EP3733825A1 - Détergent ou nettoyant comprenant au moins deux phases - Google Patents

Détergent ou nettoyant comprenant au moins deux phases Download PDF

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Publication number
EP3733825A1
EP3733825A1 EP20173373.0A EP20173373A EP3733825A1 EP 3733825 A1 EP3733825 A1 EP 3733825A1 EP 20173373 A EP20173373 A EP 20173373A EP 3733825 A1 EP3733825 A1 EP 3733825A1
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EP
European Patent Office
Prior art keywords
phase
weight
washing
cleaning agent
agent according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20173373.0A
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German (de)
English (en)
Inventor
Oliver Kurth
Inga Kerstin Vockenroth
David MATULLA
Volker Blank
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3733825A1 publication Critical patent/EP3733825A1/fr
Pending legal-status Critical Current

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    • 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
    • C11D3/2041—Dihydric 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D3/16—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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/384—Animal products
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to a washing or cleaning agent, in particular a cleaning agent for hard surfaces, with at least two mutually different phases.
  • Washing or cleaning agents are usually in solid form (for example as a powder) or in liquid form (or also as a flowing gel).
  • liquid detergents or cleaning agents are enjoying increasing popularity with consumers.
  • Solid washing or cleaning agents have the advantage that, in contrast to liquid washing or cleaning agents, they do not require any preservatives.
  • Liquid supply forms are increasingly gaining acceptance on the market, in particular because of their rapid solubility and the associated rapid availability of the active ingredients they contain. This offers the consumer the opportunity to use shorter washing programs and still get a good cleaning performance.
  • the object on which the present application is based is therefore achieved by a washing or cleaning agent which comprises at least one first phase and at least one different second phase, the at least one first phase being solid and the at least one second phase comprises at least one polymer and at least one polyhydric alcohol.
  • 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 various features, for example ingredients, physical properties, external appearance, etc.
  • Different phases can preferably be distinguished optically.
  • the at least one first phase can be clearly distinguished from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, then these can also be differentiated from one another with the naked eye, because they differ from one another, for example, in terms of color. The same applies if there are two or more second 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 speed with which the phase dissolves in water and thus the speed and the sequence in which the ingredients contained in the respective phase are released.
  • the at least one second phase is dimensionally stable at room temperature.
  • the at least one polymer is brought into contact with the at least one polyhydric alcohol. This gives a flowable mixture which can be brought into a desired shape.
  • a second phase is obtained, which remains in the specified shape, i.e. is dimensionally stable.
  • the solidification time is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes.
  • the at least one second phase yields to pressure, but does not deform as a result, but rather returns to the initial state after the pressure has ceased.
  • the at least one second phase is preferably elastic, in particular linear-elastic.
  • the at least one second phase is also preferably transparent, which results in a good visual impression.
  • the at least one second phase is cut-resistant. It can be cut, for example, with a knife after solidification, without it being destroyed any further apart from the cut made. Furthermore, the at least one second phase is particularly flexible. Due to its flexibility and elasticity, it can take any shape. This also means breaking strength, which enables good handling, particularly with regard to transport and storage, but also consumption.
  • At least one as used herein means 1 or more, i. 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 bleach catalyst thus means, for example, at least one type of bleach catalyst, i. that one type of bleach catalyst or a mixture of several different bleach catalysts can be meant.
  • the information relates to all compounds of the specified type that are contained in the composition / mixture, i.e. that the composition does not contain any further compounds of this type beyond the specified amount of the corresponding compounds.
  • molar masses these details always relate to the number-average molar mass M n , unless explicitly stated otherwise.
  • the number average of the molar mass 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 molar mass M w can also be determined by means of GPC, as described for M n .
  • the at least one first phase is in compressed form.
  • the washing or cleaning agent according to the invention thus comprises at least one first solid, compressed phase and at least one second phase which comprises at least one polymer and at least one polyhydric alcohol.
  • the second phase must solidify within the shortest possible time. Long solidification times would lead to long production times and thus to high costs.
  • the solidification time means the period of time during which the at least one second phase changes from a flowable state to a dimensionally stable state that is non-flowable at room temperature.
  • room temperature is understood to mean a temperature of 20 ° C. This can take place, without having a restrictive effect, by crosslinking the at least one polymer.
  • the second phase must be stable in storage, specifically under normal storage conditions.
  • the second phase according to the invention is part of a washing or cleaning agent. Washing or cleaning agents are usually stored in a household for a certain period of time. They are usually stored near the washing machine.
  • the second phase should be stable for such storage.
  • the second phase should therefore be stable even after a storage time of, for example, 4 to 12, in particular 10 to 12 weeks or longer at a temperature of up to 40 ° C., especially at 30 ° C., especially at 25 ° C. or at 20 ° C. be and not deform during this time or otherwise change in consistency.
  • the surface of the second phase should differ significantly from the first phase, for example by a pronounced gloss.
  • the surface of the solid at least one first phase is usually not glossy but matt, dull or dull, so that a gloss enables a good differentiation, which makes the detergent or cleaning agent attractive to the consumer, possible.
  • a change in volume or shrinkage during storage would be disadvantageous, since this would result in poor consumer acceptance of the product.
  • Leakage of liquid or exudation of constituents from the second phase is also undesirable.
