EP3599274A1 - Poche d'agent de nettoyage multiphase - Google Patents

Poche d'agent de nettoyage multiphase Download PDF

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Publication number
EP3599274A1
EP3599274A1 EP19186476.8A EP19186476A EP3599274A1 EP 3599274 A1 EP3599274 A1 EP 3599274A1 EP 19186476 A EP19186476 A EP 19186476A EP 3599274 A1 EP3599274 A1 EP 3599274A1
Authority
EP
European Patent Office
Prior art keywords
weight
phase
gel
detergent
particulate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19186476.8A
Other languages
German (de)
English (en)
Inventor
Matthias Sunder
Luca Bellomi
Oliver Kurth
Robert Stephen Cappleman
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
Publication of EP3599274A1 publication Critical patent/EP3599274A1/fr
Pending legal-status Critical Current

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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
    • C11D17/044—Solid 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D2111/12—Soft surfaces, e.g. textile
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the invention relates to a detergent and / or cleaning agent portion, which comprises at least one chamber and a water-soluble envelope, characterized in that it comprises at least one particulate phase, the at least one particulate phase being brought into direct contact with at least one liquid composition, and corresponding manufacturing processes.
  • Detergents or cleaning agents are usually in solid form (for example as tablets) or in liquid form (or also as a flowing gel). Liquid washing or cleaning agents in particular are enjoying increasing popularity among consumers.
  • Solid detergents or cleaning agents have the advantage that, unlike liquid detergents or cleaning agents, they do not require any preservatives.
  • Liquid forms of offer are becoming increasingly popular on the market, in particular due to their rapid solubility and the associated rapid availability of the active ingredients they contain. This gives the consumer the opportunity to use time-reduced washing programs and still get good cleaning performance.
  • Solid detergent formulations with a high surfactant content generally show high stickiness and poor pouring or flow behavior. This leads to poorer meterability during manufacture. In particular, only lower bulk densities are achieved, so that larger volumes have to be used for the same performance of the cleaning agent. Larger cavities must then be used, particularly in pre-proportioned detergent portions, but this is generally limited by the size of the metering chamber.
  • the object of the present invention is therefore to provide detergent or cleaning agent portions which are compact and at the same time have good, in particular even improved washing or cleaning performance.
  • a first object of the present invention relates to a detergent and / or cleaning agent portion, which comprises at least one chamber and a water-soluble envelope, characterized in that it comprises at least one particulate phase, the at least one particulate phase in direct contact with at least one liquid composition brought.
  • the detergent or cleaning agent portions according to the invention are more compact due to the direct contact of the particulate phase with a liquid composition.
  • the particulate phase is so to speak impregnated with the liquid phase.
  • the liquid phase preferably moves into the particulate phase or is absorbed in some other way by it, e.g. B. in that the liquid composition diffuses into the pores of the particulate phase.
  • a second subject of the present invention relates to a manufacturing process for detergent or cleaning agent portions, which leads to more compact detergent and / or cleaning agent portions with good or even improved cleaning. This manufacturing process is explained in more detail below.
  • the manufacturing process according to the invention also leads to a higher compactness of the cleaning agent in the case of the pouches, which are filled with formulations which can be poured well, by contacting compositions which would otherwise have a negative effect on the pourability.
  • product changes, e.g. to other surfactants or amounts of surfactants or perfumes.
  • surfactants In particular with surfactants, a higher surfactant content, in particular with liquid surfactants, can be achieved than with normal, particulate formulations, since these should be as free-flowing as possible for better processability.
  • the detergent and / or cleaning agent portion can have one or more chambers. At least one particulate phase is brought into direct contact with at least one liquid phase in the at least one chamber.
  • a phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous.
  • a phase differs from another phase by different features, for example ingredients, physical properties, external appearance or spatial separation or arrangement etc.
  • different phases can be optically distinguished.
  • the at least one particular phase must be clearly distinguished from other phases. If the washing or cleaning agent according to the invention has more than one particulate phase, these can likewise be distinguished from one another with the naked eye because they differ from one another, for example in terms of their coloring. The same applies if there are two or more phases. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a color or transparency difference.
  • Phases in the sense of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye.
  • the individual phases can have different properties, such as, for example, the rate at which the phase dissolves in water and thus the rate and the order in which the constituents contained in the respective phase are released.
  • a particulate phase is to be understood as a granular mixture of a solid composition.
  • the particulate phase is formed from a large number of loose, solid particles, which in turn comprise so-called grains.
  • the term particulate phase comprises particles, grains, powders and / or granules.
  • a grain is a term for the particulate constituents of powders (grains are the loose, solid particles), dusts (grains are the loose solid particles), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures.
  • a preferred embodiment of the granular mixture of the composition of the particulate phase is the powder and / or the granulate, if the term "powder” or “granulate” is used here, it is also encompassed that these are also mixtures of different powders or different granules , Accordingly, the term powder and granules means mixtures of different powders with different granules.
  • Said solid-shaped particles of the granular mixture in turn preferably have a particle diameter X 50.3 (volume average) of 10 to 1500 ⁇ m, more preferably of 200 ⁇ m to 1200 ⁇ m, particularly preferably from 600 ⁇ m to 1100 ⁇ m. These particle sizes can be determined by sieving or by means of a particle size analyzer Camsizer from Retsch.
  • particulate phases can be changed more easily in their appearance or composition compared to a compressed tablet.
  • texture differences such as coarse and fine particles, as well as particles or areas with different colors, as a whole or as colored speckles, can thus be used to improve an optically appealing appearance.
  • This also offers improved solubility compared to compressed tablets even without the addition of disintegrants.
  • At least one as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • the information relates to the type of ingredient and not to the absolute number of molecules.
  • At least one bleaching catalyst thus means, for example, at least one kind of bleaching catalyst, i.e. that one type of bleaching catalyst or a mixture of several different bleaching catalysts can be meant.
  • the information relates to all compounds of the specified type which are contained in the composition / mixture, i.e. that the composition contains no further compounds of this type beyond the stated amount of the corresponding compounds.
  • the number average molecular weight can be determined, for example, by means of gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 with THF as the eluent.
  • the weight average molecular weight M w can also be determined by means of GPC, as described for M n .
  • the detergent and / or cleaning agent portion is characterized in that the at least one particulate phase is free-flowing, preferably at the time of addition. This is important for the preparation of the detergent or cleaning agent portions, so that a uniform filling of such portion packs is possible both with regard to the same amount and the same composition.
  • the granular mixture serving as the particulate phase of the solid composition of the present invention is preferably in free-flowing form (particularly preferably as free-flowing powder and / or free-flowing granules).
  • the agent of the portion according to the invention thus comprises at least one particulate phase (a phase of a free-flowing, granular mixture of a solid composition).
  • the flowability of a granular mixture, particularly the particulate phase affects the ability to flow freely under its own weight.
  • the pourability is determined by measuring the time for 1000 ml of detergent or cleaning agent powder to flow out of a standardized pouring test funnel with an outlet of 16.5 mm diameter, which is initially closed at its outlet direction, by measuring the time for the granular mixture to completely flow out, particularly the particulate phase measured after opening the outlet and compared with the outlet speed (in seconds) of a standard test object whose outlet speed is defined as 100%.
  • the defined sand mixture for the calibration of the trickle equipment is dry sea sand. Sea sand with a particle diameter of 0.4 to 0.8 mm is used, available for example from Carl Roth, Germany CAS no. [14808-60-7]. For drying, the sea sand is dried for 24 hours at 60 ° C in a drying cabinet on a plate with a maximum layer height of 2 cm.
  • Preferred embodiments of the particulate phases according to the invention have an angle of repose / embankment of from 26 to 35, from 27 to 34, from 28 to 33, the angle of repose according to the method mentioned below after 24 h after the preparation of the granular mixture of the solid composition / the particulate phase , and storage at 20 ° C is determined.
  • Such angles of repose have the advantage that the cavities can be filled with the at least one particulate phase comparatively quickly and precisely.
  • a powder funnel with a content of 400 ml and a drain with a diameter of 25 mm is just hung on a tripod.
  • the funnel is closed manually using a operating knurled wheel at a speed of 80 mm / min, so that the granular mixture, in particular the particulate phase, preferably the powder and / or granulate, for example the powder, trickles out.
  • the height of the cone and the diameter of the cone are determined for the individual particulate phases.
  • the slope angle is calculated from the quotient of the cone height and the cone diameter * 100.
  • Such granular mixtures of a solid composition are particularly suitable, in particular those particulate phases, preferably the powders and / or granules, e.g. the powders which have a flowability in% of the standard test substance specified above of greater than 40%, preferably greater than 50, in particular greater than 55%, particularly preferably greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75 % exhibit.
