DE102017201095A1 - Surfactants in capsules with optimized cloud point - Google Patents

Abstract

The present invention relates to a surfactant formulation which comprises at least one liquid surfactant in a water-soluble casing, and to washing or cleaning agents, in particular dishwashing detergents, preferably automatic dishwashing detergents, which contain a corresponding surfactant formulation in a water-soluble casing.

Description

The present invention relates to a surfactant formulation which comprises at least one liquid surfactant in a water-soluble casing, and to washing or cleaning agents, in particular dishwashing detergents, preferably automatic dishwashing detergents, which contain a corresponding surfactant formulation in a water-soluble casing.

Surfactants are used in different areas of everyday life. A prominent area is the use as detergents or cleaners and especially as dishwashing detergents. In addition to hand dishwashing detergents, this also includes those which can be used in the automatic cleaning of dishes, ie in dishwashers.

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.

A manual cleaning of hard surfaces and especially of crockery occurs in everyday life increasingly in the background. Connected to this is the requirement of the consumer that mechanically cleaned dishes are cleaned particularly well and even better than with manual cleaning. Accordingly, a completely clean at first glance of food or drink residues dishes is then not considered properly cleaned, if it still has small spots after machine cleaning. Such stains can be, for example, locally-limited stains (so-called spotting) or staining spots (so-called filming), which are caused, in particular, by insufficient rinsing performance of the washing or cleaning agent.

The addition of rinse aids at the end of a washing program during machine cleaning should ensure that the cleaning water or rinse water runs as completely as possible from the dishes. This is to ensure that the different surfaces are residue-free and flawless gloss at the end of the washing program.

The prior art describes different approaches with which the rinse aid performance can be improved. So that beats EP-A-0851024 a two-layer detergent tablet before. In the relevant second layer, an azidifying agent and a continuous medium having a melting point of between 55 ° C and 70 ° C and scale inhibitors are included. Due to the high-melting continuous medium acid and scale inhibitors should be released delayed and cause a clear rinse effect.

Especially liquid surfactants (liquid at 20 ° C) are particularly suitable to improve the rinsing performance of detergents or cleaners, especially dishwashing detergents, preferably automatic dishwashing detergents. In particular, the reduction of the mocking on glass and porcelain is in the foreground here. Despite various solutions described in the prior art, there remains a need to improve the rinse performance.

In addition to improving rinse performance, consumers have become increasingly accustomed to conveniently dosing pre-portioned automatic detergents or cleaners such as dishwashing detergents. In particular, solid products in the form of tablets are becoming increasingly popular. The problem with these is that the liquid surfactants which are preferred for the rinsing performance are difficult to incorporate into corresponding pulverulent cleaning agents and in particular those in the form of tablets. Too high amounts of liquid surfactants sticks the powder and can not be pressed or processed in other forms in single portions.

There is therefore a need for the provision of a surfactant formulation which improves the rinse aid performance and at the same time can be combined with a tablet or general with a solid washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, in particular in portioned form. The object underlying the present invention could be achieved by a surfactant formulation in a water-soluble casing, wherein the cloud point of the surfactant formulation is above the release temperature of the casing.

In a first embodiment, the object underlying the present invention therefore relates to a surfactant formulation having a cloud point T _CP in a water-soluble casing having a release temperature T _F , characterized in that the surfactant formulation comprises one, two or more liquid surfactants and the cloud point T _CP the surfactant formulation is from 5 ° C to 40 ° C above the release temperature T _{F of} the enclosure. More preferably, the at least one liquid surfactant is a nonionic surfactant.

A surfactant formulation according to the invention enables a particularly good rinse performance. The rinse performance of liquid nonionic surfactants and surfactant formulations is highest near the cloud point. The formulation according to the invention in the water-soluble coating now makes it possible for the surfactant formulation to be at least partially released from the coating before reaching the clouding temperature or the cloud point T _CP . Thus, a timely release of the at least one liquid surfactant in a washing or cleaning cycle is ensured. At the same time, the water-soluble coating enables the combination of the surfactant formulation with any detergents or cleaners whose rinse performance can be improved.

