DE102017201094A1 - Detergent or detergent portion comprising at least two phases - Google Patents

Abstract

The present invention relates to a washing or cleaning agent, in particular a cleaning agent for hard surfaces, in particular dishwashing detergent, preferably a machine dishwashing detergent, comprising a water-soluble casing with a continuous circumferential sealing seam and two mutually different phases.

Description

The present invention relates to a washing or cleaning agent portion, in particular a cleaning agent for hard surfaces, in particular dishwashing detergent, preferably a machine dishwashing detergent, comprising a water-soluble casing with a continuous circumferential sealing seam and two mutually different phases.

Detergents or cleaners are usually in solid form (for example as tablets) or in liquid form (or as a flowing gel). In particular, liquid detergents or cleaners are becoming increasingly popular with consumers.

Solid washing or cleaning agents have the advantage that, in contrast to liquid detergents or cleaning agents, they do not require any preservatives. Liquid supply forms are increasingly gaining acceptance on the market, in particular due to their rapid solubility and the associated rapid availability of the active ingredients contained. This offers the consumer the opportunity to use time-shortened rinse programs and still obtain a good cleaning performance.

Further, consumers have become accustomed to conveniently metering pre-portioned machine washing or cleaning agents, such as dishwashing detergents, and use these products in the form of tablets (solid detergents or cleaners) or in the form of bags, usually with a liquid wash - or detergent are filled. Disposable portions in water-soluble bags enjoy the consumer not only because of increasing popularity, because the consumer with the chemical composition is no longer in contact, but not least because of the attractive appearance of the bag. The appearance of the dosage form is becoming increasingly important. In addition to a good cleaning performance and a sufficient storage stability, a good appearance is one of the reasons for choosing a product.

From the consumer's point of view, it is now desirable to combine the advantages of both forms of supply and to provide a formulation which is improved over the prior art, in particular for conventionally liquid detergents or cleaners. It should be possible both a one-time portioning and at the same time a visually appealing appearance for the consumer can be achieved. Surprisingly, it has been found that by formulating a flexible phase, which is combined with a powdery phase, this goal can be achieved. It is particularly suitable if the powdery phase is free-flowing, since thus process-related a more targeted filling of the water-soluble casing, in particular when filling a cavity produced by deep drawing, can be achieved. Furthermore, raw materials can be incorporated easier and better, in particular, this is advantageous when it comes to new raw materials or such raw materials that would otherwise deteriorate the compressibility of tablets. In addition, the optical appearance of the powder compared to a compressed tablet can be better changed, in particular texture differences, such as coarse and fine particles and particles or areas with different colors, total or as colored speckles, can be used to improve a visually appealing appearance , In addition, the powder offers improved solubility even without the addition of disintegrants in comparison to compressed tablets.

In a first embodiment, the object underlying the present application is therefore achieved by a washing or cleaning agent, comprising a water-soluble envelope, which has at least one continuous circumferential sealing seam, which lies substantially in one plane, and at least one first phase and at least a second phase different therefrom, characterized in that the at least one first phase is powdery and pourable and the at least one second phase comprises at least one polymer and at least one polyhydric alcohol.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various features, such as ingredients, physical properties, appearance, etc. Preferably, different phases can be visually distinguished. Thus, for the consumer, the at least one first phase is clearly distinguishable from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, then these can likewise be differentiated from one another by the naked eye, because they differ, for example, from one another in color. The same applies if two or more second phases are present. Also in this case, a visual differentiation of the phases, for example due to a color or transparency difference is possible. Phases in the sense of the present invention are thus inherently closed areas that can be optically distinguished by the consumer from the naked eye. The individual phases may have different properties in use, such as the rate at which the phase dissolves in water and thus the rate and order of release of the ingredients contained in the respective phase.

According to the invention, the at least one second phase is dimensionally stable at room temperature. In the preparation, the at least one polymer is contacted 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 given form, ie is dimensionally stable. This period, the solidification time, is preferably 15 minutes or less, preferably 10 minutes or less, more preferably 5 minutes or less. In this case, the at least one second phase yields to pressure, but does not deform as a result, but returns to the initial state after the pressure has ceased to exist. The at least one second phase is preferably elastic, in particular linear-elastic. The at least one second phase is also preferably translucent (translucent) or transparent, resulting in a good visual impression. Preferably, the transmission of the second phase (without dye) is in a range between 100% and 20%, between 100% and 30%, in particular between 100% and 40%. To measure the light transmittance (transmission), the patency was determined in% at 600 nm against water as a reference at 20 ° C. The mass was poured into the designated 11 mm round cuvettes and measured after 12 h storage time at room temperature in a LICO 300 color measuring system according to Lange.

The at least one second phase is a solid gel phase. She is cut firm. It can, for example, be cut with a knife after solidification without being further destroyed except for the cut made. Furthermore, the at least one second phase is particularly flexible. Due to its flexibility and elasticity, it can take any shape. This also means a breaking strength, whereby a good handling, in particular with regard to transport and storage but also the consumption is possible.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. All percentages are by weight unless otherwise specified. Numeric ranges indicated in the format "from x to y" include the above values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints are also captured.

"At least one" as used herein means 1 or more, i. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the type of ingredient, not the absolute number of molecules. Thus, "at least one bleach catalyst" means, for example, at least one type of bleach catalyst, i. that is, one type of bleach catalyst or a mixture of several different bleach catalysts may be meant. The term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.

When referring to molecular weights herein, these references always refer 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 using THF as the eluent. The mass average molecular weight M _w can also be determined by GPC, as described for M _n .

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

The at least one first phase of the present invention is in powdery and free-flowing form. The washing or cleaning agent according to the invention thus comprises at least a first powdery and free-flowing phase, and at least one second phase comprising at least one polymer and at least one polyhydric alcohol.

The flowability of a powdered solid affects its ability to trickle freely under its own weight. The flowability is determined in the flow time of 1000 ml detergent or cleaning powder from a standard, initially closed at its outlet trickle funnel with a spout of 16.5 mm diameter by measuring the time for the complete outflow of the powder after opening the spout and compared with the exit speed (in seconds) of a standard test sand whose exit velocity is defined as 100%. The defined sand mixture for calibrating the Rieselapparatur is dry sea sand.

Particularly suitable are those powders which have a flowability in% to the standard test substance given above of greater than 40%, preferably greater than 55%, in particular greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75% ,

Lower values for the flowability are rather not suitable, since from a process engineering point of view an exact dosage of the powder is necessary. In particular, the values greater than 60% have proved to be advantageous, since only small variations in the metered amount or the composition result from the good meterability of the powder. The more accurate dosage leads to a constant product performance, economic losses due to overdose are thus avoided. Furthermore, it is advantageous that the powders are easy to dose, so to achieve a faster flow of the dosing process. Furthermore, it is better avoided by such a good flowability that powder reaches the part of the water-soluble sheath, which is intended for the production of the sealed seam and should therefore remain as powder-free as possible.

For the measurement of the elasticity of the at least one second phase, a force / displacement diagram was created. The mass was poured into a 47 × 19 × 8 mm shaped body and stored at room temperature for 12 h before the measurement. The sample was taken in modified plastic inserts with the external dimension 25x20x20mm with a recess for the mass to be measured of 10 × 10 × 20mm. The measuring device used was a Lloyd LRX + (Lloyd Instruments) with a 5kN measuring head, with a feed rate of 50 mm / min and a measurement pickup at 1 N bias (zero point). As a result, the force is given in N, which is necessary to compress the molded body by 8mm. Due to the elasticity of the molded body, the initial dimensions of the molding set after the measurement within a period of 15 minutes again. The values measured in this way (for compression by 8 mm) are preferably between 10 N and 40 N, preferably between 15 N and 30 N.

