EP3574073A1 - Détergent comprenant au moins deux phases - Google Patents

Détergent comprenant au moins deux phases

Info

Publication number
EP3574073A1
EP3574073A1 EP18701335.4A EP18701335A EP3574073A1 EP 3574073 A1 EP3574073 A1 EP 3574073A1 EP 18701335 A EP18701335 A EP 18701335A EP 3574073 A1 EP3574073 A1 EP 3574073A1
Authority
EP
European Patent Office
Prior art keywords
phase
acid
weight
washing
cleaning agent
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
EP18701335.4A
Other languages
German (de)
English (en)
Inventor
Oliver Kurth
Luca Bellomi
Inga Kerstin Vockenroth
Klaus Dorra
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3574073A1 publication Critical patent/EP3574073A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/2075—Carboxylic acids-salts 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts 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
    • C11D3/37—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
    • 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

  • Washing or cleaning agent comprising at least two phases
  • the present invention relates to a washing or cleaning agent, in particular a
  • Hard surface cleaning agents having at least two different phases.
  • Detergents or cleaners are usually in solid form (for example as a powder) or in liquid form (or as a flowing gel). Solid washing or cleaning agents have the advantage that, in contrast to liquid detergents or cleaners, no
  • Liquid supply forms are increasingly gaining acceptance on the market, in particular due to their rapid solubility and the associated rapid availability of the active ingredients contained. This offers the consumer the opportunity to use time-shortened rinse programs and still obtain a good cleaning performance.
  • pouched products often change their visual appearance, often creating associations with reduced performance and cleaning performance for the consumer.
  • the object underlying the present application is therefore achieved by a washing or cleaning agent comprising at least a first phase (1) and at least one second phase (2) different therefrom
  • the at least one first phase (1) is solid and in particular powdery and
  • the at least one second phase (2) comprises at least one polymer, at least one polyhydric alcohol and at least one organic acid, wherein the pH of a 1% solution of the at least one second phase (2) in water at 20 ° C 6 or less.
  • 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, such as ingredients, physical properties, appearance, etc.
  • different phases can be visually distinguished.
  • the at least one first phase is clearly distinguishable visually from the at least one second phase.
  • the surface of the second phase for example, should differ significantly from the first phase by a pronounced gloss.
  • the surface of the solid at least a first phase is usually not glossy but dull, dull or dull, so that a gloss is a good distinction, which makes the detergent or cleaning agent attractive to the consumer, is possible.
  • the washing or cleaning agent according to the invention has more than one first phase, then these can likewise be differentiated from one another by the naked eye, because they differ, for example, from one another in color.
  • two or more second phases are present.
  • a visual differentiation of the phases for example due to a color or transparency difference is possible.
  • Phases in the context of the present invention are thus self-contained areas that are from the consumer can be visually distinguished from each other by the naked eye.
  • the individual phases may have different properties in use, such as the rate at which the phase dissolves in water and thus the rate and order of release of the ingredients contained in the respective phase.
  • the at least one second phase is dimensionally stable at room temperature.
  • the at least one polymer is contacted with the at least one polyhydric alcohol and the acid. This gives a flowable mixture which can be brought into a desired shape.
  • a second phase is obtained which remains in the given form, ie is dimensionally stable. This period, the
  • Solidification time is preferably 15 minutes or less, preferably 10 minutes or less, more preferably 5 minutes.
  • the at least one second phase yields to pressure, but does not deform as a result, but returns to the initial state after the pressure has ceased to exist.
  • the at least one second phase is preferably elastic, in particular linear-elastic.
  • the at least one second phase is also preferably transparent, resulting in a good visual impression.
  • the least a second phase is thus gelatinous. It is preferably free of solid substances that are not present in dissolved form.
  • the at least one second phase is thus not a solid, powdery phase.
  • the at least one second phase is cut-resistant. It can, for example, be cut with a knife after solidification without being further destroyed except for 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 a breaking strength, whereby a good handling, in particular with regard to transport and storage but also the consumption is possible.
  • At least one bleach catalyst means 1 or more, that is, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • at least one bleach catalyst means at least one type of bleach catalyst, that is, one type of bleach catalyst or a mixture of several different bleach catalysts.
  • weight information refers to all compounds of the specified type which are contained in the composition / mixture, that is to say 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 mass average molecular weight M w can also be determined by GPC, as described for M n .
  • the at least one first phase is present in compressed form.
  • the washing or cleaning agent according to the invention thus comprises at least a first solid, compressed phase, as well as at least one second phase comprising at least one polymer, and at least one polyhydric alcohol and at least one organic acid.
  • Solidification time means the period of time during which the at least one second phase changes from a free-flowing to a dimensionally stable state which is not flowable at room temperature. This can be done, but without limitation, by crosslinking the at least one polymer.
  • Room temperature is understood to mean a temperature of 20 ° C.
  • the second phase must be storage stable, under normal storage conditions.
  • the second phase according to the invention is part of a washing or cleaning agent. washing or detergents are usually stored in a household over a period of time. Storage usually takes place near the washing machine. For such storage, the second phase should be stable.
  • the second phase in particular after a storage time of, for example, 4 to 12, especially 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 stable and do not deform or otherwise change in consistency at this time.
  • a disadvantage would be a change in volume or shrinkage during storage, since this would make the acceptance of the product at the consumer low. Also leakage of liquid or exudation of components from the second phase is undesirable. Again, on the one hand the visual impression of relevance. By the escape of liquid, such as solvent, the stability of the second phase can be influenced, so that the components are no longer stable and thereby also the washing or
  • 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, for example, that no ingredients or solvents from one phase to another 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 by Color change, formation of moist edges, blurring boundary between the two phases or the like,
  • a second phase comprising an organic acid enables particularly good storage stability and a particularly good combination with an at least first solid phase.