In a further embodiment, the present invention thus relates to a washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, which identifies a surfactant formulation according to the invention. The washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, is particularly preferably a portioned washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent. In particular, it is a compacted washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, which has two or more phases, one of the phases being a solid, in particular compressed phase and the other phase a surfactant formulation in a water-soluble coating as described herein.

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" or "at least one" as used herein means 1 or more, that is 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, that is, one type of bleach catalyst or a mixture of several different bleach catalysts. 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. If aggregate states (solid, liquid) are mentioned in the present applications, these relate, unless stated otherwise, to room temperature (20 ° C.) at atmospheric pressure of 1 bar.

In accordance with the invention, the novel surfactant formulations in a water-soluble casing enable a simple introduction of liquid surfactants, which have a positive effect on the final rinse performance and in particular on the reduction of spotting on glass and porcelain. Surprisingly, the deposition of fat in the filter is also reduced.

Release temperature T _F in the context of the present invention is the temperature at which the surfactant formulation can escape from the water-soluble coating. In this case, the water-soluble sheath may be deformed at this time, for example, or already substantially dissolved in a solvent. The type of release of the surfactant formulation is irrelevant. The release temperature thus defines the temperature at which the surfactant formulation is released into the environment.

According to the invention, the release temperature T _F in water at 20 ° C (and normal pressure of 1bar) is determined. A beaker filled with tap water (T = 20 ° C) is provided with a stir bar (magnetic stirrer) and placed on a hot plate. The surfactant formulation in the enclosure is placed on the device in the beaker such that the surfactant formulation is completely surrounded by the water, but does not come into direct contact with the stir bar. This can be done, for example, that inside the beaker, a device is introduced, which does not prevent the free movement of the stirring rod and the movement of the water. The surfactant formulation can then be introduced into the beaker on this device on a suitable base, for example on a watch glass or a grid. Thus, there is a spatial distance between the bottom of the beaker on which the stir bar is located and the surfactant formulation of the invention to avoid direct contact between the stir bar and the water-soluble wrapper. Nevertheless, the surfactant formulation is completely surrounded by water. Thus, the conditions prevailing in a dishwasher can be replicated. Inside the beaker there is also a thermometer, which measures the temperature of the water in the amount of the surfactant formulations according to the invention.

The water in the beaker is stirred at a stirring speed of 600 to 1000 rpm and heated at a heating rate of 1 to 2 ° C / min. Stirring causes a uniform heating of the water in the beaker. The stirring speed is adjusted so that the water-soluble casing is not directly damaged.

The release temperature corresponds to the temperature at which the exit of the surfactant formulation can be observed. This can be done, for example, by coloring the surfactant formulation with a dye. Suitable dyes for coloring surfactant formulations are well known to those skilled in the art. The release of the dyed dye can then be observed optically without further aids.

The cloud point is the temperature at which a surfactant formulation becomes cloudy. Preferably, the cloud point T _{CP of} the surfactant formulation is in the range from 20 ° C to 75 ° C, especially from 40 ° C to 75 ° C, preferably from 50 ° C to 70 ° C. The cloud point is determined according to DIN EN 1890: 2006-9. The determination is made in cases of doubt as a 10 wt .-% solution of the surfactant in 25 wt .-% strength butyldiglycol (diethylene glycol mono-n-butyl ether) solution in water as described above DIN-specification.

The surfactant formulation according to the invention is preferably used in a washing or cleaning agent for mechanical cleaning of solid surfaces, in particular of dishes. The usual cleaning temperature of the respective programs is usually in the range of 40 ° C to 75 ° C. At the beginning and end of a cleaning program, this temperature is often not reached, but there are lower temperatures. The cloud point T _{CP of} the surfactant formulation is now in the range of the temperatures that prevail in a purification. If the cloud point is below the stated temperature, the surfactant can not distribute evenly because it precipitates too quickly. If the cloud point is too high, the temperature is not attained, or only too short, so that the desired effect, namely the improvement of the rinse aid performance, can not be achieved or can not be achieved to the desired extent.