Formulations of the at least one second phase are subject to certain minimum requirements. Thus, as already stated, the second phase must freeze within a short time as possible. Long solidification times would lead to a long production time and thus to high costs. According to the invention, solidification time means the period of time during which the at least one second phase changes from a free-flowing to a dimensionally stable state which is not flowable at room temperature. Room temperature is understood to mean a temperature of 20 ° C. This can be done, but without limitation, by crosslinking the at least one polymer.

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

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

A disadvantage would be a change in volume or shrinkage during storage, since this would make the acceptance of the product at the consumer low. Also leakage of liquid or exudation of components from the second phase is undesirable. Again, on the one hand, the visual impression of relevance. By the escape of liquid, such as solvent, the stability of the second phase can be influenced, so that the components are no longer stable and thereby the washing or cleaning effect can be influenced.

Furthermore, it is preferred that the at least one first phase and the at least one second phase are in direct contact with each other. 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 from one phase to another or that the stability, in particular storage stability, preferably at 4 weeks and 30 ° C storage temperature, and / or the aesthetics of the product in any form, for example by Color change, formation of moist-acting edges, blurring boundary between the two phases or the like is impaired.

Surprisingly, it has been shown that a particularly good storage stability is achieved when the second phase is poor in water. Low in the meaning of the present invention means that small amounts of water can be used to produce the at least one second phase. The proportion of water in the second phase is in particular 20% by weight or less, preferably 15% by weight or less, especially 12% by weight, or less, in particular between 10 and 5% by weight. The data in% by weight relate to the total weight of the second phase. This has the advantage that the small amounts of water in combination with the at least one polymer (especially in the case of PVOH and gelatin) can have a structure-forming or gel-forming action.

According to another embodiment, the at least one second phase is substantially anhydrous. This means that the second phase is preferably substantially free of water. "Substantially free" here means that in the second phase, small amounts of water may be included. This water can be introduced into the phase with one another, for example, by a solvent or as water of crystallization or due to reactions of constituents of the phase. However, no water is used as a solvent for preparing the second phase. The proportion of water in the second phase in this embodiment is 4.9 wt% or less, 4 wt% or less, preferably 2 wt% or less, more preferably 1 wt% or less, especially 0 , 5 wt .-% or less, in particular 0.1 wt .-% or 0.05 wt .-% or less. The data in% by weight relate to the total weight of the second phase.

The at least one second phase comprises at least one polymer. The at least one polymer is particularly suitable for forming a network. According to the invention, the at least one second phase may comprise a polymer, two or more polymers which are different from one another. In particular, it has one, two or more, in particular one or two, preferably a polymer, which is suitable for forming a network. In addition, the at least one second phase may comprise one or more polymers which do not form a network but lead to a thickening and thus to an increase in the dimensional stability of the at least one second phase, so-called thickening polymers. In a preferred embodiment, the at least one second phase therefore comprises at least one, preferably a polymer for network formation and one or more anionic polymers or anionic copolymers thereof.

Preferably, the at least one second phase comprises PVOH (polyvinyl alcohol) and / or gelatin as polymers suitable for network formation. Further preferably, the at least one second phase comprises a further anionic polymer, in particular polycarboxylates. These can act either as builders and / or as thickening polymer.

Polyvinyl alcohols are thermoplastics which are produced as a white to yellowish powder mostly by hydrolysis of polyvinyl acetate. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Preference is given to polyvinyl alcohols having a molecular weight of 30,000 to 60,000 g / mol.

Preference is given to polyvinyl alcohols which have as white-yellowish powder or granules with degrees of polymerization in the range of about 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) and degrees of hydrolysis of 87-99 mol%, which accordingly still have a residual content Contain acetyl groups.

In the context of the present invention, it is preferred that the at least one second phase comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mole%. In a preferred embodiment, the water-soluble packaging is at least 20 wt .-%, particularly preferably to at least 40 wt .-%, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mole% and especially 82 to 88 mole%.

PVOH powders having the aforementioned properties which are suitable for use in the at least one second phase are sold, for example, under the name Mowiol® or Poval® by Kuraray. Particularly suitable are the Poval® qualities, in particular the grades 3-83, 3-88 and 3-98 and Mowiol® 4-88 from Kuraray.

The water solubility of polyvinyl alcohol can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). As particularly preferred and particularly advantageous due to their pronounced cold water solubility, polyvinyl alcohols have been found to be acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof. To use extremely advantageous are the reaction products of polyvinyl alcohol and starch. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.

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

Surprisingly, it has been shown that PVOH and / or gelatin are particularly suitable for producing second phases which meet the requirements shown above. Therefore, at least one second phase which comprises gelatin and / or PVOH and at least one polyhydric alcohol is particularly preferred. More preferably, the at least one second phase comprises gelatin and at least one polyhydric alcohol. Also preferably, the at least one second phase comprises PVOH 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 about 5% by weight to 40% by weight, in particular from 7% by weight to 35% by weight, preferably 10% by weight. to 20% by weight. Significantly lower levels of polymer, especially gelatin and / or PVOH, do not lead to the formation of a stable gelatinous second phase. The values are in each case based on the total weight of the second phase.

Surprisingly, it has been found that with the help of gelatin within a short curing time dimensionally stable second phases can be produced. Furthermore, the shape and size of correspondingly produced phases remain stable over a long period of time. A shrinkage of size is not observed. It has been found that the necessary amount of gelatin used varies depending on the Bloom value. Preferably, therefore, the second phase comprises gelatin having a Bloom value in the range of 60 to 225. The Bloom value describes the gelatinization or gelatinizing power of gelatine. The metric is the mass in grams needed to allow a 0.5 inch diameter punch to deform the surface of a 6.67% gelatin / water mixture four millimeters deep without tearing it. The test takes place standardized at exactly 10 ° C with a preceding aging of the gelatin of 17 hours instead.

If the at least one second phase comprises gelatin having a bloom value of 150 or more, in particular from 180 to 225, preferably from 200 to 225, the proportion of gelatin, based on the total weight of the second phase, is preferably in the range from 10% by weight to 20 Wt .-%, in particular from 15 wt .-% to 18 wt .-%. 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 Wt .-% to 25 wt .-%. Preference is given to gelatin having a bloom value of 180 or more, in particular of 200 or more, especially of 225. By means of gelatine having a corresponding bloom value, the viscosity of the second phase in the preparation can be well controlled. In addition, the amount of gelatin required here is lower than with the use of gelatin with a lower Bloomwert, which can lead to a cost reduction.

According to a very particularly preferred embodiment, the at least one second phase comprises PVOH (polyvinyl alcohol). These second phases thus produced are particularly high-melting, dimensionally stable (even at 40 ° C) and change their shape even when stored not or only insignificantly. In particular, they are also less reactive with respect to a direct negative interaction with components of the powder phase. In particular, PVOH can also produce water-free or anhydrous second phases without difficulty. When PVOH is used as the polymer for the at least one second phase, thin-liquid melts are produced at 110 ° -120 ° C., which make them particularly easy to process; in particular, filling of the second phase into the water-soluble coating can be carried out quickly and accurately without that sticking takes place or the amount is metered inaccurately. Furthermore, these second phases adhere particularly well to the water-soluble coating, especially if it is also made of PVOH. This is visually beneficial. As a result of the rapid solidification of the at least one second phase with PVOH, the further processing of the second phases can take place particularly quickly. Furthermore, the good solubility of the second phases produced for the total solubility of the detergent or cleaning agent is particularly favorable.

If the at least one second phase comprises PVOH in addition to gelatin, the viscosity of the second phase in the production is increased.

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

In accordance with the invention, the at least one second phase may further comprise anionic polymers or copolymers having builder properties. This is preferably a polycarboxylate. The polycarboxylate used is preferably a copolymeric polyacrylate, preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate. The copolymers may have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.