  • the visual impression is relevant.
  • the stability of the second phase can be influenced by the escape of liquid, such as for example solvent, so that the constituents are no longer contained in a stable manner and the washing or cleaning effect can thereby also be influenced.
  • the at least one first phase and the at least one second phase should be in direct contact with one another.
  • No negative interaction means here, 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 any form, for example through Color change, formation of damp-looking edges, blurred border between the two phases or the like is impaired.
  • the second phase is essentially anhydrous.
  • the second phase is preferably essentially free of water.
  • “Essentially free” means here that small amounts of water can be contained in the second phase. This water can be introduced into the phase, for example, by a solvent or as water of crystallization or as a result of reactions of components of the phase with one another. However, no water is used as a solvent for preparing the second phase.
  • the proportion of water in the second phase is in particular 15% by weight or less or 10% by weight or less, especially 7% by weight, or less, in particular 6% by weight or 5% by weight or less , preferably 2% by weight or less, in particular 1% by weight or less, especially 0.5% by weight or less, in particular 0.1% by weight or 0.05% by weight or less.
  • the data in% by weight relate to the total weight of the second phase.
  • the at least one second phase comprises at least one polymer.
  • the at least one polymer is particularly suitable for forming a network.
  • the at least one second phase can have one polymer, two or more different polymers. In particular, it has one, two or more, in particular one or two, preferably one polymer which is suitable for forming a network.
  • the at least one second phase can have one or more polymers that do not form a network but lead to a thickening and thus an increase in the dimensional stability of the at least one second phase, so-called thickening polymers.
  • the at least one second phase therefore comprises at least one, preferably one polymer for network formation and one or more thickening polymers.
  • the at least one second phase preferably comprises PVA (polyvinyl alcohol) and / or gelatin as polymers suitable for network formation.
  • the at least one second phase also preferably comprises a thickening polymer and, in particular, polycarboxylates as thickening polymer.
  • Polyvinyl alcohols are thermoplastics which are usually produced as a white to yellowish powder by hydrolysis of polyvinyl acetate.
  • Polyvinyl alcohol (PVA) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molar mass of 30,000 to 60,000 g / mol are preferred.
  • Gelatine is a mixture of substances made from tasteless animal protein. The main component is denatured or hydrolyzed collagen, which is produced from the connective tissue of various animal species. Gelatin lacks the essential amino acid tryptophan, so it is not considered a full protein. Gelatine swells in water and dissolves when heated from around 50 ° C. When it cools down, a gel forms which, when heated again, becomes liquid again.
  • At least one second phase is therefore particularly preferred, which comprises gelatin and / or PVA and at least one polyhydric alcohol.
  • the at least one second phase particularly preferably comprises gelatin and at least one polyhydric alcohol.
  • the at least one second phase also preferably has PVA and at least one polyhydric alcohol.
  • the at least one second phase comprises the polymer suitable for network formation in a proportion of about 5% by weight to 40% by weight, in particular from 10% by weight to 35% by weight, preferably 15% by weight to 20% by weight.
  • Proportions of more than 40% by weight and in particular more than 20% by weight lead to a prolonged solidification time. The phases remain soft longer, which leads to a longer manufacturing process. The values are based on the total weight of the second phase.
  • the at least one second phase particularly preferably comprises gelatin.
  • the second phase therefore preferably has gelatin with a Bloom value in the range from 60 to 225.
  • the Bloom value describes the gel strength or gelling power of gelatine.
  • the key figure is the mass in grams that is required for a 0.5 inch diameter punch to deform the surface of a 6.67% gelatine / water mixture four millimeters deep without tearing it. The attempt finds standardized at exactly 10 ° C with a previous aging of the gelatin of 17 hours.
  • the at least one second phase comprises gelatin with a Bloom value of 150 or more, in particular from 180 to 225, preferably from 200 to 225
  • the proportion of gelatin based on the total weight of the second phase is preferably in the range from 10% by weight to 20 % By weight, in particular from 15% by weight to 18% by weight.
  • the Bloom value is less than 150, in particular from 60 to 120, preferably from 60 to 100
  • the proportion of gelatin based on the total weight of the second phase is preferably in the range from 15% by weight to 30% by weight, in particular 20 Wt% to 25 wt%.
  • Gelatin with a Bloom value of 180 or more, in particular 200 or more, especially 225 is preferred.
  • Gelatin with a corresponding Bloom value can be used to control the viscosity of the second phase during production.
  • the amount of gelatine required is less here than when using gelatine with a lower Bloom value, which can lead to a reduction in costs.
  • the toughness of the second phase is increased during production.
  • the second phase therefore preferably comprises gelatin 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, especially 5% by weight to 25% by weight, preferably 5% by weight % to 20% by weight based on the total weight of the second phase.
  • Sulphopolymers also ensure an excellent surface gloss. In addition, fingerprints are not retained.
  • the proportion of sulfopolymers, especially sulfopolymers with AMPS as the monomer containing sulfonic acid groups, for example Acusol 590, Acusol 588 or Sokalan CP50, is preferably 1% by weight to 25% by weight, in particular 3% by weight to 15% by weight. %, especially 4% by weight to 12% by weight, preferably 5% by weight to 10% by weight, based on the weight of the second phase.
