substance under consideration to the vapor pressure of the volatile reference substance diethyl ether at 20 ° C and a relative humidity of 65 ⁇ 5%.
  • Preferred organic solvents having a volatility of at least 10, and more particularly greater than 35 include polyhydric alcohols such as 2-methyl-1,3-propanediol, 1,3-propanediol, 1,2-propylene glycol and glycerin.
  • those organic solvents, in particular polyhydric alcohols, which have a volatility of more than 50 are preferred.
  • organic solvents which have a volatility of less than 10 are completely dispensed with.
  • non-volatile solvents are 1, 2 propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, dipropylene glycols, glycerol, and / or mixture thereof.
  • 1,2-propanediol, glycerol or a mixture of 1,2-propanediol and glycerol are particularly preferred.
  • the ratio of the water content of the first and the second liquid preparations to one another is between 5: 1 and 1: 5, preferably 3 : 1 and 1: 3, preferably between 2: 1 and 1: 2.
  • This has the advantage that no too large (in particular optically conspicuous) migrations of the water and / or the solvents occur between the individual liquid preparations via the water-soluble packaging. Visually conspicuous migrations can cause one of the chambers to continue to inflate more fluid is filled while the other chamber loses fluid and thereby shrinks. In particular, the shrinkage leads to visually unsightly pre-portioned cleaning agents that are not accepted by the end user.
  • additional builders can be used.
  • the additional builders that can be used include, in particular, the zeolites, silicates, bicarbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • the agents are phosphate-free.
  • crystalline layered silicates of general formula NaMSi x are 02x + i ⁇ y H2O used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the crystalline layered silicates of the formula NaMSi be x 02x + i ⁇ y H2O, for example, by Clariant GmbH
  • Na-SKS silicates
  • SKS-1 Na 2 Si 2 x 2045 ⁇ H2O, kenyaite
  • Na-SKS-2 Na2 Sii 4029 ⁇ x H2O, magadiite
  • Na-SKS-3 Na2Si80i7 H2O
  • Na-SKS-4 Na2Si409 ⁇ x H2O, makatite
  • crystalline sheet silicates of the formula NaMSix02x + i ⁇ y H2O where x is the second
  • both .beta.- and ⁇ -sodium Na2Si20s ⁇ y H2O and further especially Na-SKS-5 (a-Na 2 Si 2 0 5), Na-SKS-7 (.beta.-Na2 Si2 05, natrosilite) , Na-SKS-9 (NaHSi20s ⁇ H2O), Na-SKS-10 (NaHSi 2 0 5 ⁇ 3 H 2 0, kanemite), Na-SKS-11 (t-Na2 Si20 5) and Na-SKS-13 (NaHSi 2 0 5 ), but especially Na-SKS-6 (5-Na 2 Si20 5 ) is preferred.
  • Machine dishwashing detergents preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi x 02x + y i ⁇ H2O of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10 Wt .-%, each based on the total weight of these agents.
  • amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and secondary wash properties.
  • the dissolution delay compared to conventional amorphous sodium silicates can in various ways, for example by surface treatment, compounding, compaction compaction or by
  • the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.
  • these silicate (s) preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in the compositions in amounts of from 3 to 60 wt .-%, preferably from 8 to 50 wt. % and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent are included.
  • Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one
  • Metaphosphoric acids (HP03) n and orthophosphoric acid H3PO4 can distinguish in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations on crockery and also contribute to the cleaning performance.
  • the agents are phosphate-free.
  • phosphates are used as washing or cleaning substances in machine dishwashing detergent in the present application
  • preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate ), in amounts of 5 to 80 wt .-%, preferably from 10 to 75 wt .-% and in particular from 12.5 to 70 wt .-%, each based on the weight of the total automatic dishwashing detergent.
  • Alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances can likewise be used in addition to the alkali metal carbonates according to the invention, preference being given for the purposes of this invention to the alkali hydrogencarbonates and / or -sequicarbonates
  • Sodium hydrogen carbonate or sodium sesquicarbonate can be used.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is preferred.
  • the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • the phosphates in particular the polyphosphates, it is also possible to use other builders, such as, for example, zeolites, silicates, and in particular also the sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
  • the agent is free of water-insoluble builders and contains
  • Particularly suitable silicates are crystalline layered silicates of the general formula NaMSixO 2 + + H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and secondary wash properties.
  • one of the liquid preparations preferably at least the second liquid preparation, for example the first and the second liquid preparation (and possibly further preparations present in the cleaning agent) further contains at least one builder or co-builder, in particular selected from the group formed from citrate, aminocarboxylates (especially MGDA and / or GLDA), polyphosphates (preferably a tripolyphosphate) as well as phosphonates and mixtures thereof.
  • a builder or co-builder in particular selected from the group formed from citrate, aminocarboxylates (especially MGDA and / or GLDA) and also
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,
  • NTA nitrilotriacetic acid
  • Acidification and thus also serve to set a lower and milder pH of the automatic dishwashing detergent.
  • citric acid here are citric acid,
  • Succinic acid glutaric acid, adipic acid, gluconic acid and any mixtures thereof.
  • aminocarboxylic acids and / or their salts.
  • Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS).
  • MGDA methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • EDDS ethylenediamine diacetic acid or its salts
  • IDS iminodisuccinic acid
  • Iminodiacetic acid IDA
  • Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the detergents may contain, in particular, phosphonates as builder.
  • phosphonate compound is preferably a hydroxyalkane and / or aminoalkane phosphonate used.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.
  • Aminoalkanphosphonate are preferably
  • Ethylenediaminetetramethylenephosphonate ETMP
  • Diethylentriaminpentamethylenphosphonat DTPMP
  • Phosphonates are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