Due to the cloud point T _CP and the release temperature T _{F of} the envelope, there is a difference between the two, wherein T _CP - T _{F is} in the range of 5 ° C to 40 ° C, in particular in the range of 5 ° C to 20 ° C. This difference ensures that the liquid surfactant formulation is released before it reaches the cloud point. The water-soluble coating must not be completely dissolved. At the release temperature, the water-soluble coating usually becomes porous, so it is no longer able to keep the surfactant formulation stable inside, so that it comes to a release.

The water-soluble casing can be in the form of a bag, a bag or a capsule, for example. Different geometric shapes are possible. Particularly preferred is a capsule, which is present in a round or oval shape.

Correspondingly round or oval shapes or shapes that are approximated to this can be combined particularly well with a solid and in particular a compacted washing or cleaning agent, in particular dishwashing detergent, preferably a dishwasher detergent. Here, a corresponding solid phase can be brought into a form such that a depression is formed, which essentially has the shape of the envelope. In this trough the wrapper can then be introduced and fixed.

A round or oval shape is also an appealing form for the consumer. Corresponding beads are widely used as surfactant additives and may optionally provide an additional buying incentive through a color design.

The water-soluble casing comprises one or more water-soluble materials. It preferably comprises a water-soluble material.

The term "water-soluble" as used herein means "water-soluble" in the strict sense, but also "water-disintegratable". The term "water-soluble" in the proper sense refers to the property of a substance or an object that it or it has a solubility in distilled water, measured at 25 ° C, of at least 0.1 g / l. In some embodiments, the substance and the object have a solubility of at least 0.1 to 500 g / L, measured at 25 ° C. The term "water-disintegratable" means that the substance or the object on contact with water at temperatures between 15 and 60 ° C and especially between 20 and 45 ° C within 15, preferably within 10 minutes into small parts.

Suitable water-soluble materials are polymeric materials such as polyvinyl alcohols (optionally partially alkoxylated or acetalated), polyacrylates, polyurethanes. Polyethylene oxides, polyvinyl alcohol copolymers, cellulose and derivatives thereof, in particular methylcellulose or hydroxypropylmethylcellulose (HPMC). The water-soluble wrapper may also further contain additives such as dyes or brighteners to provide an attractive appearance.

The water-soluble coating particularly preferably comprises gelatin, a substance mixture of animal proteins whose main constituent is denatured or hydrolyzed collagen. Most preferably, it is a gelatin capsule. This can be obtained for example from a mixture of a gelatin granulate, glycerol and / or sorbitol and water, preferably gelatin granules, glycerol and water, which is then dried. The proportion of water is preferably 20% by weight or less, in particular 15% by weight or less, preferably 5% by weight to 12% by weight or 8% by weight to 10% by weight. Thus, suitable capsules can be obtained in a reasonable drying time.

A water-soluble coating of gelatin has been found to be particularly preferred. This can be combined particularly well with a solid washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent. In a corresponding compacted well, gelatin capsules can be attached without major problems.

At the same time, a gelatin capsule is sufficiently stable to be stably stored even in a larger outer packaging in which several capsules are located, without being destroyed by the prevailing mechanical pressure. On the other hand, water solubility or water dispersibility is high enough to allow release of the surfactant formulation contained in the capsule during conventional washing or cleaning cycles. In order to ensure release in the region of the release temperature, the sheath preferably has a wall thickness of from 0.3 mm to 3 mm, in particular from 0.5 mm to 1.5 mm, preferably from 0.5 mm to 1 mm.

A surfactant formulation in the sense of the present invention may comprise and in particular consist of a single liquid surfactant. However, a surfactant formulation according to the present invention may also comprise or consist of two, three, four or more different surfactants. Preferably, the surfactant formulation consists of one or two different liquid surfactants.

