Washing or cleaning agent comprising at least two phases

Abstract

The present invention relates to a washing or cleaning agent, in particular a cleaning agent for hard surfaces, comprising two distinct phases.

Description

[0001] The present invention relates to a washing or cleaning agent, in particular a cleaning agent for hard surfaces, comprising at least two distinct phases.

[0002] Washing and cleaning products are usually available in solid form (for example, as a powder) or in liquid form (or as a flowing gel). Liquid washing and cleaning products, in particular, are becoming increasingly popular with consumers.

[0003] Solid detergents and cleaning agents have the advantage that, unlike liquid detergents and cleaning agents, they do not require preservatives. Liquid products are becoming increasingly popular on the market, particularly due to their rapid solubility and the resulting quick availability of their active ingredients. This allows consumers to use shorter wash cycles while still achieving good cleaning performance.

[0004] Furthermore, consumers have become accustomed to the convenient dosing of pre-portioned machine detergents or cleaning agents, such as dishwashing liquids, and use these products in tablet form (solid detergents or cleaning agents) or in sachets, usually filled with a liquid detergent or cleaning agent. Single-use sachets filled with powder are also available. Single-use portions in water-soluble sachets are becoming increasingly popular with consumers not only because they eliminate contact with the chemical composition, but also because of the attractive appearance of the sachets. The appearance of the dosage form is gaining in importance. Besides good cleaning performance and sufficient shelf life, an appealing appearance is one of the deciding factors when choosing a product.However, products stored in bags often change their appearance, which often leads consumers to associate them with reduced performance and poorer cleaning results.

[0005] From the consumer's perspective, it is now desirable to combine the advantages of both formulations and provide an improved dosage form, particularly for typically liquid detergents or cleaning agents, compared to the current state of the art. This should allow for single-dose dispensing while simultaneously achieving a visually appealing appearance for the consumer. Surprisingly, it has been shown that this goal can be achieved by formulating a flexible phase combined with a solid phase.

[0006] In a first embodiment, the problem underlying the present application is therefore solved by a washing or cleaning agent comprising at least one first phase and at least one different second phase, wherein the at least one first phase is solid and the at least one second phase comprises at least one polymer and at least one polyhydric alcohol.

[0007] A phase, as defined in the present invention, is a spatial region in which physical parameters and chemical composition are homogeneous. A phase differs from another phase by various characteristics, such as ingredients, physical properties, external appearance, etc. Preferably, different phases can be visually distinguished. This allows the consumer to clearly differentiate at least one first phase from at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, these can also be distinguished from one another with the naked eye, for example, by their color. The same applies if two or more second phases are present. In this case, too, a visual distinction between the phases is possible, for example, based on a difference in color or transparency.Phases within the meaning of the present invention are thus self-contained regions that can be visually distinguished from one another by the consumer with the naked eye. The individual phases can exhibit different properties during use, such as the rate at which the phase dissolves in water and thus the rate and sequence of release of the ingredients contained in the respective phase.

[0008] According to the invention, the at least one second phase is dimensionally stable at room temperature. During production, the at least one polymer is brought into contact with the at least one polyhydric alcohol. This yields a flowable mixture that can be shaped as desired. After a certain period, a second phase is obtained that retains its predetermined shape, i.e., is dimensionally stable. This period, the solidification time, is preferably 15 minutes or less, more preferably 10 minutes or less, and particularly preferably 5 minutes. During this time, the at least one second phase yields to pressure but does not deform; instead, it returns to its original state after the pressure is removed. The at least one second phase is preferably elastic, particularly linearly elastic. Furthermore, the at least one second phase is preferably transparent, resulting in a pleasing visual appearance.

[0009] At least one of the second phases is cut-resistant. For example, it can be cut with a knife after solidification without sustaining further damage beyond the cut itself. Furthermore, at least one of the second phases is particularly flexible. Due to its flexibility and elasticity, it can assume any desired shape. This also translates to fracture resistance, which facilitates good handling, especially with regard to transport, storage, and use.

[0010] These and other aspects, features, and advantages of the invention will become apparent to the person skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be incorporated into any other aspect of the invention. Furthermore, it is understood that the examples contained herein are intended to describe and illustrate the invention, but do not limit it, and in particular, the invention is not limited to these examples. All percentages are weight percentages unless otherwise stated. Numerical ranges specified in the format "from x to y" include the stated values. If several preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the different endpoints are also included.

[0011] "At least one," as used herein, means one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. When referring to an ingredient, the statement refers to the type of ingredient and not the absolute number of molecules. Thus, "at least one bleach catalyst," for example, means at least one type of bleach catalyst, i.e., it could refer to one type of bleach catalyst or a mixture of several different bleach catalysts. When used with weight specifications, the statement refers to all compounds of the specified type contained in the composition / mixture, i.e., the composition contains no further compounds of that type beyond the specified quantity of the relevant compounds.

[0012] When reference is made to molar masses herein, these values ​​always refer to the number-mean molar mass Mn, unless explicitly stated otherwise. The number-mean molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 using THF as the eluent. The mass-mean molar mass Mw can also be determined by GPC, as described for Mn.

[0013] All percentages given in connection with the compositions described herein refer, unless explicitly stated otherwise, to wt%, in each case to the mixture in question.

[0014] In a preferred embodiment, the at least one first phase is in compressed form. In this embodiment, the washing or cleaning agent according to the invention thus comprises at least one first solid, compressed phase, and at least one second phase comprising at least one polymer and at least one polyhydric alcohol.

[0015] Certain minimum requirements are placed on the formulations of the at least one second phase. As already explained, the second phase must solidify within the shortest possible time. Long solidification times would lead to long production times and thus high costs. According to the invention, solidification time means the period during which, during production, the at least one second phase transitions from a flowable state to a non-flowable, dimensionally stable state at room temperature. Room temperature is defined as a temperature of 20 °C. This can be achieved, without being a limiting factor, by crosslinking the at least one polymer.

[0016] Furthermore, the second phase must be stable under normal storage conditions. The second phase according to the invention is a component of a washing or cleaning agent. Washing or cleaning agents are typically stored in a household for a certain period of time. Storage usually takes place near the washing machine. For such storage, the second phase should be stable. Thus, the second phase should, in particular, remain stable even after a storage period 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, and should not deform or otherwise change in consistency during this time.

[0017] Visually, the surface of the second phase should be clearly distinguishable from the first phase, for example, by a pronounced gloss. The surface of the solid first phase is usually not glossy but matte, dull, or lackluster, so a gloss allows for good differentiation, which makes the washing or cleaning agent attractive to the consumer.

[0018] A change in volume or shrinkage during storage would be detrimental, as this would reduce consumer acceptance of the product. Leakage of liquid or seepage of components from the second phase is also undesirable. Here, too, the visual appearance is relevant. Leakage of liquid, such as solvents, can affect the stability of the second phase, resulting in unstable components and thus potentially impacting the washing or cleaning effect.

[0019] Furthermore, it should be possible for at least one first phase and at least one second phase to be in direct contact with each other. In this case, there should be no negative interaction between the first and second phases. "No negative interaction" here means, for example, that no ingredients or solvents migrate from one phase to the other, or that the stability, in particular storage stability (preferably at 4 weeks and a storage temperature of 30 °C), and / or the aesthetics of the product are not impaired in any way, for example, by color changes, the formation of moist-looking edges, a blurring of the boundary between the two phases, or similar issues.

[0020] Surprisingly, it has been found that particularly good storage stability is achieved when the second phase is essentially anhydrous. This means that the second phase is preferably essentially free of water. "Essentially free" here means that the second phase may contain small amounts of water. This water can be introduced into the phase, for example, by a solvent, as water of crystallization, or as a result of reactions between components of the phase. However, no water is used as a solvent for the preparation of the second phase. The proportion of water in the second phase is, in particular, 15 wt.% or less, or 10 wt.% or less, particularly 7 wt.% or less, in particular 6 wt.% or 5 wt.% or less, preferably 2 wt.% or less, in particular 1 wt.% or less, in particular 0.5 wt.% or less, in particular 0.1 wt.% or 0.05 wt.% or less. The values ​​are given in wt.-% refers to the total weight of the second phase.

[0021] The at least one second phase comprises at least one polymer. This at least one polymer is particularly suitable for forming a network. According to the invention, the at least one second phase can comprise one polymer, two or more different polymers. In particular, it comprises one, two, or more, preferably one or two, polymers suitable for forming a network. Furthermore, the at least one second phase can comprise one or more polymers that do not form a network but lead to thickening and thus to an increase in the dimensional stability of the at least one second phase, so-called thickening polymers. In a preferred embodiment, the at least one second phase therefore comprises at least one, preferably one, polymer for network formation as well as one or more thickening polymers.

[0022] Preferably, the at least one second phase comprises PVA (polyvinyl alcohol) and / or gelatin as polymers suitable for network formation. More preferably, the at least one second phase comprises a thickening polymer, and in particular polycarboxylates as the thickening polymer. Polyvinyl alcohols are thermoplastic polymers that are usually produced as a white to yellowish powder by the 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.

[0023] Gelatin is a mixture of flavorless animal protein. Its 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 complete protein. Gelatin swells in water and dissolves when heated to approximately 50 °C. Upon cooling, it forms a gel, which becomes liquid again when reheated.

[0024] Surprisingly, it has been found that PVA and / or gelatin are particularly suitable for producing second phases that meet the requirements shown above. Therefore, at least one second phase comprising gelatin and / or PVA and at least one polyhydric alcohol is particularly preferred. It is also particularly preferred that the at least one second phase comprises gelatin and at least one polyhydric alcohol. Equally preferred is that the at least one second phase comprises PVA and at least one polyhydric alcohol.

