EP3325595B1 - Detergent or cleaning agent with at least two phases - Google Patents

Description

The present invention relates to a washing or cleaning agent, in particular a cleaning agent for hard surfaces, with at least two different phases.

Detergents or cleaning agents are usually present in solid form (for example as a powder) or in liquid form (or as a flowing gel). Liquid detergents or cleaning agents in particular are enjoying increasing popularity among consumers.

Solid detergents or cleaning agents have the advantage that, unlike liquid detergents or cleaning agents, they do not require any preservatives. Liquid forms of offer are becoming increasingly popular on the market, in particular due to their rapid solubility and the associated rapid availability of the active ingredients they contain. This offers the consumer the opportunity to use time-reduced washing programs and still get good cleaning performance.

Furthermore, consumers have become accustomed to convenient dosing of pre-portioned machine washing or cleaning agents, such as dishwashing detergents, and use these products in the form of tablets (solid washing or cleaning agents) or in the form of sachets, which are usually washed with a liquid - or cleaning agents are filled, whereby bags filled with powder are also possible as single servings. Disposable portions in water-soluble bags are becoming increasingly popular not only because the consumer no longer comes into contact with the chemical composition, but not least because of the bag's attractive appearance. The appearance of the dosage form is becoming increasingly important. In addition to good cleaning performance and sufficient storage stability, good optics is one of the reasons for choosing a product. However, products stored in bags often change their visual appearance, which often gives consumers associations with reduced performance and poorer cleaning performance.

From the point of view of the consumer, it is now desirable to combine the advantages of both types of offer and to provide a dosage form which is improved compared to the prior art, in particular for usually liquid detergents or cleaning agents. Both a single portioning should be possible and at the same time an optically appealing appearance should be achieved for the consumer. Surprisingly, it has been shown that through a Formulating a flexible phase, which is combined with a fixed phase, this goal can be achieved.

The documents EP 1 754 775 A2 , US 6 486 117 B1 and WO 03/062360 each describe detergent tablets with a second phase comprising a polyhydric alcohol. The post-published patent applications EP 2 924106 and WO 2016/042130 disclose multi-phase compositions comprising 1,2-propanediol and glvcerin.

In a first embodiment, the object on which the present application is based is therefore achieved by a washing or cleaning agent which comprises at least one first phase and at least one different second phase, the at least one first phase being fixed and the at least one second phase comprises at least one polymer and at least two polyhydric alcohols, a first polyhydric alcohol being an alkanetriol and a second polyhydric alcohol being an alkanediol and the at least one second phase (2) comprising gelatin and / or polyvinyl alcohol (PVA) as the polymer.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by different characteristics, for example ingredients, physical properties, external appearance, etc. Different phases can preferably be distinguished optically. For the consumer, the at least one first phase must be clearly distinguished from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, these can likewise be distinguished from one another with the naked eye, because they differ from one another, for example, in their coloring. The same applies if there are two or more second phases. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a color or transparency difference. Phases in the sense of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye. When used, the individual phases can have different properties, such as, for example, the rate at which the phase dissolves in water and thus the rate and the order in which the constituents contained in the respective phase are released.

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 gives a flowable mixture which can be brought into a desired shape. After a certain period of time, a second phase is obtained, which remains in the specified form, i.e. is dimensionally stable. This period, the solidification time, is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes. The at least one second phase yields under pressure, but does not deform as a result, but rather returns to the initial state after the pressure has dropped. The at least one second phase is preferably elastic, in particular linear-elastic. The at least one second phase is also preferably transparent, which gives a good visual impression.

The at least one second phase is cut-resistant. For example, it can be cut with a knife after solidification without being further destroyed apart from the cut performed. Furthermore, the at least one second phase is particularly flexible. Due to the flexibility and elasticity it can take any shape. This also means breaking strength, which enables good handling, particularly with regard to transport and storage, but also consumption.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not restricted to these examples. Unless otherwise stated, all percentages are% by weight. Numerical ranges that are specified in the format "from x to y" include the values mentioned. If several preferred numerical ranges are specified in this format, it goes without saying that all ranges which result from the combination of the different end points are also covered.

"At least one" as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In relation to an ingredient, the information relates to the type of ingredient and not to the absolute number of molecules. "At least one bleaching catalyst" thus means, for example, at least one kind of bleaching catalyst, i.e. that one type of bleaching catalyst or a mixture of several different bleaching catalysts can be meant. Together with the weight information, the information relates to all compounds of the specified type which are contained in the composition / mixture, i.e. that the composition contains no further compounds of this type beyond the stated amount of the corresponding compounds.

If reference is made here to molecular weights, this information always relates to the number-average molecular weight M _n , unless explicitly stated otherwise. The number average molecular weight can be determined, for example, by means of gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 with THF as the eluent. The mass average molecular weight M _w can also be determined by means of GPC, as described for M _n .

Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein relate to% by weight, in each case based on the mixture in question.

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 a first solid, compressed phase and at least one second phase which comprises at least one polymer and at least one polyhydric alcohol.

Certain minimum requirements are imposed on the formulations of the at least one second phase. As already stated, 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 of time during which the at least one second phase during production changes from a flowable state to a dimensionally stable state which is not flowable at room temperature. Room temperature is understood to be a temperature of 20 ° C. This can take place, however, without being restrictive, by crosslinking the at least one polymer.

Furthermore, the second phase must be stable in storage, namely under normal storage conditions. The second phase according to the invention is part of a washing or cleaning agent. Detergents or cleaning agents are usually stored in a household for a certain period of time. Storage is usually near the washing machine. The second phase should be stable for such storage. Thus, the second phase in particular should also be stable after a storage time of, for example, 4 to 12, in particular 10 to 12 weeks or longer at a temperature of up to 40 ° C., in particular at 30 ° C., in particular at 25 ° C. or at 20 ° C. be and do not deform or otherwise change their consistency during this time.