  • the granular mixture, in particular the particulate phase, preferably the powder and / or granules, e.g. the powder can be dosed well, so that the dosing process runs faster. Furthermore, it is better avoided by such good pourability that the granular mixture, in particular the particulate phase, preferably the powder and / or granules, e.g. the powder reaches the part of the water-soluble coating which is intended for the production of the sealed seam and should therefore remain as granule-free as possible, in particular powder-free.
  • the at least one liquid composition comprises perfume preparations and / or surfactants, preferably nonionic surfactants.
  • the at least one liquid composition is preferably low in water, in particular essentially water-free.
  • Low water in the sense of the present invention means that small amounts of water can be used to produce a phase or composition.
  • the proportion of water in this phase or composition is in particular 20% by weight or less, preferably 15% by weight or less, particularly 12% by weight or less, in particular between 10 and 5% by weight.
  • the percentages by weight relate to the total weight of the respective phase or composition.
  • the at least one liquid composition is essentially water-free.
  • Anhydrous in the sense of the invention means that the respective phase or composition is preferably essentially free of water.
  • “Essentially free” here means that small amounts of water can be present in the phase or composition. This water can, for example, be introduced into the phase by means of a solvent or as water of crystallization or due to reactions of components of the phase with one another. However, small amounts, in particular no water, are used as solvents for the preparation of the corresponding phase or composition.
  • the proportion of water in the phase or composition in this embodiment is 4.9% by weight or less, 4% by weight or less, preferably 2% by weight or less, in particular 1% by weight or less, particularly 0.5% by weight or less, in particular 0.1% by weight or 0.05% by weight or less.
  • the percentages by weight relate to the total weight of the respective phase or composition.
  • the weight ratio of the total amount of the at least one liquid composition to the total amount of the at least one particulate phase is from 1: 800 to 5: 1, in particular from 1: 600 to 2: 1, preferably from 1: 500 to 2: 1, for example from 1: 450 to 1: 1.
  • the proportion by weight of the at least one liquid composition to the total weight of the composition is formed from the at least one liquid composition and the at least one particulate composition from 0.0001 to 25% by weight, in particular 0.005 to 20% by weight, preferably 0.1 to 18% by weight, very particularly preferably 0.2 to 15% by weight, is preferred.
  • the total amount of the at least one liquid composition relative to the total amount of the at least one particulate phase is from 1: 200 to 5: 1, in particular from 1 : 100 to 1: 1, preferably from 1:50 to 1: 2, for example from 1:20 to 1: 5 and / or the proportion by weight of the at least one liquid composition to the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition is 0.01 to 25% by weight, in particular 0.1 to 20% by weight, preferably 1 to 18% by weight, very particularly preferably 3 to 15% by weight.
  • the washing or cleaning agent according to the invention preferably comprises at least one surfactant.
  • This surfactant is selected from the group of anionic, nonionic and cationic surfactants.
  • the washing or cleaning agent according to the invention can also contain mixtures of several surfactants selected from the same group.
  • both the at least one particulate phase and the at least one liquid composition each comprise at least one surfactant.
  • only the at least one particulate phase or only the at least one liquid composition comprise at least one surfactant.
  • the phases or preparations it is also possible for the phases or preparations to have different or the same surfactant or the same surfactants.
  • Particulate phases according to the invention and liquid compositions thus preferably comprise at least one surfactant, preferably at least one nonionic surfactant.
  • All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. These are specified in more detail below.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22 and preferably 12 to 18 C atoms and G is the symbol , which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • the washing or cleaning agents according to the invention in particular cleaning agents for automatic dishwashing, particularly preferably contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants which consist of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol, of ethylene oxide per mol of alcohol won, used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 alcohol preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Preferred surfactants come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex 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 found in the context of the present invention for the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block follows from the other groups.
  • R 1 is a straight-chain or branched, saturated or, or polyunsaturated, C 6-24 alkyl or alkenyl radical
  • each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and the indices w, x, y, z independently of one another represent integers from 1 to 6.
  • Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is generally unbranched, the linear radicals being from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues.
  • nonionic surfactants are preferred in which R 1 in the above formula for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 or R 3 are selected independently of one another from - CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are also suitable.
  • Nonionic surfactants of the above formula are preferably used, in which R 2 and R 3 for a radical —CH 3 , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.
  • nonionic surfactants are nonionic surfactants of the general formula R 1 O (AlkO) x M (OAlk) y OR 1 , where R 1 and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M represents an alkyl radical from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical with 1 are up to 18 carbon atoms.
  • Nonionic surfactants of the general formula are preferred R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y -CH 2 CH (OH) -R 2 , wherein R, R 1 and R 2 independently of one another are an alkyl radical or alkenyl radical having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.
  • R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 in which R represents a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms and n and m independently of one another have values from 20 to 30.
  • Corresponding compounds can be obtained, for example, by reacting HO-CHR-CH 2 -OH alkyldiols with ethylene oxide, followed by a reaction with an alkyl epoxide to block the free OH functions to form a dihydroxy ether.
  • nonionic surfactants with one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the cleaning agent preparations according to the invention can be significantly improved.
  • Those end group-capped poly (oxyalkylated) nonionic surfactants which, according to the following formula, are particularly preferred in addition to a radical R 1 , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where n stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60.
  • Particularly preferred are surfactants of the above formula in which R 1 is C 7 to C 13 , n is an integer from 16 to 28 and R 2 is C 8 to C 12 .
  • R 1 is a linear or branched aliphatic hydrocarbon radical with 4 up to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.
  • the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2 -hydroxydecylether.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, iso-propyl, n -Butyl, 2-butyl or 2-methyl-2-butyl, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the formula above can R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
  • 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 can be different if x> 2.
  • the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
  • the at least one particulate and / or the at least one gel phase and / or liquid preparation preferably contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, the weight fraction of the nonionic surfactant in the total weight of the gel phase preferably being 0.5% by weight .-% to 30 wt .-%, preferably 5 wt .-% to 25 wt .-% and in particular 10 wt .-% to 20 wt .-%.
  • the nonionic surfactant of the particulate and / or gel phase and / or liquid preparation is selected from nonionic surfactants of the general formula R 1 -O (CH 2 CH 2 O) ⁇ CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which R 1 and R 2 independently of one another are an alkyl radical or alkenyl radical having 4 to 22 carbon atoms; R 3 and R 4 independently of one another represent H or an alkyl or alkenyl radical having 1 to 18 carbon atoms and x and y independently of one another values between 1 and 40.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 in which R 3 and R 4 are H and the indices x and y are preferred independently of one another assume values from 1 to 40, preferably from 1 to 15.
  • Particularly preferred are particularly compounds of the general formula R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which the radicals R 1 and R 2 independently of one another are saturated alkyl radicals with 4 to Represent 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.
  • Such compounds of the general formula are also preferred R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which one of the radicals R 1 and R 2 is branched.
  • Compounds of the general formula are very particularly preferred R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which the indices x and y independently assume values from 8 to 12.
  • the stated C chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical mean values which can be an integer or a fraction for a specific product. Because of the manufacturing processes, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers for the C chain lengths as well as for the degrees of ethoxylation or alkoxylation.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
  • the nonionic surfactant which is solid at room temperature, preferably has propylene oxide units (PO) in the molecule.
  • PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight, of the total molecular weight of the nonionic Identify surfactants.
  • nonionic surfactants with melting points above room temperature which are particularly preferably to be used in the particulate phase or liquid composition contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • the weight fraction of the nonionic surfactant in the total weight of the particulate phase is from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight ,
  • anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms.
  • anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms.
  • the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups.
  • Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
  • cationic and / or amphoteric surfactants such as betaines or quaternary ammonium compounds can also be used. However, it is preferred that no cationic and / or amphoteric surfactants are used.
  • the total amount of the at least one liquid composition comprising at least one nonionic surfactant to the total amount of the at least one particulate phase has a weight ratio of 1: 200 to 5: 1, in particular 1: 100 to 1: 1, preferably of 1:50 to 1: 2, for example from 1:20 to 1: 5 and / or the proportion by weight of the at least one liquid composition to the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition from 0.01 to 25% by weight. %, in particular 0.1 to 20% by weight, preferably 1 to 18% by weight, very particularly preferably 3 to 15% by weight.
  • the surfactant content of the at least one liquid composition is at least 50% by weight, in particular at least 70% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight, based on the total weight of the liquid composition.
  • These can be both liquid surfactants themselves and mixtures of liquid and / or solid surfactants with solvents, preferably organic solvents, in order to improve the incorporation of the surfactants.