  • the at least one second phase therefore comprises gelatin and a sulfopolymer and at least one polyhydric alcohol.
  • the at least one second phase can furthermore comprise thickening polymer.
  • It is preferably a polycarboxylate.
  • Used as a polycarboxylate preferably a copolymeric polyacrylate, preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers can have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • the unsaturated dicarboxylic acids can of course also be used.
  • H 2 C CH-X-SO 3 H
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , - CH 2 CH 2 CH 3 and -CH (CH 3 ) 2
  • 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-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-sulphate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
  • the sulfonic acid groups can be wholly or partly in neutralized form, which means that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • 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, in the case of copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, preferably in each case from 5 to 95% by weight; the proportion of the monomer containing sulphonic acid groups is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50% by weight, the monomers here are preferably selected from those mentioned above.
  • 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 application.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 g ⁇ mol ⁇ 1 , preferably from 4000 to 25,000 g ⁇ mol 1 and in particular from 5000 to 15,000 g ⁇ mol 1 .
  • the copolymers furthermore comprise at least one nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups.
  • nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups.
  • 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, ethylcyclohexyn, 1-octene, ⁇ -olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C 22
  • the at least one second phase can also contain further polymers, such as PEG, in particular those polyethylene glycols with an average molecular weight between about 200 and 8000, between about 800 and 4000 g / mol, particularly preferably with an average molecular weight between 1000 and 2000 g / mol , for example around 1500 g / mol (INCI: PEG1500), which increase the stability of the second phase.
  • PEG polyethylene glycols with an average molecular weight between about 200 and 8000, between about 800 and 4000 g / mol, particularly preferably with an average molecular weight between 1000 and 2000 g / mol , for example around 1500 g / mol (INCI: PEG1500), which increase the stability of the second phase.
  • the at least one second phase comprises at least one polyhydric alcohol.
  • the at least one polyhydric alcohol enables a dimensionally stable, non-flowable second phase to be produced within a short solidification time of 15 minutes or less, in particular of 10 minutes or less.
  • polyhydric alcohols 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 has been replaced by an OH group.
  • a polyhydric alcohol thus corresponds to the general formula [KW] (OH) x , where KW stands for a hydrocarbon that 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 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.
  • the at least one second phase particularly preferably comprises at least one alkanetriol and / or at least one alkanediol, in particular at least one C 3 to C 10 alkanediol 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 alkanetriol and / or at least one C 3 to C 5 alkanediol, as a polyhydric alcohol. It preferably comprises an alkanetriol and an alkanediol as at least one polyhydric alcohol.
  • the at least second phase therefore comprises at least one polymer, in particular gelatin and / or PVA, and at least one alkanediol and at least one alkanetriol, in particular an alkanetriol and an alkanediol.
  • a second phase which comprises at least one polymer, in particular gelatin and / or PVA, as well as a C 3 to C 8 alkanediol and a C 3 to C 8 alkanetriol.
  • a second phase is further preferred, which comprises at least one polymer, in particular gelatin and / or PVA, as well as 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. thereof.
  • the amount of polyhydric alcohol or polyhydric alcohols used in the second phases according to the invention is preferably at least 45% by weight, in particular 55% by weight or more.
  • Preferred quantity ranges here are from 5% by weight to 75% by weight, in particular from 10% by weight to 70% by weight, based on the total weight of the second phase.
  • the C 3 - to 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).
  • 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 preferably 1,3-propanediol and / or 1,2-propanediol.
  • the diol 1,3-propanediol is particularly preferred. It has surprisingly been found that particularly good results are achieved with mixtures which comprise glycerol and 1,3-propanediol and / or 1,2-propanediol.
  • the second phase particularly preferably comprises gelatin, glycerol and 1,3-propanediol or gelatin, 1,1,1-trimethylolpropane and 1,3-propanediol.
  • a particularly preferred second phase therefore comprises gelatin or PVA as the polymer and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols.
  • the proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based on the total weight of the second phase is preferably 5% by weight up to 70% by weight, in particular 10% by weight to 65% by weight, especially 20% by weight to 40% by weight.
  • the total proportion of alkanetriol (s), based on the total weight of the second phase is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20% by weight to 40% by weight.
  • the proportion of glycerol based on the total weight of the second phase is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20 wt% to 40 wt%.
  • the proportion of 1,1,1-trimethylolpropane based on the total weight of the second phase is preferably 5% by weight to 70% by weight, in particular 10% by weight % to 65% by weight, especially 20% to 40% by weight.
  • the proportion of 2-amino-2-hydroxymethyl-1,3-propanediol, based on the total weight of the second phase is preferably 5 % By weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20% by weight to 40% by weight.
  • the amount of alkanediols is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20 wt% to 40 wt%.
  • the proportion of alkanediol, in particular 1,3-propanediol, based on the total weight of the second phase is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20% by weight to 45% by weight. If the second phase contains 1,3-propanediol, then the proportion of 1,3-propanediol, based on the total weight of the second phase, is in particular 10% by weight to 65% by weight, especially 20% by weight up to 45% by weight.
  • a second phase is preferred, which comprises 20 to 45% by weight of 1,3 propanediol and 10% by weight to 65% by weight of 2-amino-2-hydroxymethyl-1,3-propanediol, each based on the total weight of the second phase.
