EP3599269A1 - Agent de nettoyage à protection contre la corrosion du verre - Google Patents

Agent de nettoyage à protection contre la corrosion du verre Download PDF

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Publication number
EP3599269A1
EP3599269A1 EP19186480.0A EP19186480A EP3599269A1 EP 3599269 A1 EP3599269 A1 EP 3599269A1 EP 19186480 A EP19186480 A EP 19186480A EP 3599269 A1 EP3599269 A1 EP 3599269A1
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EP
European Patent Office
Prior art keywords
weight
gel
gel phase
phase
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19186480.0A
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German (de)
English (en)
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EP3599269B1 (fr
Inventor
Oliver Kurth
Michael Kreis
Thomas Doering
Robert Stephen Cappleman
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP3599269A1 publication Critical patent/EP3599269A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • 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
    • C11D2111/18—Glass; Plastics

Definitions

  • the invention relates to detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, comprising at least one low-water, preferably essentially water-free gel phase which contains a water-soluble zinc salt, preferably zinc chloride, zinc sulfate and / or zinc acetate, particularly preferably zinc acetate.
  • a water-soluble zinc salt preferably zinc chloride, zinc sulfate and / or zinc acetate, particularly preferably zinc acetate.
  • cleaning agents preferably dishwashing agents, in particular machine dishwashing agents
  • divalent metal salts such as bismuth or zinc salts are used in particular to prevent damage to glasses (glass corrosion).
  • the patent application EP 1797166 describes, for example, water-containing compositions which, in addition to polyvalent metal compounds, contain at least 8% by weight of a nonionic surfactant with a cloud point of less than 32 ° C.
  • 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. Pre-portioned forms of supply are popular with consumers because of the easier dosage. Pre-portioned flowing gels are often problematic because they tend to leak, for example when packaged in single or multi-chamber bags.
  • the object of the present invention is to provide cleaning agents, in particular dishwashing agents, preferably machine dishwashing agents, which can be produced simply and cost-effectively.
  • a first subject of the present invention thus relates to detergents comprising a low-water, preferably essentially water-free gel phase which contains at least one water-soluble zinc salt.
  • the zinc salt to be used according to the invention is water-soluble, which means that it has a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and in particular 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 PCA (zinc 5-oxopyrrolidine-2-carboxylate), zinc benzoate, zinc chloride, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate , Zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • the water-soluble zinc salt used is zinc chloride, zinc acetate or zinc sulfate, in particular anhydrous zinc salt (anhydrate), particularly preferably zinc acetate (anhydrate).
  • the zinc salt in the gel phase is preferably in an amount of 0.05% by weight to 3% by weight, particularly preferably in an amount of 0.1% by weight to 2.4% by weight, in particular in one Amount of 0.2 wt .-% to 1.0 wt .-%, based on the total weight of the gel phase.
  • Zinc salts can also be contained in a solid phase that may be present.
  • 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.
  • the presence of zinc salts in the gel phase contributes to stabilizing the gel and improving the processability. It proves particularly disadvantageous if the gel can no longer be processed within a short time after production. If the gel becomes too viscous within a short time after production, it can no longer be dosed in the usual way. Furthermore, yellowing of the gel is frequently observed, which visually displeases the end user and leads to the latter perceiving the product as "no longer fresh” or "no longer usable". For the production process, this means that the gel only has to be freshly prepared in small quantities and at short time intervals to ensure that the gel is still filled into the product. In particular, the time window in which the gel phase can be processed (standing time) is significantly extended by the addition of the zinc salt.
  • An advantage of the invention is that the gel batches have a longer service life and thus a corresponding cleaning agent can be produced in a more cost-effective and resource-saving manner.
  • 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 characterized by the dispersion of a fixed, but distributed substance with long or highly branched particles and / or gel-forming agents, formed 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 (e.g. a composition) by specifically bringing this molding compound into a predetermined shape, e.g. by pouring a liquid composition into a mold and then curing the liquid composition, e.g. as part of a sol-gel process.
  • a molding compound e.g. a composition
  • 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 at least one gel phase is also preferably translucent (translucent) or transparent, which gives a good visual impression.