Visually, the surface of the second phase should differ significantly from the first phase, for example due to its pronounced gloss. The surface of the solid at least one first phase is usually not glossy but matt, lackluster or dull, so that a gloss makes it possible to make a good distinction which makes the detergent or cleaning agent attractive to the consumer.

A disadvantage would be a change in volume or shrinkage during storage, as this would result in low acceptance of the product by the consumer. Leakage of liquid or exudation of components from the second phase is also undesirable. Here too, the visual impression is relevant. The stability of the second phase can be influenced by the escape of liquid, such as, for example, solvent, so that the constituents are no longer contained in a stable manner and the washing or cleaning action can also be influenced thereby.

Furthermore, it should be possible for the at least one first phase and the at least one second phase to be in direct contact with one another. In this case there should be no negative interaction between the first phase and the second phase. No negative interaction here means, for example, that no ingredients or solvents pass from one phase to the other or that the stability, in particular storage stability, preferably at 4 weeks and 30 ° C. storage temperature, and / or the aesthetics of the product in some form, for example by Color change, formation of moist-looking edges, blurring boundary between the two phases or the like is impaired.

Surprisingly, it has been shown that particularly good storage stability is achieved when the second phase is essentially water-free. This means that the second phase is preferably essentially free of water. “Essentially free” here means that small amounts of water can be present in the second phase. This water can be introduced into the phase, for example, by means of a solvent or as water of crystallization or due to reactions of constituents of the phase with one another. 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% by weight or less or 10% by weight or less, particularly 7% by weight or less, in particular 6% by weight or 5% by weight or less , preferably 2% by weight or less, in particular 1% by weight or less, particularly 0.5% by weight or less, in particular 0.1% by weight or 0.05% by weight or less. The percentages by weight relate to the total weight of the second phase.

The at least one second phase comprises at least one polymer. The at least one polymer is particularly suitable for forming a network. According to the invention, the at least one second phase can comprise a polymer, two or more different polymers. In particular, it has one, two or more, in particular one or two, preferably a polymer, which is suitable for forming a network. In addition, the at least one second phase can have one or more polymers which do not form a network, but which lead to a thickening and thus 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 a polymer for network formation and one or more thickening polymers.

The at least one second phase comprises PVA (polyvinyl alcohol) and / or gelatin as polymers suitable for network formation. The at least one second phase further preferably comprises a thickening polymer and in particular polycarboxylates as the thickening polymer Polyvinyl alcohols are thermoplastic materials, which are usually produced as white to yellowish powder by hydrolysis of polyvinyl acetate. Polyvinyl alcohol (PVA) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molecular weight of 30,000 to 60,000 g / mol are preferred.

Gelatin is a mixture of tasteless animal protein. The main component is denatured or hydrolyzed collagen, which is produced from the connective tissue of various animal species. Gelatin lacks the essential amino acid tryptophan, so it is not considered a full-fledged protein. Gelatin swells in water and dissolves when heated above 50 ° C. A gel forms on cooling, which becomes liquid again when heated again.

Surprisingly, it has been shown that PVA and / or gelatin are particularly suitable for producing second phases which meet the requirements shown above. It is therefore particularly preferred to have at least one second phase which contains gelatin and / or PVA and at least one polyhydric alcohol. The at least one second phase particularly preferably comprises gelatin and at least one polyhydric alcohol. The at least one second phase likewise preferably has PVA and at least one polyhydric alcohol.

According to the invention, the at least one second phase comprises the polymer suitable for network formation in a proportion of approximately 5% by weight to 40% by weight, in particular 10% to 35% by weight, preferably 15% by weight. up to 20% by weight. Significantly lower proportions of polymer, in particular gelatin and / or PVA, do not lead to the formation of a stable gel-like second phase. On the contrary, there is a permanent flow here. Proportions of more than 40% by weight and in particular of more than 20% by weight lead to an extended hardening time. The phases remain soft longer, which leads to an extended manufacturing process. The values are based on the total weight of the second phase.

The at least one second phase particularly preferably comprises gelatin. Surprisingly, it has been shown that with the help of gelatin, dimensionally stable second phases can be produced within a short curing time. In addition, the shape and size of the phases produced in this way remains stable over a long period. No shrinking in size can be observed. It has been shown that the required amount of gelatin used varies depending on the bloom value. The second phase therefore preferably has gelatin with a bloom value in the range from 60 to 225. The bloom value describes the gelatin strength or gelling strength of gelatin. The key figure is the mass in grams that is required so that a stamp 0.5 inch in diameter deforms the surface of a 6.67% gelatin / water mixture four millimeters deep without tearing it. The attempt takes place standardized at exactly 10 ° C with a previous aging of the gelatin of 17 hours.

If the at least one second phase comprises gelatin with a bloom value of 150 or more, in particular from 180 to 225, preferably from 200 to 225, the proportion of gelatin based on the total weight of the second phase is preferably in the range from 10% by weight to 20 % By weight, in particular from 15% by weight to 18% by weight. If the bloom value is less than 150, in particular from 60 to 120, preferably from 60 to 100, the proportion of gelatin, based on the total weight of the second phase, is preferably in the range from 15% by weight to 30% by weight, in particular 20 % By weight to 25% by weight. Gelatin with a bloom value of 180 or more, in particular of 200 or more, particularly 225 is preferred. Gelatin with a corresponding bloom value allows the viscosity of the second phase to be controlled well during production. In addition, the amount of gelatin required is lower here than when using gelatin with a lower bloom value, which can lead to a cost reduction.

If the at least one second phase also includes PVA in addition to gelatin, the toughness of the second phase in production is increased.

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

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

Unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH are used as unsaturated carboxylic acid (s), in which R ¹ to R ³ independently of one another are -H, -CH ₃ , one straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH2, -OH or -COOH as defined above or for -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ independently of one another are —H, —CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or -COOH or for -COOH or -COOR ⁴ R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group which is 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 -.