  • the at least one liquid composition does not comprise a surfactant but a perfume preparation such that the total amount of the liquid composition relative to the total amount of the at least one particulate phase is from 1: 800 to 1:50, in particular from 1: 600 to 1: 100, preferably from 1: 500 to 1: 200, for example from 1: 400 to 1: 250 and / or the proportion by weight of the at least one liquid composition to the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition 0.001 is up to 2% by weight, in particular 0.005 to 1.0% by weight, preferably 0.1 to 0.8% by weight, very particularly preferably 0.15 to 0.5% by weight.
  • the washing or cleaning agent according to the invention comprises, in addition to the at least one particulate phase and the at least one liquid composition, at least one further gel phase.
  • a gel-like phase hereinafter also referred to as gel phase, is to be understood as a composition / phase which has an internally structuring network.
  • This internally structuring (spatial) network is formed by the dispersion of a solid but distributed substance with long or highly branched particles and / or gel-forming agent in at least one liquid (the at least one liquid is liquid at 20 ° C.).
  • Such gel phases are thermoreversible.
  • This gel phase can be, for example, flowable or dimensionally stable. According to the invention, however, the gel phase is preferably dimensionally stable at room temperature.
  • the gel former preferably xanthan, gelatin or polyvinyl alcohol and / or its derivatives
  • a solvent preferably an organic solvent, preferably one or more polyhydric alcohol (s).
  • s polyhydric alcohol
  • a gel phase is obtained which remains in the specified form, i.e. is dimensionally stable.
  • the solidification time is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes or less.
  • the at least one gel phase yields under pressure, but does not deform as a result, but rather returns to the initial state after the pressure has dropped.
  • the at least one gel phase is preferably elastic, in particular linear-elastic.
  • the at least one gel phase is preferably a shaped body.
  • a molded body is a single body that stabilizes itself in its impressed shape.
  • This dimensionally stable body is formed from a molding compound (for example a composition) by specifically bringing this molding compound into a predetermined shape, for example by pouring a liquid composition into it a casting mold and then curing the liquid composition, for example as part of a sol-gel process.
  • solidification time means the period of time during which the at least one gel phase changes from a flowable state to a dimensionally stable state which is not flowable at room temperature.
  • Room temperature is understood to be a temperature of 20 ° C.
  • the at least one gel phase is preferably a solid gel phase. It is cut-resistant. For example, it can be cut with a knife after solidification without being further destroyed apart from the cut performed.
  • the gel phase must be stable in storage, and that under normal storage conditions.
  • the gel phase according to the invention is part of a cleaning agent. Cleaning agents are usually stored in a household for a certain period of time. Storage is usually near the washing machine or dishwasher.
  • the gel phase should be stable for such storage.
  • the gel phase should in particular also be stable after a storage time of, for example, 4 to 12 weeks, in particular 10 to 12 weeks or longer at a temperature of up to 40 ° C., in particular at 30 ° C., in particular at 25 ° C. or at 20 ° C. be and do not deform or otherwise change their consistency during this time.
  • the gel phase and a solid phase, in particular a powder phase are in direct contact with one another, the gel phase penetrates into the interstices of the immediately underlying powder phase in the storage period of 4 weeks at 25 ° C., preferably at most 1 mm.
  • a disadvantage would be a change in volume or shrinkage during storage, as this would result in low consumer acceptance of the product. Leakage of liquid or exudation of components from the gel phase is also undesirable. Here, too, the visual impression is relevant.
  • the stability of the gel phase can be influenced by the escape of liquid, such as, for example, solvents, so that the constituents are no longer contained in a stable manner and the washing or cleaning action can also be influenced thereby.
  • the at least one gel phase is preferably low in water. This has the advantage that the small amounts of water in combination with PVOH can have a structure or gel-forming effect. According to a preferred embodiment, the at least one gel phase is essentially water-free.
  • cleaning agents preferably dishwashing detergents, in particular machine dishwashing detergents, contain at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, in an amount of 0.05 to 3% by weight, in particular 0.1 to 2.4% .-%, very particularly preferably from 0.2 to 1.0 wt .-%, based on the total weight of the gel phase.
  • the cleaning agents according to the invention preferably dishwashing agents, in particular machine dishwashing agents, contain a gel former in the gel phase (gel phase), preferably selected from gelatin, xanthan and / or polyvinyl alcohol, in particular gelatin or polyvinyl alcohol, particularly preferably polyvinyl alcohol, in an amount of 4 up to 40, in particular from 6 to 30% by weight, particularly preferably in an amount of 7 to 24% by weight, very particularly preferably 8 to 22% by weight, in particular for example 14 to 20% by weight, in each case based on the total weight of the gel phase.
  • a gel former in the gel phase gel phase
  • gel phase preferably selected from gelatin, xanthan and / or polyvinyl alcohol, in particular gelatin or polyvinyl alcohol, particularly preferably polyvinyl alcohol, in an amount of 4 up to 40, in particular from 6 to 30% by weight, particularly preferably in an amount of 7 to 24% by weight, very particularly preferably 8 to 22% by weight, in particular for example 14 to 20% by weight, in
  • the at least one gel phase particularly preferably comprises PVOH (polyvinyl alcohol) and / or their derivatives.
  • PVOH polyvinyl alcohol
  • Polyvinyl alcohols are thermoplastic materials that are usually produced as white to yellowish powder by hydrolysis of polyvinyl acetate.
  • Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents.
  • Polyvinyl alcohols with a molecular weight of 30,000 to 60,000 g / mol are preferred.
  • preferred PVOH derivatives are copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers.
  • Suitable anionic monomers are preferably vinyl acetic acid, alkyl acrylates, maleic acid and their derivatives, in particular monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, fumaric acid and their derivatives, in particular monoalkyl fumarate (in particular monomethyl fumarate), dialkyl fumarate (especially fumarate), dialkyl fumarate itaconic acid and its derivatives, especially monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and derivatives thereof, Monoalkylcitraconklare (especially Methylcitraconat) Dialkylcitraconklare (Dimethylcitraconat), citraconic acid, mesaconic acid (methylfumaric) and their derivatives, Monoalkylmesaconat, Dialkylmesaconat, mesaconic
  • Particularly preferred derivatives of PVOH are those which are selected from copolymers of polyvinyl alcohol with a monomer, in particular selected from the group of the monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, and their combinations, and the alkali metal salts or esters of the above mentioned monomers.
  • a monomer in particular selected from the group of the monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, and their combinations, and the alkali metal salts or esters of the above mentioned monomers.
  • the values given for polyvinyl alcohols themselves apply to the suitable molar masses.
  • the at least one gel phase comprises a polyvinyl alcohol and / or its derivatives, preferably polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 Mol% and especially 82 to 88 mol%.
  • polyvinyl alcohols which are white-yellowish powders or granules with degrees of polymerization in the range from about 100 to 2500 (molar masses from about 4000 to 100,000 g / mol) and degrees of hydrolysis from 80 to 99 mol%, preferably from 85 to 90 mol %, in particular from 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.
  • PVOH powders with the properties mentioned above, which are suitable for use in the at least one gel phase, are marketed, for example, under the name Mowiol® or Poval® by Kuraray. Suitable is e.g. also Exceval® AQ4104 from Kuraray. Mowiol C30, the Poval® qualities, in particular the qualities 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, very particularly preferably Poval 4-88 S2, and Mowiol® 4- are particularly suitable. 88 from Kuraray.
  • the water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water.
  • the reaction products of polyvinyl alcohol and starch are to be used extremely advantageously.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to the desired values.
  • At least one gel phase is therefore particularly preferred which, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, has PVOH and at least one polyhydric alcohol.
  • the at least one gel phase particularly preferably has PVOH and at least one polyhydric alcohol.
  • the at least one gel phase comprises at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, PVOH and / or its derivatives in a proportion of approximately 4% by weight to 40% by weight, in particular 6% by weight. % to 30% by weight, preferably from 7 to 24% by weight, particularly preferably between 8% by weight to 22% by weight.
  • Significantly lower proportions of PVOH do not lead to the formation of a stable gel phase.
  • the values are based on the total weight of the gel phase.
  • the at least one gel phase comprises PVOH (polyvinyl alcohol).
  • the gel phases thus produced are particularly high-melting, dimensionally stable (even at 40 ° C.) and do not change their shape, or only insignificantly, even during storage. In particular, they are also not very reactive with regard to a direct negative interaction with constituents of the granular mixture, in particular the powder phase.
  • PVOH can also generate water-free or water-free gel phases without difficulty.