[0025] According to the invention, the at least one second phase comprises the polymer suitable for network formation in a proportion of approximately 5 wt.% to 40 wt.%, in particular 10 wt.% to 35 wt.%, preferably 15 wt.% to 20 wt.%. Significantly lower proportions of polymer, especially gelatin and / or PVA, do not lead to the formation of a stable, gel-like second phase. Instead, permanent deliquescing is observed. Proportions of more than 40 wt.%, and in particular more than 20 wt.%, result in a prolonged solidification time. The phases remain soft for a longer period, leading to a longer manufacturing process. The values ​​are in each case based on the total weight of the second phase.

[0026] Preferably, at least one second phase comprises gelatin. Surprisingly, it has been shown that dimensionally stable second phases can be produced using gelatin within a short curing time. Furthermore, the shape and size of the phases produced accordingly remain stable over a long period. No shrinkage is observed. It has been shown that the required amount of gelatin varies depending on the Bloom value. Preferably, the second phase therefore comprises gelatin with a Bloom value in the range of 60 to 225. The Bloom value describes the gel strength or gelling power of gelatin. This value represents the mass in grams required for a 0.5-inch diameter stamp to deform the surface of a 6.67% gelatin / water mixture to a depth of four millimeters without tearing it.The experiment is conducted in a standardized manner at exactly 10 °C with a prior aging of the gelatin for 17 hours.

[0027] If the at least one second phase comprises gelatin with a Bloom value of 150 or more, in particular 180 to 225, preferably 200 to 225, the proportion of gelatin based on the total weight of the second phase is preferably in the range of 10 wt.% to 20 wt.%, in particular 15 wt.% to 18 wt.%. If the Bloom value is less than 150, in particular 60 to 120, preferably 60 to 100, the proportion of gelatin based on the total weight of the second phase is preferably in the range of 15 wt.% to 30 wt.%, 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. Using gelatin with a suitable Bloom value allows for good control of the viscosity of the second phase during production. Furthermore, the amount of gelatin required is lower here than when using gelatin with a lower Bloom value, which can lead to a reduction in costs.

[0028] If at least one second phase contains PVA in addition to gelatin, the viscosity of the second phase is increased during production.

[0029] Surprisingly, it has been shown that gelatin, in combination with anionic polymers or copolymers, particularly sulfopolymers, leads to the formation of second phases with insensitive surfaces. These surfaces can be touched by the end user without any material adhering to their hands. Even within packaging, no material abrasion occurs. Therefore, the second phase preferably comprises gelatin and an anionic copolymer / polymer. The proportion of the anionic polymer is preferably 1 wt.% to 35 wt.%, particularly 3 wt.% to 30 wt.%, especially 5 wt.% to 25 wt.%, and preferably 5 wt.% to 20 wt.%, based on the total weight of the second phase. Sulfopolymers also ensure an excellent surface gloss. Furthermore, fingerprints are not retained.Therefore, the proportion of sulfopolymers, in particular sulfopolymers with AMPS as the sulfonic acid group-containing monomer, for example Acusol 590, Acusol 588 or Sokalan CP50, is preferably 1 wt.% to 25 wt.%, in particular 3 wt.% to 15 wt.%, particularly 4 wt.% to 12 wt.%, and preferably 5 wt.% to 10 wt.% based on the weight of the second phase. In a particularly preferred embodiment, the at least one second phase therefore comprises gelatin, a sulfopolymer, and at least one polyhydric alcohol.

[0030] According to the invention, the at least one second phase can further comprise a thickening polymer. Preferably, this is a polycarboxylate. Preferably, a copolymeric polyacrylate, preferably a sulfopolymer, preferably a copolymeric polysulfonate, or preferably a hydrophobically modified copolymeric polysulfonate is used as the polycarboxylate. The copolymers can have two, three, four, or more different monomer units. Preferred copolymeric polysulfonates contain, in addition to sulfonic acid group-containing monomer(s), at least one monomer from the group of unsaturated carboxylic acids.

[0031] Unsaturated carboxylic acids of the formula R 1< (R 2< )C=C(R 3< )COOH are particularly preferred as unsaturated carboxylic acid(s), in which R 1< to R 3< independently represent -H, -CH 3 , a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, mono- or poly-unsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups substituted with -NH2, -OH or -COOH as defined above, or -COOH or -COOR 4< , where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon group with 1 to 12 carbon atoms.

[0032] Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof. Unsaturated dicarboxylic acids can, of course, also be used.

[0033] For sulfonic acid group-containing monomers, those of the formula R 5< (R 6< )C=C(R 7< )-X-SO 3 H are preferred, in which R 5< to R 7< independently represent -H, -CH 3 , a straight-chain or branched saturated alkyl group with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl group with 2 to 12 carbon atoms, alkyl or alkenyl groups substituted with -NH 2 , -OH or -COOH, or -COOH or -COOR 4<, where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon group with 1 to 12 carbon atoms, and X represents an optional spacer group selected from -(CH 2 ) n - with n = 0 to 4. -COO-(CH 2 ) k - with k = 1 to 6, -C(O)-NH-C(CH 3 ) 2 -, - C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.

[0034] Among these monomers, preferred are those of the formulas H₂C=CH-X-SO₃H, H₂C=C(CH₃)-X-SO₃H, or HO₃SX-(R₆<)C=C(R₇<)-X-SO₃H, in which R₆< and R₇< are independently selected from -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, and -CH(CH₃)₂, and X represents an optional spacer group selected from -(CH₂)ₙ (n = 0 to 4), -COO-(CH₂)ₖ (k = 1 to 6), -C(O)-NH-C(CH₃)₂, -C(O)-NH-C(CH₃)₂, and -C(O)-NH-CH(CH₃)₂. )-CH 2 -.

[0035] Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, metallylsulfonic acid, allyloxybenzenesulfonic acid, metallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and mixtures of the aforementioned acids or their water-soluble salts. In the polymers, the sulfonic acid groups can be present wholly or partially in neutralized form, meaning 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 especially for sodium ions.The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

[0036] The monomer distribution of the copolymers preferably used according to the invention is, in the case of copolymers containing only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, preferably 5 to 95 wt.% each, and particularly preferably the proportion of the sulfonic acid group-containing monomer is 50 to 90 wt.% and the proportion of the carboxylic acid group-containing monomer is 10 to 50 wt.%, the monomers being preferably selected from those mentioned above. The molar mass of the sulfo copolymers preferably used according to the invention can be varied to adapt the properties of the polymers to the desired application. Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 g·mol⁻¹, preferably of 4000 to 25,000 g·mol⁻¹, and particularly of 5000 to 15,000 g·mol⁻¹.

[0037] In a further preferred embodiment, the copolymers comprise, in addition to a carboxyl group-containing monomer and a sulfonic acid group-containing monomer, at least one nonionic, preferably hydrophobic, monomer. The use of these hydrophobically modified polymers has particularly improved the rinsing performance of dishwashing detergents according to the invention.

[0038] Particularly preferably, the at least one second phase further comprises an anionic copolymer, wherein the anionic copolymer is a copolymer comprising i) carboxylic acid group-containing monomers ii) sulfonic acid group-containing monomers iii) non-ionic monomers, especially hydrophobic monomers are used.

[0039] Preferably, nonionic monomers of the general formula R 1< (R 2< )C=C(R 3< )-XR 4< are used, in which R 1< to R 3< independently represent -H, -CH 3 or - C 2 H 5, X represents an optional spacer group selected from -CH 2 -, - C(O)O- and -C(O)-NH-, and R 4< represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 22 carbon atoms.

[0040] Particularly favored 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-diemethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-Octadecene and C 22-α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 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, N-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, N-(2-ethylhexyl)acrylamide, octyl acrylateMethacrylic acid octyl ester, N-(octyl)acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N-(lauryl)acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N-(stearyl)acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N-(behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

[0041] According to the invention, the at least one second phase can also comprise further polymers, such as PEG, in particular polyethylene glycols with an average molar mass between about 200 and 8000, between about 800 and 4000 g / mol, particularly preferably with an average molar mass between 1000 and 2000 g / mol, for example around 1500 g / mol (INCI: PEG1500), which increase the stability of the second phase.

[0042] The at least one second phase comprises at least one polyhydric alcohol. The at least one polyhydric alcohol enables the production of a dimensionally stable, non-flowing second phase within a short solidification time, which is 15 minutes or less, in particular 10 minutes or less. Polyhydric alcohols within the meaning of the present invention are hydrocarbons in which two, three, or more hydrogen atoms are replaced by OH groups. The OH groups are bonded to different carbon atoms. No single carbon atom has two OH groups. This is in contrast to (simple) alcohols,in which only one hydrogen atom in hydrocarbons is replaced by an OH group. Polyhydric alcohols with two OH groups are called alkanediols, polyhydric alcohols with three OH groups are called alcanetriols. A polyhydric alcohol thus corresponds to the general formula [KW](OH) x , where KW represents a hydrocarbon that is linear or branched, saturated or unsaturated, substituted or unsubstituted. Substitution can occur, for example, with -SH or -NH- groups. Preferably, KW is a linear or branched, saturated or unsaturated, unsubstituted hydrocarbon. KW comprises at least two carbon atoms. The polyhydric alcohol comprises 2, 3, or more OH groups (x = 2, 3, 4 ...), with only one OH group bonded to each carbon atom of KW. Particularly preferably KW comprises 2 to 10, i.e. 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms.Particularly suitable are polyhydric alcohols with x=2, 3, or 4 (for example, pentaerythritol with x=4). x=2 (alkanediol) and / or x=3 (alkanetriol) are preferred.