Most preferably, the at least one liquid surfactant of the surfactant formulation is a nonionic surfactant. Nonionic surfactants are particularly useful for improving the rinse performance of machine-based cleaning of hard surfaces, and particularly dishes.

The at least one surfactant of the surfactant formulation is therefore in particular a preferably nonionic surfactant which has a cloud point T _CP in the range from 20 ° C to 75 ° C, in particular from 40 ° C to 75 ° C, preferably from 50 ° C to 70 ° C. having. Corresponding surfactants are well known to the person skilled in the art.

Particularly preferably, the at least one liquid surfactant of the surfactant formulation is a low foaming, in particular ethoxylated and / or propoxylated nonionic surfactant. Suitable examples are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters. Particularly preferred are nonionic surfactants from the group of alkoxylated alcohols. Particularly preferred nonionic surfactants are alkoxylated, advantageously ethoxylated or ethoxylated and propoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and / or propylene oxide (PO) per mole of alcohol. The alcohol radical can be linear or preferably methyl-branched in the 2-position, or linear and methyl-branched radicals can be present in the mixture as they are usually present in oxo alcohol radicals. Particularly preferred are alcohol ethoxylates in which the primary alcohol has 8 to 15 C atoms and in particular 10 to 12 or 13 C atoms. The corresponding alcohol is ethoxylated or ethoxylated and propoxylated. The degree of alkoxylation is preferably 1 to 12 mol Alkyloxidpromol, alcohol in particular 2 to 10 mol and more preferably 6 to 12 mol. If the alcohol is only ethoxylated, this is to be understood as the amount of EO, the alcohol is ethoxylated and propoxylated, so This is the amount of EO and PO to understand.

Particularly preferred nonionic surfactants which are used in a surfactant formulation according to the invention are linear or branched, in particular branched, alcohol ethoxylates, the alcohol having 10 to 15 and in particular 10, 11, 12 to 15, or 13 carbon atoms. The average degree of ethoxylation is 2 to 10 moles of ethylene oxide (EO) per mole of alcohol, in particular 3 to 9, preferably 3 to 8 and in particular 3 to 6. Likewise, the nonionic surfactant is preferably an alcohol-ethylene oxide-propylene oxide addition product, and in particular a C _{8 -20-} Alcoholpolyalkylenglycolether, in particular a C _10-18 -Alkoholpolyalkylenglycolether, preferably a C _10-12 - or C _11-15 -Alkoholpolyalkylenglycolether.

In an embodiment in which the present invention relates to a washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent having two or more phases, wherein a first of the phases, a solid, in particular compressed phase, and the other second phase, a surfactant formulation according to the invention in a water-soluble casing, not only the second phase in the sense of the surfactant formulation may have a surfactant. Also, the first, preferably solid and in particular compressed or compacted phase may have one, two, three or more surfactants. A corresponding surfactant / surfactants is / are preferably selected from the group of anionic, nonionic and / or cationic surfactants. In particular, both phases comprise at least one nonionic surfactant.

A particularly preferred washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwasher detergent, thus comprises a first solid phase in the form of a compacted tablet and a second phase in the form of the surfactant formulation according to the invention, wherein both the first and the second phase comprise at least one nonionic surfactant exhibit. In a further preferred embodiment, the first solid phase may itself comprise one, two or more solid phases, a phase being visually distinguishable by the end user from one another without further aids. According to the invention, a phase is thus a self-contained spatial area of a washing or cleaning agent, in particular a dishwashing agent, preferably a machine dishwashing agent, which is visually distinguishable from another area without further aids.

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. They are preferably contained in the at least one first and / or at least one second phase. The same or different surfactants may be included in the phases. For the inventive surfactant formulation in the second phase, the aforementioned surfactants are particularly preferred.

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 dishwashing detergents, preferably automatic dishwashing detergents, contain in the at least one first and / or second phase 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.Particularly preferred nonionic surfactants which have proven themselves in the context of the present invention are 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.