  • low-viscosity melts result at 110-120 ° C., which can be processed particularly easily as a result, in particular the gel phase can be poured into the water-soluble coating quickly and accurately without any Gluing takes place or the amount is metered inaccurately. Furthermore, these gel phases adhere particularly well to the water-soluble coating, especially if it is also made from PVOH. This is also visually advantageous.
  • the rapid solidification of the at least one gel phase with PVOH means that the gel phases can be further processed particularly quickly.
  • the good solubility of the gel phases produced is particularly favorable for the overall solubility of the cleaning agent.
  • gel phases with such short solidification times are advantageous so that the at least one solid phase metered thereon, comprising granular mixtures, in particular powder, does not sink into the gel which has not yet solidified or is too soft. This leads to less appealing detergent portions.
  • the at least one gel phase is dimensionally stable so that as few interactions as possible can take place between the solid and the gel phase. If the at least one gel phase also includes gelatin in addition to PVOH, the toughness of the gel phase is increased during production.
  • the present invention furthermore relates to cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, which in the gel phase are at least one organic solvent, in particular selected from 1,2-propanediol, 1,3-propanediol, glycerol, 1,1,1 -Trimethylolpropane, triethylene glycol, dipropylene glycol, polyethylene glycols and / or mixtures thereof.
  • cleaning agents preferably dishwashing agents, in particular machine dishwashing agents, which in the gel phase are at least one organic solvent, in particular selected from 1,2-propanediol, 1,3-propanediol, glycerol, 1,1,1 -Trimethylolpropane, triethylene glycol, dipropylene glycol, polyethylene glycols and / or mixtures thereof.
  • the at least one gel phase preferably comprises at least one polyhydric alcohol.
  • the at least one polyhydric alcohol also enables the production of a dimensionally stable, non-flowable gel phase within a short setting time, within 15 minutes or less, in particular 10 minutes or less.
  • Polyhydric alcohols in the context of the present invention are hydrocarbons in which two, three or more hydrogen atoms have been replaced by OH groups. The OH groups are bound to different carbon atoms. A carbon atom does not have two OH groups. This is in contrast to (simple) alcohols, in which only one hydrogen atom in hydrocarbons is replaced by one OH group.
  • Polyhydric alcohols with two OH groups are referred to as alkane diols, polyhydric alcohols with three OH groups as alkane triols.
  • a polyhydric alcohol thus corresponds to the general formula [KW] (OH) x , where KW is a hydrocarbon which is linear or branched, saturated or unsaturated, substituted or unsubstituted. Substitution can take place, for example, with SH or NH groups.
  • KW is preferably a linear or branched, saturated or unsaturated, unsubstituted hydrocarbon. KW comprises at least two carbon atoms.
  • KW particularly preferably comprises 2 to 10, that is to say 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.
  • the at least one gel phase particularly preferably comprises at least one alkanetriol and / or at least one alkanediol, in particular at least one C 3 to C 10 alkanetriol and / or at least one C 3 to C 10 alkanediol, preferably at least one C 3 to C 8 alkanetriol and / or at least one C 3 to C 8 alkanediol, especially at least one C 3 to C 6 alkanediol and / or at least one C 3 to C 5 alkanediol as polyhydric alcohol. It preferably comprises an alkanetriol and an alkanediol as at least one polyhydric alcohol.
  • the at least gel phase therefore comprises at least one polymer, in particular PVOH or PVOH with gelatin, and at least one alkanediol and at least one alkanetriol, in particular an alkanetriol and an alkanediol.
  • a gel phase comprising at least one polymer, PVOH or PVOH with gelatin, as well as a C 3 to C 8 alkanediol and a C 3 to C 8 alkanetriol.
  • a gel phase is further preferred which comprises at least one polymer, in particular PVOH or PVOH with gelatin, and also a C 3 to C 5 alkanediol and a C 3 to C 6 alkanetriol.
  • the polyhydric alcohols do not include any derivatives such as ethers, esters, etc.
  • the at least one organic solvent in the gel phase is present in amounts of 30 to 90% by weight, in particular 40 to 85% by weight, particularly preferably of 50 to 80 wt .-%, based on the total weight of the gel phase.
  • the amount of polyhydric alcohol or polyhydric alcohols used in gel phases according to the invention is preferably at least 45% by weight, in particular 55% by weight or more.
  • Preferred quantitative ranges are from 45% by weight to 85% by weight, in particular from 50% by weight to 80% by weight, based on the total weight of the gel phase.
  • the C 3 -C 6 alkanetriol is preferably glycerol and / or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (also called 1,1,1-trimethylolpropane) and / or 2-amino-2- (hydroxymethyl) -1,3-propanediol (TRIS, trishydroxymethylaminoethane) and / or 1,3,5-pentanetriol.
  • the C 3 - to C 6 -alkanetriol glycerol and / or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (also called 1,1,1-trimethylolpropane) is particularly preferred.
  • the C 3 - to C 5 -alkanediol is, for example, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,3-propanediol and / or 1,2-propanediol, preferably 1, 3-propanediol and / or 1,2-propanediol.
  • the chain length of the diol and in particular the position of the OH groups have an influence on the transparency of the gel phase.
  • the OH groups of the diol are therefore preferably not arranged on immediately adjacent C atoms. In particular, there are three or four carbon atoms, in particular 3 carbon atoms, between the two OH groups of the diol.
  • the diol 1,3-propanediol is particularly preferred. Surprisingly, it has been shown that particularly good results are achieved with mixtures which comprise glycerol and 1,3-propanediol and / or 1,2-propanediol.
  • polyethylene glycol (s) with an average molar mass of 200 to 600 g / mol are preferably additionally used in the at least one gel phase or the gel phases.
  • polyethylene glycols with an average molecular weight between about 200 and about 600 g / mol, preferably between 300 and 500 g / mol, particularly preferably between 350 and 450 g / mol, for example around 400 g / mol INCI: PEG400) used.
  • Detergent portions according to the invention are thus characterized in that they have polyethylene glycol (s) with an average molecular weight of 300 to 500 g / mol, in particular of 350 to 450 g / mol.
  • the at least one gel phase or the gel phases each based on the total weight of the gel phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, (preferably in amounts of 0.1 to 2 , 4 wt .-%, particularly preferably from 0.2 to 1.0 wt .-%), polyvinyl alcohol and at least one polyhydric alcohol, optionally additionally polyethylene glycols with an average molecular weight of about 200 to 600 g / mol in amounts of 5 to Contain 30% by weight, preferably from 8 to 26% by weight, in particular from 10 to 22% by weight, based on the total weight of the at least one gel phase.
  • at least one water-soluble zinc salt in particular zinc sulfate and / or zinc acetate, in particular zinc acetate
  • polyvinyl alcohol and at least one polyhydric alcohol optionally additionally polyethylene glycols with an average molecular weight of about 200 to 600 g /
  • polyethylene glycol (s) with an average molecular weight of 200 to 600 g / mol in combination with polyvinyl alcohol and / or its derivatives makes a decisive contribution to reducing the setting times.
  • polyethylene glycols in particular those with a molecular weight of 350 to 450 g / mol, in particular by 400 g / mol, increase the sol-gel temperature.
  • the amount of polyethylene glycol (s) with an average molecular weight of 350 to 450 g / mol, for example around 400 g / mol, is 10 to 22% by weight, based on the total weight of the gel phase.
  • a particularly preferred gel phase therefore comprises at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (for example zinc acetate anhydrate), PVOH, polyethylene glycol (s) with an average molecular weight of 200 to 600 g / mol and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols.
  • a non-flowable consistency that is stable at room temperature can be achieved, which remains dimensionally stable even after a long storage period.
  • a corresponding phase is also transparent and has a glossy surface.
  • a particularly preferred gel phase therefore comprises gelatin or PVOH as a polymer and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols.
  • the gel phase in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably of 0.2 to 1.0% by weight) of an alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, the proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based on the total weight of the gel phase , between 3 and 75% by weight, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.
  • an alkanetriol in particular glycerol or 1,1,1-trimethylolpropane
  • the proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane based on the total weight of the gel phase , between 3 and 75% by weight, preferably 5% by weight to 70% by weight
  • the total proportion of alkanetriol (s), based on the total weight of the gel phase is between 3 and 75% by weight, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.
  • the proportion of glycerol based on the total weight of the gel phase is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20 % By weight to 40% by weight.
  • the proportion of 1,1,1-trimethylolpropane, based on the total weight of the gel phase is preferably 5% by weight to 70% by weight, in particular 10% by weight. % to 65% by weight, particularly preferably 18 to 45% by weight, particularly preferably 20% by weight to 40% by weight.