  • the transmission of the gel phase (without dye) is preferably in a range between 100% and 20%, between 100% and 30 %, especially between 100% and 40%.
  • the transmittance was determined in% at 600 nm against water as a reference at 20 ° C. The mass was poured into the provided 11 mm round cuvettes and measured after a storage time of 12 h at room temperature in a LICO 300 color measuring system according to Lange.
  • the at least one gel phase is low in water.
  • Low water in the sense of the present invention means that small amounts of water can be used to produce the at least one gel phase.
  • the proportion of water in the gel phase 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 data in% by weight relate to the total weight of the gel phase. This has the advantage that the small amounts of water in combination with PVOH can have a structure or gel-forming effect.
  • the at least one gel phase is essentially water-free.
  • the gel phase is preferably essentially free of water.
  • “Essentially free” here means that small amounts of water can be present in the gel phase. 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, only small amounts, in particular no water, are preferably used as solvents for the preparation of the gel phase.
  • the proportion of water in the gel phase 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 wt% or less, especially 0.1 wt% or 0.05 wt% or less.
  • the data in% by weight relate to the total weight of the gel phase.
  • the water-soluble zinc salt is used in the gel phase in the form of an anhydrous zinc salt, in particular anhydrous zinc sulfate or zinc acetate, preferably zinc acetate anhydrate.
  • 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 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 do not are contained more stably and the washing or cleaning effect can also be influenced thereby.
  • 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.
  • detergents preferably dishwashing detergents, in particular machine dishwashing detergents, which are packaged as detergent portions, which preferably contain the active substances necessary for a cleaning cycle, as a total amount of the water-soluble zinc salts, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate , in the detergent portion, preferably 0.0004 to 0.5 g, preferably 0.001 to 0.2 g, in particular 0.02 to 0.06 g.
  • the individual detergent portion which is used to carry out an individual cleaning cycle in particular is added to a cleaning cycle of a machine dishwasher, 0.0005 to 1 g, preferably 0.01 to 0.5 g, in particular 0.02 to 0 , 06 g which contains water-soluble zinc salts, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate.
  • a single portion of detergent according to the invention which is added in particular to a cleaning cycle in an automatic dishwasher, contains 0.001 to 0.5 g, in particular 0.02 to 0.05 g, of water-soluble zinc salts, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, based on the total amount of detergent.
  • 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), especially 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) Dialkylcitraconkladre (Dimethylcitraconat), citraconic acid, mesaconic acid (methylfumaric) and their derivatives, Monoalkylmesaconat, Dialkylmesaconat, mesa
  • 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 for example known under the name Mowiol® or Poval® sold by Kuraray.
  • Exceval® AQ4104 from Kuraray is also suitable.
  • 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 covering, especially if it is also made of 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 is decisive for this contributes 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 up 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, 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.
  • 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 an alkanetriol, in particular glycerol or 1,1,1-trimethylolpropan
  • 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
  • zinc acetate preferably in amounts of 0.1 to 2.4% by weight, particularly preferably of 0 , 2 to 1.0% by weight
  • 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 glycerin and 1,3-propanediol are included as polyhydric alcohols.
  • 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 possibly 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 wt .-%, preferably between 1 and 15 wt .-%, in particular between 5 and 12 wt .-%, for example 8 to 11 wt .-% triethylene glycol
  • the at least one gel phase further preferably comprises a further anionic polymer, in particular polycarboxylates. These can either act as builders and / or as a thickening polymer. According to the invention, 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.
  • the copolymers can have two, three, four or more different monomer units. In addition to monomer (s) containing sulfonic acid groups, 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 independently selected 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-propane sulfonic acid, Allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and mixtures of said Acids or their
  • 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 molecular weights of 2,000 to 200,000 g-mol- 1 , preferably 4,000 to 25,000 g-mol -1 and in particular 5,000 to 15,000 g-mol -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.
  • 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 a polyhydric 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 of zinc sulfate and / or zinc acetate, in particular of 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 cleaning agent preferably dishwashing agent, in particular machine dishwashing agent, is a detergent portion in a water-soluble envelope with one or more chambers / compartments.
  • the cleaning agent is preferably packaged as a single-use detergent portion, so that it is used to carry out a dishwasher cycle and is essentially (largely) consumed in the process.