  • a second phase is also preferred which contains 20 to 45% by weight of 1,3 propanediol and 10% by weight to 65% by weight of 1,1,1-trimethylolpropane, based in each case on the total weight of the second phase.
  • Particularly preferred is a second phase which contains 20 to 45% by weight of 1,3 propanediol and 10% by weight to 65% by weight of glycerol, based in each case on the total weight of the second phase.
  • the weight ratio is preferably 3: 1 to 2: 1.
  • the weight ratio is 2: 1 if glycerol and 1,3-propanediol are contained as polyhydric alcohols.
  • the washing or cleaning agent according to the invention preferably comprises at least one surfactant.
  • This surfactant is selected from the group of anionic, nonionic and cationic surfactants.
  • the washing or cleaning agent according to the invention can also contain mixtures of several surfactants selected from the same group.
  • the at least one first phase and the at least one second phase each comprise at least one surfactant.
  • only the at least one first phase or only the at least one second phase comprise at least one surfactant.
  • both phases comprise a surfactant, they are preferably different surfactants.
  • the first and second phases to have the same surfactant or the same surfactants.
  • At least one first and / or second 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. These are specified in more detail below.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol , which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half that.
  • surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • the washing or cleaning agents according to the invention in particular cleaning agents for automatic dishwashing, particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Ethoxylated nonionic surfactants which are composed of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol, are particularly preferred were obtained.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol with 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 with 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.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) non-ionic surfactants are also characterized by good foam control.
  • non-ionic surfactants which have proven to be particularly preferred for the low-foaming non-ionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • nonionic surfactants of the general formula preferably in which R 1 is a straight-chain or branched, saturated or mono- 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 stand for whole numbers from 1 to 6.
  • Preferred nonionic surfactants of the above formula can be prepared from the corresponding alcohols R 1 -OH and ethylene oxide or alkylene oxide by known methods.
  • 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 usually unbranched, the linear radicals from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or radicals which are methyl-branched in the 2-position or linear and methyl-branched radicals in a mixture, as are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula represents an alkyl radical with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • butylene oxide in particular comes into consideration as the alkylene oxide unit, which is contained in the preferred nonionic surfactants alternating with the ethylene oxide unit.
  • R 2 and 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 first 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 are independently of one another for values between 1 and 70; and M for an alkyl radical from 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 having 1 to 18 carbon atoms.
  • Nonionic surfactants of the general formula are preferred here 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 , where R, R 1 and R 2 independently of one another represent 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 is 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 alkyl diols HO-CHR-CH 2 -OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close off the free OH functions with the formation of a dihydroxy ether.
  • the cleaning performance of preparations according to the invention can be significantly improved, both in comparison to surfactant-free systems and in comparison to systems which contain alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • 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.
  • R 1 is C 7 to C 13
  • n is an integer natural number from 16 to 28 and R 2 is C 8 to C 12 are particularly preferred.
  • R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 represents a linear or branched aliphatic hydrocarbon radical with 4, are particularly preferred 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.
  • Especially the C (EO) -2-hydroxyalkyl ether 15-40 8-10 fatty alcohol (PO) 1 - - to the group of these nonionic surfactants include the C, for example 2-26 Fettatkohol- (PO) 1 (EO) 22 -2 hydroxydecyl ether.
  • nonionic surfactants that can be used with preference 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 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or one Methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5.
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or one Methyl, ethyl, n-propyl, iso
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 can 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.
  • R 3 H, —CH 3 or —CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula can be different if x> 2.
  • the value 3 for x has been chosen as an example and can be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (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 ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • the at least one first and / or the at least one second phase preferably contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, the proportion by weight of the nonionic surfactant in the total weight of the second phase preferably from 0.5% by weight to 30% % By weight, preferably 5% by weight to 25% by weight and in particular 10% by weight to 20% by weight.
  • the nonionic surfactant of the first and / or second 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 R 1 and R 2 independently of one another represent 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 radical or alkenyl radical having 1 to 18 carbon atoms and x and y independently of one another have values between 1 and 40.
  • 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 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 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 14 represent carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.
  • the specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the nonionic surfactants represent statistical mean values which, for a specific product, can be an integer or a fraction. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but rather of mixtures, which can result in mean values and fractional numbers for both the carbon chain lengths and 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 points 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 which 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 contain polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule are up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic Make up surfactants.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25 weight percent of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylol propane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.
  • the weight fraction of the nonionic surfactant in the total weight of the first 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.
  • B a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms.
  • the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups, and hydroxyl groups.
  • Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium as well as 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 instead of the surfactants mentioned or in conjunction with them. However, it is preferred that no cationic and / or amphoteric surfactants are used.
  • the second phase is therefore free from surfactants, in particular from nonionic surfactants.
  • Preferred washing or cleaning agents according to the invention are further characterized in that they contain less than 1.0% by weight and in particular no anionic surfactant in the at least one first and / or the at least one second phase, in particular in the first phase the addition of anionic surfactants has proven to be disadvantageous with regard to the phase properties, in particular their hardness, friability (abrasion behavior) and post-hardening behavior.
  • the at least one second phase can also contain sugar.