  • suitable organic acids have a pKa of from 0 to 8, in particular from 1 to 4.5; more preferably from 1, 5 to 4. If an organic acid has several pK s values, the pKsi value is meant according to the invention.
  • citric acid particularly suitable are citric acid, glutaric acid, tartaric acid, glycolic acid, oxalic acid and / or amidosulfuric acid.
  • these acids can be used alone or in combination with each other.
  • an acid is used alone.
  • citric acid is used as organic acid, this is to be understood as meaning the anhydrate or the monohydrate.
  • Oxalic acid can be used in particular in the form of a dihydrate.
  • glutaric acid has been used, a very rapid curing time has resulted, so glutaric acid is preferred from this point of view.
  • a slower cure is possible compared to other acids with amidosulfuric acid. Since short cure times are preferred, amidosulfuric acid is less preferred.
  • the organic acid is particularly preferably selected from citric acid (anhydrate or monohydrate), glutaric acid, tartaric acid, glycolic acid and / or oxalic acid, particularly preferably citric acid (anhydrate or monohydrate), glutaric acid and / or tartaric acid.
  • Tartaric acid is preferably L (+) tartaric acid.
  • L (+) tartaric acid and citric acid both anhydrate and monohydrate show comparable properties of the at least one second phase.
  • Citric acid is particularly preferably used in the form of anhydrate or monohydrate, since they are inexpensive to obtain and good products in terms of
  • the pH of the at least one second phase has an influence on the stability of the washing or cleaning agent as a whole. In particular, this influences the interaction between the at least one first fixed and the at least one second phase.
  • the first phase is present as a solid and especially compressed phase. This is preferably a powdered washing or cleaning agent in the form of a tablet.
  • the at least one first phase is also preferably in direct contact with the at least one second phase.
  • the problem here is often that there are interactions between the first and the second phase, so that the components contained in the at least one first phase are solved by the second phase. As a result, the adhesion between the two phases can be adversely affected, so that there is a separation of the two.
  • the pH of a 1% solution of the at least one second phase (2) in water at 20 ° C 6 or less is preferably in the range from 1 to 5, in particular in the range from 2 to 4.
  • the pH was determined during the preparation of the at least one second phase (2). In this case, a first sampling took place immediately after the mixing of all components which are contained in the second phase, as well as at the end of the manufacturing process. The pH did not change significantly.
  • the proportion of organic acid contained in the at least one second phase (2) is dependent on the type of acid, but is preferably in the range of 5 wt .-% to 20 wt .-%, in particular of 7 wt. -% to 14 wt .-%, based on the total weight of the second phase (2). Corresponding amounts of organic acid are sufficient to allow the desired pH. At the same time, one more organic acid does not provide for another
  • the at least one second phase (2) is substantially free of water.
  • the at least one second phase (2) is preferably substantially free of water.
  • Substantially free here means that in the second phase small amounts of water can be contained.
  • This water can be used, for example, as water of crystallization or due to
  • Reactions of constituents of the phase are introduced into the phase with each other. However, no water is added in the production of 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 (2).
  • the at least one second phase (2) comprises at least one polymer.
  • the at least one polymer is particularly suitable for forming a network.
  • the at least one second phase may comprise a polymer, or two or more polymers which are different from one another. In particular, it has one, two or more, in particular one or two, preferably a polymer, which is suitable for forming a network.
  • the at least one second phase may comprise one or more polymers which do not form a network, but to a thickening and thus to increase the dimensional stability of at least lead a second phase, called thickening polymers.
  • the at least one second phase therefore comprises at least one, preferably a polymer for network formation and one or more thickening polymers.
  • the at least one second phase comprises PVA (polyvinyl alcohol) and / or gelatin as polymers suitable for network formation.
  • the at least one second phase comprises a thickening polymer and in particular polycarboxylates as thickening polymer.
  • Polyvinyl alcohols are thermoplastics which are produced as a white to yellowish powder mostly by hydrolysis of polyvinyl acetate.
  • Polyvinyl alcohol (PVA) is resistant to almost all anhydrous organic solvents. Preference is given to polyvinyl alcohols having a molecular weight of 30,000 to 60,000 g / mol.
  • Gelatine is a mixture of 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-fledged protein.
  • Gelatin swells in water and dissolves when heated from about 50 ° C. Upon cooling, a gel forms, which becomes liquid on renewed heating.
  • At least one second phase which comprises gelatin and / or PVA and at least one polyhydric alcohol and at least one organic acid is particularly preferred. More preferably, the at least one second phase comprises gelatin, at least one polyhydric alcohol. Also preferably, the at least one second phase comprises PVA, at least one polyhydric alcohol and at least one organic acid.
  • 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 30, in particular 18 to 28 wt .-%.
  • the phases remain soft for longer, resulting in a prolonged solidification time and thus a prolonged manufacturing process.
  • the at least one second phase (2) comprises gelatin.
  • the second phase comprises gelatin having a Bloom value in the range of 60 to 225.
  • the Bloom value describes the gelatinization or gelatinizing power of gelatine.
  • the metric is the mass in grams needed to allow a 0.5 inch diameter punch to deform the surface of a 6.67% gelatin / water mixture four millimeters deep without tearing it. The test takes place standardized at exactly 10 ° C with a preceding aging of the gelatin of 17 hours instead.