[0043] Particularly preferably, the at least one second phase 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 C8 alkanetriol and / or at least one C3 to C8 alkanediol, particularly at least one C3 to C6 alkanetriol and / or at least one C3 to C5 alkanediol as a polyhydric alcohol. More preferably, it comprises an alkanetriol and an alkanediol as at least one polyhydric alcohol. In a preferred embodiment, the at least second phase therefore comprises at least one polymer, in particular gelatin and / or PVA, as well as at least one alkanediol and at least one alkanetriol, in particular an alkanetriol and an alkanediol. Equally preferred is a second phase comprising 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, comprising 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.

[0044] Surprisingly, it has been shown that particularly short solidification times can be achieved when combining a corresponding triol (alkanetriol) with a corresponding diol (alkanediol). The resulting second phases are also transparent and have a glossy surface, which contributes to the appealing visual appearance of the detergent or cleaning agent according to the invention. The terms diol and alkanediol are used synonymously here. The same applies to triol and alkanetriol.

[0045] According to the invention, the polyhydric alcohols do not include derivatives such as ethers, esters, etc. thereof.

[0046] The amount of polyhydric alcohol(s) used in the second phases according to the invention is preferably at least 45% by weight, and in particular 55% by weight or more. Preferred ranges are from 5% by weight to 75% by weight, and in particular from 10% by weight to 70% by weight, based on the total weight of the second phase.

[0047] Preferred are the C 3 to C 6 alkanetriol 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).

[0048] Particularly preferred are the C3 to C6 alkanetriol glycerol and / or 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (also called 1,1,1-trimethylolpropane). The C3 to C5 alkanediol is preferably 1,3-propanediol and / or 1,2-propanediol. Surprisingly, it has been found that the chain length of the diol, and in particular the position of the OH groups, influences the transparency of the second phase. Preferably, therefore, the OH groups of the diol are not arranged on immediately adjacent carbon atoms. In particular, there are three or four carbon atoms, and especially three carbon atoms, between the two OH groups of the diol. The diol 1,3-propanediol is particularly preferred. Surprisingly, it has been found that particularly good results are obtained with mixtures comprising glycerol and 1,3-propanediol and / or 1,2-propanediol. The second phase preferably comprises gelatin, glycerin and 1,3-propanediol or...Gelatin, 1,1,1-trimethylolpropane, and 1,3-propanediol. A dimensionally stable, non-flowable consistency at room temperature can be achieved within a solidification time of 10 minutes or less, and this consistency remains stable even after prolonged storage. Furthermore, such a phase is transparent and has a glossy surface. A particularly preferred second phase therefore comprises gelatin or PVA as the polymer and 1,3-propanediol and glycerin or 1,1,1-trimethylolpropane as polyhydric alcohols.

[0049] If the second phase comprises an alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, the proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based on the total weight of the second phase, is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, in particular 20 wt.% to 40 wt.%.

[0050] If the second phase comprises several alkanetriol(s), the total proportion of alkanetriol(s), based on the total weight of the second phase, is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, especially 20 wt.% to 40 wt.%.

[0051] If glycerol is included as an alkanetriol in the second phase, the proportion of glycerol based on the total weight of the second phase is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, especially 20 wt.% to 40 wt.%.

[0052] If 1,1,1-trimethylolpropane is present in the second phase, the proportion of 1,1,1-trimethylolpropane based on the total weight of the second phase is preferably 5 wt.% to 70 wt.%, particularly 10 wt.% to 65 wt.%, and especially 20 wt.% to 40 wt.%. If 2-Amino-2-Hydroxymethyl-1,3-propanediol is present...

[0053] If 2-Amino-2-Hydroxymethyl-1,3-propanediol is contained in the second phase, the proportion of 2-Amino-2-Hydroxymethyl-1,3-propanediol, based on the total weight of the second phase, is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, and especially 20 wt.% to 40 wt.%.

[0054] If several alkanediols are contained in the second phase, the amount of alkanediols, based on the total weight of the second phase, is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, and especially 20 wt.% to 40 wt.%.

[0055] If the second phase comprises an alkanediol, in particular 1,3-propanediol, the proportion of alkanediol, in particular 1,3-propanediol, based on the total weight of the second phase, is preferably 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, and particularly 20 wt.% to 45 wt.%. If 1,3-propanediol is contained in the second phase, the proportion of 1,3-propanediol, based on the total weight of the second phase, is in particular 10 wt.% to 65 wt.%, and particularly 20 wt.% to 45 wt.%.

[0056] A second phase is preferably comprising 20 to 45 wt% 1,3-propanediol and 10 wt% to 65 wt% 2-amino-2-hydroxymethyl-1,3-propanediol, each based on the total weight of the second phase. A second phase comprising 20 to 45 wt% 1,3-propanediol and 10 wt% to 65 wt% 1,1,1-trimethylolpropane, each based on the total weight of the second phase, is also preferably preferred. A second phase comprising 20 to 45 wt% 1,3-propanediol and 10 wt% to 65 wt% glycerol, each based on the total weight of the second phase, is particularly preferred.

[0057] It has been shown that rapid solidification of a second phase at 20 °C is possible in these areas, and that the resulting phases are storage-stable and transparent. The glycerin content, in particular, affects the curing time.

[0058] If the at least one second phase according to the invention comprises a C3 to C6 alkanetriol and a C3 to C5 alkanediol, the weight ratio is preferably 3:1 to 2:1. In particular, the weight ratio is 2:1 if glycerol and 1,3-propanediol are included as polyhydric alcohols. Surprisingly, it has been found that at these weight ratios, storage-stable, glossy, transparent second phases can be obtained within short solidification times at 20°C of 10 minutes or less.

[0059] The washing or cleaning agent according to the invention preferably comprises at least one surfactant. This surfactant is selected from the group consisting of anionic, nonionic, and cationic surfactants. The washing or cleaning agent according to the invention may also contain mixtures of several surfactants selected from the same group.

[0060] According to the invention, the at least one first phase and the at least one second phase each comprise at least one surfactant. However, it is also possible that only the at least one first phase or only the at least one second phase comprises at least one surfactant. If both phases comprise a surfactant, these are preferably different surfactants. However, it is also possible that the first and second phases contain the same surfactant or surfactants. According to the invention, the at least one first and / or second phase preferably contains at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used. Preferably, weakly foaming nonionic surfactants are used, in particular alkoxylated, especially ethoxylated, weakly foaming nonionic surfactants. These are specified in more detail below.

[0061] Suitable nonionic surfactants include, for example, alkyl glycosides of the general formula RO(G) x, where R corresponds to a primary straight-chain or methyl-branched, particularly 2-position methyl-branched, aliphatic residue with 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol representing a glucose unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably, x is between 1.2 and 1.4.

[0062] Another class of preferably used non-ionic surfactants, which are used either as the sole non-ionic surfactant or in combination with other non-ionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

[0063] Non-ionic surfactants of the amine oxide type, for example N-cocosalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides, may also be suitable. The amount of these non-ionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, and in particular not more than half of it.

[0064] Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

[0065] The washing or cleaning agents according to the invention, particularly cleaning agents for machine dishwashing, preferably contain non-ionic surfactants from the group of alkoxylated alcohols. Preferably, alkoxylated, advantageously ethoxylated, and especially 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 are used as non-ionic surfactants. The alcohol residue may be linear or, preferably, methyl-branched at the 2-position, or the mixture may contain both linear and methyl-branched residues, as is typically the case in oxo alcohol residues. However, alcohol ethoxylates with linear residues from 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 particularly preferred.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.

[0066] Preferred alcohol ethoxylates exhibit a narrow range of homologs (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohols with 14 EO, 25 EO, 30 EO, or 40 EO.

[0067] Ethoxylated niotenes obtained from C6-20 monohydroxyalkanols, C6-20 alkylphenols, or C16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles, and particularly more than 20 moles of ethylene oxide per mole of alcohol are particularly preferred. A particularly preferred niotene is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C16-20 alcohol), preferably a C18 alcohol, and at least 12 moles, preferably at least 15 moles, and particularly at least 20 moles of ethylene oxide. Among these, the so-called "narrow-range ethoxylates" are particularly preferred.

[0068] Preferred surfactants come from the groups of alkoxylated niotonic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) niotonic surfactants are also characterized by good foam control.

[0069] Particularly preferred niotenes for low-foaming niotenes within the scope of the present invention have proven to be those comprising alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, wherein one to ten EO or AO groups are bonded together before a block of the other groups follows. Here, nonionic surfactants of the general formula are used. preferably, in which R 1< represents a straight-chain or branched, saturated or, in particular, polyunsaturated C 6-24 -alkyl or -alkenyl group; 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 represent integers from 1 to 6.

[0070] Preferred niotenes of the above formula can be prepared from the corresponding alcohols R1-OH and ethylene or alkylene oxide by known methods. The R1 group in the above formula can vary depending on the origin of the alcohol. If native sources are used, the R1 group has an even number of carbon atoms and is generally unbranched, with linear groups from native alcohols with 12 to 18 carbon atoms, for example, from coconut, palm, tallow, or oleyl alcohol, being preferred. Alcohols accessible from synthetic sources include, for example, the Guerbet alcohols or methyl-branched groups at the 2-position, or linear and methyl-branched groups in the mixture, as are commonly found in oxo alcohol groups.Regardless of the type of alcohol used to produce the niotenes contained in the agents, niotenes are preferred in which R 1< in the above formula represents an alkyl group with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and particularly 9 to 11 carbon atoms.