  • sugars include monosaccharides, disaccharides and oligosaccharides.
  • the second phase comprises disaccharides, especially 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 second Phase. In higher amounts, the sugar does not dissolve completely in the second phase and leads to cloudiness.
  • the use of sugar in particular in a proportion of 10% by weight to 15% by weight, reduces the development of moisture and thus improves the adhesion to at least one first phase.
  • builders such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, can be advantageous.
  • the use of phosphates is largely or completely dispensed with.
  • the agent contains preferably less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s).
  • the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate (s).
  • the builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates.
  • the proportion by weight of the total builders in the total weight of the compositions 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 as meaning 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 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.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as nitro-tetracarboxylic acids, such as nitricarboxylic acids diacetic acid (also known as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycine diacetic acid (MGDA) and their derivatives and mixtures of these.
  • Preferred Salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.
  • polymeric polycarboxylates organic polymers with a large number of (in particular more than ten) carboxylate functions in the macromolecule
  • polyaspartates organic polymers with a large number of (in particular more 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 of these should be mentioned in particular.
  • washing or cleaning agents according to the invention in particular dishwashing detergents, preferably automatic dishwashing detergents, contain one or more salts of citric acid, that is to say citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to Contain 20 wt .-%, each based on the total weight of the agent.
  • dishwashing detergents preferably automatic dishwashing detergents
  • dishwashing detergents 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, 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 detergents or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents.
  • one or more other builders can also be included.
  • Preferred washing or cleaning agents in particular dishwashing agents, preferably automatic dishwashing agents, are characterized by a builder combination of citrate and carbonate and / or hydrogen carbonate.
  • a mixture of carbonate and citrate is used, the amount of carbonate preferably 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 preferably from 5 to 35% by weight, in particular 10 to 25% by weight, very particularly preferably 15 to 20% by weight, based in each case on the total amount of cleaning agent, the total amount of these two builders preferably being 20 to 65 % By weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight.
  • one or more other builders can also be included.
  • the washing or cleaning agents according to the invention can contain, in particular, phosphonates as a further builder.
  • a hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates.
  • Phosphonates are preferably used in agents according to the invention in amounts from 0.1 to 10% by weight, in particular in amounts from 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 agent.
  • citrate, (hydrogen) carbonate and phosphonate are particularly preferred. These can be used in the abovementioned amounts. In particular, amounts of, based on the total weight of the agent, 10 to 25% by weight of citrate, 10 to 30% by weight of carbonate (or hydrogen carbonate), and 2.5 to 7.5% by weight Phosphonate used.
  • washing or cleaning agents in particular dishwashing detergents, preferably machine dishwashing detergents, are characterized in that they contain at least one further phosphorus-free builder in addition to citrate and (hydrogen) carbonate and optionally phosphonate.
  • 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 (IDSDS) and ethylenediamine disuccinate (preferably from MGDA or GLDA.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDSDS iminodisuccinate
  • ethylenediamine disuccinate preferably from MGDA or GLDA.
  • the percentage by weight of the further phosphorus-free builder, in particular of MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, in particular 7 to 25 Wt%.
  • the use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granulates which 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.
  • 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 mass of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molecular weights from 1100 to 10000 g / mol, and particularly preferably from 1200 to 5000 g / mol, can be preferred.
  • the content of (homo) polymeric polycarboxylates in the washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight. %.
  • Washing or cleaning agents according to the invention can furthermore contain crystalline layered silicates of the general formula NaMSi x O 2x + 1 ⁇ y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a Na 2 O: SiO 2 module of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which can also be used are preferably delayed in dissolution and have secondary washing properties.
  • the content of silicates is below 10% by weight, preferably below 5% by weight and in particular below 2 wt .-% limited.
  • the washing or cleaning agents according to the invention can also contain alkali metal hydroxides.
  • These alkali carriers are in the Detergents or cleaning agents, and in particular in the at least one second 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% by weight and in particular between 0.5 and 5% by weight, each based on the total weight of the detergent or cleaning agent.
  • Alternative washing or 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 first and / or the at least one second phase.
  • enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.
  • These enzymes are in principle 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 as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilase enzymes, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ß. stearothermophilus, from Aspergillus niger and A. oryzae as well as the improved further developments of the aforementioned amylases for use in cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
  • lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order 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 (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect.
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are added in order to increase the activity of the oxidoreductases concerned (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.
  • a protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
  • Cleansing-active proteases and amylases 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 as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.
  • the enzymes for the at least one first and / or the at least one second 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 solidified as in a Gel are enclosed or in those of the core-shell type, in which an enzyme-containing core is coated with a water-, air- and / or chemical-impermeable protective layer.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.
  • Particularly preferred cleaning agents are those which, based in each case 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 first and / or the at least one second phase of the washing or cleaning agent according to the invention can contain further ingredients.
  • these include, for example, anionic, cationic and / or amphoteric surfactants, bleaches, bleach activators, bleach catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (especially in the at least one first phase), additives to improve the drainage and drying behavior, to adjust the viscosity, for stabilization, UV stabilizers, pearlescent agents (INCI Opacifying Agents; for example glycol distearate, for example Cutina® AGS from Cognis, or mixtures containing this, for example Euperlane® from Cognis ), Preservatives (for example the technical 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7) also known as bronopol, which is commercially available,
  • Agents according to the invention preferably contain at least one alkanolamine as a further solvent.