  • the proportion of 2-amino-2-hydroxymethyl-1,3-propanediol, based on the total weight of the gel phase is preferably 5% by weight. % to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.
  • the proportion of alkanediols, based on the total weight of the gel phase is preferably 5% by weight to 70% by weight, in particular 7% by weight to 65% by weight, particularly 10 wt% to 40 wt%.
  • the gel phase in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably of 0.2 up to 1.0% by weight) of at least one alkanediol, in particular 1,3-propanediol or 1,2-propanediol, the proportion of alkanediol, in particular 1,3-propanediol or 1,2-propanediol, based on the total weight the gel phase, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 45% by weight.
  • at least one water-soluble zinc salt in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably of 0.2 up to 1.0% by weight) of at least one alkanediol, in particular 1,3-propane
  • the proportion of 1,3-propanediol, based on the total weight of the gel phase is in particular 10% by weight to 65% by weight, particularly 20% by weight to 45 wt .-%.
  • water-soluble zinc salt in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably from 0.2 to 1.0% by weight) 20 to 45% by weight of 1,3-propanediol and / or 1, 2-propanediol and 10 wt .-% to 65
  • a gel phase containing 20 to 45% by weight of 1,3 propanediol and / or 1,2-propanediol and 10% by weight to 65% by weight of 1,1,1-trimethylolpropane, based in each case on the Total weight of the gel phase.
  • a gel phase which contains 20 to 45% by weight of 1,3 propanediol and / or 1,2-propanediol and 10% by weight to 65% by weight of glycerol, in each case based on the total weight of the gel phase, is particularly preferred. It has been shown that a rapid solidification at 20 ° C. of a gel phase is possible in these areas, the phases obtained are stable in storage and transparent. The proportion of glycerine in particular has an effect on the curing time.
  • the at least one gel phase according to the invention based on the total weight of the gel phase, has at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably of 0 , 2 to 1.0% by weight) of a C 3 to C 6 alkanetriol and a C 3 to C 5 alkanediol, their weight ratio is preferably 3: 1 to 1: 2.
  • the weight ratio is from 2: 1 to 1: 1.5, preferably from 1.5: 1 to 1: 1.2, preferably from 1.3 to 1: 1 if glycerol and 1,3-propanediol are polyhydric alcohols are included.
  • triethylene glycol in addition to the alkanols mentioned above, triethylene glycol can be present in the at least one gel phase, in particular the gel phases described above as preferred, in particular if this phase is PVOH and, if appropriate, polyethylene glycols with an average molecular weight of 200 to 600 g / mol contains.
  • Triethylene glycol advantageously accelerates the solidification of the gel phase (s). It also results in the resulting gel phase, if at all, only slightly, unobservably, exchanging liquid with the environment. In particular, this improves the visual impression of the resulting detergent portions.
  • the at least one gel phase based in each case on the total weight of the gel phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight , particularly preferably from 0.2 to 1.0% by weight) 1,3- and / or 1,2-propanediol, particularly preferably 1 to 3.5% by weight 1,3-propanediol, and glycerol between 0 , 1 and 20% by weight, preferably between 1 and 15 % By weight, in particular between 5 and 12% by weight, for example 8 to 11% by weight of triethylene glycol
  • the washing or cleaning agent according to the invention in particular at least the at least one gel phase, preferably both the particulate phase and the gel phase, comprises a further anionic polymer, in particular polycarboxylates.
  • a further anionic polymer in particular polycarboxylates.
  • the at least one gel phase can further comprise anionic polymers or copolymers with builder properties. It is preferably a polycarboxylate.
  • a copolymeric polyacrylate, preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate is preferably used as the polycarboxylate.
  • copolymers can have two, three, four or more different monomer units.
  • preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.
  • the low-water gel phase contains a polymer comprising at least one monomer containing sulfonic acid groups.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids can also be used.
  • H 2 C CH-X-SO 3 H
  • R 6 and R 7 are selected independently of one another from -H, -CH 3 , -CH 2 CH 3 , - CH 2 CH 2 CH 3 and -CH (CH 3 ) 2
  • the gel phase contains a polymer comprising, as the monomer containing sulfonic acid groups, acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
  • the sulfonic acid groups in the polymers can be wholly or partly in neutralized form, that is to say that the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • metal ions preferably alkali metal ions and in particular by sodium ions.
  • the use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in each case in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from the aforementioned.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 g-mol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers in addition to the monomer containing carboxyl groups and monomer containing sulfonic acid groups, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C 22
  • the gel phase therefore preferably comprises PVOH, polyethylene glycol (s) with an average molecular weight of 200 to 600 g / mol, at least one polyhydric alcohol and an anionic copolymer / polymer.
  • the proportion of the anionic polymer is preferably 1% by weight to 35% by weight, in particular 3% by weight to 30% by weight, particularly 4% by weight to 25% by weight, preferably 5% by weight. % to 20 wt .-%, for example 10 wt .-% based on the total weight of the gel phase.
  • monomer (s) containing sulfonic acid groups contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in particular in the sulfopolymers mentioned with AMPS as the monomer containing sulfonic acid groups, for
  • the at least one gel phase therefore comprises PVOH and a sulfopolymer, in particular the preferred copolymeric polysulfonates which, in addition to monomer (s) containing sulfonic acid groups, contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, and at least one polyvalent one Alcohol.
  • polyethylene glycols mentioned with an average molecular weight of 200 to 600 g / mol in addition to the polyethylene glycols mentioned with an average molecular weight of 200 to 600 g / mol, further polyalkylene glycols, in particular further polyethylene glycols with an average molecular weight between about 800 and 8000, can be contained in the at least one gel phase.
  • the above-mentioned polyethylene glycols are particularly preferably used in amounts of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 15 to 25, preferably in each case based on the total weight of the gel phase ,
  • Very particularly preferred embodiments of the present invention comprise as at least one gel phase, based in each case on the total weight of the gel phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.2 to 1.0% by weight).
  • at least one water-soluble zinc salt in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.2 to 1.0% by weight).
  • the zinc salts in particular zinc sulfate and / or zinc acetate, especially zinc acetate (for example in the anhydrous form of the salt) into water-poor gel phases which contain polymers containing carboxylate and / or sulfonic acid groups
  • the amount of Zinc salt in the anhydrous gel phase of 0.2 to 1.0 wt .-%, for example 0.5 wt .-% is selected.
  • the washing or cleaning agents according to the invention comprise at least one further ingredient selected from the group consisting of builders, polymers, bleaching agents, bleach activators, bleaching catalysts, enzymes, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, Dyes, additives to improve drainage and drying behavior, disintegration aids, preservatives, pH regulators, fragrances and perfume carriers.
  • builder substances such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builder substances, can be advantageous.
  • the use of phosphates is largely or completely dispensed with.
  • the agent preferably contains less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s).
  • the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate (s).
  • the builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates.
  • the weight fraction of the total builders in the total weight of agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.
  • Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule.
  • Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, Tri- and tetracarboxylic acids.
  • the polycarboxylic acids can also carry further functional groups, such as hydroxyl or amino groups.
  • aminocarboxylic acids in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as nitrutinotronic acid, for example nitrontractic acids, such as nitrinotronic acid, for example (nitraminotriestric acid), such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid -diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid
  • polymeric polycarboxylates organic polymers with a large number of (in particular greater than ten) carboxylate functions in the macromolecule
  • polyaspartates organic polymers with a large number of (in particular greater than ten) carboxylate functions in the macromolecule
  • polyacetals polyacetals and dextrins.
  • the free acids typically also have the property of an acidifying component.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • washing or cleaning agents according to the invention in particular dishwashing agents, preferably machine dishwashing agents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, particularly 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to Contain 20 wt .-%, each based on the total weight of the agent.
  • washing or cleaning agents according to the invention are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the weight fraction of these builders based on the total weight of the cleaning agent according to the invention, preferably 5 to 70 wt .-%, preferably 15 to 60 wt .-% and in particular 20 to 50 wt .-%.
  • the combination of two or more builders from the group mentioned above has been found to be particularly suitable for the cleaning and rinsing performance of detergents or cleaning agents according to the invention
  • Dishwashing detergents preferably automatic dishwashing detergents, have proven to be advantageous.
  • one or more other builders may also be included.
  • Preferred washing or cleaning agents are characterized by a combination of builders of citrate and carbonate and / or hydrogen carbonate.
  • a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular 10 to 35% by weight, very particularly preferably 15 to 30% by weight and the amount of citrate is preferably from 5 to 35% by weight, in particular 10 to 25% by weight, very particularly preferably 15 to 20% by weight, in each case based on the total amount of the cleaning agent, the total amount of these two Builders are preferably 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight.