Unsaturated carboxylic acid (s) used are, with particular preference, unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a 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 -NH 2, -OH or -COOH as defined above or -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, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

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 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 -NH ₂ , -OH or -COOH or -COOH or -COOR ⁴ wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional 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 is an optional spacer group selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts. In the polymers, the sulfonic acid groups may be wholly or partly in neutralized form, that is, that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby 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 end use. Preferred cleaning agents are characterized in that the copolymers have molecular weights of from 2000 to 200,000 g.mol ^-1 , preferably from 4000 to 25,000 g.mol ^-1 and in particular from 5000 to 15,000 g.mol ^-1 .

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

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

eingesetzt wird.Particularly preferably, the at least one second phase further comprises an anionic copolymer, wherein the anionic copolymer comprises a copolymer

1. i) monomers containing carboxylic acid groups
2. ii) sulfonic acid group-containing monomers
3. iii) nonionic monomers, especially hydrophobic monomers

is used.

The nonionic monomers used are preferably 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 , X is an optionally present spacer group selected from -CH ₂ -, - C (O) O- and -C (O) -NH-, and R ^{4 is} 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-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 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, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methacrylic acid methyl ester, N- (methyl) acrylamide, 2-ethylhexyl acrylate, methacrylic acid 2-ethylhexyl ester, N- (2-ethylhexyl) acrylamide, octyl acrylate, octyl acrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate, and N- (Behenyl) acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

According to the invention, the at least one second phase may also contain other polymers. Preference is given here to the presence of polyalkylene glycols, in particular polyethylene glycols in the second phase.

In particular, those polyethylene glycols having an average molecular weight between about 100 and 8000 are suitable. Particularly preferred are the abovementioned polyethylene glycols in amounts of 1 to 40 wt .-%, preferably 5 to 35 wt .-%, in particular 10 to 30 wt .-%, for example 15 to 25, preferably in each case based on the total weight of the second phase used.

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

According to a further preferred embodiment, in the at least one second phase which also contains gelatin as polymer, polyethylene glycols are suitable which have an average molecular weight of between about 200 and 8000, between about 400 and 4000 g / mol, particularly preferably with an average molecular weight between 1000 and 2000 g / mol, for example by 1500 g / mol (INCI: PEG1500), which increase the stability of the second phase. These are preferably used in the abovementioned amounts. For example, it is advantageous to use in second phases comprising gelatin, based on the total weight of the at least one second phase, from 5 to 10% by weight of polyethylene glycol having an average molar mass between 1000 and 2000 g / mol.

A very particularly preferred embodiment relates to at least one second phase or phases which contain polyvinyl alcohol as polymer in combination with polyethylene glycols. Particularly preferred in combination with polyvinyl alcohol are polyethylene glycols having an average molecular weight between about 100 and about 2000 g / mol, preferably between 200 and 1000 g / mol, more preferably between 300 and 800 g / mol, for example about 400 g / mol INCI: PEG400 ) used.

In particular, it is advantageous that the at least one second phase or the second phases comprising polyvinyl alcohol additionally polyethylene glycols having an average molecular weight of about 300 to 800 g / mol in amounts of 10 to 30 wt.% Based on the total weight of the at least one second phase contain. Surprisingly, it has been shown that the addition of polyethylene glycols, in particular of those having average molecular weights of up to 800 g / mol to the at least one second phase, especially in the second phases comprising polyvinyl alcohol, leads to an acceleration of the solidification time of the second phases. This is of great advantage, in particular for the production-technical processes, since the further processing of the second phases in the solidified state can take place much more quickly and therefore generally less expensively.

The at least one second phase comprises at least one polyhydric alcohol. The at least one polyhydric alcohol makes it possible to produce a dimensionally stable, non-flowable second phase within a short solidification time which is within 15 minutes or less, in particular 10 minutes or less. Polyhydric alcohols in the context of the present invention are hydrocarbons in which two, three or more hydrogen atoms are replaced by OH groups. The OH groups are bonded to different carbon atoms. One carbon atom does not have two OH groups. This is in contrast to (simple) alcohols, in which in hydrocarbons only one hydrogen atom is replaced by an OH group. Polyhydric alcohols with two OH groups are referred to as alkanediols, polyhydric alcohols with three OH groups as alkanetriols. A polyhydric alcohol thus corresponds to the general formula [KW] (OH) _x , where KW is a hydrocarbon which is linear or branched, saturated or unsaturated, substituted or unsubstituted. Substitution can take place, for example, with -SH or -NH groups. Preferably, KW is a linear or branched, saturated or unsaturated, unsubstituted hydrocarbon. KW comprises at least two carbon atoms. The polyhydric alcohol comprises 2, 3 or more OH groups (x = 2, 3, 4 ...), with only one OH group attached to each carbon atom of the hydrocarbon. Particularly preferably, KW 2 comprises 10 to 10, ie 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. In particular polyhydric alcohols with x = 2, 3 or 4 (for example, for example, pentaerythritol with x = 4) can be used. Preferably, x = 2 (alkanediol) and / or x = 3 (alkanetriol).

Particularly preferably, 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 -alkanetriol and / or at least one C ₃ - to C ₅ -alkanediol as polyhydric alcohol. Preferably, it comprises an alkanetriol and an alkanediol as at least one polyhydric alcohol. In a preferred embodiment, the at least second phase therefore comprises at least one polymer, in particular gelatin and / or PVOH, 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 PVOH, and a C ₃ - to C ₈ -alkanediol and a C ₃ - to C ₈ -alkanetriol. Further preferred is a second phase which comprises at least one polymer, in particular gelatin and / or PVOH, and a C ₃ - to C ₅ -alkanediol and a C ₃ - to C ₆ -alkanetriol.

Surprisingly, it has been found that particularly short solidification time can be achieved in the combination of a corresponding triol (alkanetriol) with a corresponding diol (alkanediol). The resulting second phases are also transparent and have a shiny surface, which provide an appealing visual impression of the washing or cleaning agent according to the invention. The terms diol and alkanediol are used interchangeably herein. The same applies to triol and alkanetriol.

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

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

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

The C ₃ to C ₆ alkanetriol is particularly preferably glycerol and / or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (also called 1,1,1-trimethylolpropane). The C ₃ to C ₅ alkanediol is preferably 1,3-propanediol and / or 1,2-propanediol. Surprisingly, it has been found that the chain length of the diol and in particular the position of the OH groups has an influence on the transparency of the second phase. Preferably, therefore, the OH groups of the diol are not arranged on immediately adjacent C atoms. In particular, between the two OH groups of the diol are three or four carbon atoms, in particular 3 carbon atoms. Most preferably, the diol is 1,3-propanediol. Surprisingly, it has been shown that mixtures which comprise glycerol and 1,3-propanediol and / or 1,2-propanediol give particularly good results.

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 dimensionally stable, non-flowable consistency can be achieved at room temperature, which remains dimensionally stable even after prolonged storage. In addition, a corresponding phase is transparent and has a shiny surface. A particularly preferred second phase therefore comprises gelatin or PVOH as 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, then the proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based on the Total weight of the second phase, preferably 5 wt .-% to 70 wt .-%, in particular 10 wt .-% to 65 wt .-%, especially 20 wt .-% to 40 wt .-%.

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

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

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

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

If several alkanediols are optionally contained in the second phase, the proportion of alkanediols, based on the total weight of the second phase, is preferably 5% by weight to 70% by weight, in particular 7% by weight to 65% by weight. , especially 10 wt .-% to 40 wt .-%.

If the second phase comprises at least one alkanediol, in particular 1,3-propanediol or 1,2-propanediol, the proportion of alkanediol, in particular 1,3-propanediol or 1,2-propanediol, based on the total weight of the second phase, is preferred 5 wt .-% to 70 wt .-%, in particular 10 wt .-% to 65 wt .-%, especially 20 wt .-% to 45 wt .-%. If 1,3-propanediol is contained in the second phase, the proportion of 1,3-propanediol, based on the total weight of the second phase, is in particular 10% by weight to 65% by weight, especially 20% by weight. to 45% by weight.