[0071] In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit, which alternates with the ethylene oxide unit in the preferred niotenes. However, other alkylene oxides are also suitable, where R2 and R3 are independently selected from -CH2CH2-CH3 or -CH(CH3)2, respectively. Niotenes of the above formula are preferably used, where R2 and R3 represent a residue of -CH3, w and x independently represent values ​​of 3 or 4, and y and z independently represent values ​​of 1 or 2.

[0072] Other preferred non-ionic surfactants of the first phase are non-ionic surfactants of the general formula R 1< O(AlkO) x M(OAlk) y OR 2< , where R 1< and R 2< independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl group with 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl group with 2 to 4 carbon atoms; x and y independently represent values ​​between 1 and 70; and M represents an alkyl group from the group CH 2 , CHR 3< , CR 3< R 4< , CH 2 CHR 3< and CHR 3< CHR 4< , where R 3< and R 4< independently represent a branched or unbranched, saturated or unsaturated alkyl group with 1 to 18 carbon atoms.

[0073] Preferably nonionic surfactants of the general formula 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 represent an alkyl or alkenyl group with 6 to 22 carbon atoms; x and y independently represent values ​​between 1 and 40.

[0074] Particularly preferred are compounds of the general formula R1 -CH(OH)CH2 -O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2, in which R represents a linear, saturated alkyl group with 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently have values ​​of 20 to 30. Such compounds can be obtained, for example, by reacting alkyldiols HO-CHR-CH2-OH with ethylene oxide, followed by a reaction with an alkyl epoxide to seal the free OH groups and form a dihydroxy ether.

[0075] Preferred nonionic surfactants are those of the general formula R 1< -CH(OH)CH 2 O-(AO) w -(AO) x -(A"O) y -(A‴O) z -R 2< , in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl residue; R 2< represents hydrogen or a linear or branched hydrocarbon residue with 2 to 26 carbon atoms; A, A', A" and A‴ independently represent a residue 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 represent values ​​between 0.5 and 120, where x, y and / or z can also be 0.

[0076] By adding the aforementioned non-ionic surfactants of the general formula R 1< -CH(OH)CH 2 O-(AO) w -(A'O) x -(A"0) y -(A‴O) z -R 2< , hereinafter also referred to as "hydroxy mixed ether", the cleaning performance of preparations according to the invention can surprisingly be significantly improved, both in comparison to surfactant-free systems and in comparison to systems containing alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

[0077] The use of these non-ionic surfactants with one or more free hydroxyl groups on one or both terminal alkyl groups can significantly improve the stability of the enzymes contained in the cleaning preparations according to the invention.

[0078] Particularly preferred are end-group-capped poly(oxyalkylated) niosurfactants which, according to the following formula

[0079] In addition to a residue R1<, which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, the compound further comprises a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue R2< with 1 to 30 carbon atoms, where n represents values ​​between 1 and 90, preferably values ​​between 10 and 80, and particularly values ​​between 20 and 60. Surfactants of the above formula in which R1< represents C7 to C13, n represents a natural number from 16 to 28, and R2< represents C8 to C12 are particularly preferred.

[0080] Particularly preferred are surfactants of the formula R1< O[CH2CH(CH3)O] x [CH2CH2O] y CH2CH(OH)R2< , where R1< represents a linear or branched aliphatic hydrocarbon residue with 4 to 18 carbon atoms or mixtures thereof, R2< represents a linear or branched hydrocarbon residue with 2 to 26 carbon atoms or mixtures thereof, and x represents values ​​between 0.5 and 1.5 and y represents a value of at least 15. Examples of these nonionic surfactants include the C2-26 fatty alcohol (PO)1-(EO)15-40-2-hydroxyalkyl ethers, and in particular the C8-10 fatty alcohol (PO)1-(EO)22-2-hydroxydecyl ethers.

[0081] Particularly preferred are end-group-capped poly(oxyalkylated) niotenes of the formula R 1< O[CH 2 CH 2 O] x [CH 2 CH(R 3< )O] y CH 2 CH(OH)R 2< , in which R 1< and R 2< independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon residue with 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 , preferably, however, represents -CH 3, and x and y independently represent values ​​between 1 and 32, wherein niotenes with R 3< = -CH 3 and values ​​for x from 15 to 32 and y from 0.5 and 1.5 are particularly preferred.

[0082] Other preferably usable niotenes are the end-capped poly(oxyalkylated) niotenes of the formula R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< , in which R 1< and R 2< represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 1 to 30 carbon atoms, R 3< represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl residue, x represents values ​​between 1 and 30, k and j represent values ​​between 1 and 12, preferably between 1 and 5. If the value x > 2, each R 3< in the formula above 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 residues with 6 to 22 carbon atoms, with residues having 8 to 18 carbon atoms being particularly preferred.For the remainder R 3<, H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values ​​for x are in the range of 1 to 20, especially from 6 to 15.

[0083] As described above, each R3< in the formula above can be different if x > 2. This allows the alkylene oxide unit within the square brackets to be varied. For example, if x represents 3, the R3< group can be chosen to form ethylene oxide (R3<= H) or propylene oxide (R3<= CH3) units, which can be joined together in any order, such as (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO), and (PO)(PO)(PO). The value 3 for x is chosen here as an example and can certainly 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.

[0084] Particularly preferred end-capped poly(oxyalkylated) alcohols of the formula above have values ​​of k = 1 and j = 1, so that the above formula simplifies to R1< O[CH2CH(R3< )O] x CH2CH(OH)CH2OR2<. In the latter formula, R1<, R2<, and R3< are defined as above, and x represents numbers from 1 to 30, preferably from 1 to 20, and particularly from 6 to 18. Surfactants in which the R1< and R2< substituents have 9 to 14 carbon atoms, R3< represents hydrogen, and x takes on values ​​from 6 to 15 are particularly preferred. Finally, the nonionic surfactants of the general formula R1< -CH(OH)CH2O-(AO) w -R2< have proven to be particularly effective, in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or -alkenyl residue; R 2< represents a linear or branched hydrocarbon residue with 2 to 26 carbon atoms; A represents a residue from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ), preferably for CH 2 CH 2 , and w represents values ​​between 1 and 120, preferably 10 to 80, in particular 20 to 40.

[0085] Examples of these non-ionic surfactants include the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4 - 22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.

[0086] Preferably, the at least one first and / or the at least one second phase contains at least one non-ionic surfactant, preferably a non-ionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the non-ionic surfactant in the total weight of the second phase is preferably 0.5 wt.% to 30 wt.%, preferably 5 wt.% to 25 wt.% and in particular 10 wt.% to 20 wt.%.

[0087] In a further preferred embodiment, 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 which R 1< and R 2< independently represent an alkyl or alkenyl group with 4 to 22 carbon atoms; R 3< and R 4< independently represent H or an alkyl or alkenyl group with 1 to 18 carbon atoms; and x and y independently represent values ​​between 1 and 40.

[0088] 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 R 3< and R 4< stand for H and the indices x and y independently take values ​​from 1 to 40, preferably from 1 to 15.

[0089] 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 R 1< and R 2< groups are independently saturated alkyl groups with 4 to 14 carbon atoms and the indices x and y independently take values ​​of 1 to 15 and in particular of 1 to 12.

[0090] Compounds of the general formula R1< -O(CH2CH2O)xCR3< R4< (OCH2CH2)yOR2< are also preferred, in which one of the R1< and R2< substituents is branched. Compounds of the general formula R1< -O(CH2CH2O)xCR3< R4< (OCH2CH2)yOR2< are particularly preferred, in which the indices x and y independently take on values ​​from 8 to 12.

[0091] The specified carbon chain lengths and degrees of ethoxylation or alkoxylation of the niotenes represent statistical averages, which may be whole numbers or fractions for a specific product. Due to the manufacturing processes, commercial products of the aforementioned formulas usually do not consist of a single individual compound, but rather of mixtures. This can result in average values ​​for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation, and consequently, fractions.

[0092] Of course, the aforementioned non-ionic surfactants (niotenes) can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.

[0093] Particularly preferred in the at least one first phase are nonionic surfactants having a melting point above room temperature. Nonionic surfactant(s) with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C, and especially between 26.6 and 43.3°C, is / are particularly preferred.

[0094] Suitable nonionic surfactants with melting or softening points within the specified temperature range include, for example, low-foaming nonionic surfactants that can be solid or highly viscous at room temperature. If nonionic surfactants that are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pa·s, preferably above 35 Pa·s, and particularly above 40 Pa·s. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

[0095] The niotenoid, which is solid at room temperature, preferably contains propylene oxide (PO) units in the molecule. Preferably, such PO units constitute up to 25 wt.%, particularly preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols that additionally contain polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such niotenoid molecules preferably constitutes more than 30 wt.%, particularly preferably more than 50 wt.%, and especially more than 70 wt.% of the total molar mass of such niotenoids. Preferred compositions are characterized in that they contain ethoxylated and propoxylated niotenoids in which the propylene oxide units constitute up to 25 wt.%, preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant.

[0096] Further niotenes, particularly preferred for use in the first phase, with melting points above room temperature, contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend comprising 75 wt% of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol ethylene oxide and 44 mol propylene oxide, and 25 wt% of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 mol ethylene oxide and 99 mol propylene oxide per mol trimethylolpropane.

[0097] In a preferred embodiment, the weight fraction of the non-ionic surfactant in the total weight of the first phase is 0.1 to 20 wt.%, particularly preferably 0.5 to 15 wt.%, and especially 2.5 to 10 wt.%.