  • one or more other builders can also be included.
  • the washing or cleaning agents according to the invention can contain, in particular, phosphonates as further builders.
  • a hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates in agents according to the invention are preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight, in each case based on the total weight of the agent.
  • citrate, (hydrogen) carbonate and phosphonate are particularly preferred. These can be used in the amounts mentioned above. In particular, in this combination, amounts of 10 to 25% by weight citrate, 10 to 30% by weight carbonate (or bicarbonate), and 2.5 to 7.5% by weight, based in each case on the total weight of the composition. Phosphonate used.
  • washing or cleaning agents in particular dishwashing agents, preferably machine dishwashing agents, are characterized in that, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, they contain at least one further phosphorus-free builder.
  • this is selected from the aminocarboxylic acids, the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic diacetate (ASDA), Hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic diacetate
  • HEIDA Hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • EDDS ethylenediamine disuccinate
  • a particularly preferred combination is,
  • the percentage by weight of the further phosphorus-free builder, in particular the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight.
  • the use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules that contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder are advantageous.
  • the combination of at least three, in particular at least four builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents. It can also contain other builders.
  • Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1100 to 10000 g / mol, and particularly preferably from 1200 to 5000 g / mol, can in turn be preferred from this group.
  • the content of (homo) polymeric polycarboxylates in the washing or cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight. %.
  • Detergents or cleaning agents according to the invention can also contain crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.
  • washing or cleaning agents in particular dishwashing agents, preferably machine dishwashing agents, the content of silicates, based on the total weight of the washing or cleaning agent, limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • the washing or cleaning agents according to the invention can furthermore contain alkali metal hydroxides.
  • alkali carriers are particularly preferred in the washing or cleaning agents and in particular in the at least one gel phase only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight preferably between 0.1 and 5% by weight and in particular between 0.5 and 5% by weight, in each case based on the total weight of the washing or cleaning agent.
  • Alternative washing or cleaning agents according to the invention are free of alkali metal hydroxides.
  • Cleaning agents according to the invention preferably contain enzyme (s) in the at least one particulate and / or the at least one gel phase.
  • enzyme include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures.
  • these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred.
  • Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 % by weight to 5% by weight, based on active protein.
  • the protein concentration can be determined using known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • 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 and the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors.
  • suitable precursors include, for example, those originally from Humicola lanuginosa (Thermomyces lanuginosus) available or further developed lipases, especially those with the amino acid exchange in positions D96LT213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenol oxidases) can be used according to the invention.
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.
  • a protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • damage such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Detergents can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.
  • Proteases and amylases that are active in cleaning are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers or other auxiliaries.
  • the enzymes for the at least one particulate and / or the at least one gel-like phase can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes solidify as in a solidified one Gels are included or in those of the core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in layers.
  • Capsules of this type are known per se Methods, for example applied by shaking or roll granulation or in fluid bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein.
  • Particularly preferred are cleaning agents which, based on their total weight, 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of the respective enzyme preparations contain.
  • the at least one particulate and / or the at least one gel phase of the washing or cleaning agent according to the invention can contain further ingredients.
  • these include, for example, anionic, cationic and / or amphoteric surfactants, bleaching agents, bleach activators, bleaching catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protection agents, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (in particular in the at least one particulate phase), additives to improve the runoff and drying behavior, to adjust the viscosity, to stabilize, UV stabilizers, pearlescent agents, preservatives, antimicrobial agents (disinfectants), pH adjusting agents in amounts of usually not more than 5% by weight.
  • Agents according to the invention preferably contain at least one alkanolamine as a further solvent.
  • the alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the alkanolamine is preferably present in agents according to the invention in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight.
  • the at least one gel phase is free from alkanolamine and the alkanolamine is only present in the at least one particulate phase.
  • detergents or cleaning agents according to the invention contain at least one zinc salt as a glass corrosion inhibitor as a further constituent.
  • the zinc salt can be an inorganic or organic zinc salt.
  • the zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature).
  • the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt in cleaning agents according to the invention is preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1 wt .-% to 2 wt .-%, based on the total weight of the detergent.
  • polyethyleneimines as are available, for example, under the name Lupasol® (BASF)
  • BASF can preferably be used in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight. -%, are used as glass corrosion inhibitors.
  • Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (for example Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example Sokalan® CP 10 from BASF, Ludwigshafen (Germany )), modified polycarboxylate Na salt (for example Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-7608 from BASF, Ludwigshafen (Germany)) and polyether siloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide segments (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren® 5840, Tegopre
  • Builder substances suitable as additives are, in particular, polyaspartic acid sodium salt, ethylenediamine triacetate coconut alkylacetamide (for example Rewopol® CHT 12 from Evonik, Essen (Germany)), methylglycinediacetic acid tri-sodium salt and acetophosphonic acid.
  • Mixtures with surfactant or polymeric additives show synergisms in the case of Tegopren® 5843 and Tegopren® 5863.
  • the use of Tegoprene types 5843 and 5863 is, however, less preferred when used on hard surfaces made of glass, in particular glass dishes, since these can pull silicone surfactants onto glass.
  • the additives mentioned are dispensed with.
  • a preferred washing or cleaning agent in particular dishwashing agent, preferably further comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleaching catalyst. Where available, these are only contained in the at least one particulate phase.
  • cleaning agents according to the invention contain an oxygen bleaching agent from the group sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • Bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Sodium percarbonate is particularly preferred for its good bleaching performance.
  • a particularly preferred oxygen bleach is sodium percarbonate.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which carry 0- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multi-acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven to be particularly suitable.
  • TAED tetraacetylethylenediamine
  • the bleaching catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe-Cu and Ru-amine complexes can also be used as bleaching catalysts.
  • Complexes of manganese are used with particular preference in oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S.
  • Ligands which have nitrogen donor functions are preferably used.
  • bleaching catalyst (s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN) contain.
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • Suitable manganese complexes are, for example, [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 2 ( ⁇ -OAc) 1 (TACN ) 2 ] (BPh 4 ) 2 , [Mn IV 4 ( ⁇ -O) 6 (TACN) 4 ] (ClO 4 ) 4 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN ) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn IV 2 ( ⁇ -O) 3 ( Me-TACN) 2 ] (PF 6 ) 2 and [Mn IV 2 ( ⁇ -O) 3 (Me / Me-TACN) 2 ] (PF 6 ) 2 (with OAc
  • the washing or cleaning agent according to the invention comprises at least one particulate phase and at least one gel phase.
  • the washing or cleaning agent can thus have one, two, three or more different particulate phases; it can also have one, two, three or more different gel-like phases.
  • the washing or cleaning agent according to the invention preferably comprises a particulate phase and a gel phase.
  • the washing or cleaning agent particularly preferably comprises two particulate phases and a gel phase. It preferably comprises two particulate phases and two gel-like phases. Also preferred is an embodiment in which the washing or cleaning agent comprises three particulate phases and one or two gel-like phases.
  • the weight ratio of the total of the at least one particulate phase to the total of the at least one gel phase is generally 40: 1 to 2: 1, in particular 20: 1 to 4: 1, preferably 12: 1 to 6: 1, for example 10: 1 to 8: 1.
  • the total weight of all phases in a detergent portion can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 14 to 16 g per detergent or detergent portion. In this weight ratio there is a good concentration of the respective ingredients of the particulate or gel phase in one cleaning process.
  • the at least one particulate phase and the at least one gel-shaped phase adjoin one another over the full or partial area. It is preferred that the two phases directly adjoin one another.
  • the stability is important in addition to the shortest possible solidification time of the at least one gel-like phase.
  • Stability here means that constituents contained in the gel-like phase do not pass into the at least one particulate phase but, even after prolonged storage, the at least one particulate phase and the gel-like phase are optically separate from one another and do not interact with one another, such as, for example, liquid diffusion Components from one phase to the other or reaction of components from one phase with those in the other phase.
  • the washing or cleaning agents according to the invention are characterized in that the at least one gel phase is less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight Anionic surfactant, each based on the total weight of the gel phase comprises phase.
  • the at least one gel phase is preferably essentially free of anionic surfactants. Essentially free means that the at least one gel phase contains less than 0.05% by weight of anionic surfactant, based in each case on the total weight of the phase gel.
  • anionic surfactant adversely affect curing.
  • the agent according to the invention in particular the at least one gel phase, can also have sugar.
  • sugars include sugar alcohols, monosaccharides, disaccharides and oligosaccharides.
  • the at least one gel phase comprises at least one sugar alcohol, preferably mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol and xylitol.
