EP3102660B1 - Multi-phase pre-portioned detergent - Google Patents

Description

The present invention relates to pre-portioned multi-phase detergents, in particular automatic dishwashing detergents and their use.

Hard surface cleaners, such as dishwashing detergents, are available to the consumer in a variety of forms. In addition to the traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance. The consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.

The importance of concentrated compositions, in which in particular the water content is reduced compared to conventional compositions, increases. Thus, for the consumer, compositions whose water content is as low as possible are particularly desirable.

Further, consumers have become accustomed to conveniently dosing pre-portioned automatic dishwashing detergents and have been using these products primarily in the form of tablets. In order to bring a multi-phase dishwashing detergent, which combines the above-mentioned advantages of solid and liquid compositions, into a pre-portioned form, the use of water-soluble films in the form of bags or multi-chamber shaped bodies lends itself.

Disposable portions, in particular water-soluble bags or multi-chamber tablets made of water-soluble material, 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. For the consumer, it is therefore a nuisance if the bags lose their attractive appearance.

Multifunctional automatic dishwashing detergents save the user the separate use of rinse aid and the refilling of salt in the dishwasher. In addition to suitable surfactants, certain builders are used in their formulations which achieve a good rinse aid result and counteract the formation of coatings even at higher water hardness.

Modern dishwashers provide for dosing of cleaning products before a dosing, which automatically opens during the wash program and releases the product. The size of the metering chamber is however limited in its capacity.
For a good cleaning performance, however, sufficient quantities of various functional blocks of the dishwashing detergent formulation, such as builder, alkalinity, enzymes, surfactants, etc., must be made available. This means that the available volume of the dosing chamber must be used optimally in order to produce a sufficient amount of the active substances and thus a good cleaning performance.

The object of the present invention was to provide a multi-phase pre-portioned detergent, in particular dishwashing detergent, preferably automatic dishwashing detergent, with at least one liquid and at least one solid, preferably pulverulent phase, which fits into the dispensing compartment of the dishwasher and still exhibits good cleaning performance.

This object is achieved by a pre-portioned detergent, preferably machine dishwashing detergent, in a package having at least two compartments, comprising at least one solid, preferably pulverulent phase and at least one liquid phase, characterized in that the detergent contains 2 to 20% by weight, in particular 2 to 10% by weight (based on the total weight of the composition) of polymeric or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers and the solid phase (or solid phases) less than 1 wt .-% (based on the weight of the solid phase), polymeric and / or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers, wherein the cleaning agent contains less than 1% by weight of phosphate, based on the total weight of the cleaning agent.

In particular in cleaning agents, in particular in those which contain only small amounts of phosphate or which are substantially free of phosphates, co-builders must be used in addition to the phosphate-containing and / or phosphate-free builders in order to achieve a sufficiently high complexation of divalent cations from the used Rinse water, usually local tap water to ensure that otherwise leave on the dishes coverings.

Polymeric, polycarboxylate-containing cobuilders are usually marketed as aqueous preparations. In aqueous machine dishwashing detergents, they are therefore usually formulated directly into the aqueous cleaning agents. If they are to be used in solid formulations, they must first be dried time-consuming and energy-intensive and then formulated as granules. Then they are particularly suitable for solid, especially granular products.

For use in liquid, non-aqueous cleaning agents, especially in machine dishwashing detergents, the aqueous preparations of co-builders are not suitable due to the high water input.

In a multi-phase pre-portioned detergent, in particular machine dishwashing detergent, which contains at least one solid and one liquid phase, which is optimized in terms of the dimensions of the metering chamber in dishwashers, a space-saving formulation must be used in particular.

If it is desired to use polymeric polycarboxylate-containing components and / or polymers containing sulfonic acid groups in liquid cleaning agents, in particular liquid machine dishwashing detergents, which are preferably essentially free of water, the solid components must be finely distributed (as a dispersion) in an organic matrix and also stable in storage in the dispersion remain and must not sediment. Most preferably, in such liquid formulations that are substantially free of water, the dried (de-watered) polycarboxylate-containing component and / or the sulfonic acid group-containing polymers are used in finely ground form.

The cleaning agent according to the invention, in particular machine dishwashing detergent, contains a total of 2 to 20 wt .-%, in particular 2 to 10 wt .-% (each based on the total weight of the composition, ie the total weight of all phases) polymeric or co-polymeric polycarboxylates or sulfonic acid-containing polymers.