  • 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 coatings which contain polyvinyl alcohol or a 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.
  • Polyvinyl alcohol copolymers which are also preferred comprise, in addition to vinyl alcohol, an ethylenically unsaturated one 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.
  • Other additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble 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. Leakage of product from the wrapping, for example onto the surface of the portion, would be disadvantageous since the consumer would then use the product would come into contact. This is exactly what should be avoided if possible with a portion of detergent 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 of the same material and in 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 solid phase and the at least one gel phase can be arranged in any combination with one another within the water-soluble coating.
  • a solid phase can be arranged on or next to a gel phase.
  • the cleaning agent according to the invention has a solid phase and a gel phase. It is also conceivable that a solid phase is surrounded by gel phases. Embedding one phase in another is also included according to the invention.
  • the gel phase is in a cast form, for example in the form of a gel core, which is surrounded by a solid phase. There may also be 2 or more cavities separated from one another which are filled with the at least one gel phase.
  • the cleaning agent comprises two gel phases, it being possible for the two gel phases to have different compositions.
  • Such cleaning agents preferably comprise 3, 4, 5 or 6 or more gel phases, it being possible for these gel phases to have the same or different compositions.
  • a preferred object of the present invention is a cleaning agent, preferably dishwashing agent, in particular machine dishwashing agent, which additionally comprises at least one solid, in particular particulate phase and optionally at least one further liquid / gel-like or solid phase.
  • solid means that the composition is in solid form under standard conditions (temperature 25 ° C., pressure 1013 mbar).
  • Suitable solid phases are, on the one hand, granular mixtures of a solid composition, such as powders and / or granules, in particular powdery phases.
  • solid compositions / phases which have increased dimensional stability compared to the loose powder, for example powder or granule preparation which have been compressed by compression before or after being enclosed in the film, e.g. due to the restoring forces of the film after deep-drawing or directly compressed compositions such as compresses or tablets. This at least one solid phase can be in direct contact with the gel phase.
  • cleaning agent portions in particular multi-chamber bags, in which the solid and the gel phase are in spatial proximity, but separate from one another.
  • the two chambers can be separated, for example, by a film, in particular a water-soluble film, or also by a sealing seam (preferably a sealing seam of 3 mm or less).
  • a sealing seam preferably a sealing seam of 3 mm or less.
  • a powdery phase in the sense of the present invention is to be understood as a granular mixture which is formed from a large number of loose, solid particles which in turn comprise so-called grains.
  • the term powder phase comprises powders and / or granules as defined below.
  • 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 solid phase is the powder and / or the granules, if the term "powder” or "granules" is used here, it is also encompassed that these are also mixtures of different powders or different granules , Mixtures are also corresponding with powder and granulate different powder with different granules meant.
  • Said solid-form particles of the granular batch preferably have a particle diameter X 50, 3 (volume average) of from 10 to 1500 microns, more preferably from 200 microns to 1200 microns, more preferably of 600 .mu.m to 1100 .mu.m. These particle sizes can be determined by sieving or by means of a particle size analyzer Camsizer from Retsch.
  • the granular mixture serving as the solid 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 solid phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one gel phase as defined above.
  • a particularly preferred object of the present invention are cleaning agents, in particular cleaning agent portions, in which the gel phase is in direct contact, for example in a chamber, with which at least one solid phase is contained.
  • the at least one solid phase and the at least one gel phase are in direct contact with one another.
  • No negative interaction means, for example, that no ingredients or solvents pass from one phase to the other or that the stability, in particular storage stability, preferably at 4 weeks and 30 ° C. storage temperature, and / or the aesthetics of the product in some form, for example by Color change, formation of wet-looking edges, blurring boundary between the two phases or the like is impaired.
  • a gel phase preferably a dimensionally stable gel phase, comprising at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, which is combined with a granular mixture of a solid composition, in particular a powdery phase
  • this goal can be achieved. It is particularly suitable if the granular mixture of a solid composition, in particular the powdery phase, is free-flowing, since a process-specific filling of the water-soluble coating, in particular when filling a cavity produced by deep drawing, can thus be achieved.