[0098] All anionic surfactants are suitable for use in dishwashing detergents. These are characterized by a water-soluble anionic group, such as a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group with approximately 8 to 30 carbon atoms. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups. Suitable anionic surfactants are preferably in the form of sodium, potassium, and ammonium salts, as well as mono-, di-, and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group. However, zinc, manganese(II), magnesium, calcium, or mixtures thereof can also serve as counterions.

[0099] Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

[0100] Instead of or in combination with the surfactants mentioned above, cationic and / or amphoteric surfactants, such as betaines or quaternary ammonium compounds, can also be used. However, it is preferred that no cationic and / or amphoteric surfactants are used.

[0101] Surfactants influence the opacity of the second phase. In an equally preferred embodiment, the second phase is therefore free of surfactants, in particular nonionic surfactants.

[0102] Preferred washing or cleaning agents according to the invention are further characterized in that they contain less than 1.0 wt.% and in particular no anionic surfactant in the at least one first and / or the at least one second phase, especially in the first phase, since 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.

[0103] Substances that also serve as ingredients in cosmetic products are referred to below, where applicable, according to the International Nomenclature of Cosmetic Ingredients (INCI). Chemical compounds bear an INCI name in English. The INCI names can be found in the "International Cosmetic Ingredient Dictionary and Handbook, 7th Edition (1997)," published by The Cosmetic, Toiletry and Fragrance Association (CTFA), Washington, D.C. (USA). The abbreviation CAS indicates that the following sequence of numbers is a designation from the Chemical Abstracts Service.

[0104] In addition to the surfactants, the at least one second phase can also contain sugars. According to the invention, sugars comprise monosaccharides, disaccharides, and oligosaccharides. Preferably, the second phase comprises disaccharides, in particular sucrose. The proportion of sucrose is 0 wt.% to 30 wt.%, in particular 5 wt.% to 25 wt.%, and most preferably 10 wt.% to 20 wt.%, based on the weight of the second phase. In higher quantities, the sugar does not dissolve completely in the second phase and leads to turbidity. The use of sugar, in particular in a proportion of 10 wt.% to 5 wt.% to 15 wt.%, reduces moisture development and thus improves adhesion to the at least one first phase.

[0105] The use of builder substances (structural materials) such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids, and mixtures of these substances, preferably water-soluble builder substances, can be advantageous.

[0106] In a preferred embodiment according to the invention, the use of phosphates (including polyphosphates) is largely or completely omitted. In this embodiment, the composition preferably contains less than 5 wt.%, more preferably less than 3 wt.%, and particularly less than 1 wt.% phosphate(s). Most preferably, in this embodiment, the composition is completely phosphate-free, i.e., it contains less than 0.1 wt.% phosphate(s).

[0107] The framework materials include, in particular, carbonates, citrates, phosphonates, organic framework materials, and silicates. The weight fraction of the total framework materials in the total weight of the composition according to the invention is preferably 15 to 80 wt.% and particularly 20 to 70 wt.%.

[0108] Suitable organic framework materials according to the invention are, for example, polycarboxylic acids (polycarboxylates) that can be used in the form of their sodium salts. Polycarboxylic acids are understood to be those carboxylic acids that carry more than one, in particular two to eight, preferably two to six, in particular two, three, four, or five acid functions in the entire molecule. Dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and pentacarboxylic acids, in particular di-, tri-, and tetracarboxylic acids, are thus preferred as polycarboxylic acids. The polycarboxylic acids may also carry further functional groups, such as hydroxyl or amino groups.Examples include 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 nitrilotriacetic acid (NTA), glutamine-N,N-diacetic acid (also known as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA) and their derivatives, as well as 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.

[0109] Other suitable organic framework materials include polymeric polycarboxylates (organic polymers with a large number of carboxylate functional groups in the macromolecule, especially more than ten), polyaspartates, polyacetals and dextrins.

[0110] In addition to their building block effect, free acids typically also possess the property of an acidifying component. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof are particularly noteworthy in this regard.

[0111] Particularly preferred washing or cleaning agents according to the invention, especially dishwashing detergents, preferably machine dishwashing detergents, contain one or more salts of citric acid, i.e., citrates, as one of their essential building blocks. These are preferably contained in a proportion of 2 to 40 wt.%, particularly 5 to 30 wt.%, particularly 7 to 28 wt.%, particularly preferably 10 to 25 wt.%, and most preferably 15 to 20 wt.%, in each case based on the total weight of the agent.

[0112] Particularly preferred is the use of carbonate(s) and / or hydrogen carbonate(s), preferably alkali carbonate(s), particularly preferably sodium carbonate (soda), in amounts of 2 to 50 wt.%, preferably 4 to 40 wt.% and particularly 10 to 30 wt.%, most preferably 10 to 24 wt.%, in each case based on the weight of the agent.

[0113] Particularly preferred washing or cleaning agents according to the invention, especially dishwashing detergents, preferably machine dishwashing detergents, are characterized in that they contain at least two builder substances from the group consisting of silicates, phosphonates, carbonates, aminocarboxylic acids, and citrates, wherein the weight fraction of these builder substances, based on the total weight of the cleaning agent according to the invention, is preferably 5 to 70 wt.%, preferably 15 to 60 wt.%, and particularly 20 to 50 wt.%. The combination of two or more builder substances from the aforementioned group has proven advantageous for the cleaning and rinsing performance of washing or cleaning agents according to the invention, especially dishwashing detergents, preferably machine dishwashing detergents. In addition to the builder substances mentioned here, one or more other builder substances may also be included.

[0114] Preferred washing or cleaning agents, in particular dishwashing detergents, preferably machine dishwashing detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate. In a particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, wherein the amount of carbonate is preferably 5 to 40 wt.%, in particular 10 to 35 wt.%, most preferably 15 to 30 wt.%, and the amount of citrate is preferably 5 to 35 wt.%, in particular 10 to 25 wt.%, most preferably 15 to 20 wt.%, each based on the total amount of the cleaning agent, wherein the total amount of these two builders is preferably 20 to 65 wt.%, in particular 25 to 60 wt.%, more preferably 30 to 50 wt.%. Furthermore, one or more additional builders may be included.

[0115] The washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, may contain phosphonates as a further building block. A hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues are preferably suitable as aminoalkane phosphonates. Phosphonates are preferably present in compositions according to the invention in amounts of 0.1 to 10 wt.%, in particular in amounts of 0.5 to 8 wt.%, and most preferably in amounts of 2.5 to 7.5 wt.%, in each case based on the total weight of the composition.

[0116] The combined use of citrate, (hydrogen) carbonate, and phosphonate is particularly preferred. These can be used in the quantities mentioned above. In particular, this combination uses amounts of 10 to 25 wt% citrate, 10 to 30 wt% carbonate (or hydrogen carbonate), and 2.5 to 7.5 wt% phosphonate, each based on the total weight of the product.

[0117] Further particularly preferred washing or cleaning agents, especially dishwashing detergents, preferably machine dishwashing detergents, are characterized in that, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, they contain at least one further phosphorus-free structural component. In particular, this component is selected from the aminocarboxylic acids, wherein the further phosphorus-free structural component is preferably selected from methylglycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyl iminodiacetate (HEIDA), iminodisuccinate (IDS), and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA. A particularly preferred combination is, for example, citrate, (hydrogen) carbonate, and MGDA, and optionally phosphonate.

[0118] The wt.% proportion of the further phosphorus-free builder, in particular MGDA and / or GLDA, is preferably 0 to 40 wt.%, particularly 5 to 30 wt.%, and especially 7 to 25 wt.%. The use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules containing as little water as possible and / or exhibiting lower hygroscopicity (water absorption at 25 °C, normal pressure) compared to the non-granulated powder are advantageous. The combination of at least three, in particular at least four, builders from the group mentioned above has proven advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents. Additional builders may also be included.

[0119] Suitable organic framework materials include polymeric polycarboxylates, such as the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those with a relative molecular mass of 500 to 70,000 g / mol. Particularly suitable polymers are polyacrylates, preferably with a molecular mass of 1,000 to 20,000 g / mol. Due to their superior solubility, short-chain polyacrylates from this group, with molar masses of 1,100 to 10,000 g / mol, and especially preferably 1,200 to 5,000 g / mol, are particularly preferred.

[0120] The content of (homo)polymeric polycarboxylates in the washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, is preferably 0.5 to 20 wt.%, preferably 2 to 15 wt.% and in particular 4 to 10 wt.%.

[0121] Washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, can further utilize as a framework material crystalline layered silicates of the general formula NaMSi x O 2x+1 · y H 2 O, where M represents 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 is a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a modulus Na 2 O : SiO 2 of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and particularly from 1:2 to 1:2.6, which are preferably retardant and exhibit secondary washing properties, can also be used.

[0122] In certain washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, the silicate content, based on the total weight of the washing or cleaning agent, is limited to amounts below 10 wt.%, preferably below 5 wt.% and in particular below 2 wt.%.

[0123] In addition to the aforementioned builders, the washing or cleaning agents according to the invention may further contain alkali metal hydroxides. These alkali carriers are preferably used in the washing or cleaning agents, and in particular in the at least one second phase, only in small quantities, preferably in quantities below 10 wt.%, more preferably below 6 wt.%, more preferably below 5 wt.%, particularly preferably between 0.1 and 5 wt.%, and especially between 0.5 and 5 wt.%, in each case based on the total weight of the washing or cleaning agent. Alternative washing or cleaning agents according to the invention are free of alkali metal hydroxides.