Preferred among these monomers are those of the formulas H ₂ C = CH-X-SO ₃ H, H ₂ C = C (CH ₃ ) -X-SO ₃ H or HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X represents an optionally available spacer group which is 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 -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts. The sulfonic acid groups in the polymers can be wholly or partly in neutralized form, that is to say that the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in each case in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from the aforementioned. The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a further preferred embodiment, in addition to the monomer containing carboxyl groups and the monomer containing sulfonic acid groups, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers in particular has improved the rinse aid performance of dishwashing detergents according to the invention.

1. i) Carbonsäuregruppen-haltige Monomere
2. ii) Sulfonsäuregruppen-haltige Monomere
3. iii) nichtionische Monomere, insbesondere hydrophobe Monomere eingesetzt wird.

The at least one second phase particularly preferably further comprises an anionic copolymer, a copolymer comprising as the anionic copolymer

1. i) Monomers containing carboxylic acid groups
2. ii) Monomers containing sulfonic acid groups
3. iii) nonionic monomers, in particular hydrophobic monomers, is used.

Monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , are preferably used as nonionic monomers , X represents an optionally available spacer group which is selected from -CH ₂ -, - C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, 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-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid butyl ester, acrylate, acrylate, acrylate, acrylate N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, octyl acrylate, Me octyl thacrylate, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, methacrylate and N- (behenyl) acrylate, in particular, their mixtures, acrylate or acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

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

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-flowable second phase within a short setting time, within 15 minutes or less, in particular 10 minutes or less. Polyhydric alcohols in the context of the present invention are hydrocarbons in which two, three or more hydrogen atoms have been replaced by OH groups. The OH groups are bound to different carbon atoms. A carbon atom has no two OH groups. This differs from (simple) bound. A carbon atom has no two OH groups. This differs from (simple)

Alcohols in which only one hydrogen atom in hydrocarbons is replaced by one OH group. Polyhydric alcohols with two OH groups are referred to as alkane diols, polyhydric alcohols with three OH groups as alkane triols. A polyhydric alcohol thus corresponds to the general formula [KW] (OH) _x , where KW is a hydrocarbon which is linear or branched, saturated or unsaturated, substituted or unsubstituted. Substitution can take place, for example, with -SH or -NH groups. KW is preferably a linear or branched, saturated or unsaturated, unsubstituted hydrocarbon. KW comprises at least two carbon atoms. The polyhydric alcohol comprises 2, 3 or more OH groups (x = 2, 3, 4 ...), only one OH group being bound to each C atom of the KW. KW particularly preferably comprises 2 to 10, that is to say 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. In particular, polyhydric alcohols with x = 2, 3 or 4 (for example, pentaerythritol with x = 4) can be used. X = 2 (alkanediol) and / or x = 3 (alkanetriol) is preferred.

The at least one second phase comprises at least one alkanetriol and / or at least one alkanediol, in particular at least one C ₃ to C ₁₀ alkanetriol and / or at least one C ₃ to C ₁₀ alkanediol, preferably at least one C ₃ to C ₈ Alkanetriol and / or at least one C ₃ to C ₈ alkanediol, especially at least one C ₃ to C ₆ alkanediol and / or at least one C ₃ to C ₅ alkanediol as polyhydric alcohol. It preferably comprises an alkanetriol and an alkanediol as at least one polyhydric alcohol. The at least second phase therefore comprises at least one polymer, gelatin and / or PVA, and at least one alkanediol and at least one alkanetriol, in particular an alkanetriol and an alkanediol. Likewise preferred is a second phase which comprises at least one polymer, in particular gelatin and / or PVA, as well as a C ₃ to C ₈ alkanediol and a C ₃ to C ₈ alkanetriol. A second phase is further preferred which comprises at least one polymer, in particular gelatin and / or PVA, and also a C ₃ to C ₅ alkanediol and a C ₃ to C ₆ alkanetriol.

Surprisingly, it has been found that when a corresponding triol (alkane triol) is combined with a corresponding diol (alkane diol), particularly short solidification times can be achieved. The second phases obtained are also transparent and have a glossy surface, which provide an appealing visual impression of the washing or cleaning agent according to the invention. The terms diol and alkanediol are used synonymously in the present case. The same applies to triol and alkanetriol.

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

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

The C ₃ -C ₆ alkanetriol is preferably glycerol and / or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (also called 1,1,1-trimethylolpropane) and / or 2-amino-2- (hydroxymethyl) -1,3-propanediol (TRIS, trishydroxymethylaminoethane).

The C ₃ - to C ₆ -alkanetriol glycerol and / or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (also called 1,1,1-trimethylolpropane) is particularly preferred. The C ₃ to C ₅ alkanediol is preferably 1,3-propanediol and / or 1,2-propanediol. Surprisingly, it has been shown that the chain length of the diol and in particular the position of the OH groups have an influence on the transparency of the second phase. The OH groups of the diol are therefore preferably not arranged on immediately adjacent C atoms. In particular, there are three or four carbon atoms, in particular 3 carbon atoms, between the two OH groups of the diol. The diol 1,3-propanediol is particularly preferred. Surprisingly, it has been found that particularly good results are achieved with mixtures which comprise glycerol and 1,3-propanediol and / or 1,2-propanediol. The second phase particularly preferably comprises gelatin, glycerol and 1,3-propanediol or gelatin, 1,1,1-trimethylolpropane and 1,3-propanediol. Here, within a solidification time of 10 minutes or less, a non-flowable consistency that is stable at room temperature can be achieved, which remains dimensionally stable even after prolonged storage. A corresponding phase is also transparent and has a glossy surface. A particularly preferred second phase therefore comprises gelatin or PVA as a polymer and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols.

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% by weight up to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.

If the second phase optionally comprises several alkanetriol (s), the total proportion of alkanetriol (s), based on the total weight of the second phase, is preferably 5% by weight to 70% by weight, in particular 10% by weight 65% by weight, particularly 20% by weight to 40% by weight.