  • the at least one second phase (2) comprises gelatin having 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 of 10% by weight. % to 30 wt .-%, in particular from 15 wt .-% to 25 wt .-%.
  • 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 having a bloom value of 180 or more, in particular of 200 or more, especially of 225 Preference is given to gelatin having a bloom value of 180 or more, in particular of 200 or more, especially of 225.
  • the viscosity of the second phase in the preparation can be well controlled.
  • the amount of gelatin required here is lower than that of the
  • the toughness of the second phase (2) is increased during production.
  • the second phase comprises gelatin and an anionic one Copolymer / polymer.
  • the proportion of the anionic polymer is preferably 1 wt .-% to 35 wt .-%, in particular 3 wt .-% to 30 wt .-%, especially 5 wt .-% to 25 wt .-%, preferably 5 wt. % to 20 wt .-% based on the total weight of the second phase.
  • Sulfopolymers also provide excellent surface gloss. In addition, stay
  • the proportion of sulfopolymers, in particular sulfopolymers with AMPS as a sulfonic acid group-containing monomer for example Acusol 590, Acusol 588 or Sokalan CP50, preferably 1 wt .-% to 25 wt .-%, in particular 3 wt .-% to 15 wt. %, especially 4 wt .-% to 12 wt .-%, preferably 5 wt .-% to 10 wt .-% based on the weight of the second phase.
  • the at least one second phase comprises gelatin as well as a sulfopolymer and at least one polyhydric alcohol.
  • the at least one second phase (2) may further comprise at least one
  • Thickening polymer include. This is preferably a polycarboxylate.
  • the polycarboxylate is preferably a copolymeric polyacrylate, preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified
  • copolymeric polysulfonate may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting 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,
  • H 2 C CH-X-SO 3 H
  • H 2 C C (CH 3 ) -X-SO 3 H or H0 3
  • SX- (R 6 ) C C (R 7 ) -X-SO 3 H
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salt
  • Sulfonic acid groups in whole or in part in neutralized form that is, 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 against sodium ions.
  • metal ions preferably alkali metal ions and in particular against sodium ions.
  • the use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the share of
  • the molecular weight of the invention Sulfo copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred detergents are characterized in that the copolymers have molecular weights from 2000 to 200,000 g mor, preferably 4,000 to 25,000 g mor 1 and especially 5,000 to 15,000 g mol.
  • the copolymers include besides
  • Carboxyl-containing monomer and sulfonic acid-containing monomer further at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible, in particular, to improve the rinse aid performance of dishwashing compositions according to the invention.
  • the at least one second phase further comprises an anionic one
  • nonionic monomers especially hydrophobic monomers
  • 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-dimethlyhexene-1,3,5-dimethylhexene-1 , 4,4-dimethylhexane-1, ethylcyclohexene, 1-octene, ⁇ -olefins of 10 or more
  • Carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22- ⁇ -olefin, 2-styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2 Ethyl 4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, Ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, A / - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, A / - (2-ethylhexyl) acrylamide
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • the at least one second phase may also contain other polymers, such as
  • PEG in particular those polyethylene glycols having an average molecular weight between about 200 and 8000, between about 800 and 4000 g / mol, more preferably with an average molecular weight between 1000 and 2000 g / mol, for example, about 1500 g / mol (INCI:
  • the at least one second phase (2) further comprises at least one polyhydric alcohol.
  • the at least one polyhydric alcohol makes it possible to produce a dimensionally stable, non-flowable second phase within a short solidification time which is 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 are replaced by OH groups. The OH groups are each different
  • a carbon atom thus has no two OH groups.
  • Polyhydric alcohols with two OH groups are referred to as alkanediols, polyhydric alcohols with three OH groups as alkanetriols.
  • 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 be effected, for example, with -SH or -NH groups.
  • KW is a linear or branched, saturated or unsaturated, unsubstituted hydrocarbon.
  • KW comprises at least two carbon atoms.
  • KW comprises 2 to 10, ie 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms.
  • the at least one second phase (2) comprises at least one alkanediol.
  • the alkanediol is particularly preferably a C3 to Cio-alkanediol, more preferably a C3 to Cs alkanediol.
  • the at least one second phase (2) particularly preferably comprises at least one alkanetriol and / or at least one alkanediol, in particular at least one C3 to C10 alkanetriol and / or at least one C3 to C10 alkanediol, preferably at least one C3 to C5 Alkanetriol and / or at least one C3 to Cs alkanediol, especially at least one C3 to C6 alkanetriol and / or at least one C3 to C5 alkanediol as a polyhydric alcohol. It preferably comprises a
  • 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 especially an alkanetriol and an alkanediol.
  • a second phase comprising at least one polymer, in particular gelatin and / or PVA, at least one organic acid, and a C3 to Cs alkanediol and a C3 to Cs alkanetriol.
  • a second phase comprising at least one polymer, in particular gelatin and / or PVA, at least one organic acid, and a C3 to Cs alkanediol and a C3 to C6 alkanetriol.
  • a second phase comprising at least one polymer, in particular gelatin and / or PVA, at least one organic acid, and a C3 to Cio alkanediol, in particular a C3 to Cs alkanediol.
  • diol and alkanediol are used interchangeably herein. The same applies to triol and alkanetriol.
  • the polyhydric alcohols do not include derivatives such as ethers, esters, etc.
  • the amount of polyhydric alcohol or polyhydric alcohol used in the second phase of the present invention is preferably at least 45% by weight, more preferably 55% by weight or more.