Preference is given to a second phase which comprises from 20 to 45% by weight of 1,3-propanediol and / or 1,2-propanediol and from 10% by weight to 65% by weight of 2-amino-2-hydroxymethyl-1,3- propanediol, each based on the total weight of the second phase contains. Also preferred is a second phase comprising 20 to 45 wt .-% of 1,3-propanediol and / or 1,2-propanediol and 10 wt .-% to 65 wt .-% 1,1,1-trimethylolpropane, each based on the total weight of the second phase. Particular preference is given to a second phase which comprises 20 to 45% by weight of 1,3-propanediol and / or 1,2-propanediol and 10% by weight to 65% by weight of glycerol, in each case based on the total weight of the second phase, contains.

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

Comprises according to the invention at least a second phase, a C ₃ - to C ₆ -Alkantriol and a C ₃ - to C ₅ - alkanediol, so the weight ratio is preferably 3: 1 to 2: 1. In particular, the weight ratio is 2: 1, when glycerol and 1,3-propanediol are included as polyhydric alcohols. Surprisingly, it has been found that at these weight ratios within short solidification times at 20 ° C. of 10 minutes or less, storage-stable, shiny, transparent second phases can be obtained.

According to a further preferred embodiment, in addition to the abovementioned alkanols, triethylene glycol may be present in the at least one second phase, in particular the second phases described above as preferred, in particular if this phase contains PVOH as the polymer. Triethylene glycol advantageously accelerates the solidification of the second phase (s). It is particularly preferred if the at least one second phase, in addition to 1,3- and / or 1,2-propanediol and glycerol between 0.1 and 20 wt .-%, preferably between 1 and 15 wt .-%, in particular between 5 and 12 wt .-%, for example, 8 to 11 wt .-% triethylene glycol.

Very particularly preferred embodiments of the present invention comprise as at least a second phase 8 to 20% by weight of PVOH, 15 to 30% by weight of 1,3-propanediol, 30 to 40% by weight of glycerol, 5 to 15% by weight. % Sulfonic acid group-containing polyacrylate copolymer, optionally 2 to 10 wt.% 1,2-propanediol, and optionally 2-15 wt .-% triethylene glycol or polyethylene glycol (preferably having an average molecular weight of 200-600 g / mol), wt .-% in each case based on the total weight of the second phase.

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

Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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

Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). 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.

Of particular preference are ethoxylated nonionic surfactants selected from C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and especially more than 20 moles of ethylene oxide per mole 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 especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

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

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.In the context of the present invention, particularly preferred nonionic surfactants have been found to be the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

preferred in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for 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 may vary depending on the origin of the alcohol. When native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x are independently of one another values of 3 or 4 and y and z are independently of one another values of 1 or 2.

Other 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 are a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical with 4 to 22 carbon atoms; Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M is an alkyl radical selected from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.

Nonionic surfactants of the general formula are preferred here R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH _{2) y} -CH ₂ CH (OH) -R ^2, wherein R, R ¹ and R ² independently represent an alkyl group or alkenyl group having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.

Particular preference is given here to compounds of the general formula R ^{1 is} -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30. Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH ₂ -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close 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 here 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 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• - A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH _2, -CH ₂ -CH (CH 3), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
• - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.

By the addition of 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 , also referred to below as "hydroxy mixed ethers", surprisingly, the cleaning performance of inventive preparations can be significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

By using these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the detergent formulations according to the invention can be markedly improved.

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 R²für C₈ bis C₁₂ steht.Particularly preferred are end-capped poly (oxyalkylated) nonionic surfactants which, according to the following formula

in addition to a radical R ¹ which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, wherein n stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Especially 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 .

Particularly preferred are 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 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15. The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

Particular preference is furthermore given to those end-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 in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other 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 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 X is butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. 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, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when 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 may be joined 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 selected here by way of example and may well be greater, with the variation width 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-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such 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 latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15. Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proved 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 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ), preferably 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 include, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

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

In a further preferred embodiment the nonionic surfactant of the first and / or second phase is selected from non-ionic surfactants of 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 represent an alkyl or alkenyl radical having 4 to 22 carbon atoms; R ³ and R ⁴ independently of one another represent H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and x and y independently of one another represent values between 1 and 40.

Preference is given here in particular to 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, are in which R ³ and R ⁴ is H, and the subscripts x and y are independently of one another assume values from 1 to 40, preferably from 1 to 15. Particularly preferred compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the Radicals R ¹ and R ² independently of one another represent saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12. Also preferred are those 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 one of the radicals R ¹ and R ^{2 is} branched. Very particularly preferred compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the indices x and y are independently values 8-12 accept.

The stated C chain lengths and degrees of ethoxylation or degree of alkoxylation of the nonionic surfactants represent statistical averages, which may be an integer or a fractional number for a specific product. Due to the production process commercial products of the formulas mentioned are usually not from an individual representative, but from mixtures, which can result in both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation averages and resulting broken numbers.

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.

Particular preference is given in the at least one first phase to those nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially 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 may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

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

More particularly preferred nonionic surfactants to be used in the first phase having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

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

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

Instead of or in combination with the surfactants mentioned, it is also possible to use cationic and / or amphoteric surfactants, such as betaines or quaternary ammonium compounds. 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, especially nonionic surfactants.

Preferred washing or cleaning agents according to the invention are furthermore 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 at least one second phase, in particular in the first phase the addition of anionic surfactants has proved disadvantageous with regard to the phase properties, in particular their hardness, friability (abrasion behavior) and post-curing behavior.

Substances which also serve as ingredients of cosmetic products are hereinafter referred to as appropriate according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English. The INCI name can be found in the International Cosmetic Ingredient Dictionary and Handbook, 7th Edition (1997), published by The Cosmetic, Toiletry and Fragrance Association (CTFA), Washington D.C. (USA) is issued. The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.

In addition to the surfactants, the at least one second phase may continue to comprise sugar. According to the invention, sugars comprise sugar alcohols, monosaccharides, disaccharides and oligosaccharides. In a preferred embodiment, the at least one second phase comprises at least one sugar alcohol, preferably mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol and xylitol. Particularly preferred is xylitol.

In a further embodiment, the second phase may comprise disaccharides, especially sucrose. The proportion of sucrose is 0 wt .-% to 30 wt .-%, in particular 5 wt .-% to 25 wt .-%, particularly preferably 10 wt .-% to 20 wt .-%, based on the weight of the second Phase. In higher amounts, the sugar does not dissolve completely in the second phase, causing it to cloud. The use of sugar, in particular in a proportion of 10% by weight to 5% by weight, reduces the moisture development and thus improves the adhesion to the at least one first phase.

The use of builders (builders) such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, may be advantageous.

In a preferred embodiment according to the invention, the use of phosphates (including polyphosphates) is largely or completely omitted. The agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). Most preferably, in this embodiment, the agent is completely phosphate-free, i. the agents contain less than 0.1% by weight of phosphate (s).

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

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, especially 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 thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, for example nitrilotriacetic acid (NTA), glutamine-N, N -diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are Salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

In addition to their builder effect, the free acids typically also have the property of an acidifying component. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred detergents or cleaners according to the invention, in particular dishwashing agents, preferably automatic dishwasher detergents, 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 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to Contain 20 wt .-%, each based on the total weight of the composition.

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

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

Preferred washing or cleaning agents, in particular dishwashing detergents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate. In a very particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight. and the amount of citrate is preferably from 5 to 35 wt .-%, in particular 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total amount of the cleaning agent, wherein the total amount of these two Builders preferably 20 to 65 wt .-%, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is. In addition, one or more further builders may additionally be included.

The washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, may in particular contain phosphonates as further builder. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are preferably present in compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight, in each case based on the total weight of the agent.

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

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

The percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight. Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules. Advantageous in this case are those 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. The combination of at least three, in particular at least four, builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwasher detergents. In addition, other builders may be included.