  • the cleaning agents according to the invention contain phosphates, in particular tripolyphosphates, it is preferred that they contain as further constituent preferably one or more builder (s) (builder / cobuilder) in addition to the phosphate-containing builder component.
  • builder builder / cobuilder
  • builders other than the phosphate-containing builder component include in particular those described above as further builders, preferably citrates, phosphonates, MGDA, GLDA, iminodisuccinic acid, iminodiacetic acid, EDDS (ethylenediamine-N, N'-disuccinic acid) or the salts of said acids, other organic Cobuilders and silicates.
  • Particularly preferred phosphate-containing detergents contain citrate, for example sodium or potassium citrate, as one of their essential builders other than the phosphate-containing builder component. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of citrate are preferred according to the invention. Additionally or alternatively, particularly preferred phosphate-containing cleaning agents can be used as one of the phosphate-containing detergents.
  • Builder component different builder phosphonates, such as HEDP included.
  • the cleaning agents of the invention may further contain a sulfopolymer.
  • the sulfopolymer is contained in the second liquid phase.
  • the proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1, 0 to 15 wt .-%, in particular from 2 to 14 wt .-%, especially from 3 to 12 wt .-%, especially from 4 to 8 wt .-%.
  • the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymer (s).
  • the sulfopolymers can also be used as solids, for example as granules.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)
  • Monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid,
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • Sulfonic acid-containing copolymers is inventively preferred.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the share of
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol "1 , preferably from 4000 to 25,000 gmol " 1 and in particular from 5000 to 15,000 gmol 1 .
  • the copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • Rinse performance of automatic dishwashing detergent according to the invention can be improved.
  • Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • nonionic monomers are preferably monomers of the general formula
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing Monomers 60 to 80 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • the detergents may contain alkali metal hydroxides.
  • These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
  • alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
  • Cleaning agents according to the invention are free of alkali metal hydroxides.
  • the agents according to the invention preferably contain at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphorous surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes , Fragrances, bitter substances, and antimicrobial agents.
  • at least one further constituent preferably selected from the group consisting of anionic, cationic and amphorous surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes , Fragrances, bitter substances, and antimicrobial agents.
  • Alkali metal bicarbonate (s)), dye (s), perfumes and / or preservatives Alkali metal bicarbonate (s)), dye (s), perfumes and / or preservatives.
  • one of the liquid preparations preferably the second liquid preparation, preferably contains one or more substances selected from the group consisting of pH regulators, anionic, cationic and amphoteric surfactants, bleach activators, bleach catalysts, enzymes, thickeners,
  • Sequestering agents electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, perfumes, bitter substances, and antimicrobial agents.
  • the second liquid preparation contains one or more of the substances selected from the group consisting of pH adjusters, anionic, cationic and amphoteric surfactants, enzymes, thickeners,
  • Sequestering agents electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, perfumes, bitter substances, and antimicrobial agents.
  • Dyes are preferably present in at least one, preferably in the first and the second liquid preparation, in particular in all preparations.
  • Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • fatty acid cyanamides sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-Cs-Os-alkyl esters, sulfosuccinamates,
  • Fatty acid sarcosinates Fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R ''')(R' v ) (R v ) N + CH 2 COO ' , in which R i is an alkyl radical having 8 to 25, preferably 10 to 21, carbon atoms and optionally interrupted by hetero atoms or heteroatom groups R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • Suitable cationic surfactants are the quaternary
  • surface-active compounds in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • glass corrosion inhibitors used are polyethyleneimines or zinc salts, preferably zinc salts, in particular zinc acetate. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.
  • the enzymes include in particular proteases, amylases, lipases, hemicellulases,
  • Cellulases perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
  • Detergents according to the invention contain enzymes
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens
  • lipases or cutinases are also usable according to the invention.
  • lipases or cutinases in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, those originally from Humicola lanuginosa
  • Thermomyces lanuginosus or in particular those with one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, more preferably all of the exchanges D96L, T213R and N233R.
  • enzymes can be used which are termed hemicellulases
  • mannanases xanthan lyases
  • pectin lyases pectinases
  • pectin esterases pectate lyases
  • xyloglucanases xylanases
  • pullulanases and ⁇ -glucanases.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases), can be used according to the invention to increase the bleaching effect.
  • peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric
  • Protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and
  • Total weight 0, 1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% enzyme preparations.
  • the first liquid preparation is substantially free of enzymes.
  • substantially free of enzymes means that the first liquid preparation containing the alkali metal carbonate, especially the sodium carbonate, less than 1 wt .-%, in particular less than 0, 1 wt .-% enzyme preparation (based on the total weight of the first liquid Preparation).
  • the enzymes in particular the amylase (s) and / or protease (s), are preferably used in the second liquid preparation.