  • Preferred quantitative 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 C3 to C6 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). These are particularly suitable for incorporating active ingredients homogeneously into the at least one second phase.
  • the C 3 -C 6 -alkanetriol is particularly preferably glycerol and / or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (also called 1,1,1-trimethylolpropane).
  • the C3 to Csalkanediol is preferably 1,3-propanediol and / or 1,2-propanediol.
  • the chain length of the diol and in particular the position of the OH groups has an influence on the transparency of the second phase.
  • the OH groups of the diol are not arranged on immediately adjacent C atoms.
  • between the two OH groups of the diol are three or four carbon atoms, in particular 3 carbon atoms.
  • Particularly preferred is the diol 1, 3-propanediol.
  • the second phase (2) comprises in addition to the at least one organic acid gelatin, glycerol and 1, 3-propanediol or gelatin, 1, 1, 1-trimethylolpropane and 1, 3-propanediol.
  • a dimensionally stable within a solidification time of 10 minutes or less a dimensionally stable, non-flowable consistency can be achieved at room temperature, which remains dimensionally stable even after prolonged storage.
  • a corresponding phase is transparent and has a shiny surface.
  • a particularly preferred second phase therefore comprises gelatin or PVA as polymer and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols and citric acid as organic acid.
  • 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 .-% to 70 wt .-%, in particular 10 wt .-% to 65 wt .-%, especially 20 wt .-% to 40 wt .-%.
  • the second phase optionally comprises a plurality of alkanetriol (s), 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 65 wt .-%, especially 20 wt .-% to 40 wt .-%.
  • glycerol is contained as alkanetriol in the second phase, then the proportion of glycerol based on the total weight of the second phase, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20% to 40% by weight.
  • 1, 1, 1 -Trimethylolpropan contained in the second phase the proportion of 1, 1, 1-trimethylolpropane based on the total weight of the second phase, preferably 1 wt .-% to 50 wt .-%, in particular 5 wt .-% to 30 wt .-%, especially 10 wt .-% to 20 wt .-%.
  • the proportion of 2-amino-2-hydroxymethyl-1, 3-propanediol, based on the total weight of the second phase is preferably 1 Wt .-% to 70 wt .-%, in particular 5 wt .-% to 50 wt .-%, especially 10 or 20 wt .-% to 40 wt .-%. If several alkanediols are optionally contained in the second phase, the amount is preferably 1 Wt .-% to 70 wt .-%, in particular 5 wt .-% to 50 wt .-%, especially 10 or 20 wt .-% to 40 wt .-%. If several alkanediols are optionally contained in the second phase, the amount is optionally contained in the second phase.
  • Alkanediols based on the total weight of the second phase, preferably 5 wt .-% to 70 wt .-%, in particular 10 wt .-% to 65 wt .-%, 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 15 wt .-% to 65 wt .-%, especially 30 wt .-% to 60 wt .-%.
  • Is 1, 3-propanediol in the second phase the proportion of 1, 3-propanediol, based on the total weight of the second phase, in particular 10 wt .-% to 65 wt .-%, especially 20 wt .-% to 45% by weight.
  • the weight ratio is preferably 3: 1 to 2: 1.
  • the weight ratio is 2: 1, when glycerol and 1, 3-propanediol are included as polyhydric alcohols.
  • Temperatures can be improved if the at least one second phase (2) 2-methyl-2-hydroxymethyl-1, 3-propanediol and / or 2-ethyl-2-hydroxymethyl-1, 3-propanediol, especially 2-methyl-2 -hydroxymethyl-1,3-propanediol.
  • the at least one phase furthermore comprises 2-methyl-2-hydroxymethyl-1,3-propanediol and / or 2-ethyl-2-hydroxymethyl-1,3-propanediol, in particular 2-methyl-2-hydroxymethyl- 1, 3-propanediol, in particular in a proportion of 25 wt .-% or less, preferably from 20 wt .-% or less, each based on the total weight of the at least one second phase (2).
  • 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
  • the at least one first phase (1) and the at least one second phase (2) each comprise at least one surfactant.
  • the at least one first phase (1) or only the at least one second phase (2) comprise at least one surfactant.
  • both phases comprise a surfactant, they are preferably different surfactants.
  • the first and second phases have the same surfactant or surfactants.
  • At least one first and / or second phases according to the invention preferably contain at least one nonionic surfactant.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. 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 is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • Indicating oligoglycosides is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • nonionic surfactants 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 having 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 may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • the washing or cleaning agents according to the invention contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 linear and methyl-branched radicals may be contained in the mixture, as they usually in Oxoalkoholresten present.
  • EO ethylene oxide
  • alcohol ethoxylates having linear residues of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol.
  • Preferred ethoxylated alcohols include, for example Ci2-i4-alcohols with 3 EO or 4 EO, Cs-n-alcohol with 7 EO, Cis-is alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 2 -i8 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4 alcohol with 3 EO and C12-18 alcohol with 5 EO.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank 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 have been obtained from C 6-2o -monohydroxyalkanols or C 6-2o-alkylphenols or C 16-2o-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, used.
  • a particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20
  • Carbon atoms (Ci6-2o-alcohol), preferably a cis-alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow ranks ethoxylates” are particularly preferred.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants which alternating ethylene oxide and ethylene oxide
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R2 R3 in which R 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 -Chta, -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 are integers from 1 to 6.
  • Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R -OH and ethylene or alkylene oxide.
  • the radical R in the above formula may vary depending on the origin of the alcohol. When native sources are used, the radical R has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol , are preferred. Examples of alcohols which are accessible from synthetic sources are the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, such as are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from - CH 2 CH 2 -CH 3 or -CH (CH 3) 2 are suitable.