As organic builders, polymeric polycarboxylates are furthermore suitable; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1100 to 10 000 g / mol, and more preferably from 1200 to 5000 g / mol, may again be preferred from this group.

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

Inventive detergents or dishwashing detergents, in particular dishwashing detergents, preferably automatic dishwashing detergents, can furthermore comprise, as builders, crystalline stratiform silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

In certain detergents or cleaners according to the invention, in particular dishwashing agents, preferably automatic dishwasher detergents, the content of silicates, based on the total weight of the detergent or cleaner, is below 10% by weight, preferably below 5% by weight and in particular below 2% by weight limited.

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

As a further constituent, cleaning agents according to the invention in the at least one first and / or the at least one second phase preferably comprise enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly. Detergents according to the invention preferably contain enzymes in total amounts of from 1 × 10 ^-6 % by weight to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples include the subtilisins BPN 'and Carlsberg and their advanced forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are assigned to the subtilases but no longer to the subtilisins in the narrower sense.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids 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 substitution in the positions D96LT213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

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

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils. A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

Alternatively, the enzymes for the at least one first and / or at least one second phase can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are as solidified Are enclosed in such or of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention comprise between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein. Preference is given in particular to those cleansers which, based in each case on their total weight, are 0, 1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% of the respective enzyme preparations.

In addition to the components 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 may contain further ingredients. These include, for example, anionic, cationic and / or amphoteric surfactants, bleaches, bleach activators, bleach catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (in particular in the at least one first phase), additives to improve the operational and drying characteristics, to adjust the viscosity, to stabilize, UV stabilizers, pearlizing agents (INCI opacifying agents, for example glycol distearate, for example Cutina ^® AGS from Cognis, or mixtures comprising, for example Euperlane ^® from Cognis.. ), Preservative (for example, the technical referred to as bronopol 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7) commercially available, for example, as Myacide ® BT or Boots Bronopol BT from Boots is), antimicrobial agents (De disinfectant), pH adjusting agents in amounts of usually not more than 5 wt .-% be contained.

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

Detergents or dishwashing detergents according to the invention, in particular dishwashing detergents, in a preferred embodiment contain as further constituent at least one zinc salt as glass corrosion inhibitor. The zinc salt may be an inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. In a particularly preferred embodiment according to the invention, zinc acetate is used as the zinc salt. The zinc salt is preferably present in the detergent according to the invention in an amount of from 0.01% by weight to 5% by weight, more preferably in an amount of from 0.05% by weight to 3% by weight, in particular in an amount of 0.1 wt .-% to 2 wt .-%, based on the total weight of the cleaning agent. Additionally or alternatively to the o.g. Salts (in particular the zinc salts) may polyethyleneimines, such as those available under the name Lupasol® (BASF), preferably used in an amount of 0 to 5 wt .-%, in particular 0.01 to 2 wt .-%, as glass corrosion inhibitors become.

Polymers suitable as additives maleic acid-acrylic acid copolymer Na salt are, in particular (for example Sokalan ^® CP 5 from the company 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 (such as Silwet ^® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide-modified heptamethyltrisiloxane (For example, Silwet ^® L-7608 BASF, Ludwigshafen (Germany)) and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren ^® 5840, Tegopren ^® 5843, Tegopren ^® 5847, Tegopren® ^® 5851, Tegopren® ^® 5863 or Tegopren® ^® 5878 from Evonik , Essen (Germany). As additives suitable builders are especially polyaspartic acid sodium salt, Ethylendiamintriacetatkokosalkylacetamid (eg Rewopol® ^® CHT 12 from Evonik, Essen (Germany)), methylglycine-trisodium salt and acetophosphonic. Blends with surfactant or polymeric additives exhibit synergism 5863 in the case of Tegopren 5843 and Tegopren ^{® ®.} However, the use of Tegopren grades 5843 and 5863 is less preferred when applied to hard surfaces of glass, especially glassware, since these can apply silicone surfactants to glass. In a particular embodiment of the invention, the additives mentioned are dispensed with.

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

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

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

The bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe-Cu and Ru ammine complexes can also be used as bleach catalysts. It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN). 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 ] (ClO4) 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 and at least a second phase. The washing or cleaning agent may thus have one, two, three or more different first phases; it may also have one, two, three or more distinct second phases. The washing or cleaning agent according to the invention preferably comprises a first phase and a second phase. Particularly preferably, the washing or cleaning agent comprises two first phases and a second phase. It preferably comprises two first phases and two second phases. Further preferred is an embodiment in which the washing or cleaning agent comprises three first phases and one or two second phases.

In this case, the weight ratio of the at least one first phase to the at least one second phase is preferably 20: 1 to 8: 1. The total weight of the phase in a detergent portion may be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 14 to 16 g. In this weight ratio results in a good concentration of the respective ingredients of the first and second phase in a cleaning process.

According to the invention, the at least one first phase and the at least one second phase adjoin one another completely or partially. It is preferred that the two phases immediately adjoin one another.

If the at least one first phase and the at least one second phase adjoin one another completely or partially, the stability is important in addition to the shortest possible solidification time of the at least one second phase. Stability here means that constituents containing in the second phase do not transgress into the at least one first phase, but also after prolonged storage the at least one first phase and the second phase are optically separated from each other and do not interact with each other, such as diffusion of liquid Ingredients from one to the other phase or reaction of constituents of one phase with those in the other phase. Surprisingly, it has been shown that this can be made possible by a second phase which comprises glycerol, gelatin and at least one C ₃ -C ₅ -alkanediol or glycerin, PVOH and at least one C ₃ -C ₅ -alkanediol.

According to a particularly preferred embodiment, the washing or cleaning agents according to the invention are characterized in that the at least one second phase less than 1 wt .-%, in particular less than 0.5 wt .-%, in particular less than 0.1 wt .-% Anionic surfactant, each based on the total weight of the second phase.

Preferably, the at least one second phase is substantially free of anionic surfactants. Substantially free means that the at least one second phase contains less than 0.05% by weight of anionic surfactant, based in each case on the total weight of the second phase.

It has been found in this context that the presence of 1% by weight of anionic surfactant in the at least one second phase leads to poorer foaming behavior and poorer rinse behavior of the overall composition. Furthermore, higher amounts of anionic surfactants adversely affect the cure.

Water-soluble cladding

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.

It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol ^-1 , preferably 20,000 to 500,000 gmol ^-1 , more preferably 30,000 to 100,000 gmol ^-1 and especially from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

In addition, a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above may be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers. A preferred additional polymer is polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred. Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

It may be preferred that the film material contains further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the name M84720, M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The water-soluble wrapper preferably has at least partially a bittering agent having a bitter value of between 1,000 and 200,000, especially those selected from quinine sulfate (bitter value = 10,000), naringin (bitter value = 10,000), sucrose octaacetate (bitter value = 100,000), quinine hydrochloride and mixtures thereof. In particular, the outer surface of the water-soluble casing is at least partially coated with a bittering agent having a bitter value between 1,000 and 200,000. In this connection, it is particularly preferable that the water-soluble coating is coated with at least 50%, preferably at least 75%, and most preferably at least 90%, with the bittering agent having a bitter value between 1,000 and 200,000. The application of the bittering agent with a bitter value between 1,000 and 200,000, for example, by means of printing, spraying or deletion.

According to the invention, the water-soluble casing has at least one continuous peripheral sealing seam, which lies substantially in one plane. This is favorable in terms of process, since only one single sealing step, possibly using only a single sealing tool, is necessary for a circumferential sealing seam, which lies essentially in one plane. The continuous circumferential sealing seam results in a better closure over such multi-sealed coverings and excellent sealing of the sealed seam and thus of the cover itself. Leakage of product from the cover, e.g. on the surface of the portion would be disadvantageous because the consumer would then come in contact with the product. Exactly this should be avoided if possible with a washing or cleaning agent portion with a water-soluble coating.