If glycerol is present as alkanetriol in the second phase, the proportion of glycerol based on the total weight of the second phase is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight. especially 20% by weight to 40% by weight.

If 1,1,1-trimethylolpropane is contained in the second phase, the proportion of 1,1,1-trimethylolpropane based on the total weight of the second phase is preferably 5% by weight to 70% by weight, in particular 10% by weight .-% to 65 wt .-%, especially 20 wt .-% to 40 wt .-%. Is 2-amino-2-hydroxymethyl-1,3-propanediol

If 2-amino-2-hydroxymethyl-1,3-propanediol contains 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% by weight % to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.

If several alkanediols are optionally present in the second phase, the amount of alkanediols, based on the total weight of the second phase, is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20% by weight to 40% by weight.

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% by weight to 70% by weight, in particular 10% by weight to 65% by weight, especially 20% by weight to 45% by weight. 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% by weight to 65% by weight, particularly 20% by weight up to 45% by weight.

Preferred is a second phase, the 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. Likewise preferred is a second phase which contains 20 to 45% by weight of 1,3 propanediol and 10% by weight to 65% by weight of 1,1,1-trimethylolpropane, in each case based on the total weight of the second phase. A second phase which contains 20 to 45% by weight of 1,3-propanediol and 10% by weight to 65% by weight of glycerol, in each case based on the total weight of the second phase, is particularly preferred.

It has been shown that a rapid solidification at 20 ° C. of a second phase is possible in these areas, the phases obtained are stable in storage and transparent. The amount of glycerin in particular has an effect on the curing time.

If the at least one second phase according to the invention has a C ₃ to C ₆ alkanetriol and a C ₃ to C ₅ 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 present as polyhydric alcohols. Surprisingly, it has been shown that at these weight ratios storage-stable, shiny, transparent second phases can be obtained within short solidification times at 20 ° C. of 10 minutes or less.

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

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 for only the at least one first phase or only the at least one second phase to comprise at least one surfactant. If both phases comprise a surfactant, they are preferably different surfactants. However, it is also possible for the first and second phases to have the same surfactant or the same surfactants. At least one first and / or second phases according to the invention preferably contain at least one nonionic surfactant. All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. These are specified in more detail below.

Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol , which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA. The washing or cleaning agents according to the invention, in particular cleaning agents for automatic dishwashing, particularly preferably contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _8-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO.

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

Particular preference is given to ethoxylated nonionic surfactants which consist of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol, of ethylene oxide per mol of alcohol were used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide. Among these, the so-called "narrow range ethoxylates" are particularly preferred.

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

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder einbeziehungsweise mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² beziehungsweise R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, -CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.Particularly preferred nonionic surfactants have been found in the context of the present invention for the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. These in turn include surfactants with EO-AO-EO-AO blocks preferred, in each case one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here are nonionic surfactants of the general formula

preferred, in which R ^{1 is} a straight-chain or branched, saturated or, or polyunsaturated, C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another represent integers from 1 to 6.

Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. Regardless of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, nonionic surfactants are preferred in which R ¹ in the above formula for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from —CH ₂ CH ₂ —CH ₃ or —CH (CH ₃ ) ₂ are also suitable. Nonionic surfactants of the above formula are preferably used, in which R ² and R ³ for a radical —CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

Further preferred nonionic surfactants of the first phase are nonionic surfactants of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , where
R ¹ and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M for an alkyl radical from the Group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.

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 are} preferred,
wherein R, R ¹ and R ² independently of one another are an alkyl radical or alkenyl radical having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.

Compounds 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 O-CH ₂ CH (OH) -R ² are particularly preferred here,
in which R represents a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms and n and m independently of one another have values from 20 to 30. Corresponding compounds can be obtained, for example, by reacting HO-CHR-CH ₂ -OH alkyldiols with ethylene oxide, followed by reaction with an alkyl epoxide to block the free OH functions to form a dihydroxy ether.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für Wasserstoff oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A, A', A" und A''' unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
• w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

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 radical;
• R ^{2 represents} hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', A "and A""independently of one another for a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
• w, x, y and z stand for values between 0.5 and 120, where x, y and / or z can also be 0.

By adding the aforementioned nonionic 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 a surfactant-free system and in comparison to systems which contain alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

The use of these nonionic surfactants with one or more free hydroxyl groups on one or both terminal alkyl radicals can significantly improve the stability of the enzymes contained in the cleaning agent preparations according to the invention.

neben einem Rest R¹, welcher für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen steht, weiterhin einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest R² mit 1 bis 30 Kohlenstoffatomen aufweisen, wobei n für Werte zwischen 1 und 90, vorzugsweise für Werte zwischen 10 und 80 und insbesondere für Werte zwischen 20 und 60 steht. Insbesondere bevorzugt sind Tenside der vorstehenden Formel, in denen R¹ für C₇ bis C₁₃, n für eine ganze natürliche Zahl von 16 bis 28 und R² für C₈ bis C₁₂ steht.Those end group-capped poly (oxyalkylated) nonionic surfactants which, according to the following formula, are particularly preferred

in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where n stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Particularly preferred are surfactants of the above formula in which R ^{1 is} C ₇ to C ₁₃ , n is an integer from 16 to 28 and R ^{2 is} C ₈ to C ₁₂ .

Surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 up to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15. The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecyl ether.

End group-capped poly (oxyalkylated) nonionic surfactants 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 are also particularly preferred,
in which R ¹ and R ² independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} selected independently of one another from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH3, -CH (CH ₃ ) ₂ , but preferably stands for -CH ₃ , and x and y independently of one another have values between 1 and 32, nonionic surfactants with R ³ = -CH ₃ and values for x of 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² ,
in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or one Methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5. When the value x> 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x> 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa .

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C 6-24-Alkyl- oder -Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht.