  • the optical appearance of the granular mixture of a solid composition, in particular of the powder can be changed better compared to a compressed tablet, in particular texture differences, such as coarse and fine particles, and particles or areas with different colors, as a whole or as colored speckles, can be so can be used to improve a visually appealing appearance.
  • the granular batch of solid composition, in particular the powder also offers improved solubility compared to compressed tablets even without the addition of disintegrants.
  • 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, etc.
  • Different phases can preferably be distinguished optically.
  • the at least one solid phase must be clearly distinguished from the at least one gel phase. If the cleaning agent according to the invention has more than one solid phase, these can also be distinguished from one another with the naked eye, because they differ from one another in terms of color, for example. The same applies if there are two or more gel 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.
  • the at least one solid phase of the present invention comprises a granular mixture of a solid composition, in particular it is in powdery and free-flowing form.
  • the cleaning agent according to the invention thus comprises at least one solid powdery and free-flowing phase, and at least one gel phase, the at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, and at least one polyvinyl alcohol, as a gel former, at least PVOH and / or its derivatives, in particular preferably comprises at least PVOH and at least one polyhydric alcohol.
  • the flowability of a granular mixture, in particular a powdery solid, the powdery phase, preferably the powder and / or granules affects its ability to flow freely under its own weight.
  • the flowability is determined by preferring the flow time of 1000 ml of detergent powder from a standardized flow test funnel with a flow of 16.5 mm in diameter, which is initially closed at its discharge direction, by measuring the time for the granular mixture, in particular the powdered phase, to flow completely of the powder and / or granules, for example the powder after the opening of the outlet is measured and compared with the outlet speed (in seconds) of a standard test sample, the outlet speed of which 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].
  • 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 solid 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 hours after the production of the granular mixture of the solid composition, in particular the powdery one solid phase, preferably the powder and / or granules 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 solid phase comparatively quickly and precisely.
  • a powder funnel with 400 ml content and a drain with a diameter of 25 mm is just hung in a tripod.
  • the funnel is moved upwards by means of a manually operated knurling wheel at a speed of 80 mm / min, so that the granular mixture, in particular the powdery phase, preferably the powder and / or granulate, e.g. the powder trickles out.
  • the height of the cone and the diameter of the cone are determined for the individual solid 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 such powdery 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 powdery phase preferably the powder and / or granules, for example the powder
  • the granular mixture, in particular the powdery phase preferably the powder and / or granulate, for example the powder
  • the granular mixture, in particular the powdery phase preferably the powder and / or granulate, for example the powder
  • the granular mixture serving as the solid 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 solid phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one previously defined gel phase.
  • the 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 cleaning agent according to the invention can also contain mixtures of several surfactants selected from the same group.
  • the at least one solid phase and / or the at least one gel phase comprise at least one surfactant. It is possible that only the at least one solid phase or only the at least one gel phase comprise at least one surfactant. If both phases comprise a surfactant, they are preferably different surfactants. However, it is also possible for the solid and gel phases to have the same surfactant or the same surfactants. At least one solid and / or gel phase according to the invention preferably contain 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, such as alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides or amine oxides. Particularly preferred nonionic surfactants are specified in more detail below.
  • 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 represents 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 which R 1 in the above formula represents 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 of the solid phase are nonionic surfactants of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 , 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-hydroxyatkytether.
  • the at least one solid and / or the at least one gel phase preferably contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of the 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% by weight. -%, preferably 5 wt .-% to 25 wt .-% and in particular 10 wt .-% to 20 wt .-%.
  • the nonionic surfactant of the solid and / or gel phase is selected from nonionic surfactants 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 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.
  • R 1 -O (CH 2 CH 2 O) ⁇ 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 R 1 -O (CH 2 CH 2 O) ⁇ CR 3 R 4 (OCH 2 CH 2 ) y OR 2 are very particularly preferred, 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.
  • Nonionic surfactants which have a melting point above room temperature.
  • 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 molecular weight 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 used in the solid phase contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverse block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol 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 solid 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 or sulfonate group and a lipophilic alkyl group with about 8 to 30 carbon atoms.
  • anionic group such as. B. a carboxylate, sulfate or sulfonate 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 gel phase is therefore free of nonionic surfactants, in particular free of surfactants. "Free from” means that the gel phase contains less than 1.0% by weight and in particular less than 0.1% by weight, preferably no surfactant or nonionic surfactant).