The cleaning agents according to the invention may in particular contain a sulfonic acid group-containing polymer (hereinafter also referred to as sulfopolymer). The proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, most preferably 2.0 to 14 wt .-%, in particular from 4 to 14 wt .-%, especially from 4.5 to 12 wt .-%. The sulfopolymer is used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which may optionally additionally be ground. The sulfopolymer used is preferably a copolymeric polysulfonate, for example a hydrophobically modified copolymeric polysulfonate.
In particular, the inventive cleaning agent contains a total of 2 to 20 wt .-%, in particular 2 to 10 wt .-% (each based on the total weight of the composition) (co) polymeric polycarboxylates and sulfonic acid-containing polymers.

In a most preferred embodiment, the solid phase (s) are substantially free of polymeric or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers. In this context, this means that the solid phase or phases are less than 1% by weight (based on the weight of the solid phase or the total weight of all solid phases), polymeric or co-polymeric polycarboxylates and sulfonic acid group-containing Contain polymers. The cleaning agent itself preferably contains from 2 to 20% by weight (based on the total weight of the cleaning agent (total weight of all phases)) of polymeric or co-polymeric polycarboxylates and sulfonic acid-containing polymers.

The polymeric or copolymeric polycarboxylates are suitable according to the invention as builders, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g / mol. The polyacrylate or the polyacrylates are used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which may optionally additionally be ground.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of about 1000 to 20,000, in particular from 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of about 1000 to 10,000, of 2,000 to 10,000 g / mol, and particularly preferably of 3,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

For the purposes of the invention, polycarboxylic acids (carboxylic acids having more than one carboxylate function) in monomeric form are not to be understood as polymeric polycarboxylates.
In particular, it does not include those polycarboxylic acids as described in detail below as organic cobuilders and which may be present in the liquid phase (s) as well as the solid phase (s) according to the invention (ie they are is not included in the amounts indicated for polymeric polycarboxylates and are thus not taken into account for the quantitative restrictions).

The cleaning agents according to the invention can, as described above, contain a sulfonic acid group-containing polymer (also referred to below as sulfopolymer). The sulfopolymer used is preferably a copolymeric polysulfonate, for example 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.

As unsaturated carboxylic acid (s), it is particularly preferred to use 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, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as above is defined or is -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, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-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 sulfonic acid-containing monomers are 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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals 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

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 which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-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 partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for 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 molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a further preferred embodiment, in addition to the 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 automatic dishwashing detergents according to the invention.

Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.

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 is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 1 to 22 carbon atoms or a 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-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-alpha-olefin, 2-styrene, alpha Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, Acrylsä ureoctylester, Methacrylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, and Methacrylsäurebehenylester N- (Behenyl) acrylamide or mixtures thereof.

The monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Another important class of builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.

Particularly preferred is the use of MGDA or GLDA or salts thereof. In particular, MGDA is used. MGDA can be used preferably as granules, and particularly preferably in the solid phase. Particular preference is given to those MGDA granules which contain as little water as possible and / or have low hygroscopicity.

Particularly preferred is the use of MGDA or salts thereof in a total amount of 3 to 50 wt .-% based on the total weight of the cleaning agent.

The detergents may contain, in particular, phosphonates as 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. Phosphonate-containing components are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
With regard to the proportion of the phosphonate unit (independently of the hydroxyalkane and / or aminoalkane portion), the compositions according to the invention contain from 0.01 to 25% by weight, preferably from 5 to 20% by weight, from 8 to 15% by weight. % Phosphonate (in each case based on the total weight of the composition). According to the invention, the phosphonates are preferably contained in the solid phase (s).

"Substantially free of water" as used herein means that a composition contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight. Contains% water. The water content, as defined herein, refers to the water content determined by Karl Fischer titration.

According to the invention, the liquid phase is according to "substantially free of water", this means that the liquid phase less than 7 wt .-%, in particular less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt .-% water. The water content as defined herein refers to the water content determined by Karl Fischer titration.

In particular, all liquid phases and all solid phases of the detergent of the invention are "substantially free of water", i. each of the individual phases contains in each case less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, particularly preferably less than 1% by weight of water (in each case based on the total weight of the respective phase ).

"Liquid" as used herein with respect to the cleaning agent of the present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian fluids having a yield point.

"At least one" as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more.

"solid" as used herein with respect to the cleaning composition of the invention includes all solid compositions, and includes in particular powdered, granulated, amorphous, compressed, in particular pressed, tabletted compositions. In addition to powdery constituents, powdery compositions may also partially contain granules.