Further preferably used nonionic surfactants are those 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 having 4 to 22 Carbon atoms; Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; 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 R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y -CH ₂ CH (OH) -R ² , where R R ¹ and R ² independently represent an alkyl 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 -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 where 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 represents} 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 of one another 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 "O) _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.

neben einem Rest R¹, welcher für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen steht, weiterhin einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest R² mit 1 bis 30 Kohlenstoffatomen aufweisen, wobei n für Werte zwischen 1 und 90, vorzugsweise für Werte zwischen 10 und 80 und insbesondere für Werte zwischen 20 und 60 steht. Insbesondere bevorzugt sind Tenside der vorstehenden Formel, in denen R¹ für C₇ bis C₁₃, n für eine ganze natürliche Zahl von 16 bis 28 und R² für C₈ bis C₁₂ steht.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 of 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 is} 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 solid 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 phase is preferably from 0.5% by weight to 30% by weight, preferably 5% by weight .-% to 25 wt .-% and in particular 10 wt .-% to 20 wt .-% is.

In a further preferred embodiment the nonionic surfactant of the solid 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 which R ¹ and R ² independently represent an alkyl group or alkenyl group 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. Especially preferred particular 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 are independently saturated alkyl radicals having from 4 to Represent 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.

In addition, said solid phase can further customary in the art auxiliaries, such as enzymes, builders, fragrances, other solvents, bleach activators, bleach catalysts, thickeners, sequestering agents, electrolytes, corrosion inhibitors, especially silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, additives to improve the operational and drying characteristics, to adjust the viscosity, to stabilize, UV stabilizers, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ^® AGS Cognis, or mixtures comprising, for example Euperlane ^® Cognis), preservatives (for example, the technical also known as Bronopol 2-bromo-2-nitro-1,3-diol (CAS 52-51-7), which is commercially available for example as Myacide ^® BT or as Boots Bronopol BT from Boots) , antimicrobial effects offe (disinfectant), pH adjusting agent in amounts of usually not more than 5 wt .-%. The corresponding auxiliaries may also be included in the phase with the surfactant formulation according to the invention. However, this phase is preferably free of excipients and comprises exclusively surfactants.

If a washing or cleaning agent according to the invention, in particular a dishwashing detergent, preferably an automatic dishwashing detergent, has an enzyme or an enzyme preparation, then the US Pat corresponding phase preferably nonionic surfactants having one or more free hydroxy on one or both terminal alkyl radicals. Corresponding hydroxy mixed ethers can improve the stability of the enzymes.

Suitable anionic surfactants in the washing or cleaning agents are all anionic surface-active substances. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group of 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. If the washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, has anionic surfactants, these are preferably in the first phase. The second phase particularly preferably comprises only nonionic surfactant (s) as surfactant (s).

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.

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.

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, that is, the agents contain less than 0.1% by weight of phosphate (e).

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.

If builders are present in the agent according to the invention, they are preferably exclusively in the at least one first phase. 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 the 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 from 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 preferably present only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below, in the washing or cleaning agents, in particular dishwashing agents, preferably automatic dishwashing agents and in particular in the at least one second phase 5 wt .-%, more preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the detergent or cleaning agent used. Alternative washing or cleaning agents according to the invention are free of alkali metal hydroxides.

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

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae and the improved for use in detergents developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from β. 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 preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein. Particular preference is given to detergents which, based in each case on their total weight, are from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight, of the particular enzyme preparations contain.

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, in particular dishwashing detergent, preferably automatic dishwashing detergent, 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, in particular in the at least one first phase, 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 above-mentioned salts (especially zinc salts) may polyethyleneimines described, for example, under the name Lupasol ^® (BASF) can be obtained, preferably in an amount of 0 to 5 wt .-%, particularly 0.01 to second %, are used as glass corrosion inhibitors.

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 automatic dishwasher 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, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe-Cu and Ru ammine complexes 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 ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (with OAc = OC (O) CH ₃ ).