[0124] As a further component, cleaning agents according to the invention preferably contain enzyme(s) in the at least one first and / or the at least one second phase. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are, in principle, of natural origin; starting from the natural molecules, improved variants are available for use in cleaning agents and are therefore preferably employed. Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 x 10⁻⁶ wt.% to 5 wt.% based on active protein. The protein concentration can be determined using known methods, for example, the BCA method or the biuret method.

[0125] Among the proteases, those of the subtilisin type are preferred. Examples include 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 enzymes thermitase, proteinase K, and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the strict sense.

[0126] Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae, as well as the improved developments of the aforementioned amylases for use in detergents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948) are particularly noteworthy for this purpose.

[0127] Lipases or cutinases can also be used according to the invention, particularly because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed from it, especially those with the amino acid substitution at positions D96LT213R and / or N233R, most preferably all of the substitutions D96L, T213R and N233R.

[0128] Furthermore, enzymes collectively known as hemicellulases can be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases, and β-glucanases.

[0129] To enhance the bleaching effect, 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. Advantageously, preferably organic, and especially aromatic, compounds that interact with the enzymes are added to enhance the activity of the respective oxidoreductases (enhancers) or to ensure electron flow in cases of significantly different redox potentials between the oxidizing enzymes and the contaminants (mediators). A protein and / or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation, or degradation, for example, by physical influences, oxidation, or proteolytic cleavage.When proteins and / or enzymes are produced microbially, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. For this purpose, cleaning agents may contain stabilizers; the provision of such agents represents a preferred embodiment of the present invention.

[0130] Cleaning-active proteases and amylases are generally not supplied as pure proteins, but rather as stabilized preparations suitable for storage and transport. These pre-prepared formulations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization, or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with low water content, and / or containing stabilizers or other additives.

[0131] Alternatively, 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, such as those in which the enzymes are enclosed as if in a solidified gel, or in core-shell type capsules in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are produced using methods known per se, for example, by shake or roll granulation or in fluid-bed processes. Advantageously, such granules are low in dust, for example, by applying polymeric film formers, and are stable during storage due to the coating.

[0132] Furthermore, it is possible to combine two or more enzymes so that a single granule has multiple enzyme activities.

[0133] As can be seen from the preceding explanations, the enzyme protein constitutes 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 wt.%, preferably between 0.2 and 30 wt.%, particularly preferably between 0.4 and 20 wt.%, and especially between 0.8 and 10 wt.% of the enzyme protein. Particularly preferred are cleaning agents which, based on their total weight, contain 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and especially 0.5 to 8 wt.% of the respective enzyme preparations.

[0134] In addition to the components already mentioned, 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, bleaching agents, bleaching activators, bleaching catalysts, further solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver preservatives, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (especially in the at least one first phase), additives for improving flow and drying properties, for adjusting viscosity, for stabilization, UV stabilizers, pericarpenes (INCI: Opacing Agents; for example, glycol distearate, for example, Cutina® AGS from Cognis, or mixtures containing it, for example, Euperlane® from [Company Name]).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 from Boots as Myacide® BT or Boots Bronopol BT), antimicrobial agents (disinfectants), pH adjusters in quantities of usually no more than 5% by weight.

[0135] As a further solvent, compositions according to the invention preferably contain at least one alkanolamine. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanololamine, and ethanololamine, and mixtures thereof. The alkanolamine is preferably present in compositions according to the invention in an amount of 0.5 to 10 wt.%, and in particular in an amount of 1 to 6 wt.%. In a preferred washing or cleaning agent, the at least one second phase is free of alkanolamine, and the alkanolamine is present only in the at least one first phase.

[0136] According to the invention, washing or cleaning agents, in particular dishwashing detergents, contain in a preferred embodiment at least one zinc salt as a glass corrosion inhibitor. The zinc salt can be an inorganic or organic zinc salt. The zinc salt used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l, and especially above 5 g / l (all solubilities at a water temperature of 20°C). 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 consisting of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, and zinc p-toluenesulfonate. In a particularly preferred embodiment according to the invention, zinc acetate is used as the zinc salt. The zinc salt is preferably contained in cleaning agents according to the invention in an amount of 0.01 wt.% to 5 wt.%, particularly preferably in an amount of 0.05 wt.% to 3 wt.%, and especially in an amount of 0.1 wt.% to 2 wt.%, based on the total weight of the cleaning agent. In addition to or as an alternative to the aforementioned salts (especially the zinc salts), polyethyleneimines, such as those available, for example, under the name Lupasol® (BASF), can preferably be added in an amount of 0 to 5 wt.%, particularly 0.01 to 2 wt.%.-%, are used as glass corrosion inhibitors.

[0137] Suitable polymers as additives include, in particular, maleic acid-acrylic acid copolymer sodium salt (e.g., Sokalan® < CP 5 from BASF, Ludwigshafen, Germany), modified polyacrylic acid sodium salt (e.g., Sokalan® < CP 10 from BASF, Ludwigshafen, Germany), modified polycarboxylate sodium salt (e.g., Sokalan® < HP 25 from BASF, Ludwigshafen, Germany), polyalkylene oxide, modified heptamethyltrisiloxane (e.g., Silwet® < L-77 from BASF, Ludwigshafen, Germany), polyalkylene oxide, modified heptamethyltrisiloxane (e.g., Silwet® < L-7608 from BASF, Ludwigshafen, Germany), and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide segments (polyether blocks)), preferably water-soluble linear polyethersiloxanes with terminal polyether blocks such as Tegopren®< 5840, Tegopren®< 5843, Tegopren®< 5847, Tegopren®< 5851, Tegopren®< 5863 or Tegopren®< 5878 from Evonik,Essen (Germany). Suitable additive building blocks include, in particular, polyaspartic acid sodium salt, ethylenediamine triacetate cocosalkylacetamide (for example, Rewopol® < CHT 12 from Evonik, Essen (Germany)), methylglycine diacetic acid trisodium salt, and acetophosphonic acid. Mixtures with surfactant or polymeric additives show synergistic effects in the case of Tegopren® < 5843 and Tegopren® < 5863. However, the use of Tegopren types 5843 and 5863 is less preferred for application on hard glass surfaces, especially glassware, because these silicone surfactants can adhere to glass. In a particular embodiment of the invention, the aforementioned additives are omitted.

[0138] A preferred washing or cleaning agent, in particular a dishwashing detergent, preferably further comprises a bleaching agent, in particular an oxygen bleaching agent, and optionally a bleaching activator and / or bleaching catalyst. These, if present, are contained exclusively in the at least one first phase.

[0139] As a preferred bleaching agent, 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. Other suitable bleaching agents include, for example, peroxypyrophosphates, citrate perhydrates, and pericy salts or peracids that provide H₂O₂, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid, or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids, with alkyl peroxy acids and aryl peroxy acids being particularly examples. Sodium percarbonate is especially preferred because of its good bleaching performance. Sodium percarbonate is a particularly preferred oxygen bleaching agent.

[0140] Suitable bleaching activators include compounds that, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, particularly 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances bearing O- and / or N-acyl groups of the specified number of carbon atoms and / or optionally substituted benzoyl groups are suitable. Multiply acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) proving particularly suitable.

[0141] The bleaching catalysts are bleach-enhancing transition metal salts or transition metal complexes, such as Mn, Fe, Co, Ru, or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes with nitrogen-containing tripod ligands, as well as Co, Fe, Cu, and Ru ammine complexes, can also be used as bleaching catalysts. Manganese complexes in oxidation states II, III, IV, or IV are particularly preferred, preferably containing one or more macrocyclic ligands with the donor functions N, NR, PR, O, and / or S. Ligands with nitrogen donor functions are especially favored.It is particularly preferred to use bleaching catalyst(s) in the compositions according to the invention, which contain as macromolecular ligands 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). Suitable manganese complexes are, for example, [Mn III< 2 (µ-O) 1 (µ-OAc) 2 (TACN) 2 ](ClO 4 ) 2 , [Mn III< Mn IV< (µ-O) 2 (µ-OAc) 1 (TACN) 2 ](BPh 4 ) 2 , [Mn IV< 4(µ-O) 6 (TACN) 4 ](ClO 4 ) 4 , [Mn III< 2 (µ-O) 1 (µ-OAc) 2 (Me-TACN) 2 ](ClO 4 ) 2 , [Mn III< Mn IV< (µ-O) 1 (µ-OAc) 2 (Me-TACN) 2 ](ClO 4 ) 3 , [Mn IV< 2 (µ-O) 3 (Me-TACN) 2 ](PF 6 ) 2 and [Mn IV< 2 (µ-O) 3 (Me / Me-TACN) 2 ](PF 6 ) 2 (with OAc = OC(O)CH 3 ).

[0142] When benzoic acid, salicylic acid or lactic acid are used as pH regulators and / or buffer substances, these compounds can support or enhance the antibacterial effect of the silver and / or the silver compound.

[0143] The washing or cleaning agent according to the invention comprises at least one first phase (1) and at least one second phase (2). The washing or cleaning agent can thus have one, two, three, or more distinct first phases (1); likewise, it can have one, two, three, or more distinct second phases (2). Preferably, the washing or cleaning agent according to the invention comprises one first phase (1) and one second phase (2). Particularly preferably, the washing or cleaning agent comprises two first phases (1) and one second phase (2). More preferably, it comprises two first phases (1) and two second phases (2). A further preferred embodiment is one in which 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 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) and second phase (2) in a cleaning process.