The cleaning agent according to the invention is present in a water-soluble packaging.
The water-soluble packaging allows a portioning of the detergent. The amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.

Preferably, this is a disposable portion, the detergent is preferably in an amount sufficient to carry out the cleaning, in machine dishwashing detergents in particular a cycle or a complete program run of a dishwasher).

The water-soluble packaging in this case has at least two or more spatially separated compartments (chambers) in which spatially separated at least one solid, preferably pulverulent, and at least one liquid phase are filled.

Particularly suitable are two-chamber bags or two-chamber tablets which contain a solid and a liquid phase in separate compartments.

Furthermore, particularly multi-chamber packages (multi-chamber bags or multi-chamber shaped bodies) are suitable which contain a powdery phase in at least one of the separated compartments and a liquid phase in at least one other compartment. A phase is understood here to mean a detergent (partial) composition which, in combination with the other phase or phases, results in a cleaning agent, in particular a machine dishwashing detergent.

The cleaning agent according to the invention, in particular machine dishwashing detergent, can also be present in a water-soluble packaging, which in particular contains more than two, so for example, three, four, five or six compartments.

Preferably, the package contains two, three or more chambers (compartments), wherein one, two or more of these chambers are filled with liquid phases, which are preferably different from each other, and in particular one or more mutually different ingredients.

Preferred are pre-portioned detergents in which the water-soluble package contains one, two or more solid phase chambers (compartments) in addition to one, two or more liquid phases. When two or more solid phases are provided, it is preferred that they be of different composition and / or have a different solid form.

Particular preference is given to pre-portioned cleaning compositions which have at least one solid, preferably at least one pulverulent phase and at least one liquid phase in separate compartments.

Also preferred are pre-portioned detergents which have at least one solid, preferably at least one compressed phase and one liquid phase in separate compartments.

It may also be preferable for the pre-portioned cleaning agent to have two or more solid phases, of which at least one powdery and at least one compressed and at least one, also two, three or more liquid phases are in each case separate compartments.

It is further preferred that the pre-portioned detergent, in particular the multi-chamber bag, contains a solid, one of which is different powdery and two liquid phases in each separate compartments.

According to a preferred embodiment, the at least one liquid phase in the cleaning agent according to the invention is substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol;
Substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, means that in the liquid phase (in the case of several liquid phases in each individual liquid phase) less than 5 Wt .-%, preferably less than 3 wt .-% of such organic compounds are contained, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol. In particular, according to the invention, the presence of usually short-chain organic solvents having an average molecular weight of less than 175 g / mol, such as dipropylene glycol dimethyl ether, preferably less than 150 g / mol, such as decane, octane, dipropylene glycols, glycerol, propanediols, monoethanolamine, diethanolamine be avoided, which are particularly prone to migration between the compartments.

In the (or the liquid phase (s)), said organic components, preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, in each case only to a proportion of less be contained as 5 wt .-%, preferably of less than 3 wt .-% (each based on the composition of the individual liquid phase).

The total amount of the organic components contained in the liquid phase or the liquid phases, preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, is not more than 20 wt .-% (relative on the total weight of each liquid phase).

If the pre-portioned cleaning agent, in particular machine dishwashing detergent, comprises a plurality of liquid phases in separate compartments, it is very particularly preferred according to the invention that each of the liquid phases is essentially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol (except the components mentioned under a), since otherwise there is a migration of the components between the individual liquid phases in the separate compartments.

According to a preferred embodiment, the liquid phase (are the liquid phases) of the cleaning agent according to the invention, in particular machine dishwashing, substantially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol and at 20 ° C and 1 bar are liquid.

• R¹ ausgewählt ist aus -H, -CH₃, geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten,C_2-24-Alkyl- oder -Alkenylrest steht;
• R², R³, R⁴, R⁵,jeweils unabhängig voneinander ausgewählt sind aus -H, -CH₃,-CH₂CH₃, -CH₂CH₂CH₃, CH(CH₃)₂, vorzugsweise -H oder -CH₃;
• R⁶ ausgewählt ist aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, -CH₂-CH₂-CH₂CH₃, -CH₂CH(CH₃)₂, -C(CH₃)₃, C_5-24-Alkyl- oder -Alkenyl, sowie-CH₂CH(OH)R⁷
• mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl-oder-Alkenylrest;
  und
• w, x, y, z jeweils unabhängig voneinander Werte von 1 bis 120 annehmen können und wobei x, y und/oder z =0 sein können,

The pre-portioned detergents according to the invention, in particular machine dishwashing detergents, preferably comprise in the liquid phase, in one of the liquid phases, in particular in all liquid phases,
at least one, preferably two, three, four or more alkoxylated components according to formula I.