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

The washing or cleaning agent according to the invention, in particular dishwashing detergent, preferably automatic dishwashing detergent, can be tightly enveloped by a water-soluble film or contained in a water-soluble bag.

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

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

enthalten."Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

contain.

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

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

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

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

The water solubility of polyvinyl alcohol can be 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.

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

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

In the case of a tight envelope, in each case a disposable portion of the washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, is enclosed. For the coated detergent or cleaning agent portion according to the invention, it is important that the coating rests close to its surface at any point of the tablets. Ideally, the envelope is even under tension, which is not absolutely necessary. This dense covering of the envelope is conducive to disintegration: upon first contact with water, the envelope will pass a small amount of water at some point, and at first it does not need to dissolve at all. At this point, the disintegrant contained in the tablet begins to swell. As a result, the wrapper suddenly ruptures as a result of the volume increase of the tablet and releases the tablet. If the wrapper is not tight, the mechanism described here will not work as the tablet can swell without bursting the wrapper. In this case, the use of a swellable disintegrating agent is superior to a gas-developing system, since its explosive effect in each case leads to a rupture of the casing. In a gas-evolving system, the explosive effect may "fizzle out" of the enclosure by leakage of the gas from a leak.

Preferred detergent or cleaning agent portions according to the invention are characterized in that the distance between the disposable portion and water-soluble coating over the entire surface is 0.1 to 1000 μm, preferably 0.5 to 500 μm, particularly preferably 1 to 250 μm and in particular 2.5 to 100 microns, is.

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

For example, this wrapping can be done by placing a water-soluble lower film on a conveyor chain or a mold (s) tool, then one or more detergent or cleaning agent portion (s) are placed on the lower film; Subsequently, a water-soluble upper film placed on the washing or cleaning agent portion (s) on the lower film and then fixed on the lower film including the washing or cleaning agent portion (s), Alternatively, this step can also be done by a single-strand film, which then as Hose is placed around the disposable portions. This is followed by sealing and optional cutting of the films. Subsequently, then the shrinking of the film by the use of hot air or infrared radiation, optionally with pressing done.

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

In the following exemplary embodiments, the inventive surfactant formulation and detergents or cleaners according to the invention, in particular dishwashing agents, preferably automatic dishwashing detergents, are described in a nonlimiting manner.

EXAMPLES

Example 1: Clouding points of different surfactants

The cloud point measurement was carried out as a 10% by weight solution in 25% by weight of butyl diglycol in water. The results are shown below. Surfactant no. T _CP / ° C surfactant S1 35 C10-12 10 (EO + PO) (C _10-12 Alcohol Polyalkylene Glycol Ether) S2 55 C10-12 6PO4EO (C _10-12 Alcohol Polyalkylene Glycol Ether) S3 70 C13 6EO (C ₁₃ -alcohol-polyethylene glycol ether) S4 74 Fatty alcohol alkoxylate

Example 2: Determination of the Release Temperature

To determine the release temperature, 5 gelatin capsules filled with a blue-colored surfactant formulation were used. As were soft gelatin capsules with a wall thickness of 0.8 mm. The cloud point of the surfactant formulation was 50 ° C to 70 ° C.

A beaker (volume: 2L, flat shape) filled with 1.5L water (tap water, 14-16 ° dH, T = 20 ° C, p = 1bar) was fitted with a stir bar (magnetic stirrer) and placed on a hot plate. Inside the beaker was a metal device that ensured a space between the stir bar and the gelatin capsule without interfering with the agitation.

The gelatin capsules were placed on a watch glass (diameter: 8 cm) and carefully placed on the watch glass on the metal device in the beaker. The capsules were completely surrounded by water. Inside the beaker, there was also a rod thermometer, which measured the temperature of the water in the amount of the surfactant formulations according to the invention.

The water in the beaker was stirred at a stirring speed of 800 rpm and heated at a heating rate of about 1.5 ° C / min.