The water-soluble coating may preferably be produced from at least 2 packaging parts. The at least two packaging parts are preferably water-soluble, so that no packaging parts remain in the dishwasher, which can then lead to problems in the dishwasher. It is not necessary that the at least two packaging parts are different. They may preferably be made of the same material and in the same way. In a preferred embodiment, these are two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.

In a further embodiment, the at least two packaging parts may be made of different material, e.g. be made of different films or of material with two different properties (e.g., hot and cold water soluble film). In this embodiment, it is preferable that a water-soluble film and another packaging part made by injection molding are combined.

According to a particularly preferred embodiment of the present invention, the water-soluble casing comprises at least one at least partially plastically deformed film. In particular, this plastic deformation of the film can be produced by methods known to the person skilled in the art, such as deep-drawing (with and without application of a vacuum), blowing or stamping. In particular, the water-soluble sheath comprises at least one at least partially plastically deformed foil which has been produced by deep-drawing.

The at least one first phase and the at least one second phase may be arranged within the water-soluble casing in any desired combination with one another. Thus, a first phase may be arranged on or next to a second phase. In this embodiment, the washing or cleaning agent according to the invention has a first phase and a second phase. It is also conceivable that a first phase is surrounded by second phases. Embedding one phase in another is also included according to the invention. In a further, particularly preferred arrangement, the second phase is in the form of a gel core, which is surrounded by the first phase. There may also be two separate cavities, the be filled with the at least one second phase. In this embodiment, the washing or cleaning agent comprises two second phases, wherein the two second phases may have different compositions.

1. a) Bereitstellen einer Form mit mindestens einer Formmulde; optional enthaltend einen Steg zur Unterteilung des Bodens der Formmulde
2. b) Zuführen einer wasserlöslichen Folie auf die Formmulde;
3. c) Ausbilden einer offenen Kammer in der Formmulde, durch Verformung der wasserlöslichen Folie;
4. d) Befüllen der offenen Kammer oder Teilen davon mit wenigstens einer zweiten Phase wie sie vorstehend beschrieben ist;
5. e) optional Befüllen der offenen Kammer oder Teilen davon mit wenigstens einer weiteren zweiten Phase, wie sie vorstehend beschrieben sind, wobei diese zweite Phase optional von der zweiten Phase gemäß d) verschieden sein kann;
6. f) Optional Erstarren Lassen der zweiten Phase(n);
7. g) anschließend Befüllung der offenen Kammer mit wenigstens einer ersten, von der wenigstens einen zweiten Phase verschiedenen Phase, wie sie vorstehend beschrieben ist;
8. h) Bereitstellung eines zweiten wasserlöslichen Films als Deckel;
9. i) Übereinander Bringen der offenen Kammer und des Deckels, zur Versiegelung der Portionspackung an einem Versiegelungsbereich;
10. j) Versiegeln des Deckels mit der offenen Kammer.

A further subject of the present invention is a process for the production of washing and / or cleaning agent sachets, in particular detergent sachets, containing a product with at least one first and at least one, different second phase, comprising:

1. a) providing a mold with at least one mold cavity; optionally containing a web for dividing the bottom of the mold cavity
2. b) supplying a water-soluble film to the mold cavity;
3. c) forming an open chamber in the mold cavity by deforming the water-soluble film;
4. d) filling the open chamber or parts thereof with at least a second phase as described above;
5. e) optionally filling the open chamber or parts thereof with at least one further second phase as described above, which second phase may optionally be different from the second phase according to d);
6. f) optionally solidifying the second phase (s);
7. g) then filling the open chamber with at least a first phase different from the at least one second phase as described above;
8. h) providing a second water-soluble film as a lid;
9. i) bringing the open chamber and lid over one another to seal the sachet at a sealing area;
10. j) sealing the lid with the open chamber.

The product is preferably a dishwashing detergent, preferably a machine dishwashing detergent.

The mold comprises at least one trough (mold cavity). For example, the mold may be provided as a single mold or as part of an array of treadmill shapes, as known in the treadmill and drum process. The mold comprises an area on which the film can be placed, e.g. a seal region typically defined around the opening of a mold cavity. The mold cavity can have different geometries, if there are edges, it is advantageous that they are rounded. Rounded edges and / or dome-shaped troughs serve to pull the film somewhat more homogeneously as the film is drawn into the trough, thereby keeping the film thickness uniform, and to avoid breakage or tear points, which in turn results in a more stable one Portion pack leads.

Optionally, but according to a particular embodiment, the mold preferably contains at least one mold cavity which has a web for subdividing the bottom of the mold cavity. As a result, bulges or pockets form in the formed chamber, which visually create a positive appearance. In particular, if only the areas of these bulges are completely or partially, preferably almost completely filled with the / the second phase (s), this area is once again clearly separated from the powdery first phase and visually creates a particularly good appearance.

The water-soluble film can be fed from a roll and fed to the mold cavity. The foil is positioned and held on the mold. The holding can take place through suction holes on the molding surface, which is not part of the mold cavity. The film can also be held by mechanical means on the mold, such as brackets. For example, the foil may be held in place by a punch which presses on the sealing area. In the continuous production processes, e.g. Drum method and treadmill method, it is preferable that the speed of the film is adapted to the speed of the treadmill formed from the molds so that the film is not unnecessarily pulled thinner by adhering to a running mold.

After the film is held in place relative to the mold cavity, a cavity is formed in the mold cavity region by at least partially conforming the film to the mold cavity. The adaptation is produced by elastic and / or plastic deformation. Preferably, the film deformation has a greater plastic than elastic portion. The deformation of the water-soluble film is produced for example by deep drawing or by means of suitable stamp. A preferred variant is deep-drawing, by applying negative pressure (forming pressure) in the mold cavity, to the mold cavity preferably comprises small openings, preferably in the bottom region, which are connected by appropriate lines air pressure moderately connected to a vacuum pump.

After forming the open chamber, these or parts thereof are filled in step d) with the at least one second phase of the product. As soon as the at least one second phase has solidified, if necessary after an additional period of time which is necessary for solidification, further product constituents (further second phases according to optional step e) or at least a first phase according to step g)) can then be introduced into the chamber become. In this case, the at least one first phase according to step g) is preferably pulverulent, in particular powdery and free-flowing.

It is preferable in the above-mentioned production method that the chamber containing the second phase is not completely filled with the second phase (in step d). In this case, the chamber may be filled with the / the second phase (s) preferably only in part, preferably only in the lower region or only in the region or just above the region of the protrusions or pockets of the chamber formed by the optional web according to a).

If the chamber or parts thereof is filled with at least two second phases, it is preferred according to a particular embodiment that these second phases are substantially the same or differ only slightly, for example by a different dye. They preferably have a very similar, in particular the same, composition with regard to the active ingredients used (apart from excipients such as, for example, dyes). In this case, in particular migration phenomena between the second phases, and thus the expression of a non-advantageous optics during storage by, for example, inflated or shrunken phases, are avoided.

When filled with product, preferably the deformed foil is kept in the trough during filling. For example, under negative pressure, the negative pressure is broken only after the seal. Wherein the vacuum after forming the chamber in relation to the Formierdruck, may have a lower strength (higher pressure), which only fulfills the holding function.

The chamber is filled by the introduction of at least a first and at least a second phase, in particular by those as described above as being according to the invention.

It is important that the seal area remains free of product. For example, if the chamber is at least partially elastically deformed, this elastic deformation after filling and prior to sealing should not degrade such that the product flows over and out of the open chamber and thus contaminates the seal area.

According to a particular embodiment, the lid is positioned on the open chamber so that in the next step the lid can be applied to the sealing area. The position of the lid is generally determined relative to the position of the chamber. If the chamber is moving with a moving mold in a treadmill, the lid must move equally so that the relative position to the chamber remains the same.