Particularly preferred end group-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15. Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 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 radical;
• R ^{2 represents} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ), preferably CH ₂ CH ₂ , and
• w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

The group of these nonionic surfactants includes, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

The at least one first and / or the at least one second phase preferably contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of the hydroxy mixed ethers, the weight fraction of the nonionic surfactant in the total weight of the second phase preferably being 0.5% by weight to 30% % By weight, preferably 5% by weight to 25% by weight and in particular 10% by weight to 20% by weight.

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 R ¹ and R ² independently of one another are an alkyl radical or alkenyl radical having 4 to 22 carbon atoms; R ³ and R ^{4 are} independently H or an alkyl or alkenyl group having 1 to 18 carbon atoms and x and y are independently values between 1 and 40.

Compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which R ³ and R ^{4 are} H and the indices x and y are preferred independently of one another assume values from 1 to 40, preferably from 1 to 15.

Particularly preferred are particularly compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _× CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the radicals R ¹ and R ² independently of one another are saturated alkyl radicals with 4 to Represent 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.

Also preferred are those compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _× CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which one of the radicals R ¹ and R ^{2 is} branched. Compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _× CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the indices x and y independently assume values from 8 to 12, are very particularly preferred.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the nonionic surfactants represent statistical mean values which can be an integer or a fraction for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers both for the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation.

Of course, the aforementioned nonionic surfactants (nonionic surfactants) can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.

Particularly preferred in the at least one first phase are those nonionic surfactants which have 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 in particular between 26.6 and 43.3 ° C. is / are particularly preferred .

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

The nonionic surfactant which is solid at room temperature preferably has propylene oxide units (PO) in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight, of the total molecular weight of the nonionic Identify surfactants.

Further nonionic surfactants with melting points above room temperature which are particularly preferably used in the first phase contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

In a preferred embodiment, the weight fraction of the nonionic surfactant in the total weight of the first phase is from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight .

All anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.

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

Instead of the surfactants mentioned or in combination with them, 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.

Surfactants affect the opacity of the second phase. In another preferred embodiment, the second phase is therefore free of surfactants, in particular nonionic surfactants.

Preferred washing or cleaning agents according to the invention are further characterized in that they contain less than 1.0% by weight and in particular no anionic surfactant in the at least one first and / or the at least one second phase, in particular in the first phase, 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-curing behavior.

Substances that also serve as ingredients of cosmetic products are referred to below in accordance with the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds have an INCI name in English. The INCI designation are the " International Cosmetic Ingredient Dictionary and Handbook, 7th Edition (1997) "by The Cosmetic, Toiletry and Fragrance Association (CTFA), Washington DC (USA ) is published. The statement CAS means that the following sequence of numbers is a designation of the Chemical Abstracts Service.

In addition to the surfactants, the at least one second phase can also have sugar. According to the invention, sugars include monosccharides, disaccharides and oligosaccharides. Preferably the second phase comprises disaccharides, in particular sucrose. The proportion of sucrose is 0% by weight to 30% by weight, in particular 5% by weight to 25% by weight, particularly preferably 10% by weight to 20% by weight, based on the weight of the second Phase. In higher amounts, the sugar does not completely dissolve you in the second phase and leads to clouding of the same. The use of sugar, in particular in a proportion of 10% by weight to 5 to 15% by weight, reduces the development of moisture and thus improves the adhesion to at least one first phase.

The use of builder substances (builders) 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.

In an embodiment preferred according to the invention, the use of phosphates (also polyphosphates) is largely or completely dispensed with. In this embodiment, the agent preferably contains less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). In this embodiment, the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate (s).

The builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates. The weight fraction of the total builders in the total weight of agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.

Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule. Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids can also carry further functional groups, such as hydroxyl or amino groups. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as, for example, nitramino-nitric acids, such as, for example, nitramino-triacids, such as, for example, nitraminotriestric acids, such as, for example, nitraminotriestric acids, such as, for example, nitraminotriestric acids, such as, for example, nitraminotriestric acids, such as, for example, nitraminotriestric acids -diacetic acid (also known as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA) and their derivatives and mixtures thereof. Preferred Salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers with a large number of (in particular greater than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

In addition to their builder action, the free acids typically also have the property of an acidifying component. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Particularly preferred washing or cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, particularly 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to Contain 20 wt .-%, each based on the total weight of the agent.

Also particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate (soda), in amounts of 2 to 50% by weight, preferably 4 to 40% by weight. -% and in particular from 10 to 30 wt .-%, very particularly preferably 10 to 24 wt .-%, each based on the weight of the agent.

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

Preferred washing or cleaning agents, in particular dishwashing agents, preferably machine dishwashing agents, are characterized by a combination of builders of citrate and carbonate and / or bicarbonate. In one according to the invention very particularly In a preferred embodiment, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular 10 to 35% by weight, very particularly preferably 15 to 30% by weight, and the amount of citrate is preferably from 5 to 35% by weight, in particular 10 to 25% by weight, very particularly preferably 15 to 20% by weight, in each case based on the total amount of the cleaning agent, the total amount of these two builders preferably being 20 to 65 % By weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight. In addition, one or more other builders can also be included.

The washing or cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, can contain, in particular, phosphonates as further builders. A hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. Phosphonates in agents according to the invention are preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight based on the total weight of the agent.

The combined use of citrate, (hydrogen) carbonate and phosphonate is particularly preferred. These can be used in the amounts mentioned above. In particular, in this combination, amounts of 10 to 25% by weight citrate, 10 to 30% by weight carbonate (or bicarbonate), and 2.5 to 7.5% by weight, based in each case on the total weight of the composition. Phosphonate used.

Further particularly preferred washing or cleaning agents, in particular dishwashing agents, preferably machine dishwashing agents, are characterized in that, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, they contain at least one further phosphorus-free builder. In particular, this is selected from the aminocarboxylic acids, the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate, particularly preferably from EDDS MGDA or GLDA. A particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and, if appropriate, phosphonate.