  • the alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and propanolamine and mixtures thereof.
  • the alkanolamine is contained in agents according to the invention preferably 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 second phase is free from alkanolamine and the alkanolamine is only contained in the at least one first phase.
  • detergents or cleaning agents according to the invention contain at least one zinc salt as a glass corrosion inhibitor as a further component.
  • the zinc salt can be an inorganic or organic zinc salt.
  • the zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and 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 zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt is in cleaning agents according to the invention 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% by weight to 2% by weight, based on the total weight of the cleaning agent.
  • Salts especially the zinc salts
  • 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 sodium 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®, T
  • 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 polymer additives show synergisms in the case of Tegopren® 5843 and Tegopren® 5863.
  • the use of the Tegopren types 5843 and 5863 is, however, less preferred for use on hard surfaces made of glass, in particular glass dishes, because these silicone surfactants can be absorbed onto glass.
  • the additives mentioned are dispensed with.
  • a preferred washing or cleaning agent in particular dishwashing detergent, preferably further comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst. If available, these are only included in the at least one first phase.
  • cleaning agents according to the invention contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate.
  • Further bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which provide H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • bleaches from the group of organic bleaches can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.
  • Sodium percarbonate is particularly preferred because of 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 peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry 0- and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multiple acylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • TAED tetraacetylethylenediamine
  • the bleach catalysts are bleach-intensifying transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru-amine complexes can also be used as bleach catalysts.
  • Manganese complexes in the II, III, IV or IV oxidation state which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference.
  • Ligands are preferably used which have nitrogen donor functions.
  • bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane Me TACN
  • 2-methyl-1,4,7-triazacyclononane Me TACN
  • Suitable manganese complexes are, for example, [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 2 ( ⁇ -OAc) 1 (TACN ) 2 ] (BPh 4 ) 2 , [Mn IV 4 ( ⁇ -O) 6 (TACN) 4 ] (ClO 4 ) 4 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN ) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 1 ( ⁇ -OAC) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn IV 2 ( ⁇ -O) 3 ( Me-TACN) 2 ] (PF 6 ) 2 and [Mn IV 2 ( ⁇ -O) 3 (Me / Me-TACN) 2 ] (PF 6 ) 2 (with OAc
  • the washing or cleaning agent according to the invention comprises at least a first phase (1) and at least a second phase (2).
  • the washing or cleaning agent can thus have one, two, three or more different first phases (1); it can also have one, two, three or more different second phases (2).
  • the washing or cleaning agent according to the invention preferably comprises a first phase (1) and a second phase (2).
  • the washing or cleaning agent particularly preferably comprises two first phases (1) and a second phase (2). It preferably comprises two first phases (1) and two second phases (2). Also preferred is an embodiment in which the detergent or cleaning agent comprises three first phases (1) and one or two second phases (2).
  • the weight ratio of the at least one first phase (1) to the at least one second phase (2) is preferably 20: 1 to 8: 1.
  • the total weight of phase (1) in a cleaning agent portion can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 14 to 19 g. This weight ratio results in a good concentration of the respective ingredients of the first (1) or second phase (2) in one cleaning process.
  • the at least one first phase (1) and the at least one second phase (2) adjoin one another over the full or partial area. It is preferred that the two phases directly adjoin one another. However, it is also possible that the at least one first phase (1) or the at least one second phase (2) or the at least one first phase (1) and the at least one second phase (2) are closely wrapped in a water-soluble film or in one water-soluble pouch is / are included.
  • the entire agent is preferably contained in a water-soluble bag or, particularly preferably, is tightly enclosed by a water-soluble film.
  • Stability means that components contained in the second phase do not pass into the at least one first phase, but also after prolonged storage the at least one first phase and the second phase are optically separate from one another and do not interact with one another, such as diffusion of liquid components from one phase to the other or reaction of components of one phase with those in the other phase or Loss of adhesion of the second phase (2) on the in particular compressed, compacted first phase (1) due to the leakage of liquid.
  • a second phase comprising glycerine, gelatin and at least one C 3 - to C 5 -alkanediol.
  • the water-soluble film or the water-soluble bag preferably comprises a water-soluble polymer.
  • Some preferred water-soluble polymers which are preferably used as water-soluble packaging, are polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinylpyrrolidones, polyethylene oxides, celluloses and gelatin, with polyvinyl alcohols and acetalized polyvinyl alcohols being particularly preferred.
  • Polyvinyl alcohols (abbreviation PVAL, occasionally also PVOH) is the name for polymers with the general structure which also contain structural units of the type in small proportions (approx. 2%).
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 87-99 mol%, i.e. they contain one more Residual content of acetyl groups.
  • the water-soluble packaging at least partially comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and above all 82 to Is 88 mole percent.
  • 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 a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention that the packaging material comprises a polyvinyl alcohol whose molecular weight is in the range from 5,000 g mol -1 to 100,000 g mol -1 , preferably from 10,000 g mol -1 to 90,000 g mol -1 , particularly preferably from 12,000 g mol -1 to 80,000 g mol -1 and in particular from 15,000 g mol -1 to 70,000 g mol -1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, particularly preferably between about 240 to about 1680 and in particular between about 260 to about 1500.