R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ (Formula I)

in which

• R ^{1 is} selected from -H, -CH ₃ , straight-chain or branched, saturated or mono- or polyunsaturated, C _2-24 alkyl or alkenyl radical;
• R ² , R ³ , R ⁴ , R ^{5 are} each independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , preferably -H or -CH ₃ ;
• R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-24 alkyl or alkenyl, and -CH ₂ CH (OH) R ⁷
• with R ^{7 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical;
  and
• w, x, y, z can each independently of one another assume values of 1 to 120 and where x, y and / or z = 0,

The liquid phase or the liquid phases of the cleaning agents according to the invention contain at least one component according to a).

Preferably, the liquid phase or contain the liquid phases of the cleaning agent according to the invention at least one component according to a), which is selected from the polyalkylene glycols of formula (I) with

R'-O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶ (Formula I)

R ¹ = H, R ⁶ = H; R ² , R ³ , R ⁴ , R ⁵ , each independently selected from H, -CH ₃ , and w, x, y, z = 1 to 50.

Under the o.g. Formula (I) are also a large part of the nonionic surfactants to grasp. Low-foaming alkoxylated nonionic surfactants, in particular ethoxylated, low-foaming nonionic surfactants, are preferably used with preference. In preferred embodiments, the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.

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.

Particularly preferred nonionic surfactants used are 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 (I)

R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; R ² , R ⁴ , R ⁶ each = -H; each group R ³ or R ^{5 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.

Thus, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.

• R¹ für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• R², R³, R⁴, R⁵,jeweils unabhängig voneinander ausgewählt sind aus -H, -CH₃,-CH₂CH₃, -CH₂CH₂CH₃, CH(CH₃)₂, vorzugsweise -H oder -CH₃;
• R⁶ ausgewählt ist aus -CH₂CH(OH)R⁷
  mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder -Alkenylrest;
  und

w, x, y und z für Werte zwischen 1 und 120 stehen, wobei x, y und/oder z auch 0 sein können.Further preferred nonionic surfactants here are those of the general formula

R ² -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶

With

• R ^{1 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• R ² , R ³ , R ⁴ , R ^{5 are} each independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , preferably -H or -CH ₃ ;
• R ^{6 is} selected from -CH ₂ CH (OH) R ⁷
  R ^{7 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical;
  and

w, x, y and z are values between 1 and 120, where x, y and / or z can also be 0.

With these surfactants, also referred to below as "hydroxy mixed ethers", the cleaning performance of the preparations according to the invention can be significantly improved both in comparison to surfactant-free system and in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols contain

• R¹ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• R²=H,
• R⁶ ausgewählt ist aus -CH₂CH(OH)R⁷
  mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder -Alkenylrest;
  und
• w=1 bis 120, vorzugsweise 10 bis 80, insbesondere 15 bis 40; und x,y,z=0 ist.

Finally, the nonionic surfactants of the general formula (I) have proven to be particularly effective.

R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶

With

• R ^{1 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• R ² = H,
• R ^{6 is} selected from -CH ₂ CH (OH) R ⁷
  R ^{7 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical;
  and
• w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.

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

Also preferred are also surfactants of the formula (I)

R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) x- (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶

wherein R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, y, z = 0; R ² = CH ₃ , R ³ = -H, R ⁶ = a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and w for values of 1 and 2 (for mixtures of such products also numerical values between 1 and 2, eg 1.5) and x stands for a value of at least 15.

The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

• Mit y,z=0 sowie R²=H, R⁶=-CH₂CH(OH)R⁷
• mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder -Alkenylrest;

in der R¹ unabhängig von R⁷ für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht, R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, -CH(CH₃)₂, vorzugsweise jedoch für -CH₃ steht, und w und x unabhängig voneinander für Werte zwischen 1 und 32 stehen, wobei Niotenside mit R³ = -CH₃ und Werten für w von 15 bis 32 und x von 0 und 2 (bei Mischungen solcher Produkte auch Zahlenwerte zwischen 0 und 2) ganz besonders bevorzugt sind.Preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶

• With y, z = 0 and R ² = H, R ⁶ = -CH ₂ CH (OH) R ⁷
• R ^{7 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical;

in which R ¹ independently of R ^{7 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 represents -CH ₃ , and w and x independently of one another represent values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for w of 15 to 32 and x of 0 and 2 (in the case of mixtures of such products also numerical values between 0 and 2) are very particularly preferred.