From a temperature of 32 ° C, the dissolution of the gelatin capsules could be observed. This was reflected in the separation of streaks on the capsule walls and the associated slight turbidity of the water. From a temperature of 39 ° C to 40 ° C, the exit of the blue-colored surfactant from the capsule residues could be observed. The release temperature was thus 39 ° C to 40 ° C and was thus below the cloud point of the surfactant formulation. The capsules had lost their original round shape.

machine

The solubility was additionally determined in the machine. For this purpose, capsules were placed in the dosing box of the Bosch dishwasher (Bosch SMS68M62 (without dishes) as described in example 2a) (small basket into which the tablet falls when the dosing box is opened.) The program eco 50 ° C variospeed was started. The temperature in the machine was monitored by means of an attached thermometer and the machine was briefly opened at 2 ° C. intervals and the condition of the gelatine capsules was checked at a temperature of 36 ° C. Before the capsule had reached a temperature of 40 ° C., the capsules were already deformed and dissolved so far that the content was dispensed into the rinsing liquor.

Example 2: clear rinse effect

To determine the rinsing effect, selected and defined dishes were rinsed 4 times and visually scrapped after the 2nd, 3rd and 4th rinsing cycles. The first rinse served as a conditioning of the dishes.

Rinse creases based on the visual appearance of the dry ware (porcelain, glasses, plastic parts and stainless steel) were assigned as parameters.

Per wash, 100 grams of soil (made from 4 grams of margarine, 4 grams of potato starch, 1.6 grams of NaCl, 16 grams of whole egg and 74.4 grams of water) were dosed to simulate a normally soiled load. Standard household machines (Miele G698 / Bosch SMS 64) were used in a 50 ° C program with a water hardness of 21 ° dH.

After completing the rinse cycle, the machine was fully opened for 30 minutes and then the clear rinse effect was visually determined in the black box (black painted room, D6500 daylight lamp). On the crockery and cutlery remaining dried water drops, streaks, coverings and films were scored on a scale of 1-10. 10 means no drops / films, 1 means heavy drops / filming. The results for the recipes tested are listed in the tables as arithmetic mean.

The following results were achieved with the following detergents and cleaners:

MGDA free formula

A phosphate-free, MGDA-free commercial dishwashing detergent in the form of a tablet with core (V1) was used. Then, the core was replaced by a surfactant-filled capsule according to the invention, various surfactants S1-S3, which are described in Example 1, were used (E1, E2, E3). As a comparison, the tablet without core was used (V2). Example no. product Glass metal porcelain plastic Spotting (Miele) V1 commercial dishwashing detergent (tablet with core) 4.1 2.6 3.9 1.3 E1 Tablet without core + 1 g S1 4.1 0.6 3.7 1.7 E2 Tablet without core + 1 g S2 4.0 n / A 4.7 1.7 E3 Tablet without core + 1 g S3 4.0 2.6 4.1 1.4 V2 Tablet without core 2.0 0.7 3.2 1.6

When omitting the core (V2), a worsening of the clear rinse effect on several substrates could be seen.

With the addition of the surfactants according to the invention, this deficit can be partially reversed (E1, E2, E3). Depending on the cloud point (T _CP ), it can be seen that a lower T _CP surfactant is poorer in metal (E1), whereas a high T _CP surfactant (E2, E3) can compensate for all deficiencies. Only a surfactant with medium T _CP (E2) can even gain an advantage in porcelain.

MGDA-containing formulation

Example no. product Glass metal porcelain plastic Spotting (Bosch) V3 MGDA-containing dishwashing detergent (tablet with core) 4.6 4.8 3.9 3.6 E4 Tablet without core + 1 g S4 3.9 0.3 3.4 1.9 E5 Tablet without core + 1 g S2 4.7 4.7 4.4 4.3 E6 Tablet without core +1 g S3 4.6 4.3 4.2 4.0

Here, a surfactant formulation according to the invention S2, S3, S4 was added to a phosphate-free, commercially available MGDA-containing formula. The procedure was as described above.

Again, the high T _CP surfactant shows a worsening of the rinse performance. The surfactant S2 again shows the best performance with improvements to porcelain and plastic.