  • nonionic surfactants of the first phase are nonionic surfactants of the general formula
  • R 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 is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
  • x and y independently represent values between 1 and 70;
  • M is an alkyl radical of the Group CH 2, CHR 3, CR 3 R 4, CH 2 CHR 3 and CHR 3 CHR 4, wherein R 3 and R 4 independently 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 is -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 ,
  • R, R and R 2 independently represent an alkyl group or alkenyl group having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.
  • R is -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 ,
  • 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 of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.
  • Preferred nonionic surfactants here are those of the general formula R-CH (OH) CH 2 O- (AO) w- (AO) x- (A "O) y - (A" O) z R 2 , in which
  • R is a straight-chain or branched, saturated or mono- or polysubstituted
  • R 2 is hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, ⁇ ', A "and A'" independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ),
  • - w, x, y and z are values between 0.5 and 120, where x, y and / or z are also 0
  • R-CH (OH) CH 2 O- (AO) w- (AO) x- (A "0) y- (A” O) z R 2 also referred to below as "hydroxy mixed ether"
  • hydroxy mixed ether also referred to below as "hydroxy mixed ether”
  • nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the detergent formulations according to the invention can be markedly improved.
  • end-capped poly (oxyalkylated) nonionic surfactants which, according to the following formula
  • R which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2
  • R stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60.
  • surfactants of the formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] yCH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched one
  • the group of these nonionic surfactants includes, for example, the C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular also the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,
  • R and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3, -CH 2 CH 3, -CH 2 CH 2 -CH 3, - CH (CH 3) 2, but preferably represents -Ch
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] jOR 2 ,
  • R and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x are values between 1 and 30
  • k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R 3 in the above formula
  • R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] kCH (OH) [CH 2 ] jOR 2 be different.
  • R and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic
  • Hydrocarbon radicals having 6 to 22 carbon atoms with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -Chta or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • R 0 [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R 1 R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R and R 2 Have 9 to 14 carbon atoms, R 3 is H and x assumes values of 6 to 15.
  • the nonionic surfactants of the general formula R - CH (OH) CH 2 O - (AO) w - R 2 have proven to be particularly effective, in which
  • R is a straight-chain or branched, saturated or mono- or polysubstituted
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A is a radical from the group CH 2 CH 2, CH 2 CH 2 CH 2, CH 2 CH (CH 3), preferably for
  • CH2CH2 stands, and w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.
  • the group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • the at least one first and / or at least one second phase preferably contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the second phase is preferably from 0.5% by weight to 30% Wt .-%, preferably 5 wt .-% to 25 wt .-% and in particular 10 wt .-% to 20 wt .-% is.
  • nonionic surfactant of the first and / or second phase is selected from nonionic surfactants of the general formula
  • R -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y O -R 2 in which R and R 2 independently represent an alkyl 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 represent values between 1 and 40.
  • R -O (CH 2 CH 2 O) xCR 3 R 4 (OCH 2 CH 2 ) yO-R 2 in which the radicals R and R 2 independently of one another represent saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y independently of one another represent values from 1 to 15 and in particular from 1 to 12 assume.
  • R -O (CH 2 CH 2 O) xCR 3 R 4 (OCH 2 CH 2 ) yO-R 2 , in which one of the radicals R and R 2 is branched.
  • R -0 (CH2CH20)
  • XCR 3 (OCH 2 CH 2)
  • y O-R 2 in the accept the indices x and y are independently values of 8 to 12
  • Alkoxylation levels of the nonionic surfactants represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the Herste II process exist commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is suitable for both the C-chain lengths and for the Degree of ethoxylation or degrees of alkoxylation may give mean values and numbers which are subsequently broken.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may 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 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units (PO) in the molecule.
  • PO propylene oxide units
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • 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 constitutes more than 30% by weight, more 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 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • nonionic surfactants to be used in the first phase having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles 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
  • Trimethylolpropane contains.
  • the proportion by weight of the nonionic surfactant in the total weight of the first phase in a preferred embodiment 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.
  • Suitable anionic surfactants in dishwashing detergents are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts having 2 to 4 C 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
  • Ethercarbon yarn having 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.
  • the at least one second phase (2) is therefore free of surfactants, in particular of nonionic surfactants.
  • Phase properties in particular their hardness, friability (abrasion behavior) and
  • the at least one second phase (2) may continue to comprise sugar.
  • sugars comprise monoscartides, disaccharides and oligosaccharides.
  • the second phase comprises disaccharides, especially sucrose.
  • the proportion of sucrose is 0 wt .-% to 30 wt .-%, in particular 5 wt .-% to 25 wt .-%, particularly preferably 10 wt .-% to 20 wt .-%, based on the weight of the second Phase.
  • the sugar does not dissolve completely in the second phase, causing it to cloud.
  • the use of sugar in particular in a proportion of 10% by weight to 5% by weight, reduces the moisture development and thus improves the adhesion to the 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, may be advantageous.
  • the use of phosphates is largely or completely omitted.
  • the agent in the at least one first and / or the at least one second phase, in particular in the at least one first and the at least one second phase 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 completely phosphate-free, i. the agents contain less than 0.1% by weight of phosphate (s).
  • the builders include in particular carbonates, citrates, phosphonates, organic acids, and organic acids.
  • the proportion by weight of the total builders in the total weight of compositions according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight. These are preferably contained in the at least one first phase.
  • Suitable organic builders according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids 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 Carry acid functions throughout the molecule.
  • Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups. These are, for example, 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, especially aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine-N, N-diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA),
  • NTA nitrilotriacetic acid
  • glutamine-N glutamine-N
  • N-diacetic acid also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA
  • Methylglycinediacetic acid and its derivatives and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.
  • polymeric polycarboxylates organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the
  • Macromolecule Polyaspartates, polyacetals and dextrins.
  • the free acids typically also have the property of an acidifying component.
  • an acidifying component In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these may be mentioned here.
  • washing or cleaning agents according to the invention, in particular
  • Dishwashing agents preferably automatic dishwashing agents, contain as one of their essential builders one or more salts of citric acid, ie citrates. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to Contain 20 wt .-%, each based on the total weight of the composition.
  • washing or cleaning agents according to the invention, in particular
  • Dishwashing agents preferably automatic dishwasher detergents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates,
  • Amino carboxylic acids and citrates contain, wherein the weight fraction of these builders, based on the total weight of the cleaning agent according to the invention, preferably 5 to 70 wt .-%, preferably 15 to 60 wt .-% and in particular 20 to 50 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has for the cleaning and rinsing performance of inventive detergents or cleaning agents, in particular
  • Dishwashing detergents preferably automatic dishwasher detergents, have proved to be advantageous.
  • one or more other builders may additionally be present.
  • Preferred washing or cleaning agents in particular dishwashing detergents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate.
  • a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight.
  • the amount of citrate is preferably from 5 to 35% by weight, in particular from 10 to 25% by weight, very particularly preferably from 15 to 20% by weight, based in each case on the total amount of the cleaning agent, the total amount of these two being Builders preferably 20 to 65 wt .-%, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is. In addition, one or more further builders may additionally be included.
  • washing or cleaning agents according to the invention in particular dishwashing detergents, preferably automatic dishwashing detergents, can be used as further builders in particular
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • hydroxyalkane phosphonates the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance.
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are preferably present in compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular in amounts of 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 particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-%
  • washing or cleaning agents in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized in that they contain, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, at least one further phosphorus-free one
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic diacetic acid
  • HEIDA Hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • EDDS ethylenediamine disuccinate
  • a particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.
  • the percentage by weight of the further phosphorus-free builder, in particular of 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.
  • Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules.
  • MGDA granules which contain as little water as possible and / or a lower hygroscopicity compared to the non-granulated powder
  • Dishwashing detergents preferably automatic dishwasher detergents, have proved to be advantageous.
  • other builders may be included.
  • organic builders polymeric polycarboxylates are also suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid,
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1100 to 10 000 g / mol, and particularly preferably from 1200 to 5000 g / mol, may again be preferred from this group.
  • Dishwashing detergent preferably automatic dishwashing detergent, on (homo) polymers
  • Polycarboxylates is preferably 0.5 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 10 wt .-%.
  • Inventive washing or cleaning compositions especially dishwashing detergent, preferably automatic dishwashing agents as a builder may also crystalline layered silicates of general formula NaMSix02x + i y ⁇ H2O wherein M is sodium or hydrogen, x is a Number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and
  • Dishwashing agents preferably automatic dishwasher detergents, the content of silicates, based on the total weight of the washing or cleaning agent, to amounts below 10 wt .-%, preferably below 5 wt .-% and in particular below 2 wt .-% limited.
  • the washing or cleaning agents according to the invention may furthermore comprise alkali metal hydroxides.
  • These alkali carriers are in the washing or cleaning agents and in particular in the at least one second phases preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the detergent or cleaning agent used.
  • Alternative washing or cleaning agents according to the invention are free of alkali metal hydroxides.
  • cleaning agents according to the invention in the at least one first and / or the at least one second phase preferably comprise enzyme (s).
  • enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.
  • enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
  • Detergents according to the invention preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 % by weight to 5% by weight, based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ .
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • lipases or cutinases in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, those originally from Humicola lanuginosa
  • Lipases available, or further developed lipases, in particular those with the amino acid exchange in positions D96LT213R and / or N233R, more preferably all of the exchanges D96L, T213R and N233R.
  • enzymes can be used which are termed hemicellulases
  • mannanases xanthan lyases
  • pectin lyases pectinases
  • pectin esterases pectate lyases
  • xyloglucanases xylanases
  • pullulanases and ⁇ -glucanases.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • oxidases oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • These prefabricated preparations include, for example, by granulation, extrusion or lyophilization of solid preparations obtained or, in particular in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing with water and / or with stabilizers or other auxiliaries.
  • the enzymes for the at least one first and / or 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 are as solidified Gel are included or in those of the core-shell type in which an enzyme-containing core with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and
  • detergents which, based in each case on their total weight, are from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 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 may 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 (in particular in the at least one first phase), additives to improve the expiry and
  • Active ingredients in amounts of usually not more than 5% by weight may be included.
  • solvent agents according to the invention preferably contain at least one alkanolamine.
  • the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.
  • the at least one second phase is free of alkanolamine and the alkanolamine is contained only in the at least one first phase.
  • Detergents or cleaners according to the invention in particular dishwashing detergents, in a preferred embodiment contain as further constituent at least one zinc salt
  • the zinc salt may 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, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature).
  • the inorganic zinc salt is preferably selected from the group consisting of
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt is preferably present in the detergent according to the invention in an amount of from 0.01% by weight to 5% by weight, more preferably in an amount of from 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 cleaning agent.