  • Preferred cleaning agents according to the invention are further characterized in that they contain less than 1.0% by weight and in particular less than 0.1% by weight in the at least one solid and / or the at least one gel phase, in particular in the solid phase. preferably contain no anionic surfactant.
  • the cleaning agents according to the invention are characterized in that the at least one gel phase is each less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight, of anionic surfactant to the total weight of the gel 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 gel phase.
  • the gel phase contains less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.05% by weight of fatty acid salts or soaps.
  • the at least one gel phase can have sugar.
  • sugars include sugar alcohols, monosaccharides, disaccharides and oligosaccharides.
  • the at least one gel phase comprises at least one sugar alcohol different from glycerol, preferably at least one monosaccharide or disaccharide sugar alcohol. Mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol and xylitol are particularly preferred.
  • Particularly preferred monosaccharide sugar alcohols are pentitols and / or hexitols. Xylitol and / or sorbitol is very particularly preferred.
  • the gel phase can 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 completely dissolve in the gel phase and leads to 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 solid phase.
  • 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, ie 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.
  • dishwashing agents preferably machine dishwashing agents
  • these are preferably present in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, particularly 7 to 28% by weight preferably contain 10 to 25 wt .-%, very particularly preferably 15 to 20 wt .-%, each based on the total weight of the agent.
  • dishwashing agents preferably machine dishwashing agents
  • dishwashing agents are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the proportion by weight of these builders, based on the total weight of the cleaning agent according to the invention, is preferably 5 to 70% by weight, preferably 15 to 60% by weight and in particular 20 to 50% by weight.
  • the combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents.
  • one or more other builders may also be included.
  • Preferred cleaning agents in particular dishwashing agents, preferably machine dishwashing 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 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 from 2.5 to 7.5% by weight, in each case based on the total weight of the composition.
  • 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.
  • dishwashing agents preferably machine dishwashing agents
  • dishwashing agents contain, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, 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 acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate, particularly preferably from EDDS MGDA or GLDA.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • ethylenediamine disuccinate particularly preferably from EDDS MGDA or GLDA.
  • 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 (homo) polymeric polycarboxylates content of the cleaning agents according to the invention is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight.
  • 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 as a builder, preferably a number from 1.9 to 22 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.
  • the cleaning agents according to the invention can also contain alkali metal hydroxides.
  • These alkali carriers are used in the cleaning agents and in particular in the at least one gel phase, preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent.
  • Alternative cleaning agents according to the invention are free from alkali metal hydroxides.
  • cleaning agents according to the invention preferably contain enzyme (s) in the at least one solid and / or the at least one gel phase.
  • enzymes 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, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular 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, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously concentrated as possible, low in water and / or mixed with stabilizers or other auxiliaries.
  • the enzymes for the at least one solid and / or the at least one gel 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 are as in a solidified gel are included or in those of the core-shell type in which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers.
  • Capsules of this type are applied by methods known per se, for example by 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 1 and 40% by weight, preferably between 2 and 30% by weight, particularly preferably between 3 and 25% 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 solid and / or the at least one gel phase of the 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, further 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 solid phase), additives to improve the drainage and drying behavior, to adjust the viscosity, to stabilize, UV stabilizers, 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 their mixtures.
  • 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 essentially free of alkanolamine, ie the at least one gel phase contains less than 1% by weight, in particular less than 0.5% by weight, preferably less than 0.1% by weight, particularly preferably less than 0.05% by weight of alkanolamine and the alkanolamine is only present in the at least one solid phase.
  • polyethyleneimines such as those available under the name Lupasol® (BASF), preferably in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight, can be 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 cleaning agent in particular machine 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 solid phase.
  • cleaning agents according to the invention contain an oxygen bleaching agent from the group sodium percarbonate, sodium perborate tetrahydrate and Sodium perborate.
  • 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
  • the cleaning agent according to the invention preferably comprises at least one solid phase and at least one gel phase.
  • the cleaning agent can thus have one, two, three or more different solid phases; it can also have one, two, three or more different gel phases.