  • the water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which are 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 due to their extremely good cold water solubility.
  • the reaction products of polyvinyl alcohol and starch are extremely advantageous.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set to the desired values in a targeted manner.
  • the water-soluble bag is preferably from 10 ⁇ m to 500 ⁇ m, in particular from 20 ⁇ m to 400 ⁇ m, particularly preferably from 30 ⁇ m to 300 ⁇ m, especially from 40 ⁇ m to 200 ⁇ m, in particular from 50 ⁇ m to 150 ⁇ m.
  • a particularly preferred polyvinyl alcohol is available, for example, under the trade name M8630 (Monosol).
  • the water-soluble film which is preferably used in the tight envelope), particularly preferably comprises polyvinyl alcohol, as described above, the starting thickness preferably being from 10 ⁇ m to 100 ⁇ m, in particular from 12 ⁇ m to 60 ⁇ m, particularly preferably from 15 ⁇ m to 50 ⁇ m, in particular from 20 ⁇ m to 40 ⁇ m, in particular from 22 ⁇ m to 35 ⁇ m, is used.
  • a single portion of the detergent or cleaning agent is coated in each case.
  • the coating lies tightly against the surface of the tablets at every point.
  • the envelope is even under tension, but this is not absolutely necessary.
  • This tight fit of the cover is conducive to disintegration: the first time it comes into contact with water, a small amount of water will let through at some point, and it does not have to come off at first. At this point the disintegrant contained in the tablet begins to swell. As a result of the increase in volume of the tablet, the envelope now suddenly tears open and the tablet is released.
  • the mechanism described here does not work if the casing is not tightly fitting, since the tablet can swell without the casing being ruptured as a result.
  • the use of a swellable disintegrant is superior to a gas-generating system, since its disintegrating effect always leads to the covering being torn open.
  • the explosive effect can "fizzle out" as the gas escapes from a leak in the casing.
  • Preferred washing or cleaning agent single portions according to the invention are characterized in that the distance between the single portion and the water-soluble cover over the entire surface is 0.1 to 1000 ⁇ m, preferably 0.5 to 500 ⁇ m, particularly preferably 1 to 250 ⁇ m and in particular 2.5 to 100 ⁇ m.
  • the film envelope is first placed loosely around a single portion of detergent or cleaning agent and welded and then shrunk onto it, so that there is close contact between the film packaging and the cleaning agent concentrate. Accordingly, one-time washing or cleaning agent portions according to the invention are characterized in that the cover is a film packaging shrunk onto it.
  • this wrapping can take place in that a water-soluble lower film is placed on a transport chain or a mold (s), then one or more detergent or cleaning agent portions are placed on the lower film; then a water-soluble upper film is placed on the detergent or cleaning agent portion (s) on the lower film and this is then fixed on the lower film, including the washing or cleaning agent portion (s).
  • this step can also be carried out by a single-strand film, which is then used as Tubing around the disposable portions. This is followed by sealing and optional cutting of the foils. Then the film can then be shrunk on using hot air or infrared radiation, optionally with pressure applied.
  • the at least one first phase (1) of the washing or cleaning agent according to the invention in particular the dishwashing detergent, preferably the automatic dishwashing detergent, is in a preferred embodiment in the form of a shaped body, in particular a compact, especially a tablet.
  • the at least one first phase (1) is particularly preferably a powdered detergent or cleaning agent which is compacted in the form of a tablet.
  • the at least one first phase (1) and the at least one second phase (2) can be arranged in any combination with one another, regardless of whether they are directly or indirectly (for example through the presence of a film, envelope or bag as described above).
  • a first phase (1) can be arranged on or next to a second phase (2), as in FIG Fig. 1 shown schematically.
  • the washing or cleaning agent according to the invention has a first phase (1) and a second phase (2). It is also conceivable that a first phase (1) is surrounded by second phases (2), or vice versa, as in FIG Figures 2a and 2b shown. Also embedding one phase in another, as in Figures 3a and 3b shown schematically, is included according to the invention. Another particularly preferred arrangement is shown in FIG Fig. 4 shown schematically.
  • the second phase (2) is in the form of a core that is embedded in the first phase (1).
  • a pool shape of the solid first phase (1) that is to say a shape with a trough into which the second phase is introduced, is particularly preferred.
  • the trough can be round, oval or square.
  • the washing or cleaning agent comprises two second phases (2), it being possible for the two second phases to have different compositions.
  • any geometries are possible.
  • the rectangular shape shown here is only an example.
  • a round or oval shape of the two phases or any polygonal configurations are also conceivable.
  • Another object of the present application is a method for cleaning hard surfaces, in particular dishes, in which the surface is processed in a manner known per se using a cleaning agent according to the invention.
  • the surface is brought into contact with the washing or cleaning agent according to the invention.
  • the cleaning takes place in particular with a cleaning machine, preferably with a dishwasher.
  • the present invention also relates to the use of a cleaning agent for cleaning hard surfaces, in particular dishes.
  • automatic dishwashing agents are compositions which can be used to clean soiled dishes in an automatic dishwashing process.