  • Salts in particular the zinc salts
  • maleic acid-acrylic acid copolymer Na salt are, in particular (for example, Sokalan CP 5 ® BASF, Ludwigshafen (Germany)), modified Polyacrylic acid Na-salt (for example Sokalan ® CP 10 from BASF, Ludwigshafen
  • modified polycarboxylate-Na-salt for example Sokalan ® HP 25 from BASF, Ludwigshafen (Germany)
  • polyalkylene oxide-modified heptamethyltrisiloxane such as Silwet ® L-77 from BASF, Ludwigshafen (Germany)
  • polyalkylene oxide, modified heptamethyltrisiloxane such as Silwet ® L-7608 from BASF, Ludwigshafen (Germany)
  • polyether copolymers of polydimethylsiloxanes having ethylene oxide / propylene oxide segments (polyether)
  • water-soluble linear for example Sokalan ® HP 25 from BASF, Ludwigshafen (Germany)
  • polyalkylene oxide-modified heptamethyltrisiloxane such as Silwet ® L-77 from BASF, Ludwigshafen (Germany)
  • polyalkylene oxide, modified heptamethyltrisiloxane such as Silwet ® L-7608 from BASF, Ludwig
  • Polyether-terminated polyether as Tegopren® ® 5840, Tegopren® ® 5843, Tegopren® ® 5847, Tegopren® ® 5851, Tegopren® ® 5863 or Tegopren® ® 5878 from Evonik, Essen (Germany).
  • suitable builders are especially polyaspartic acid Na salt, Ethylendiamintriacetatkokosalkylacetamid (eg Rewopol® ® CHT 12 from Evonik, Essen (Germany)), methylglycine-trisodium salt and acetophosphonic.
  • Blends with surfactant or polymeric additives exhibit synergism 5863 in the case of Tegopren 5843 and Tegopren ® ®.
  • Tegopren grades 5843 and 5863 are less preferred when applied to hard surfaces of glass, especially glassware, since these can apply silicone surfactants to 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. These are, if available, contained exclusively in the at least one first phase.
  • Other useful bleaching agents are, for example
  • Peroxypyrophosphates citrate perhydrates and H2O2-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred. A particularly preferred oxygen bleach is sodium percarbonate.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, comprise aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • the bleach 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 and Co, Fe-Cu and Ru ammine complexes are also known
  • Bleach catalysts usable With particular preference complexes of manganese in the oxidation state II, III, IV or IV are used, preferably one or more
  • ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (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).
  • bleach catalyst s
  • 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 may thus have one, two, three or more different first phases (1); it may also have one, two, three or more distinct 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 comprises two first phases (1) and a second phase (2). It preferably comprises two first phases (1) and two second phases (2).
  • the washing 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 the phase (1) in a detergent portion can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 14 to 19 g. In this weight ratio results in a good concentration of the respective ingredients of the first (1) and second phase (2) in a cleaning process.
  • Different arrangements are shown schematically in FIGS. 1 to 4 without being limiting.
  • the at least one first phase (1) and the at least one second phase (2) adjoin one another completely or partially. It is preferred that the two phases immediately adjoin one another. However, it is also possible for 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) to be closely enveloped by a water-soluble film or in a water-soluble bag is / are included. Preferably, the entire agent is in one
  • water-soluble pouch or, particularly preferably, tightly encased in a water-soluble film.
  • the stability is next to the shortest possible
  • Solidification time of at least one second phase (2) important. Stability here means that components contained in the second phase do not transgress 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 each other and do not interact with each other, e.g. Diffusion of liquid components from one phase to another or reaction of
  • Fluid leakage are. Surprisingly, it has been shown that this can be made possible by a second phase which comprises glycerol, gelatin and at least one C3- to Cs-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, wherein polyvinyl alcohols and acetalated polyvinyl alcohols are particularly preferably used.
  • Polyvinyl alcohols (abbreviation PVAL, occasionally PVOH) is the name for PVAL
  • Polymerization degrees in the range of about 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 87-99 mol%, so still contain a residual content of acetyl groups.
  • the water-soluble packaging at least partly 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 especially 82 to 88 mole%.
  • the water-soluble packaging consists of at least 20 wt .-%, more preferably at least 40 wt .-%, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol, the Hydrolysis degree 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%, is.
  • 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 in the range of 5,000 g mol to 100,000 g mol, preferably from 10,000 g mol to 90,000 g-mol "1 , more preferably from 12,000 g mol " 1 to 80,000 g mol "1 and in particular of 15,000 g -mol "1 to 70,000 g mol " 1 lies.
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • the water solubility of polyvinyl alcohol can be improved by post-treatment with aldehydes
  • ketones are changed.
  • Particularly preferred and particularly advantageous due to their very good cold water solubility in this case have proven to be polyvinyl alcohols with the aldehyde or keto groups of saccharides or Polysaccharides or mixtures thereof are acetalated or ketalized.
  • the reaction products of polyvinyl alcohol and starch are particularly 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 specifically to desired values.
  • the water-soluble bag preferably has a thickness of 10 ⁇ to 500 ⁇ , in particular from 20 ⁇ to 400 ⁇ , more preferably from 30 ⁇ to 300 ⁇ , especially from 40 ⁇ to 200 ⁇ , in particular from 50 ⁇ to 150 ⁇ .
  • 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 narrow enclosure), particularly preferably comprises polyvinyl alcohol, as described above, wherein as starting thickness preferably a thickness of 10 .mu.m to 100 .mu.m, in particular from 12 .mu.m to 60 .mu.m, particularly preferably from 15 .mu.m to 50 ⁇ , especially from 20 ⁇ to 40 ⁇ , in particular from 22 ⁇ to 35 ⁇ is used.