  • Xylitol is particularly preferred.
  • the agent according to the invention in particular the at least one gel phase, may comprise disaccharides, in particular sucrose.
  • the proportion of sucrose is 0% by weight to 30% by weight, in particular 5% by weight to 25% by weight, particularly preferably 10% by weight to 20% by weight, based on the weight of the gel Phase.
  • the sugar does not dissolve completely in the gel phase and leads to a clouding of the same.
  • the use of sugar in particular in a proportion of 10% by weight to 5 to 15% by weight, reduces the development of moisture and thus improves the adhesion to the at least one particulate phase.
  • the detergent or cleaning agent portion according to the invention preferably comprises a washing or cleaning agent according to the invention in a water-soluble envelope.
  • the water-soluble covering is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures.
  • the sheath can be formed from one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, can be the same or different.
  • the water-soluble envelope contain polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water soluble wrappings that are made of polyvinyl alcohol or a Containing polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, in particular cold water solubility.
  • Suitable water-soluble films for producing the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and is in particular from 40,000 to 80,000 gmol -1 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct route of synthesis is not possible. The same applies to polyvinyl alcohol copolymers which are produced from polyvinyl acetate copolymers accordingly. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the water-soluble packaging consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight, of a polyvinyl alcohol, the Degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer material containing polyvinyl alcohol suitable for producing the water-soluble covering can additionally be a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added.
  • a preferred additional polymer is polylactic acid.
  • preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred. Also preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof.
  • the film material contains further additives.
  • the film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol or mixtures thereof.
  • Further Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble wrappings of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the designation M8720, M8630, M8312, M8440, M7062, C8400 or M8900. Also suitable are films which are marketed by Nippon Gohsei under the names SH2601, SH2504, SH2707 or SH2701. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the outer surface of the water-soluble coating is at least partially coated with a bitter substance with a bitter value between 1,000 and 200,000.
  • the water-soluble coating is coated with at least 50%, preferably at least 75% and very particularly preferably at least 90% with the bitter substance with a bitter value between 1,000 and 200,000.
  • the bitter substance with a bitter value between 1,000 and 200,000 can be applied, for example, by means of printing, spraying or brushing.
  • the water-soluble covering has at least one continuously rotating sealing seam, which lies essentially in one plane.
  • This is favorable in terms of process technology, since only a single sealing step, if necessary using only a single sealing tool, is necessary for a circumferential sealing seam which lies essentially in one plane.
  • the continuous circumferential sealing seam leads to a better seal compared to such wrappings with several sealing seams and an excellent tightness of the sealing seam and thus the wrapping itself.
  • Product escaping from the wrapping, e.g. on the surface of the portion would be disadvantageous since the consumer would then come into contact with the product. This is exactly what should be avoided if possible with a portion of detergent or cleaning agent with a water-soluble coating.
  • the water-soluble envelope can preferably be produced from at least 2 packaging parts.
  • the at least two packaging parts are preferably water-soluble, so that no packaging parts remain in the dishwasher, which can then lead to problems in the dishwasher. It is not necessary that the at least two packaging parts are different. They can preferably be made from the same material and on be made the same way. In a preferred embodiment, these are two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.
  • the at least two packaging parts can be made of different materials, e.g. be made from different foils or from material with two different properties (e.g. warm and cold water soluble foil).
  • a water-soluble film and another packaging part, which was produced by injection molding, be combined be combined.
  • the water-soluble covering comprises at least one at least partially plastically deformed film.
  • this plastic deformation of the film can be produced by methods known to the person skilled in the art, such as deep drawing (with and without applying a vacuum), blow molding or stamping.
  • the water-soluble covering comprises at least one at least partially plastically deformed film, which was produced by deep drawing.
  • the at least one particulate phase and the at least one gel phase can be arranged in any combination with one another within the water-soluble coating.
  • a particulate phase can be arranged on or next to a gel phase.
  • the washing or cleaning agent according to the invention has a particulate phase and a gel phase.
  • a particulate phase is surrounded by gel-like phases. Embedding one phase in another is also included according to the invention.
  • the gel-like phase is in cast form, for example in the form of a gel core, which is surrounded by the particulate phase. There may also be 2 or more cavities separated from one another which are filled with the at least one gel phase.
  • the washing or cleaning agent comprises two gel-like phases, wherein the two gel-like phases can have different compositions.
  • Such detergents or cleaning agents preferably comprise 3, 4, 5 or 6 or more gel-like phases, it being possible for these gel-like phases to have the same or different compositions.
  • the detergent or cleaning agent portion according to the invention is characterized in that it contains a dishwashing agent, in particular a dishwashing agent for the automatic cleaning of dishes.
  • the mold comprises at least one trough (mold trough).
  • the shape can be provided, for example, as a single shape or as part of a series of shapes in the form of a treadmill, as is known from the treadmill method and from the drum method.
  • the shape includes an area on which the film can be placed, e.g. a sealing area that is typically defined around the opening of a mold cavity.
  • the mold trough can have different geometries, if edges are present, it is advantageous that they are rounded.
  • Rounded edges and / or dome-shaped troughs ensure that when the film is pulled into the trough, the film is pulled somewhat more homogeneously, and the film thickness remains uniform in this respect, and that no breakage or tear points are produced, which in turn leads to a more stable one Portion pack leads.
  • the mold contains at least one mold trough which has at least one web for dividing the bottom of the mold trough.
  • This forms one or more, preferably 2, 3, 4, 5 or 6 bulges or pockets in the shaped chamber, which optically produce a positive appearance.
  • this area is again clearly separated from the granular mixture, in particular the particulate phase, and produces a particularly good appearance .
  • the water-soluble film can be fed from a roll and guided onto the mold cavity.
  • the film is positioned and held on the mold.
  • the holding can take place through suction holes on the mold surface, which is not part of the mold cavity.
  • the film can also be held on the mold by mechanical means, such as clips.
  • the film can be held by a stamp that presses on the sealing area.
  • the speed of the film is adapted to the speed of the treadmill formed from the molds, so that the film is not unnecessarily pulled thinner by holding onto a running mold.
  • a chamber is formed in the mold cavity area by at least partially adapting the film to the mold cavity.
  • the adaptation is generated by an elastic and / or plastic deformation.
  • the film deformation preferably has a larger plastic than elastic component.
  • the deformation of the water-soluble film is e.g. generated by deep drawing or by means of suitable stamps.
  • a preferred variant is deep drawing, by the application of negative pressure (forming pressure) in the mold cavity, for this purpose the mold cavity preferably comprises small openings, preferably in the base area, which are connected to a vacuum pump in terms of air pressure by appropriate lines.
  • the open chamber is now filled.
  • filled means the filling of quantities of the particular particulate or gel phases or of the liquid compositions into the open chamber. It includes the fact that the open chamber is only partially filled by filling or filling with one of the compositions / phases. This leaves space in the open chamber for filling in further phases or compositions.
  • step d) optionally, but preferably, fills this or parts thereof with the at least one gel phase of the product. As soon as the at least one gel-like phase has solidified, possibly after an additional period of time which is necessary for the solidification, further product components can then be filled into the chamber. After a first gel phase in step d), one or more further gel phases can be filled in.
  • step e) can be filled in at least one particulate phase, the specifications and compositions of which have already been described in detail above.
  • the at least one particulate phase according to step e) is preferably a solid, comprising a granular mixture, in particular it is particulate, in particular particulate and free-flowing.
  • the open chamber which contains at least one gel-like and at least one particulate phase, is not completely filled with the gel-like phase (s).
  • the chamber can preferably be filled only partially, preferably only in the lower region or only in the region or just above the region of the bulges or pockets of the chamber formed by the optional web according to a) with the gel-like phase (s).
  • the deformed film is preferably kept in the trough during filling.
  • the negative pressure is only broken after the sealing.
  • the negative pressure after the formation of the chamber in relation to the forming pressure can have a lower strength (higher pressure), which only fulfills the holding function.
  • the sealing area remains free of product. For example, if the chamber is at least partially elastically deformed, this elastic deformation must not subside after filling and before sealing such that the product flows over and out of the open chamber and thus contaminates the sealing area.
  • the lid is positioned on the open chamber, so that the lid can be applied to the sealing area in the next step.
  • the position of the lid is generally determined relative to the position of the chamber. If the chamber moves with a movable shape in a treadmill, the lid must move equally so that the relative position to the chamber remains the same.
  • the lid is then placed on the open chamber, which is closed in this way.
  • the contact between the lid and the film in the sealing area thus closes the chamber.