The lid is then applied to the open chamber, which is closed in this way. The contact between lid and foil in the sealing area thus closes the chamber.

A preferred embodiment of the seal is a material fusion between the film and the lid, for example by dissolving the film before applying the lid, or by melting film and / or lid in the sealing area. Alternatively, the sealing is done by gluing, or welding.

The positioning, applying, and sealing can take place either in separate steps or simultaneously.

The mold can also comprise at least one second mold cavity, so that at least two open chambers are produced by process steps a) to d). The at least two chambers are formed in the same plane. It is preferred that the lid in step h) on the at least two is positioned open chambers and the lid in step i) is applied to at least both chambers for sealing the sachet to a sealing area. Since the at least two chambers are connected to the same lid, the chamber remain in a certain position relative to each other, in contrast to the prior art where adjacent chambers are connected by the web formed by the thin films of the packages.

It is particularly preferred that the lid is provided as part of a tape by feeding / transferring a tape comprising at least one lid. The singulation of the lid may take place prior to positioning, after positioning but before application, during application, or after application to the chamber.

When singulated before positioning, the lid is preferably punched out.

Lid and foil can also be separated simultaneously with the sealing. The device which produces the seal by melting consists of at least two parts, one is the mold itself and the other part is a counter-punch which presses on the mold from the lid side. It is preferred that in the sealing step, the pressure exerted during sealing by the mold and further part must be less at the sealing area than the pressure exerted in the separating area. The separation area surrounds the sealing area.

In the case of separation after sealing, the lid and foil are alternatively preferably separated from the band in the same step, and thus the portion packs are separated.

1. a) Bereitstellen einer Form mit mindestens einer Formmulde; optional enthaltend einen Steg zur Unterteilung des Bodens der Formmulde;
2. b) Zuführen einer wasserlöslichen Folie auf die Formmulde;
3. c) Ausbilden einer offenen Kammer in der Formmulde, durch Verformung der wasserlöslichen Folie;
4. d) Befüllen der offenen Kammer mit wenigstens einer ersten pulverförmigen Phase;
5. e) Bereitstellen einer zweiten Form mit mindestens einer zweiten Formmulde; optional enthaltend einen Steg zur Unterteilung des Bodens der Formmulde
6. f) Zuführen einer zweiten wasserlöslichen Folie auf die zweiten Formmulde;
7. g) Ausbilden einer zweiten offenen Kammer in der zweiten Formmulde, durch Verformung der wasserlöslichen Folie;
8. h) Befüllen der zweiten offenen Kammer oder Teilen davon mit wenigstens einer zweiten Phase, wie sie vorstehend beschrieben sind,
9. i) Optional Befüllen der zweiten offenen Kammer oder Teilen davon aus Schritt h) mit wenigstens einer weiteren zweiten Phase, wie sie vorstehend beschrieben sind, wobei diese wenigstens eine weitere zweite Phase optional von der zweiten Phase gemäß h) verschieden ist;
10. j) Optional Erstarren Lassen der zweiten Phase(n);
11. k) Übereinander Bringen der zwei offenen Kammer, zur Versiegelung der Portionspackung an einem Versiegelungsbereich, wobei die befüllten Bereiche zueinander weisen;
12. l) Versiegeln der offenen Kammern miteinander.

As an alternative, also preferred method for producing detergent portion packs according to the invention, the following is particularly suitable in particular. This method comprises the steps:

1. a) providing a mold with at least one mold cavity; optionally including a web for dividing the bottom of the mold cavity;
2. b) supplying a water-soluble film to the mold cavity;
3. c) forming an open chamber in the mold cavity by deforming the water-soluble film;
4. d) filling the open chamber with at least one first powdery phase;
5. e) providing a second mold with at least one second mold cavity; optionally containing a web for dividing the bottom of the mold cavity
6. f) supplying a second water-soluble film to the second mold cavity;
7. g) forming a second open chamber in the second mold cavity by deforming the water-soluble film;
8. h) filling the second open chamber or parts thereof with at least one second phase, as described above,
9. i) optionally filling the second open chamber or parts thereof from step h) with at least one further second phase as described above, this at least one further second phase optionally being different from the second phase according to h);
10. j) optionally solidifying the second phase (s);
11. k) bringing the two open chambers together to seal the sachet to a sealing area, the filled areas facing each other;
12. l) sealing the open chambers together.

Unless otherwise stated, this procedure also applies to the procedure described for the first method.

In this second method, two different chambers are formed, with one chamber containing at least a first phase and the other chamber at least a second phase.

Preferably, in step k), the chamber containing the at least one first, in particular pulverulent and free-flowing phase is arranged so that the powder does not fall out.

In this case, the chamber containing the at least one second phase above / above the chamber containing the at least one first phase is then preferably arranged. In this case, the filled chamber areas to each other. It is important that the at least one second phase at step k) is already solidified or gel-like or no longer flowable so that it does not run out of the chamber. After sealing, this results in a multi-phase Einkammerpouch, which has a particularly good appearance and at the same time

For both aforementioned production methods, the following preferably applies:

For the at least one first powdery phase, the above-described for the inventive cleaning agent applies. It is preferred that the at least one first phase is powdery and free-flowing. In particular, the flowability of the at least one first phase preferably has a value of greater than 55%, in particular greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75%, with respect to the standard test sand.

For the at least one second phase to be used in the method according to the invention, the one mentioned above, to which reference is explicitly made, also applies. A particular suitability of the above-described second phases for the last-mentioned method is that the fast solidification times of the gel phases, in particular the phases with PVOH as polymer greatly shorten the step of solidifying the second phase (s) and possibly even make unnecessary ,

In this context, very particularly preferred embodiments of the present invention comprise as at least a second phase 8 to 20 wt .-% PVOH, 15 to 30 wt .-% of 1,3-propanediol, 30 to 40 wt .-% glycerol, 5 to 15 Wt .-% sulfonic acid-containing polyacrylate copolymer, optionally 2 to 10 wt .-% of 1,2-propanediol, and optionally 2- 15 wt .-% triethylene glycol or polyethylene glycol (preferably having an average molecular weight of 200-600 g / mol), % By weight, based in each case on the total weight of the second phase.

Depending on the manufacturing process, the second phase (s) may be significantly above or below the sealing seam level (former method) or approximately at the level of the sealing seam (the latter method).

Another object of the present application is a method for cleaning hard surfaces, in particular of crockery, in which the surface is processed in a conventional manner using a cleaning agent according to the invention. 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, especially in automatic dishwashers.

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

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

EXAMPLES

Detergents according to the invention were prepared comprising a first phase and a second phase. Different geometries were realized. Furthermore, detergents were made comprising two first phases and one second phase. The following information relates to wt .-% of active substance based on the total weight of the respective phase.

Table 1: The first powdery and free-flowing phases had the following composition Wt .-% Citrate, Na salt 10-25 Phosphonate (eg HEDP) 0-10 MGDA, Na salt 0-40 Disilicate, Na salt 0-40 soda 10-30 Percarbonate, Na salt 5.0-20.0 Bleach catalyst (preferably Mn-based) 0.0 to 0.8 Bleach activator (eg TAED) 1.0-4.0 Nonionic surfactant (s), eg fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 1.5 to 15.0 polycarboxylate 0.5 -15 Cationic copolymer 0.0-1.0 Disintegrant - (eg Crosslinked PVP) 0.0-3.0 Protease preparation (tq) 1.0 to 7 Amylase preparation (tq) 0.2-6 Silver protection (eg benzotriazole) 0.0-1.0 Perfume 0.0-0.5 dye solution 0.0-1.5 Zn salt (eg acetate) 0.01-0.5 sodium sulphate 0.0 - 25 water 0.0 to 3 pH-adjusting agent (eg citric acid) 0.0 - 5 processing aids 0-10 Table 2: Furthermore, first free-flowing phases were prepared, which had the following composition: Wt .-% Citrate, Na salt 15-20 Phosphonate (eg HEDP) 2.5-7.5 MGDA, Na salt 0-25 Disilicate, Na salt 5-35 soda 10-25 Percarbonate, Na salt 10-15 Bleach catalyst (preferably Mn-based) 0.02-0.5 Bleach activator (eg TAED) 1-3 Nonionic surfactant (s), eg fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 2.5-10 polycarboxylate 4-10 Cationic copolymer 0 - 0.75 Disintegrant - (eg 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 to 1 Zn salt (eg acetate) 0.1-0.3 sodium sulphate 0.0 to 10 water 0.0 to 1.5 pH-adjusting agent (eg citric acid) 0-1.5 processing aids 0-5

A water-soluble wrapper in the form of an open pouch was prepared by deep-drawing a PVOH-containing film. In this open cavity, a liquid composition was poured, which gave the second phase after curing, then first phases in the form of a free-flowing solid in a pouch comprising polyvinyl alcohol were filled and the open pouch then sealed by applying a second film and sealing by heat sealing.