The percentage by weight of the further phosphorus-free builder, in particular the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25 % By weight. The use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules which contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder are advantageous. The combination of at least three, in particular at least four builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents. It can also contain other builders.

Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1100 to 10000 g / mol, and particularly preferably from 1200 to 5000 g / mol, can in turn be preferred from this group.

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

Detergents or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, can furthermore contain crystalline layered silicates of the general formula NaMSi _x O _2x +1 .yH ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.

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

In addition to the builders mentioned above, the washing or cleaning agents according to the invention can furthermore contain alkali metal hydroxides. These alkali carriers are used in the Detergents or cleaning agents, and in particular in the at least one second phase, preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the detergent or cleaning agent. Alternative washing or cleaning agents according to the invention are free from alkali metal hydroxides.

Cleaning agents according to the invention preferably contain enzyme (s) in the at least one first and / or the at least one second phase. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred. Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 % by weight to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which 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, and the further developments of the aforementioned amylases, which have been improved for use in cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from β. to highlight agaradherens (DSM 9948).

Lipases or cutinases can furthermore be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange in positions D96LT213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenol oxidases) can be used according to the invention. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling. A protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Detergents can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

Proteases and amylases that are active in cleaning are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers or other auxiliaries.

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, for example those in which the enzymes are solidified as in a Gels are included or in the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

As can be seen from the previous description, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein. Particularly preferred are cleaning agents which, based on their total weight, 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of the respective enzyme preparations contain.

In addition to the constituents mentioned so far, the at least one first and / or the at least one second phase of the washing or cleaning agent according to the invention can contain further ingredients. These include, for example, anionic, cationic and / or amphoteric surfactants, bleaching agents, bleach activators, bleaching catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protection agents, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (in particular in the at least one first phase), additives to improve the drainage and drying behavior, to adjust the viscosity, to stabilize, UV stabilizers, pearlescent agents (INCI opacifying agents; for example glycol distearate, for example Cutina® AGS from Cognis, or mixtures containing these, for example Euperlane® from Cognis ), Preservatives (e.g. the technical 2-bromo-2-nitropropane-1,3-diol, also known as bronopol ( CAS 52-51-7 ), which is commercially available, for example, as Myacide® BT or as Boots Bronopol BT from the company Boots), antimicrobial active ingredients (disinfectants), pH adjusting agents in amounts of usually not more than 5% by weight.

Agents according to the invention preferably contain at least one alkanolamine as a further solvent. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is present in agents according to the invention preferably in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight. In a preferred washing or cleaning agent, the at least one second phase is free from alkanolamine and the alkanolamine is only present in the at least one first phase.

In a preferred embodiment, detergents or cleaning agents according to the invention, in particular dishwashing detergents, contain at least one zinc salt as a glass corrosion inhibitor as a further constituent. The zinc salt can be an inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc 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 in cleaning agents according to the invention is preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1 wt .-% to 2 wt .-%, based on the total weight of the detergent. In addition or as an alternative to the above Salts (in particular the zinc salts), polyethyleneimines, as are available, for example, under the name Lupasol® (BASF), are preferably used in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight, as glass corrosion inhibitors become.

Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (for example Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example Sokalan® CP 10 from BASF, Ludwigshafen (Germany) )), modified polycarboxylate Na salt (for example Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-7608 from BASF, Ludwigshafen (Germany)) and polyether siloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide segments (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren® 5840, Tegopren® 5843 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878 from Evonik, Essen (Germany). Builder substances suitable as additives are, in particular, polyaspartic acid sodium salt, ethylenediamine triacetate coconut alkylacetamide (for example Rewopol® CHT 12 from Evonik, Essen (Germany)), methylglycinediacetic acid tri-sodium salt and acetophosphonic acid. Mixtures with surfactant or polymeric additives show synergisms in the case of Tegopren® 5843 and Tegopren® 5863. The use of Tegoprene types 5843 and 5863 is, however, less preferred when used on hard surfaces made of glass, in particular glass dishes can apply this silicone surfactant to glass. In a particular embodiment of the invention, the additives mentioned are dispensed with.

A preferred washing or cleaning agent, in particular dishwashing agent, preferably further comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleaching catalyst. Where available, these are only included in the at least one first phase.

As a preferred bleaching agent, cleaning agents according to the invention contain an oxygen bleaching agent from the group sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Sodium percarbonate is particularly preferred for its good bleaching performance. A particularly preferred oxygen bleach is sodium percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which carry 0- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multi-acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

The bleaching catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe-Cu and Ru-amine complexes can also be used as bleaching catalysts. Complexes of manganese are used with particular preference in oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleaching catalyst (s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN) included. 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 ).

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

The washing or cleaning agent according to the invention comprises at least a first phase (1) and at least a second phase (2). The washing or cleaning agent can thus have one, two, three or more different first phases (1); it can also have one, two, three or more different second phases (2). The washing or cleaning agent according to the invention preferably comprises a first phase (1) and a second phase (2). The washing or cleaning agent particularly preferably comprises two first phases (1) and a second phase (2). It preferably comprises two first phases (1) and two second phases (2). Also preferred is an embodiment in which the 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 detergent portion can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 14 to 19 g. This weight ratio results in a good concentration of the respective ingredients of the first (1) or second phase (2) in one cleaning process.

According to the invention, the at least one first phase (1) and the at least one second phase (2) adjoin one another over the full or partial area. It is preferred that the two phases directly adjoin one another. However, it is also possible for the at least one first phase (1) or the at least one second phase (2) or the at least one first phase (1) and the at least one second phase (2) to be closely enveloped by a water-soluble film or in a water-soluble bag is included. The entire agent is preferably contained in a water-soluble bag or, particularly preferably, is closely enveloped by a water-soluble film.