[0144] According to the invention, the at least one first phase (1) and the at least one second phase (2) are fully or partially adjacent to each other. It is preferred that the two phases are directly adjacent to each other. However, it is also possible that the at least one first phase (1), the at least one second phase (2), or the at least one first phase (1) and the at least one second phase (2) are tightly enclosed by a water-soluble film or contained in a water-soluble bag. Preferably, the entire composition is contained in a water-soluble bag or, more preferably, tightly enclosed by a water-soluble film.

[0145] If at least one first phase (1) and at least one second phase (2) are directly adjacent to each other, either fully or partially, stability is important in addition to the shortest possible solidification time of the at least one second phase (2). Stability here means that components contained in the second phase do not migrate into the at least one first phase, but rather that even after prolonged storage, the at least one first phase and the second phase remain optically separate and do not interact with each other, such as through diffusion of liquid components from one phase to the other, reaction of components of one phase with those in the other phase, or loss of adhesion of the second phase (2) to the first phase (1), particularly if it is compressed or compacted, due to liquid leakage.Surprisingly, it has been shown that this can be achieved by a second phase which contains glycerin, gelatin and at least one C3 to C5 alkanediol.

[0146] The water-soluble film or 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.

[0147] "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure which also contain structural units of this type in small proportions (approx. 2%).

[0148] Commercially available polyvinyl alcohols, offered as white-yellowish powders or granules with degrees of polymerization in the range of approximately 100 to 2500 (molar masses of approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 87-99 mol%, meaning they still contain a residual amount of acetyl groups.

[0149] In the context of the present invention, it is preferred that the water-soluble packaging comprises at least a proportion of a polyvinyl alcohol having a degree of hydrolysis preferably of 70 to 100 mol%, more preferably of 80 to 90 mol%, more preferably of 81 to 89 mol%, and most preferably of 82 to 88 mol%. In a preferred embodiment, the water-soluble packaging consists of at least 20 wt%, more preferably of at least 40 wt%, most preferably of at least 60 wt%, and most preferably of at least 80 wt% of a polyvinyl alcohol having a degree of hydrolysis of 70 to 100 mol%, more preferably of 80 to 90 mol%, more preferably of 81 to 89 mol%, and most preferably of 82 to 88 mol%.

[0150] Preferably, polyvinyl alcohols of a specific molecular weight range are used as packaging materials, wherein, according to the invention, it is preferred that the packaging material comprises a polyvinyl alcohol whose molecular weight is in the range of 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 particularly from 15,000 g·mol -1< to 70,000 g·mol -1<.

[0151] The degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 and approximately 2100, preferably between approximately 220 and approximately 1890, particularly preferably between approximately 240 and approximately 1680 and particularly between approximately 260 and approximately 1500.

[0152] The water solubility of polyvinyl alcohol can be modified by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols that are acetalized or ketalized with the aldehyde or ketone groups of saccharides or polysaccharides, or mixtures thereof, have proven particularly advantageous due to their exceptionally good cold water solubility. The reaction products of polyvinyl alcohol and starch are also extremely beneficial. Furthermore, the water solubility can be modified by complexation with nickel or copper salts or by treatment with dichromates, boric acid, or borax, thus allowing it to be precisely adjusted to desired values.

[0153] The water-soluble bag preferably has a thickness of 10 µm to 500 µm, particularly 20 µm to 400 µm, especially 30 µm to 300 µm, particularly 40 µm to 200 µm, and especially 50 µm to 150 µm. A particularly preferred polyvinyl alcohol is available, for example, under the trade name M8630 (Monosol).

[0154] The water-soluble film, which is preferably used in the tight wrapping, particularly preferably comprises polyvinyl alcohol as described above, wherein the initial thickness is preferably 10 µm to 100 µm, in particular 12 µm to 60 µm, particularly preferably 15 µm to 50 µm, especially 20 µm to 40 µm, and in particular 22 µm to 35 µm.

[0155] In the case of a tight coating, each single-use portion of the washing or cleaning agent is encapsulated. For the coated single-use portions of washing or cleaning agent according to the invention, it is important that the coating fits tightly against the surface of the tablets at every point.

[0156] Ideally, the coating is even under tension, although this is not strictly necessary. This tight fit of the coating promotes disintegration: Upon initial contact with water, the coating will allow a small amount of water to pass through at some point, without necessarily dissolving at first. At this point, the disintegrant contained in the tablet begins to swell. This causes the coating to suddenly rupture due to the tablet's increase in volume, releasing the tablet. With a loosely fitting coating, the mechanism described here does not work, as the tablet can swell without the coating rupturing. In this case, the use of a swellable disintegrant is superior to a gas-generating system, since the latter's bursting action always results in the coating rupturing.In a gas-generating system, the explosive effect can "dissipate" due to gas escaping from a leak in the casing.

[0157] Preferred single-use portions of washing or cleaning agents according to the invention are characterized in that the distance between the single-use portion and the water-soluble coating over the entire area is 0.1 to 1000 µm, preferably 0.5 to 500 µm, particularly preferably 1 to 250 µm and particularly 2.5 to 100 µm.

[0158] In a preferred embodiment, the film wrapping is first loosely placed around a single-use portion of washing or cleaning agent and sealed, and then shrunk onto it, so that there is close contact between the film packaging and the cleaning agent concentrate. Accordingly, single-use portions of washing or cleaning agent according to the invention are characterized in that the wrapping is a film packaging shrunk onto it.

[0159] For example, this wrapping can be achieved by placing a water-soluble underfilm onto a conveyor chain or forming tool, then placing one or more portions of washing or cleaning agent onto the underfilm; subsequently, placing a water-soluble topfilm onto the washing or cleaning agent portion(s) on the underfilm and then fixing it to the underfilm, enclosing the washing or cleaning agent portion(s). Alternatively, this step can also be performed using a single-strand film, which is then formed into a tube around the single-use portions. The films are then sealed and optionally cut. Finally, the film can be shrunk using hot air or infrared radiation, optionally with pressure.

[0160] Such water-soluble coatings are already described in patent applications WO 2004 / 031338 A and WO 2003 / 099985 A, to whose disclosure full reference is hereby made.

[0161] The at least one first phase (1) of the washing or cleaning agent according to the invention, in particular the dishwashing detergent, preferably the machine dishwashing detergent, is in a preferred embodiment in the form of a molded body, in particular a compact, especially a tablet. Particularly preferred is the at least one first phase (1) a powdered washing or cleaning agent which is compacted in the form of a tablet.

[0162] The at least one first phase (1) and the at least one second phase (2) can be arranged in any combination relative to each other, whether directly or indirectly (for example, by the presence of a film, covering, or bag as described above). Thus, a first phase (1) can be arranged on top of or next to a second phase (2), as in Fig. 1 shown schematically. In this embodiment, 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. 2a and Fig. 2b This is also illustrated by the embedding of one phase within another, as in Fig. 3a and Fig. 3b The schematic representation shown is comprised of the following according to the invention. A further, particularly preferred arrangement is shown in Fig. 4The second phase (2) is shown schematically. The second phase (2) is in the form of a core embedded in the first phase (1). A pool-like form of the solid first phase (1) is particularly preferred, i.e., a mold with a cavity into which the second phase is placed. The cavity can be round, oval, or rectangular. Alternatively, there can be two separate cavities, each filled with at least one second phase (2). In this embodiment, the washing or cleaning agent comprises two second phases (2), which can have different compositions.

[0163] In principle, any geometry is possible. The rectangular shape shown here is merely an example. Round or oval shapes for the two phases, or any polygonal configuration, are also conceivable.

[0164] Another subject matter of the present application is a method for cleaning hard surfaces, in particular dishes, in which the surface is treated in a manner known per se using a cleaning agent according to the invention. In particular, 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 a dishwasher.

[0165] Another object of the present invention is the use of a cleaning agent for cleaning hard surfaces, in particular dishes.

[0166] The presentIn a preferred embodiment, the application relates to machine dishwashing detergents. According to this application, machine dishwashing detergents are defined as compositions that can be used to clean soiled dishes in a machine dishwashing process. Thus, the machine dishwashing detergents according to the invention differ, for example, from machine rinse aids, which are always used in combination with machine dishwashing detergents and do not have an independent cleaning effect.

[0167] Insofar as the present application states that the washing or cleaning agent according to the invention comprises something in its entirety or in at least one first phase (1) or in at least one second phase (2), it is also considered disclosed that the washing or cleaning agent or the respective phase may consist of such something. In the following exemplary embodiment, the washing or cleaning agent according to the invention is described in a non-limiting manner.