  • the pH of the cleaning agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application.
  • the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5
  • the pH-adjusting agents are acids and / or alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or also
  • Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the
  • Alkalimetallhydrogencarbonate of which potassium bicarbonate and especially
  • It may also be volatile alkali, for example in the form of ammonia and / or
  • Alkanolamines which can contain up to 9 C-atoms in the molecule.
  • the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the alkanolamine is contained in agents according to the invention preferably in an amount of 0.5 to 5 wt .-%, in particular in an amount of 1 to 4 wt .-%.
  • the cleaning agent according to the invention is free of alkanolamine and ammonia.
  • the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which at the same time complexing agents or even
  • Chelating agents are.
  • Particularly preferred buffer substances are citric acid or citrates, in particular the sodium and potassium lead,
  • trisodium citrate 2H20 and tripotassium citrate ⁇ 2 ⁇ for example, trisodium citrate 2H20 and tripotassium citrate ⁇ 2 ⁇ .
  • Suitable thickeners are all viscosity regulators customarily used in detergents and cleaners, to which, for example, organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour,
  • polyacrylic and polymethacrylic compounds include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (US Pat. CTFA): carbomers), also referred to as carboxyvinyl polymers.
  • polyacrylic acids are obtainable inter alia from Fa. 3V Sigma under the tradename Polygel ® such as Polygel ® DA, and by the company. BFGoodrich under the tradename Carbopol ®, such as Carbopol ® 940 (molecular weight about 4,000,000), Carbopol ® 941 (molecular weight approximately 1,250,000) or Carbopol ® 934
  • acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C 1-4 -alkanols (INCI acrylates copolymer), for example the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and
  • Methyl methacrylate (CAS 25852-37-3) and which are obtainable for example from Messrs. Rohm & Haas under the trade names Aculyn ® and Acusol ®, and from Degussa (Goldschmidt) under the trade name Tego ® polymer, for example the anionic non- associative polymers Aculyn ® 22, Aculyn ® 28, Aculyn ® 33 (crosslinked), Acusol ® 810, Acusol ® 823 and
  • Acusol ® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of Cio-30-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci-4-alkanols formed, esters (INCI Acrylates / C 10-30 alkyl acrylate crosspolymer) and the example of the Fa. BFGoodrich are available under the trade name Carbopol ®, eg hydrophobic the
  • Carbopol ® ETD 2623 and Carbopol ® 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and Carbopol AQUA ® 30 (formerly Carbopol ® EX 473).
  • Carbopol ® ETD 2623 and Carbopol ® 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer)
  • Carbopol AQUA ® 30 (formerly Carbopol ® EX 473).
  • WO 97/38076 lists a number of polymers derived from acrylic acid which are suitable viscosity regulators.
  • Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, e.g. propoxylated guar, as well as their mixtures.
  • Other polysaccharide thickeners such as starches or cellulose derivatives, may be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g.
  • Polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 * 10 6 and for example by Kelco under the trade names Keltrol ® and Kelzan ® or by the company Rhodia under the trade name Rhodopol ® is available.
  • the second liquid preparation directly after production has a viscosity above 1000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 2000 and 10,000 mPas. After storage, the viscosity may be higher, for example, greater than 10,000 mPas, such as in the range 10000-50000 mPas, (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C). It is preferable that the second liquid preparation is flowable at room temperature.
  • the cleaning agents according to the invention are characterized in that they are stable in storage and even after a prolonged period, no phase separation occurs.
  • Detergent is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the packaging may consist of one or two or more layers of the water-soluble
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
  • the water-soluble packaging is a water-soluble packaging made of a polyvinyl alcohol or
  • the water-soluble packaging contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble packaging containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular water solubility on.
  • Suitable water-soluble films for producing the water-soluble packaging are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose
  • Molecular weight in the range of 10,000 to 1,000,000 gmol _1 , preferably from 20,000 to 500,000 gmol 1 , more preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol 1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers.
  • at least one layer of the water-soluble packaging comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • (Meth) acrylic acid-containing (co) polymers polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
  • the film material contains further additives.
  • the film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, Propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
  • Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble packaging / water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example under the designation M8630, M8534, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the cleaning agents according to the invention can be used as dishwashing detergents, in particular automatic dishwashing detergents (machine dishwashing detergents).
  • dishwashing detergents in particular automatic dishwashing detergents (machine dishwashing detergents).
  • the invention relates to a
  • Dishwashing process in particular automatic dishwashing process, in which a detergent according to the invention is used.
  • the particular embodiments described above also apply to the use or the method.
  • the cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.
  • the pre-portioned detergent according to the invention which was provided in a Zweischpouch (two-chamber bag) of PVA-containing film and 5 g of the first liquid phase (chamber I) and 15 g of the second liquid phase (chamber II) contained when used in a conventional Dishwasher a good cleaning performance on burnt stains compared to a commercial pre-portioned liquid
  • Chamber I Chamber II
  • Acrylic acid polymer Na salt - 0.5