If the at least one first phase (1) and the at least one second phase (2) adjoin one another over the full or partial area, stability is important in addition to the shortest possible solidification time of the at least one second phase (2). Stability here means that constituents contained in the second phase do not pass into the at least one first phase, but also after prolonged storage, the at least one first phase and the second phase are optically separate from one another and do not interact, such as diffusion of liquid constituents from one phase to the other or reaction of constituents of one phase with those in the other phase or Loss of adhesion of the second phase (2) on the in particular compressed, compacted first phase (1) due to liquid leakage. Surprisingly, it has been shown that this can be made possible by a second phase which has glycerol, gelatin and at least one C ₃ -C ₅ -alkanediol.

The water-soluble film or the water-soluble bag preferably comprises a water-soluble polymer. Some preferred water-soluble polymers, which are preferably used as water-soluble packaging, are polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinyl pyrrolidones, polyethylene oxides, celluloses and gelatin, polyvinyl alcohols and acetalized polyvinyl alcohols being particularly preferably used.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten."Polyvinyl alcohols" (abbreviation PVAL, sometimes also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 87-99 mol%, that is to say contain one more Residual content of acetyl groups.

In the context of the present invention, it is preferred that the water-soluble packaging comprises at least partially a polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to Is 88 mol%. In a preferred embodiment, the water-soluble packaging consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention that the packaging material comprises a polyvinyl alcohol whose molecular weight is in the range from 5,000 gmol ^-1 to 100,000 gmol ^-1 , preferably 10,000 gmol ^-1 to 90,000 gmol ^-1 , particularly preferably from 12,000 gmol ^-1 to 80,000 gmol ^-1 and in particular from 15,000 gmol ^-1 to 70,000 gmol ^-1 .

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

The water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water. The reaction products of polyvinyl alcohol and starch are to be used extremely advantageously. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to the desired values.

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

The water-soluble film, which is preferably used in the tight wrapping), particularly preferably comprises polyvinyl alcohol, as described above, the starting thickness preferably being from 10 μm to 100 μm, in particular from 12 μm to 60 μm, particularly preferably from 15 μm to 50 microns, especially from 20 microns to 40 microns, especially from 22 microns to 35 microns is used.

In the case of a tight wrapping, a single serving of the detergent or cleaning agent is wrapped. For the coated detergent or cleaning agent disposable portion according to the invention, it is important that the coating lies tightly against the surface of the tablets at every point. Ideally, the casing is even under tension, but this is not absolutely necessary. This tight fit of the covering is conducive to disintegration: the first time it comes into contact with water, the covering will let a small amount of water through at some point, although it does not need to be detached at first. At this point, the disintegrant contained in the tablet begins to swell. As a result, the casing suddenly tears open due to the increase in volume of the tablet and releases the tablet. The mechanism described here will not work if the casing is not snug because the tablet can swell without the casing being blown up. The use of a swellable disintegration agent is superior to a gas-developing system, since its explosive effect in any case leads to the casing being torn open. In a gas-generating system, the explosive effect can "dissipate" by the gas escaping from a leak in the casing.

Preferred detergent or cleaning agent disposable portions according to the invention are characterized in that the distance between the single 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 in particular 2.5 to 100 µm.

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

For example, this wrapping can be carried out by placing a water-soluble bottom film on a transport chain or a mold (s), then placing one or more detergent or cleaning agent portions (s) on the bottom film; Subsequently, a water-soluble top film is placed on the detergent or cleaning agent portion (s) on the bottom film and this is then fixed on the bottom film, including the detergent or cleaning agent portion (s). Alternatively, this step can also be carried out using a single-strand film, which is then used as Tube is placed around the disposable portions. The foils are then sealed and optionally cut. The film can then be shrink-wrapped using hot air or infrared radiation, optionally with pressure.

Such water-soluble coatings are also in the patent applications WO 2004/031338 A such as WO 2003/099985 A , the disclosure of which is hereby incorporated by reference in its entirety, has already been described.

In a preferred embodiment, the at least one first phase (1) of the washing or cleaning agent according to the invention, in particular the dishwashing agent, preferably the machine dishwashing agent, is in the form of a shaped body, in particular a compact, especially a tablet. The at least one first phase (1) is particularly preferably a powdered washing or cleaning agent which is present in compact form in the form of a tablet.

The at least one first phase (1) and the at least one second phase (2) can be arranged in any combination with one another, regardless of whether they are arranged directly or indirectly (for example due to the presence of a film, wrapping or a bag as described above). A first phase (1) can be arranged on 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 shown. Also embedding one phase in another, as in 3a and 3b schematically shown is included according to the invention. Another, particularly preferred arrangement is in Fig. 4 shown schematically. The second phase (2) is in the form of a core which is embedded in the first phase (1). A pool form of the solid first phase (1) is particularly preferred, that is to say a form with a depression into which the second phase is introduced. The trough can be round, oval or angular. There may also be two separate troughs which are filled with the at least one second phase (2). In this embodiment, the washing or cleaning agent comprises two second phases (2), wherein the two second phases can have different compositions.

Basically, any geometries are possible. The rectangular shape shown here is only exemplary. A round or oval shape of the two phases or any polygonal configurations are also conceivable.

The present application also relates to a method for cleaning hard surfaces, in particular dishes, in which the surface is processed in a manner known per se using a cleaning agent according to the invention. 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 with a dishwasher.

Another object of the present invention is also the use of a cleaning agent for cleaning hard surfaces, especially dishes.

In a preferred embodiment, the present application relates to automatic dishwashing detergents. According to this application, machine dishwashing detergents are compositions which can be used to clean soiled dishes in an automatic dishwashing process. The machine dishwashing detergents according to the invention thus differ, for example, from the machine rinse aids which are always used in combination with machine dishwashing agents and do not have their own cleaning action.

Insofar as it is stated in the present application that the washing or cleaning agent according to the invention comprises something in whole or in the at least one first phase (1) or in the at least one second phase (2), it should also be regarded as disclosed that washing or Detergent or the respective phase can consist of it. In the following embodiment, the washing or cleaning agent according to the invention is described in a non-limiting manner.