  • a preferred embodiment of the seal is a material fusion between the film and the lid, for example by loosening the film before the lid is applied, or by melting the film and / or lid in the sealing area. Alternatively, the sealing is done by gluing or welding.
  • the positioning, application, and sealing can take place either in separate steps or simultaneously.
  • the mold can also comprise at least one second mold cavity, so that at least two open chambers are produced by process steps a) to d).
  • the at least two chambers are formed in the same plane.
  • the lid in method step h) is positioned over the at least two open chambers and the lid in method step i) is applied to at least both chambers to seal the portion pack at a sealing area. Because the at least two chamber with the same Lid connected, the chamber remain in a certain position to each other, contrary to the prior art, where adjacent chambers are connected by the web, which is formed by the thin films of the packaging. It is easily possible to design three, four, five or more chambers side by side, which are filled with a corresponding number of gel-shaped phases (with the same or different composition).
  • the lid is provided as part of a band by feeding / transferring a band comprising at least one lid.
  • the lid can be separated before positioning, after positioning but before application, during application, or after application to the chamber.
  • the cover When separating before positioning, the cover is preferably punched out.
  • the lid and film can also be separated at the same time as sealing.
  • the device that produces the sealing by melting consists of at least two parts, one is the shape itself and the other part is a counter-stamp which presses onto the shape from the cover side. It is preferred that in the sealing step the pressure exerted by the mold and further part during the sealing must be lower at the sealing area than the pressure exerted in the separating area.
  • the separation area surrounds the sealing area.
  • the lid and film are alternatively separated from the band, preferably in the same step, and thus the portion packs are separated.
  • Such detergents or cleaning agents preferably comprise 3, 4, 5 or 6 or more gel-like phases, it being possible for these gel-like phases to have the same or different compositions.
  • the chamber is filled with at least one liquid composition, preferably containing perfume preparations and / or surfactants, in particular nonionic surfactants, before or after step e).
  • the at least one liquid composition can be filled into the open chamber, which may contain the already solidified at least one gel phase before the particulate phase is filled.
  • Preferred methods include that in step d) after filling the open chamber with the at least one gel phase, the gel phase solidifies or solidifies.
  • the liquid composition is preferably applied to the gel-like and already solidified phase filled in according to step c), so that the composition does not mix with the gel-phase which has not yet solidified.
  • the at least one liquid composition in particular comprising perfume preparation and / or at least one surfactant, in particular nonionic surfactant, is thus brought into direct contact with the latter by the subsequent filling of the at least one particulate phase.
  • the composition can then impregnate or move into the particulate phase.
  • the at least one particulate phase is applied before the liquid composition (preferably onto the gel-like and already solidified phase filled in according to step c).
  • the at least one liquid phase is then at least partially applied to the surface of the particulate phase and is thus in direct contact with it.
  • the liquid composition can thus impregnate the particulate composition or move into it.
  • the result is an open chamber which contains more compact compositions of detergents or cleaning agents.
  • the particulate phase in the open chamber can also be compacted by applying pressure.
  • the open chamber in step f) can be filled with at least one further composition.
  • the further composition according to step f) can be at least one further liquid composition for further impregnation, and can also relate to at least one further particulate phase and / or at least one further gel-like phase, as already described above.
  • a solidifying composition can also be introduced in step f) (alternatively or additionally, such a solidifying composition can also be added after step c)).
  • Suitable solidifying compositions are, for example, compositions such as those in DE102015213938 A1 or DE102015213939 A1 are disclosed. Reference is hereby made in full to the disclosure contained therein.
  • Multi-chamber pouches which contain at least one chamber which comprises at least one particulate phase according to the invention and at least one liquid composition, in particular additionally at least one gel-like phase according to the invention, in direct contact with one another and moreover at least one further one can also be produced in accordance with the aforementioned production processes , for example, have two, three or more further separate chambers.
  • the at least one particulate phase comprising granular mixtures of a solid composition, in particular the at least one particulate phase
  • the at least one particulate phase is particulate and free-flowing, preferably as described above.
  • gel-like phases and particulate phases to be used in the processes according to the invention, the same applies to the detergent or cleaning agent portion mentioned above, to which reference is hereby explicitly made.
  • a particular suitability of the gel-like phases described above for the process mentioned is that the rapid solidification times of the gel-like phases, in particular the phases with PVOH, at least one polyhydric alcohol and polyethylene glycol with an average molar mass of 200 to 600 g / mol, the step of solidification Allow the gel-like phase (s) to be shortened considerably and possibly even made unnecessary, since such phases cool and solidify particularly quickly, without additional cooling, long production lines or longer standing or waiting times being necessary.
  • very particularly preferred embodiments of the present invention comprise, as at least one gel phase, 8 to 22% by weight of PVOH, 15 to 30% by weight of 1,3-propanediol, 30 to 40% by weight of glycerol, 5 to 15 % By weight sulfonic acid group-containing polyacrylate copolymer, 10-22% by weight polyethylene glycol (s) with an average molecular weight of 200-600 g / mol), and optionally zinc salts, data in% by weight based in each case on the total weight of the gel Phase.
  • the gel-like phase (s) can be clearly above or below the sealing seam level (first-mentioned method) or approximately at the level of the sealing seam level (last-mentioned method).
  • the present invention further relates to detergent or cleaning agent portions such as are obtainable by one of the processes described above.
  • the present application also relates to a method for cleaning hard surfaces, in particular dishes, in which the surface is processed in a manner known per se using a cleaning agent according to the invention.
  • the surface is brought into contact with the washing or cleaning agent according to the invention.
  • the cleaning is carried out in particular with a cleaning machine, preferably with a dishwasher.
  • Another object of the present invention is also the use of a cleaning agent for cleaning hard surfaces, especially dishes, especially in automatic dishwashers.
  • Another object of the invention is the use of a detergent portion for the mechanical cleaning of laundry or textiles.
  • machine dishwashing detergents are compositions which can be used to clean dirty dishes in an automatic dishwashing process.
  • the machine dishwashing detergents according to the invention thus differ, for example, from the machine rinse aids which are always used in combination with machine dishwashing agents and do not have their own cleaning action.
  • the washing or cleaning agent according to the invention comprises something in whole or in the at least one particulate phase or in the at least one gel phase or in the at least one liquid composition, then the washing or cleaning agents or the each phase can consist of it.
  • the washing or cleaning agent according to the invention is described in a non-limiting manner.
  • Cleaning agents according to the invention were produced which comprised a solid phase and a gel phase. Different geometries were realized. Cleaning agents were also produced which comprised two solid phases and one gel phase. Cleaning agents were also produced, which comprised a solid phase as well as 3, 4 and 5 gel phases (of the same or different composition). The following information relates to% by weight of active substance based on the total weight of the respective phase (unless stated otherwise). Table 1: The solid granular mixtures of a solid composition, in particular powdery and free-flowing phases, had the following preferred composition: Wt .-% Citrate, Na salt 15-20 Phosphonate (e.g. HEDP) 2.5-7.5 MGDA, Na salt 0-25 Disilicate, sodium salt 5-35 soda 10-25 Silver protection (e.g.
  • the solid and the gel phases could be combined with one another as desired.
  • the spatial configuration of the gel phase which was liquid after the ingredients had been mixed and had a stable shape within a solidification time of a maximum of 10 minutes, was determined by the spatial configuration of the solid phase and by commercially available or self-designed shapes.
  • a water-soluble envelope in the form of an open pouch was produced by deep-drawing a PVOH-containing film.
  • a liquid composition was poured into this open cavity, which gave the gel phase after curing, and then solid phases in the form of a free-flowing solid were poured into a pouch comprising polyvinyl alcohol.
  • 1.0 g of the liquid nonionic surfactant Genapol EC 50 was metered onto the resulting particulate surface. The proportion of non-ionic surfactants could thus be increased significantly without changing other phases.
  • the open pouch is then sealed by placing a second film and sealing with a heat seal.
  • the detergent portions produced in this way were characterized by an attractive aesthetic.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Dispersion Chemistry (AREA)
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EP19186476.8A 2018-07-23 2019-07-16 Poche d'agent de nettoyage multiphase Pending EP3599274A1 (fr)

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DE102022213453A1 (de) 2022-12-12 2024-06-13 Henkel Ag & Co. Kgaa Herstellverfahren für Wasch- oder Reinigungsmittel
EP4438708A1 (fr) * 2023-03-27 2024-10-02 Henkel AG & Co. KGaA Procédé de fabrication d'un agent de nettoyage sous forme de gel
EP4438709A1 (fr) * 2023-03-27 2024-10-02 Henkel AG & Co. KGaA Procédé de fabrication d'un agent de nettoyage sous forme de gel

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