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  • Detergent Compositions (AREA)

Abstract

L'invention concerne un détergent mis à l'avance sous forme de portions, de préférence un détergent pour lave-vaisselle, dans un emballage hydrosoluble comportant au moins deux compartiments, ledit détergent comprenant au moins des première et seconde formations liquides. L'invention est caractérisée en ce que la première formulation liquide contient un carbonate de métal alcalin, de préférence du carbonate de sodium, dans une quantité de 20 à 60% en poids (sur la base du poids total de la première formulation liquide).
EP15708188.6A 2014-03-06 2015-03-04 Détergent mis à l'avance sous forme de portions comprenant au moins deux formulations liquides séparées Active EP3114198B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15708188T PL3114198T3 (pl) 2014-03-06 2015-03-04 Preporcjowany środek czyszczący obejmujący co najmniej dwa oddzielne ciekłe preparaty

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014204144.9A DE102014204144A1 (de) 2014-03-06 2014-03-06 Vorportionierte Reinigungsmittel umfassend mindestens zwei getrennte flüssige Zubereitungen
PCT/EP2015/054463 WO2015132279A1 (fr) 2014-03-06 2015-03-04 Détergent mis à l'avance sous forme de portions comprenant au moins deux formulations liquides séparées

Publications (2)

Publication Number Publication Date
EP3114198A1 true EP3114198A1 (fr) 2017-01-11
EP3114198B1 EP3114198B1 (fr) 2019-10-30

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EP15708188.6A Active EP3114198B1 (fr) 2014-03-06 2015-03-04 Détergent mis à l'avance sous forme de portions comprenant au moins deux formulations liquides séparées

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Country Link
EP (1) EP3114198B1 (fr)
DE (1) DE102014204144A1 (fr)
PL (1) PL3114198T3 (fr)
WO (1) WO2015132279A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201419691D0 (en) * 2014-11-05 2014-12-17 Armstrong John S Apparatus method and substance for washing glassware and/or dishware
US11434454B2 (en) 2017-12-22 2022-09-06 Church & Dwight Co., Inc. Laundry detergent composition
EP3770241A1 (fr) 2019-07-22 2021-01-27 Henkel AG & Co. KGaA Agent de nettoyage à protéase destiné au dosage automatique

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5004556A (en) * 1987-06-17 1991-04-02 Colgate-Palmolive Company Built thickened stable non-aqueous cleaning composition and method of use
US5798324A (en) 1996-04-05 1998-08-25 S.C. Johnson & Son, Inc. Glass cleaner with adjustable rheology
WO2002006438A1 (fr) * 2000-07-19 2002-01-24 The Procter & Gamble Company Compositions se presentant sous forme de gel pour lave-vaisselle automatique, leurs procedes de preparation et d'utilisation
US6228825B1 (en) * 2000-10-13 2001-05-08 Colgate Palmolive Company Automatic dishwashing cleaning system
DE102005041708A1 (de) * 2005-09-02 2007-03-08 Henkel Kgaa Reinigungsmittel
US20110240510A1 (en) * 2010-04-06 2011-10-06 Johan Maurice Theo De Poortere Optimized release of bleaching systems in laundry detergents

Also Published As

Publication number Publication date
PL3114198T3 (pl) 2020-04-30
DE102014204144A1 (de) 2015-09-10
EP3114198B1 (fr) 2019-10-30
WO2015132279A1 (fr) 2015-09-11

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