According to a particular embodiment, in the case of the cleaning agent, in particular machine dishwashing detergent, at least one, preferably at least two, in particular at least three of the components according to a) have a melting point (at 1 bar) of ≦ 30 ° C., preferably ≦ 25 ° C., in the liquid phase, in particular ≤ 20 ° C on.

Thus, in particular, polyethylene glycols having an average molecular weight of from 180 to 600, and also nonionic surfactants of the general formula (I)

R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-20 -alkyl or -alkenyl radical; R ² , R ⁴ , R ⁶ each = -H; R ³ , R ⁵ = CH ₃ and the indices w, x, y, z independently represent integers from 1 to 6.

Preference may be given to one of the two or both o.g. Components having a melting point of ≦ 30 ° C., preferably ≦ 25 ° C., in particular ≦ 20 ° C. (at 1 bar), may additionally contain other components according to a) which have a higher melting point, in particular at least one of those described above as being particularly preferred said ethoxylated hydroxy mixed ethers.

According to a further particular embodiment, the cleaning agent, in particular machine dishwashing detergent in the liquid phase, has as one of the components according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol or at least one polypropylene glycol, in particular at least one polyethylene glycol, with an average molecular weight between about 180 and approx 6000, preferably about 200 to about 5000, in particular between about 300 and about 4000, for example about 400, is included.
It is particularly preferred if a component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol, which has an average molecular weight between 300 and 600 g / mol.

Furthermore, it is particularly preferred if the liquid phase (at least one of the liquid phases, preferably the liquid phases) is a component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, preferably an average molecular weight between 3500 to 4500, in particular about 4000, (INCI: PEG 4000).

It is particularly preferred if the liquid phase (the liquid phases) has a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having an average molecular weight of about 4000 (INCI: PEG 4000).

The liquid phase or the at least one liquid phase, or the liquid phases of the cleaning agent according to the invention preferably additionally contain at least one nonionic surfactant, preferably one which also represents a component according to a) according to formula I.

• R¹ ausgewählt ist aus geradkettigen oder verzweigten, gesättigten C_8-16-Alkylresten;
• R² und R⁴ gleich -H, R³ und R⁵ gleich -CH₃ sind,
• R⁶ ausgewählt ist aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, -CH₂-CH₂-CH₂CH₃, -CH₂CH(CH₃)₂, -C(CH₃)₃, C_5-20-Alkyl (linear oder verzweigt),
• und unabhängig voneinander ausgewählt sind
• w = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
• x = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
• y = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3;
• z = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3, enthalten ist.

According to a further, particularly preferred embodiment, in the liquid phase as one of the components according to a) a component according to formula (I)

R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶

in which

• R ^{1 is} selected from straight-chain or branched, saturated C _8-16 -alkyl radicals;
• R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,
• R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-20 alkyl (linear or branched),
• and are independently selected
• w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
• x = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
• y = 0 to 6, preferably 1.5 to 4.5, 2 to 3;
• z = 0 to 6, preferably 1.5 to 4.5, 2 to 3, is included.

These components according to a) are particularly advantageous because they may optionally provide a basis for the liquid phase in addition to the liquid polyalkylene glycols, without organic components, in particular organic solvents having an average molecular weight of less than 175 g / mol, preferably from less than 150 g / mol, must be used.
It is particularly preferred in this case if in addition to one of the preferred components according to a) as a further preferred component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol having an average molecular weight between about 300 and about 5000, in particular approx 4000 g / mol is used.
Furthermore, it is particularly preferred if the liquid phase (the liquid phases) is additionally a component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, in particular PEG 4000 , having.

It is particularly preferred if the liquid phase (the liquid phases) has a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having an average molecular weight of about 4000 (INCI: PEG 4000).

In all the abovementioned embodiments, in particular the particularly emphasized combinations, it is preferred that the amount of all components mentioned according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).