Examples:

Cleaning agents according to the invention were produced which comprised a first phase and a second phase. Different geometries were realized. Cleaning agents were also produced, which comprised two first phases and a second phase. The following information relates to% by weight of active substance based on the total weight of the respective phase.

The first phases had the following composition: % By weight Citrate, Na salt 10-25 Phosphonate (e.g. HEDP) 0-10 MGDA, Na salt 0-40 Disilicate, sodium salt 0-40 soda 10-30 Percarbonate, Na 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), eg 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 Zn salt (e.g. acetate) 0.01-0.5 Sodium sulfate 0.0 - 25 water 0.0-3 pH adjusting agent (e.g. citric acid) 0.0 - 5 Process aids 0-10

Furthermore, the first phases were produced, which had the following composition: % By weight Citrate, Na salt 15-20 Phosphonate (e.g. HEDP) 2.5-7.5 MGDA, Na salt 0-25 Disilicate, sodium salt 5-35 soda 10-25 Percarbonate, Na salt 10-15 Bleaching catalyst (preferably Mn-based) 0.02-0.5 Bleach activator (e.g. TAED) 1-3 Non-ionic surfactant (s), eg 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 Zn salt (e.g. acetate) 0.1-0.3 Sodium sulfate 0.0 - 10 water 0.0-1.5 pH adjusting agent (e.g. citric acid) 0-1.5 Process aids 0-5

These first phases were in the form of compacted tablets with a recess on one side. A liquid composition was poured into this, which resulted in the second phase after curing. The cleaning agent obtained was in accordance with Fig. 4 shown form. The first phases were without further study. Here a second phase was brought into direct contact on the surface of the first phase.

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 groups 0-30 Non-ionic surfactant (s), eg fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 0-40 Polyethylene glycol average Mr 1000-2000 0-20 Thickener (preferably gelatin or PVA) 5-50 Process aids 0-10 Dye solution 0.0 - 1.5

Further second phases with the following composition were produced: % By weight Glycerin 20-45 Propanediol (preferably 1,3-propanediol) 10 - 30 Polycarboxylate; Homo- and / or copolymer with sulfonic acid groups 5-20 Non-ionic surfactant (s), eg fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 5-25 Polyethylene glycol average Mr 1000-2000 0-8 Thickener (preferably gelatin or PVA) 10-20 Process aids 0-5 Dye solution 0.0-0.5

The first and second phases could be combined with one another as desired. The spatial design of the second phase, which was liquid after the ingredients had been mixed and remained stable within a solidification time of about 10 to 15 minutes, was determined by the spatial Design of the first phase as well as given by customary or self-designed shapes. The liquid second phase was introduced into these molds and after the solidification time the molds were removed without the second phase changing. This allowed any geometries of the second phase to be made possible. Table 1: Examples of second phase compositions A1 A2 1,2 propanediol 0.0 31 1,3 propanediol 31 0.0 Trisodium citrate * 2 H ₂ O 8th 8th Glycerin 31 31 Gelatin 60 Bloom 15 15 Nonionic surfactant 15 15 Solidification time (20 ° C) / min 5 20th Haptics of the surface after 12 h of storage at 20 ° C dry wet

It can be seen from Table 1 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 Gelatin 60 Bloom 20th 20th 20th 20th Nonionic surfactant 1 1 1 1 Solidification time (20 ° C) / min 15 5 5 5 transparency Transparent Transparent opaque opaque Haptics of the surface after 12 h of storage at 20 ° C dry Dry greasy greasy C1 C2 1,2 propanediol 47 0.0 1,3 propanediol 0.0 47 Glycerin 20th 20th Polymer containing sulfonic acid groups (ground) 8th 8th Gelatin 180 Bloom 25th 25th Solidification time (20 ° C) / min 15 5 After storage, 40 ° C, 12 days: Liability between the first and second phase Low Very well Haptics / optics of the second phase (surface) dry, shiny, transparent dry, shiny, transparent

Claims (9)

1. A washing or cleaning agent comprising at least one first phase (1) and at least one second phase (2) that is different therefrom, 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 two polyvalent alcohols, a first polyvalent alcohol being an alkanetriol and a second polyvalent alcohol being an alkanediol, and the at least one second phase (2) comprising gelatin and/or polyvinyl alcohol (PVA) as the polymer.
2. The washing or cleaning agent according to claim 1, characterized in that the at least one second phase (2) comprises at least two polyvalent alcohols, a first polyvalent alcohol being a C₃ to C₁₀ alkanetriol, and a second polyvalent alcohol being a C₃ to C₁₀ alkanediol.
3. The washing or cleaning agent according to claim 2, characterized in that the first polyvalent 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, particularly glycerol and/or 1,1,1-trimethylolpropane, more particularly glycerol.
4. The washing or cleaning agent according to claim 2 or 3, characterized in that the second polyvalent alcohol is a C₃ to C₈ alkanediol, in particular a C₃ to C₅ alkanediol.
5. The washing or cleaning agent according to one of claims 2 to 4, characterized in that the two OH groups of the alkanediol are not arranged on immediately adjacent C atoms of the alkyl chain, and in particular three or four carbon atoms are located between the two OH groups.
6. The washing or cleaning agent according to one of claims 1 to 5, characterized in that the at least one second phase (2) is substantially water-free.
7. The washing or cleaning agent according to one of claims 1 to 6, 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 non-ionic surfactant.
8. The washing or cleaning agent according to one of claims 1 to 7, characterized in that it is present in the form of a tablet, the weight ratio of the at least one first phase (1) to the at least one second phase (2) being 20:1 to 8:1.
9. The washing or cleaning agent according to one of claims 1 to 8, characterized in that it is a dishwashing detergent, particularly a dishwashing detergent for automatically cleaning dishes.

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