  • the cleaning agent according to the invention preferably comprises a solid phase and a gel phase. This particularly preferably includes Detergent two solid phases and one gel phase. It preferably comprises two solid phases and two gel phases. Also preferred is an embodiment in which the cleaning agent comprises three solid phases and one or two gel phases.
  • the weight ratio of the total of the at least one solid 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 14: 1 to 6: 1, for example 12: 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 13 to 17 g per detergent portion. This weight ratio results in a good concentration of the respective ingredients of the solid or gel phase in one cleaning process.
  • the at least one solid phase and the at least one gel phase adjoin one another over the full or partial area. It is preferred that the two phases directly adjoin one another.
  • Stability means that constituents contained in the gel phase do not pass into the at least one solid phase but, even after prolonged storage, the at least one solid phase and the gel phase are optically separate from one another and do not interact with one another, such as diffusion of liquid constituents of one in the other phase or reaction of components of one phase with those in the other phase.
  • a gel phase which, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, also has polyethylene glycols with an average molecular weight of 200 to 600 g / mol, glycerol, PVOH and at least one C 3 - Has C 5 alkanediol, can be made possible.
  • Another object of the present invention is the use of water-soluble zinc salts, in particular zinc sulfate and / or zinc acetate, in particular in anhydrous form, particularly preferably zinc acetate anhydrate, to improve the production of a low-water gel detergent.
  • 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 cleaning agent according to the invention.
  • the cleaning takes place in particular with a cleaning machine, preferably with a dishwasher.
  • Another object of the present invention is also the use of a cleaning agent, as described above, for cleaning hard surfaces, in particular dishes, in particular in automatic dishwashers.
  • the cleaning agent according to the invention comprises something as a whole or in the at least one solid phase or in the at least one gel phase, it should also be regarded as disclosed that cleaning agents or the respective phase can consist of them.
  • the 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. cysteine
  • SILVER PROTECTION e.g. cysteine
  • 0.0 - 1.0 Percarbonate Na salt 10-15
  • Bleaching catalyst preferably Mn-based
  • TAED 0.02-0.5
  • Bleach activator e.g. TAED
  • Non-ionic surfactant for example fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 2.5-10 polycarboxylate 4 - 10 Cationic copolymer 0 - 0.75 Disintegrant - (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, then solid phases in the form of a free-flowing solid were filled in a pouch comprising polyvinyl alcohol and the open pouch was then sealed by placing a second film and sealing by means of heat sealing.
  • Table 3 Compositions of the gel phase In% by weight E1 E2 E3 V1 Anhydrous zinc acetate 0.5 1.0 2.0 0 Polymer comprising monomers containing acrylic acid and amidopropylsulfonic acid 11 11 0 11 glycerin 25 25 25 25 25, 1,3 propanediol 30 30 30 30 30 PEG 400 15 15 15 15 PVOH (Mowiol 4-88) 15 15 15 15 15 Misc (including process aids, pH adjusting agents, perfume, dye) Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100

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EP19186480.0A 2018-07-23 2019-07-16 Agent de nettoyage à protection contre la corrosion du verre Active EP3599269B1 (fr)

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EP3828255B1 (fr) * 2019-11-29 2023-11-22 Henkel AG & Co. KGaA Produit détergent à chambres multiples à contraste élevé entre les chambres
EP4067466A1 (fr) * 2021-03-30 2022-10-05 Henkel AG & Co. KGaA Détergent ou nettoyant
DE102021203176A1 (de) 2021-03-30 2022-10-06 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel
DE102021203175A1 (de) 2021-03-30 2022-10-06 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel
DE102021203178A1 (de) 2021-03-30 2022-10-06 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel
GB2607585A (en) * 2021-06-03 2022-12-14 Reckitt Benckiser Finish Bv Detergent gel composition comprising a fatty alcohol ethoxylate

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EP1797166A1 (fr) 2004-09-28 2007-06-20 The Procter and Gamble Company Compositions de detergeant de protection contre la corrosion de surface renfermant des composes metalliques polyvalents et des taux eleves de tensioactifs a faible moussage et non ioniques
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PL3599269T3 (pl) 2024-03-18
EP3599269B1 (fr) 2023-11-08

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