• 0- 40 Gew.-% mindestens einer Komponente a) gemäß Formel (I)
  
          R¹-O-(CH₂-CH(R²)-O)_w-(CH₂-CH(R³)-O)_x-(CH₂-CH(R⁴)-O)_y-(CH₂-CH(R⁵)-O)_z-R⁶
  
  wobei
  • R¹ ausgewählt ist aus geradkettigen oder verzweigten, gesättigten C_8-16-Alkylresten;
  • R² und R⁴ gleich -H, R³ und R⁵ gleich -CH₃ sind,
  • R⁶ ausgewählt ist aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, -CH₂-CH₂-CH₂CH₃, -CH₂CH(CH₃)₂, -C(CH₃)₃, C_5-20-Alkyl (linear oder verzweigt),
  • und unabhängig voneinander ausgewählt sind
  • w = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
  • x = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
  • y = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3;
  • z = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3, enthalten ist,
• 0-40 Gew.-% mindestens eines ethoxylierter Hydroxymischethers der Formel (I)
  
          R¹-O-(CH₂-CH(R²)-O)_w-(CH₂-CH(R³)-O)_x-(CH₂-CH(R⁴)-O)_y-(CH₂-CH(R⁵)-O)_z-R⁶
  
  mit
  • ∘ R¹ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
  • ∘ R²=H,
  • ∘ R⁶ ausgewählt ist aus -CH₂CH(OH)R⁷
    mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder-Alkenylrest; und
    - w=1 bis 120, vorzugsweise 10 bis 80, insbesondere 15 bis 40; und x,y,z=0 ist.
  und
• 0-50 Gew.% Polyalkylenglycole;

According to a particularly preferred embodiment, the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective total weight of the (individual) liquid phase contains:

• 0-40% by weight of at least one component a) according to formula (I)
  
  R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶
  
  in which
  • R ^{1 is} selected from straight-chain or branched, saturated C _8-16 -alkyl radicals;
  • R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,
  • R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-20 alkyl (linear or branched),
  • and are independently selected
  • w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
  • x = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
  • y = 0 to 6, preferably 1.5 to 4.5, 2 to 3;
  • z = 0 to 6, preferably 1.5 to 4.5, 2 to 3, is contained,
• 0-40% by weight of at least one ethoxylated hydroxy mixed ether of the formula (I)
  
  R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y- (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶
  
  With
  • ∘ R ^{1 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
  • ² R ² = H,
  • ⁶ R ^{6 is} selected from -CH ₂ CH (OH) R ⁷
    with R ^{7 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical; and
    w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.
  and
• 0-50% by weight of polyalkylene glycols;

It is preferred that the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,

• 5 bis 30 Gew.-% mindestens einer Komponente a) gemäß Formel (I)
  
          R¹-O-(CH₂-CH(R²)-O)_w-(CH₂-CH(R³)-O)_x-(CH₂-CH(R⁴)-O)_y-(CH₂-CH(R⁵)-O)_z-R⁶
  
  wobei
  • R¹ ausgewählt ist aus geradkettigen oder verzweigten, gesättigten C_8-16-Alkylresten;
  • R² und R⁴ gleich -H, R³ und R⁵ gleich -CH₃ sind,
  • R⁶ ausgewählt ist aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, -CH₂-CH₂-CH₂CH₃, -CH₂CH(CH₃)₂, -C(CH₃)₃, C_5-20-Alkyl (linear oder verzweigt),
  • und unabhängig voneinander ausgewählt sind
  • w = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
  • x = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
  • y = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3;
  • z = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3, enthalten ist,
• 5 bis 30 Gew.-% mindestens eines ethoxylierter Hydroxymischethers der Formel (I)
  
          R¹-O-(CH₂-CH(R²)-O)_w-(CH₂-CH(R³)-O)_x-(CH₂-CH(R⁴)-O)_y-(CH₂-CH(R⁵)-O)_z-R⁶
  
  mit
  • ∘ R¹ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
  • ∘ R²=H,
  • ∘ R⁶ ausgewählt ist aus -CH₂CH(OH)R⁷
  mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder-Alkenylrest; und
  -w=1 bis 120, vorzugsweise 10 bis 80, insbesondere 15 bis 40; und x,y,z=0 ist.
  und
• 5-40 Gew.-% Polyalkylenglycole;

According to a particularly preferred embodiment, the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective total weight of the (individual) liquid phase contains:

• 5 to 30% by weight of at least one component a) according to formula (I)
  
  R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶
  
  in which
  • R ^{1 is} selected from straight-chain or branched, saturated C _8-16 -alkyl radicals;
  • R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,
  • R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-20 alkyl (linear or branched),
  • and are independently selected
  • w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
  • x = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
  • y = 0 to 6, preferably 1.5 to 4.5, 2 to 3;
  • z = 0 to 6, preferably 1.5 to 4.5, 2 to 3, is contained,
• 5 to 30% by weight of at least one ethoxylated hydroxy mixed ether of the formula (I)
  