Table 3: The second phases used had the following composition: Wt .-% glycerin 10-50 Propanediol (preferably 1,3-propanediol) 10-50 Polycarboxylate homo- and / or copolymer with sulfonic acid-containing groups 0-30 Nonionic surfactant (s), eg fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 0-40 Polyethylene glycol average. Mr 1000-2000 0-20 Thickener (preferably gelatin or PVOH) 5-50 processing aids 0-10 dye solution 0.0-1.5 Table 4: Additional second phases having the following composition were prepared: Wt .-% glycerin 20-45 Propanediol (preferably 1,3-propanediol) 10-30 polycarboxylate; Homo- and / or copolymer with sulfonic acid-containing groups 5-20 Nonionic 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 PVOH) 10-20 processing aids 0-5 dye solution 0.0-0.5

The first and the second phases could be combined as desired. The spatial design of the second phase, which was dimensionally stable after mixing the ingredients liquid and within a solidification time of about 10 to 15 minutes, was given by the spatial design of the first phase and by commercially available or self-designed forms. In these molds, the liquid second phase was introduced and after the solidification time, the molds were removed without changing the second phase. This allowed any geometry of the second phase to be enabled. Table 5: Further examples of second phases with PVOH as polymer G1 G2 G3 G4 G5 PEG 400 17.9 23.1 23.1 13.9 27.8 30% PVOH in glycerol 35.7 30.8 30.8 55.6 55.6 1,3 propanediol - - - 27.8 13.9 glycerin - 15.4 - - - Sulfonic acid containing acrylate copolymer - 30.8 30.8 - - xylitol 26.8 - - - water 10.7 - 15.4 - - Nonionic surfactant 1 8.9 - - - - Nonionic surfactant 2 - - - 2.8 2.8 Table 6: further second phases with gelatin as polymer Gelatin, bloom number 225 29.2 25.8 24.7 1,3-propanediol 47.6 41.9 40.2 EHDP 23.2 23.6 26.8 Wassser - 6.5 6.2 Nonionic surfactant 2 - 2.2 2.1

Claims (16)

A washing or cleaning agent portion, comprising a water-soluble casing, which has at least one continuous circumferential sealing seam lying substantially in one plane, and at least one first phase and at least one second phase different therefrom, characterized in that the at least one first phase is powdery and is free-flowing, and the at least one second phase comprises at least one polymer and at least one polyhydric alcohol. Detergent or detergent portion after Claim 1 , characterized in that the at least one second phase comprises at least two polyhydric alcohols, wherein a first polyhydric alcohol, an alkanetriol, in particular a C ₃ - to C ₁₀ alkanetriol, and a second polyhydric alcohol, an alkane diol, in particular a C ₃ - to C ₁₀ alkanediol is. Detergent or detergent portion after Claim 2 , characterized in that the first polyhydric alcohol is a C ₃ - to C ₈ -alkanetriol, in particular a C ₃ - to C ₆ -alkanetriol, preferably glycerol and / or 1,1,1-trimethylolpropane and / or 2-amino-2 - (Hydroxymethyl) -1,3-propanediol, especially glycerol and / or 1,1,1-trimethylolpropane, especially glycerol. Detergent or detergent portion after Claim 2 or 3 , characterized in that the second polyhydric alcohol is a C ₃ - to C ₈ -alkanediol, in particular a C ₃ - to C ₅ -alkanediol. Detergent or cleaning agent portion according to one of Claims 2 to 4 , characterized in that the two OH groups of the alkanediol are not arranged on immediately adjacent carbon atoms of the alkyl chain and in particular are three or four carbon atoms between the two OH groups. Detergent or cleaning agent portion according to one of Claims 1 to 5 , characterized in that the at least one second phase is low in water or substantially free of water. Detergent or cleaning agent portion according to one of Claims 1 to 6 , characterized in that the at least one second phase comprises gelatin and / or PVOH, in particular PVOH, as polymer. Detergent or cleaning agent portion according to one of Claims 1 to 7 , characterized in that the at least one first phase and / or the at least one second phase comprises at least one surfactant, in particular at least one nonionic surfactant. Detergent or cleaning agent portion according to one of Claims 1 to 8th characterized in that the weight ratio of the at least one first phase to the at least one second phase is 40: 1 to 8: 1. Detergent or cleaning agent portion according to one of Claims 1 to 9 , characterized in that the at least one second phase comprises less than 1 wt .-%, in particular less than 0.5 wt .-%, in particular less than 0.1 wt .-% anionic surfactant, each based on the total weight of the second phase , Detergent or cleaning agent portion according to one of Claims 1 to 10 , characterized in that the water-soluble coating comprises polyvinyl alcohol. Detergent or cleaning agent portion according to one of Claims 1 to 11 , characterized in that it is a dishwashing detergent, in particular a dishwashing detergent for machine cleaning of dishes. Use of a detergent portion according to one of Claims 1 to 12 for machine cleaning of dishes. Process for the automatic cleaning of dishes, characterized in that a detergent portion according to one of Claims 1 to 12 used in a dishwasher. A process for the preparation of laundry and / or detergent sachets containing a product having at least a first and at least one second phase different therefrom comprising: a) providing a mold having at least one mold cavity; optionally including a web for dividing the bottom of the mold cavity; b) supplying a water-soluble film to the mold cavity; c) forming an open chamber in the mold cavity by deforming the water-soluble film; d) filling the open chamber with at least a second phase according to one of Claims 1 to 10 ; e) optionally filling the open chamber or parts thereof with at least one further second phase as described above, which second phase may optionally be different from the second phase according to d); f) optionally solidifying the at least one second phase; g) then filling the open chamber with at least one first powder phase which is different from the at least one second phase; h) providing a second water-soluble film as a lid; i) bringing the open chamber and lid over one another to seal the sachet at a sealing area; i) sealing the lid with the open chamber. A process for the preparation of laundry and / or detergent sachets containing a product having at least a first and at least one second phase different therefrom comprising: a) providing a mold having at least one mold cavity; optionally including a web for dividing the bottom of the mold cavity; b) supplying a water-soluble film to the mold cavity; c) forming an open chamber in the mold cavity by deforming the water-soluble film; d) filling the open chamber with at least one first powdery phase; e) providing a second mold with at least one second mold cavity; optionally containing a web for dividing the bottom of the mold cavity f) feeding a second water-soluble film onto the second mold cavity; g) forming a second open chamber in the second mold cavity by deforming the water-soluble film; h) filling the second open chamber or parts thereof with at least one second phase, according to one of Claims 1 to 10 ; i) optionally filling the second open chamber or parts thereof from step h) with at least one further second phase according to one of Claims 1 to 11 wherein said at least one further second phase is optionally different from the second phase according to h); j) optionally solidifying the second phase (s); k) bringing the two open chambers together to seal the sachet to a sealing area, the filled areas facing each other; I) sealing the open chambers with each other.