  • the envelope is even under tension, which is not absolutely necessary.
  • This dense covering of the envelope is conducive to disintegration: upon first contact with water, the envelope will pass a small amount of water at some point, and at first it does not need to dissolve at all. At this point, the disintegrant contained in the tablet begins to swell. This leads to the wrapping now due to the
  • volume increase of the tablet abruptly ruptures and releases the tablet. If the wrapper is not tight, the mechanism described here will not work as the tablet can swell without bursting the wrapper. In this case, the use of a swellable disintegrating agent is superior to a gas-developing system, since its explosive effect in each case leads to a rupture of the casing. At a
  • Gas evolving system may "deflate" the explosive effect by venting the gas from a leakage of the enclosure.
  • Preferred detergent or cleaning agent portions according to the invention are characterized in that the distance between the disposable portion and water-soluble coating over the entire surface is 0.1 to 1000 ⁇ , preferably 0.5 to 500 ⁇ , particularly preferably 1 to 250 ⁇ and in particular 2.5 to 100 ⁇ , is.
  • the film wrapping is first laid loosely around a washing or cleaning agent portion and welded and then shrunk onto it, so that a close contact between the film package and the detergent concentrate is given.
  • washing or cleaning agent disposable portions according to the invention are characterized in that the wrapping is a film packaging shrunk onto the latter.
  • 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 the form of a shaped body, in particular one, in a preferred embodiment
  • the at least one first phase (1) is particularly preferably a powdered washing or cleaning agent which is compacted in the form of a tablet.
  • the second phase (2) is in the form of a core, which is embedded in the first phase (1).
  • a pool shape of the solid first phase (1) ie a mold with a trough into which the second phase is introduced.
  • the trough can be round, oval or angular.
  • the washing or cleaning agent comprises two second phases (2), wherein the two second phases may have different compositions.
  • any geometry is possible.
  • the presently shown rectangular shape is exemplary only. Also conceivable are a round or oval shape of the two phases or any polygonal configurations.
  • Another object of the present application is a method for cleaning hard surfaces, in particular of crockery, in which the surface is processed in a conventional manner using a cleaning agent according to the invention.
  • the surface is brought into contact with the washing or cleaning agent according to the invention.
  • the cleaning is carried out in particular with a cleaning machine, preferably with a dishwasher.
  • Automatic dishwashing detergents are compositions which can be used to clean soiled dishes in a dishwasher automatic dishwashing process.
  • the automatic dishwasher detergents according to the invention differ, for example, from the machine rinse aid agents, which are always used in combination with automatic dishwashing detergents and do not develop their own cleaning action.
  • washing or cleaning agent comprises something in the whole or in the at least one first phase (1) or in the at least one second phase (2) is also to be regarded as disclosed that washing or cleaning Detergent or the respective phase may consist thereof.
  • the first phases had the following composition:
  • Phosphonate e.g., HEDP
  • Bleach catalyst (preferably Mn-based) 0.0-0.8
  • Disintegrant - e.g., Crosslinked PVP
  • Disintegrant - e.g., Crosslinked PVP
  • pH adjuster e.g., citric acid
  • first phases were in the form of compacted tablets with a depression on one side.
  • a liquid composition was poured, which has resulted in the second phase after curing.
  • the resulting detergent was in accordance with the shape shown schematically in Fig. 4.
  • Further first phases were without deepening.
  • a second phase was directly brought into contact with the surface of the first phase, as shown schematically in Figures 1 to 3.
  • the second phases had the following composition:
  • Propanediol (preferably 1,3-propanediol) 30-65
  • Nonionic surfactant e.g. Fatty alcohol alkoxylate, 0-40
  • Thickener (preferably gelatin or PVA) 5-50
  • Propanediol (preferably 1,3-propanediol) 30-65
  • the first and the second phases could be combined as desired.
  • the spatial design of the second phase which was liquid after the mixing of the ingredients 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 commercially available or self-designed forms. In these forms, the liquid second phase was introduced and after the
  • the second phases were combined with the first phases as described above. From first phases, tablets were produced which had a trough on one side. In this trough the second phase was introduced in still liquid form and then solidified. The resulting detergents had a structure as shown schematically in FIG.

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Abstract

La présente invention concerne un détergent, en particulier un produit pour le nettoyage des surfaces dures, qui comprend deux phases différentes l'une de l'autre.
EP18701335.4A 2017-01-24 2018-01-24 Détergent comprenant au moins deux phases Pending EP3574073A1 (fr)

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DE102017201097.5A DE102017201097A1 (de) 2017-01-24 2017-01-24 Wasch- oder Reinigungsmittel umfassend wenigstens zwei Phasen
PCT/EP2018/051664 WO2018138120A1 (fr) 2017-01-24 2018-01-24 Détergent comprenant au moins deux phases

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WO2019162138A1 (fr) * 2018-02-23 2019-08-29 Unilever N.V. Compositions solides comprenant un aminopolycarboxylate
DE102018212208A1 (de) * 2018-07-23 2020-01-23 Henkel Ag & Co. Kgaa Mehrphasiger Reinigungsmittelpouch
DE102022125211A1 (de) * 2022-09-29 2024-04-04 Henkel Ag & Co. Kgaa Geschirrreinigungsmittelportionseinheit aus Gel und verpresster Phase

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US9896648B2 (en) * 2016-03-02 2018-02-20 The Procter & Gamble Company Ethoxylated diols and compositions containing ethoxylated diols

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US20190345420A1 (en) 2019-11-14
WO2018138120A1 (fr) 2018-08-02

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