  • the automatic dishwashing agents according to the invention thus differ, for example, from the automatic rinse aid agents, which are always used in combination with automatic dishwashing agents and do not develop their own cleaning effect.
  • washing or cleaning agent comprises something in its entirety or in the at least one first phase (1) or in the at least one second phase (2), it is also to be regarded as disclosed that washing or Cleaning agent or the respective phase can consist of it.
  • inventive washing or cleaning agent is described in a non-limiting manner.
  • Cleaning agents according to the invention were produced which comprised a first phase and a second phase. Different geometries were implemented here. In addition, cleaning agents were produced which comprised two first phases and a second phase. The following information relates to% by weight of active substance based on the total weight of the respective phase.
  • the first phases had the following composition: Wt% Citrate, sodium salt 10-25 Phosphonate (e.g. HEDP) 0-10 MGDA, sodium salt 0-40 Disilicate, sodium salt 0-40 soda 10-30 Percarbonate, sodium salt 5.0-20.0 Bleach catalyst (preferably Mn-based) 0.0-0.8 Bleach activator (e.g. TAED) 1.0-4.0
  • Bleach catalyst preferably Mn-based
  • Bleach activator e.g. TAED
  • Nonionic surfactant for example fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 1.5-15.0
  • Polycarboxylate 0.5-15 Cationic copolymer 0.0-1.0 Disintegrant - (e.g.
  • the first phases were produced, which had the following composition: Wt% Citrate, sodium salt 15-20 Phosphonate (e.g. HEDP) 2.5-7.5 MGDA, sodium salt 0-25 Disilicate, sodium salt 5-35 soda 10-25 Percarbonate, sodium salt 10-15 Bleach catalyst (preferably Mn-based) 0.02-0.5 Bleach activator (e.g. TAED) 1-3 Nonionic surfactant (s), 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.
  • first phases were in the form of a compacted tablet with a depression on one side.
  • a liquid composition was poured into this which, after hardening, resulted in the second phase.
  • the detergent obtained was in accordance with the in Fig. 4 shown form.
  • a second phase was brought into direct contact on the surface of the first phase.
  • the second phases had the following composition: Wt% Glycerin 10-50 Propanediol (preferably 1,3-propanediol) 10-50 Polycarboxylate homo- and / or copolymer with sulfonic acid-containing groups 0-30 Nonionic surfactant (s), for example fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 0-40 Polyethylene glycol medium Mr 1000-2000 0-20 Thickener (preferably gelatin or PVA) 5-50 Process aids 0-10 Dye solution 0.0 -1.5
  • the first and second phases could be combined with one another as required.
  • the spatial design of the second phase which was liquid after the ingredients were mixed and dimensionally stable within a solidification time of about 10 to 15 minutes, was given by the spatial design of the first phase and by customary or self-designed shapes.
  • the liquid second phase was introduced into these molds and, after the solidification time, the molds were removed without the second phase changing. This enabled any desired geometries for the second phase.
  • Table 1 Examples of compositions of a second phase A1 A2 1,2 propanediol 0.0 31 1.3 propanediol 31 0.0 Trisodium Citrate * 2 H 2 O 8th 8th Glycerin 31 31 Gelatin 60 Bloom 15th 15th Nonionic surfactant 15th 15th Solidification time (20 ° C) / min 5 20th Surface feel after 12 h storage at 20 ° C dry wet

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DE102015213943A1 (de) * 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel umfassend wenigstens zwei Phasen
KR102674117B1 (ko) * 2017-01-24 2024-06-12 헨켈 아게 운트 코. 카게아아 적어도 2개의 상을 갖는 세제 또는 세정제 분배물
DE102017201097A1 (de) * 2017-01-24 2018-07-26 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel umfassend wenigstens zwei Phasen
DE102018221584A1 (de) * 2018-12-13 2020-06-18 Henkel Ag & Co. Kgaa Verfahren zur Herstellung mehrphasiger Wasch- oder Reinigungsmittelformkörper
FR3109392B1 (fr) * 2020-04-20 2023-06-30 Eurotab Operations Ensemble de tablette détergente
DE102021203326A1 (de) 2021-04-01 2022-10-06 Henkel Ag & Co. Kgaa Waschmittelportionseinheit
DE102021203324A1 (de) 2021-04-01 2022-10-06 Henkel Ag & Co. Kgaa Waschmittelportionseinheit
DE102021203325A1 (de) 2021-04-01 2022-10-06 Henkel Ag & Co. Kgaa Waschmittelportionseinheit
DE102021203328A1 (de) 2021-04-01 2022-10-06 Henkel Ag & Co. Kgaa Waschmittelportionseinheit
DE102022125211A1 (de) 2022-09-29 2024-04-04 Henkel Ag & Co. Kgaa Geschirrreinigungsmittelportionseinheit aus Gel und verpresster Phase

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US20200239812A1 (en) 2020-07-30
US11912963B2 (en) 2024-02-27
DE102015213943A1 (de) 2017-01-26
US20190085265A1 (en) 2019-03-21
EP3325595B1 (fr) 2020-06-17
ES2809824T3 (es) 2021-03-05
US10626352B2 (en) 2020-04-21
US20220411723A1 (en) 2022-12-29
PL3325595T3 (pl) 2021-01-11
EP3325595A1 (fr) 2018-05-30

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