[0168] The following points describe particularly suitable embodiments of the present invention: 1. A washing or cleaning agent comprising at least one first phase (1) and at least one different second phase (2), characterized in that the at least one first phase (1) is solid and, in particular, compressed, and the at least one second phase (2) comprises at least one polymer and at least one polyhydric alcohol. 2. A washing or cleaning agent according to point 1, characterized in that the at least one second phase (2) comprises at least two polyhydric alcohols, wherein a first polyhydric alcohol is an alkanetriol, in particular a C3 to C10 alkanetriol, and a second polyhydric alcohol is an alkanediol, in particular a C3 to C10 alkanediol. 3.Washing or cleaning agent according to point 2, characterized in that the first polyhydric alcohol is a C3 to C8 alkanetriol, in particular a C3 to C6 alkanetriol, preferably glycerol and / or 1,1,1-trimethylolpropane and / or 2-amino-2-(hydroxymethyl)-1,3-propanediol, especially glycerol and / or 1,1,1-trimethylolpropane, most especially glycerol. 4. Washing or cleaning agent according to point 2 or 3, characterized in that the second polyhydric alcohol is a C3 to C8 alkanediol, in particular a C3 to C5 alkanediol. 5. Washing or cleaning agent according to any one of points 2 to 4, characterized in that the two OH groups of the alkanediol are not arranged on immediately adjacent carbon atoms of the alkyl chain and, in particular, three or four carbon atoms are located between the two OH groups. 6.7. Washing or cleaning agent according to any one of points 1 to 5, characterized in that the at least one second phase (2) is substantially anhydrous. 8. Washing or cleaning agent according to any one of points 1 to 6, characterized in that the at least one second phase (2) comprises gelatin and / or PVA as a polymer. 9. Washing or cleaning agent according to any one of points 1 to 7, characterized in that the at least one first phase (1) and / or the at least one second phase (2) comprises at least one surfactant, in particular at least one niotenoid. 10. Washing or cleaning agent according to any one of points 1 to 8, characterized in that it is in the form of a tablet, wherein the weight ratio of the at least one first phase (1) to the at least one second phase (2) is 20:1 to 8:1.Washing or cleaning agent according to any one of points 1 to 9, characterized in that it is a dishwashing detergent, in particular a dishwashing detergent for machine cleaning of dishes. Examples of implementation:

[0169] Cleaning agents according to the invention were produced, comprising a first phase and a second phase. Different geometries were implemented. Furthermore, cleaning agents comprising two first phases and a second phase were produced. The following data refers to wt% active substance based on the total weight of the respective phase.

[0170] The first phases had the following composition: % by weight 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 Bleaching catalyst (preferably Mn-based) 0,0-0,8 Bleach activator (e.g. TAED) 1,0-4,0 Non-ionic surfactant(s), e.g. 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. Crosslinked PVP) 0,0 -3,0 Protease preparation (tq) 1,0 - 7 Amylase preparation (tq) 0,2- 6 Silver protection (benzotriazole) 0,0 - 1,0 perfume 0,0-0,5 dye solution 0,0 - 1,5 Zinc salt (e.g. acetate) 0,01- 0,5 Sodium sulfate 0,0 - 25 Water 0,0 - 3 pH adjusters (e.g. citric acid) 0,0 - 5 Process aids 0-10

[0171] Furthermore, initial phases were produced which had the following composition: % by weight 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 Bleaching catalyst (preferably Mn-based) 0,02-0,5 Bleach activator (e.g. TAED) 1-3 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 2,5-10 Polycarboxylate 4 - 10 Cationic copolymer 0 - 0,75 Disintegrant - (e.g. Crosslinked PVP) 0 -1,5 Protease preparation (tq) 1,5-5 Amylase preparation (tq) 0,5-3 Silver protection (benzotriazole) 0-0,5 perfume 0,05-0,25 dye solution 0,0-1 Zinc salt (e.g. acetate) 0,1-0,3 Sodium sulfate 0,0 - 10 Water 0,0-1,5 pH adjusters (e.g. citric acid) 0-1,5 Process aids 0-5

[0172] These first phases were in the form of compacted tablets with a depression on one side. A liquid composition was poured into this depression, which, after hardening, formed the second phase. The resulting cleaning agent was, according to the Fig. 4 The form shown was present. Further initial phases were present without indentation. Here, a second phase was brought into direct contact with the surface of the first phase.

[0173] The second phases had the following composition: % by weight Glycerin 10-50 Propanediol (preferably 1,3-propanediol) 10-50 Polycarboxylate homo- and / or copolymer with sulfonic acid-containing groups 0-30 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 0-40 Polyethylene glycol medium Mr 1000-2000 0-20 Thickening agent (preferably gelatin or PVA) 5-50 Process aids 0-10 dye solution 0,0 - 1,5

[0174] Further second phases were produced with the following composition: % by weight Glycerin 20 - 45 Propanediol (preferably 1,3-propanediol) 10 - 30 Polycarboxylate; homo- and / or copolymer with sulfonic acid-containing groups 5 - 20 Non-ionic surfactant(s), e.g. fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 5-25 Polyethylene glycol medium Mr 1000-2000 0 - 8 Thickening agent (preferably gelatin or PVA) 10-20 Process aids 0-5 dye solution 0,0-0,5

[0175] The first and second phases could be combined in any way desired. The spatial shape of the second phase, which was liquid after mixing the ingredients and stable within a solidification time of approximately 10 to 15 minutes, was determined by the spatial shape of the first phase as well as by commercially available or custom-designed molds. The liquid second phase was poured into these molds, and after solidification, the molds were removed without altering the second phase.

[0176] This made it possible to create any geometry 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 H₂O 8 8 Glycerin 31 31 Gelatine 60 Bloom 15 15 Non-ionic surfactant 15 15 Solidification time (20°C) / min 5 20 Surface texture after 12 hours of storage at 20°C dry moist

[0177] Table 1 shows that 1,3-propanediol leads to a faster solidification of the dimensionally stable second phase. Table 2: further examples of compositions of a second phase B1 B2 B3 B4 1,2-Propanediol 45 0,0 0,0 0,0 1,3-Propanediol 0,0 45 0,0 0,0 1,3-Butanediol 0,0 0,0 45 0,0 1,4-Butanediol 0,0 0,0 0,0 45 Glycerin 29 29 29 29 Maltodextrin 5 5 5 5 Gelatine 60 Bloom 20 20 20 20 Non-ionic surfactant 1 1 1 1 Solidification time (20°C) / min 15 5 5 5 transparency Transparent Transparent opaque opaque Surface texture after 12 hours of storage at 20°C dry Dry greasy greasy Table 3: Storage stability after 12 days at 40°C of the second phase (poured into the well of a dishwasher detergent tablet) C1 C2 1,2-Propanediol 47 0,0 1,3-Propanediol 0,0 47 Glycerin 20 20 Sulfonic acid group-containing polymer (ground) 8 8 Gelatine 180 Bloom 25 25 Solidification time (20°C) / min 15 5 After storage at 40°C for 12 days: Liability between first and second phase Small amount Very good Haptics / appearance of the second phase (surface) dry, glossy, transparent dry, glossy, transparent

Claims

1. Washing or cleaning agent comprising at least a first phase (1) and at least one second phase (2) different from the first characterized by the fact that which at least one first phase (1) is solid and which at least one second phase (2) comprises at least one polymer and at least one polyhydric alcohol.

2. Washing or cleaning agent according to claim 1, characterized by the fact that comprising at least one second phase (2) comprising at least two polyhydric alcohols, wherein a first polyhydric alcohol is an alkanetriol, in particular a C3 to C 10 -Alkanetriol, and a second polyhydric alcohol, an alkanediol, in particular a C3 to C 10 -Alkanediol is.

3. Washing or cleaning agent according to claim 2, characterized by the fact thatthe first polyhydric alcohol is a C3 to C8 alkanetriol, in particular a C3 to C6 alkanetriol, preferably glycerol and / or 1,1,1-trimethylolpropane and / or 2-amino-2-(hydroxymethyl)-1,3-propanediol, especially glycerol and / or 1,1,1-trimethylolpropane, most especially glycerol.

4. Washing or cleaning agent according to claim 2 or 3, characterized by the fact that The proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based on the total weight of the second phase, is 5 wt.% to 70 wt.%, in particular 10 wt.% to 65 wt.%, particularly preferably 20 wt.% to 40 wt.%.

5. Washing or cleaning agents according to claims 2 to 4, characterized by the fact that the second polyhydric alcohol is a C3 to C8 alkanediol, in particular a C3 to C5 alkanediol.

6. Washing or cleaning agent according to any one of claims 1 to 5, characterized by the fact that which are in direct contact with each other, at least in a first phase and at least in a second phase.

7. Washing or cleaning agent according to any one of claims 1 to 6, characterized by the fact that comprising at least one second phase comprising at least one polymer suitable for network formation in a proportion of about 5 wt.% to 40 wt.%, in particular 10 wt.% to 35 wt.%, preferably 15 wt.% to 20 wt.%, in each case based on the total weight of the second phase.

8. Washing or cleaning agent according to any one of claims 1 to 7, characterized by the fact that comprising at least one second phase (2) of gelatin and / or polyvinyl alcohol as a polymer.

9. Washing or cleaning agent according to claim 8, characterized by the fact that comprising at least one second phase (2) polyvinyl alcohol with a molar mass of 30,000 to 60,000 g / mol.

10. Washing or cleaning agent according to any one of claims 1 to 9, characterized by the fact that which is at least dimensionally stable in a second phase.

11. Washing or cleaning agent according to any one of claims 1 to 10, characterized by the fact thatin at least one second phase (2) additionally a polycarboxylate, in particular a copolymeric polyacrylate, particularly preferably a copolymeric polysulfonate, which preferably has at least one monomer from the group of unsaturated carboxylic acids in addition to sulfonic acid group-containing monomer(s).

12. Washing or cleaning agent according to any one of claims 1 to 11, characterized by the fact that comprising at least one second phase (2) as further polymers polyethylene glycols with an average molar mass between 200 and 8000, between 800 and 4000 g / mol.

13. Washing or cleaning agent according to any one of claims 1 to 12, characterized by the fact that comprising at least one first phase (1) and / or at least one second phase (2) comprising at least one surfactant, in particular at least one niotenoid.

14. Washing or cleaning agent according to any one of claims 1 to 13, characterized by the fact thatit is in the form of a tablet, wherein the weight ratio of the at least one first phase (1) to the at least one second phase (2) is 20:1 to 8:

1.

15. Washing or cleaning agent according to any one of claims 1 to 14, characterized by the fact that It is a dishwashing detergent, in particular a dishwashing detergent for machine cleaning of dishes.

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