  R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶
  
  With
  • ∘ R ^{1 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
  • ² R ² = H,
  • ⁶ R ^{6 is} selected from -CH ₂ CH (OH) R ⁷
  with R ^{7 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical; and
  -w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.
  and
• 5-40% by weight of polyalkylene glycols;

It is preferred that the amount of all of the components referred to as preferred according to a) in the liquid phase is between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,

• 5 bis 30 Gew.-% mindestens einer Komponente a) gemäß Formel (I)
  
          R¹-O-(CH₂-CH(R²)-O)_w-(CH₂-CH(R³)-O)_x-(CH₂-CH(R⁴)-O)_y-(CH₂-CH(R⁵)-O)_z-R⁶
  
  wobei
  • R¹ ausgewählt ist aus geradkettigen oder verzweigten, gesättigten C_8-16-Alkylresten;
  • R² und R⁴ gleich -H, R³ und R⁵ gleich -CH₃ sind,
  • R⁶ ausgewählt ist aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, -CH₂-CH₂-CH₂CH₃, -CH₂CH(CH₃)₂, -C(CH₃)₃, C_5-20-Alkyl (linear oder verzweigt),
  • und unabhängig voneinander ausgewählt sind
  • w = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
  • x = 1 bis 6, bevorzugt 1,5 bis 4,5, insbesondere 2 bis 3;
  • y = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3;
  • z = 0 bis 6, bevorzugt 1,5 bis 4,5, 2 bis 3, enthalten ist,
• 5 bis 30 Gew.-% mindestens eines ethoxylierter Hydroxymischethers der Formel (I)
  
          R¹-O-(CH₂-CH(R²)-O)_w-(CH₂-CH(R³)-O)_x-(CH₂-CH(R⁴)-O)_y-(CH₂-CH(R⁵)-O)_z-R⁶
  
  mit
  • ∘ R¹ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
  • ∘ R²=H,
  • ∘ R⁶ ausgewählt ist aus -CH₂CH(OH)R⁷
  mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder-Alkenylrest; und
  - w=1 bis 120, vorzugsweise 10 bis 80, insbesondere 15 bis 40; und x,y,z=0 ist.
  und
• 5-30 Gew.% Polyethylenglycole mit einem mittleren Molekulargewicht zwischen 300 und 600 g/mol sowie
• 1-20 Gew.-% Polyethylenglycole mit einem Molekulargewicht zwischen 2000 und 6000 g/mol, aufweist.

According to a particularly preferred embodiment, the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective total weight of the (individual) liquid phase contains:

• 5 to 30% by weight of at least one component a) according to formula (I)
  
  R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶
  
  in which
  • R ^{1 is} selected from straight-chain or branched, saturated C _8-16 -alkyl radicals;
  • R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,
  • R ^{6 is} selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ -CH ₂ -CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , C _5-20 alkyl (linear or branched),
  • and are independently selected
  • w = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
  • x = 1 to 6, preferably 1.5 to 4.5, in particular 2 to 3;
  • y = 0 to 6, preferably 1.5 to 4.5, 2 to 3;
  • z = 0 to 6, preferably 1.5 to 4.5, 2 to 3, is contained,
• 5 to 30% by weight of at least one ethoxylated hydroxy mixed ether of the formula (I)
  
  R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶
  
  With
  • ∘ R ^{1 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
  • ² R ² = H,
  • ⁶ R ^{6 is} selected from -CH ₂ CH (OH) R ⁷
  with R ^{7 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical; and
  w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.
  and
• 5-30 wt.% Polyethylene glycols having an average molecular weight between 300 and 600 g / mol and
• 1-20 wt .-% polyethylene glycols having a molecular weight between 2000 and 6000 g / mol.

It is preferred that the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,

• R¹ für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• R²=H,
• R⁶ ausgewählt ist aus -CH₂CH(OH)R⁷
  mit R⁷ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-26-Alkyl- oder -Alkenylrest;
  und

- w=1 bis 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40; und x,y,z=0 ist.It is very particularly preferred if, in addition to the abovementioned components, use is made of at least one ethoxylated hydroxy mixed ether of the formula (I) as further component according to a)

R ^{1 is} -O- (CH ₂ -CH (R ² ) -O) _w - (CH ₂ -CH (R ³ ) -O) _x - (CH ₂ -CH (R ⁴ ) -O) _y - (CH ₂ -CH (R ⁵ ) -O) _z -R ⁶

With

• R ^{1 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• R ² = H,
• R ^{6 is} selected from -CH ₂ CH (OH) R ⁷
  R ^{7 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-26 alkyl or alkenyl radical;
  and

w = 1 to 120, preferably 10 to 80, in particular 20 to 40; and x, y, z = 0.