Example 3: Coating inhibition

The deposit inhibition was determined in Miele GSL dishwashers in the 65 ° program after 30 cycles incl. Dirt loading at a water hardness of 21 ° dH.

The characteristics assigned were topping marks on the basis of the visual appearance of the dry items to be washed (porcelain, glasses, plastic parts and stainless steel). Shown in the result table are the arithmetic mean values of the notes of all the pieces of the respective substrates.

Per wash, 50 g of soil (71.14% city water (14-16 ° dH), 5.08% egg yolk, 2.54% tomato ketchup, 2.54% mustard, 5.08% H-milk 1.5% fat , 2.54% gravy, 0.51% potato starch, 0.41% benzoic acid, 7.11% margarine and 3.05% butterfat) to simulate a normally soiled load.

After completion of the rinse cycle, the crockery items in the black box (black painted room, D6500 daylight lamp) were visually scored. On crockery and cutlery, streaks, coatings and films are rated on a scale of 1 to 10. 10 means no coatings / films, 1 means strong coating / film formation.

The two best surfactants from Example 2 (S2, S3) were used, each with 1 g / job and 0.5 g / job dosage. Example no. product Glass glass plate porcelain plastic metal V4 commercial dishwashing detergent in the form of a tablet with core (MGDA free) 5.0 5,7 3.7 7.0 7.8 E7 Tablet without core with 500 mg S2 7.9 7.0 7.5 6.5 8.3 E8 Tablet without core with 1000 mg S2 7.9 7.0 7.5 5.5 8.6 E9 Tablet without core with 500 mg S3 5.8 5.3 6.8 6.0 8.6 E10 Tablet without core with 1000 mg S3 7.8 7.0 7.2 6.0 8.7

When using the surfactants (with T _CP of 55 ° C to 70 ° C) (E7, E8, E9, E10) an improvement in the inhibition of the coating was found. It was better to use less amount of S2 surfactant to achieve optimal performance.

Example 5: Fat deposition in the filter

A commercial phosphate-free dishwashing detergent was used as in V1.

30 rinse cycles were performed as described in Example 3. Then the amount of fat in the filter of the dishwasher was determined.

The experiment was repeated according to the invention with a dishwashing agent E2 according to the invention. No. Amount of fat [g] V1 3.2 E2 1.6

The surfactant formulation according to the invention thus significantly reduces the amount of fat deposited in the filter.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 0851024 A [0006]
• WO 2004/031338 A [0126]
• WO 2003/099985 A [0126]

Claims (8)

A surfactant formulation having a cloud point T _CP in a water-soluble casing having a release temperature T _F , characterized in that the surfactant formulation comprises one, two or more liquid surfactants and the cloud point T _{CP of} the surfactant formulation is from 5 ° C to 40 ° C above the release temperature T _E the serving lies. Surfactant formulation according to Claim 1 , characterized in that the cloud point T _CP in the range of 20 ° C to 75 ° C, in particular from 40 ° C to 75 ° C, preferably from 50 ° C to 70 ° C. Surfactant formulation according to Claim 1 or 2 , characterized in that the water-soluble envelope is a bag or a capsule, in particular a capsule. Surfactant formulation according to one of Claims 1 to 3 , characterized in that the water-soluble wrapper is a gelatin capsule. Surfactant formulation according to one of Claims 1 to 4 , characterized in that the envelope has a wall and the wall thickness is 0.3 mm to 3 mm, in particular 0.5 mm to 1.5 mm, preferably 0.5 mm to 1 mm. Surfactant formulation according to one of Claims 1 to 5 , characterized in that the at least one surfactant is at least one nonionic surfactant. Detergents or cleaning compositions comprising a surfactant formulation according to one of Claims 1 to 6 , Detergents or cleaning agents after Claim 7 characterized in that it has two or more phases, one of the phases being a solid, in particular compressed, phase, and the other phase being a surfactant formulation according to any one of Claims 1 to 6 is.