Particularly preferred are in particular the C _4-22 Fettatkohot- (EO) _10-80 -2-hydroxyalkyl, especially the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxy decyl ether and the C _4-22 fatty alcohol (EO ) _40-80 -2-hydroxyalkyl ether.

In this case, it is preferred that the amount of all components mentioned as being preferred according to a) in the liquid phase is between 10 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase) ,

According to a further embodiment, in the liquid phase (the liquid phases) additionally a end-capped nonionic surfactant according to formula II

R ⁸ O [CH ₂ CH (R ⁹ ) O] _h [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ¹⁰ ,

be contained, in particular poly (oxyalkylated) nonionic surfactants of formula II
in which R ⁸ and R ^{10 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{9 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, h are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value h ≥ 2, each R ⁹ in the above formula R ⁸ O [CH ₂ CH (R ⁹ ) O] _h [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{10 may be} different. R ⁸ and R ¹⁰ 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 ⁹ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for h are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ⁹ in the above formula may be different if h ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when h is 3, the radical R ⁹ can be selected to form ethylene oxide (R ⁹ = H) or propylene oxide (R ⁹ = 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 h has been chosen here by way of example and may well be greater, with the variation range increasing with increasing h values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

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 ⁸ O [CH ₂ CH (R ⁹ ) O] _h CH ₂ CH (OH ) CH ₂ OR ¹⁰ simplified. In the latter formula, R ⁸ , R ¹⁰ and R ^{9 are} as defined above and x represents numbers of 1 to 30, preferably 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ⁸ and R ^{10 have} 9 to 14 C atoms, R ^{9 is} H and h assumes values of 6 to 15.

According to a further preferred embodiment, the amount of all components according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).

The ratio of the weight of one or more solid phases (of which preferably at least one solid phase is powdery, (in the case of several solid / powder phases the total weight of all solid and powder phases) to the weight of one or more liquid phases (in the case of several liquid phases According to the invention, preferably 1:10 to 10: 1, particularly preferably 1: 5 to 5: 1, very particularly preferably 4: 1 to 1: 2.

According to a preferred embodiment, the cleaning agent, in particular machine dishwashing detergent, is substantially free of anionic surfactants,
Substantially free of anionic surfactants as used herein means that a composition is less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, most preferably less than 1% by weight. -%, particularly preferably less than 0.1 wt .-% anionic surfactant (based on the total weight of the composition). This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.

The water-soluble coating of the cleaning agent, the packaging, 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. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.

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 in the range of 10,000 to 1,000,000 gmol ^-1 , preferably from 20,000 to 500,000 gmol ^-1 , more preferably from 30,000 to 100,000 gmol ^-1 and in particular 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 the company MonoSol LLC, for example under the designation 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 cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwasher detergents. The corresponding use is also the subject of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used. The particular embodiments described above also apply to the use or the method.

The cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.

The pre-portioned detergent according to the invention, in particular machine dishwashing detergent, is essentially free of phosphates. This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.

Substantially free of phosphates means that the total cleaning agent resulting from the addition of all phases (or all ingredients of all compartments) is preferably substantially free of phosphate-containing components. Phosphates or else phosphate-containing components in the context of the present invention are in particular phosphates, polyphosphates and pyrophosphates. However, phosphonates or hexafluorophosphate are not covered by this term. The total detergent thus contains less than 1% by weight, preferably 0.5% by weight, of phosphate based on the total weight of the detergent (i.e., the total weight of all phases (i.e., all liquid and solid phases).

The detergents according to the invention, in particular machine dishwashing detergents, comprise builders, such as, for example, zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.

Particularly suitable silicates are crystalline layered 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 are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration. 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 preferred cleaning agents, the content of silicates, based on the total weight of the cleaning agent, to amounts below 10 wt .-%, preferably below 5 wt .-%.

In various embodiments, the pH of an aqueous solution at 20 °, containing 10 wt .-% of the total cleaning agent, in a range of 7 to 14, in particular greater than 7, in particular in a range of 8 to 13, preferably 9 to 12 ,

The compositions according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances , and antimicrobial agents.

In the detergents, preferably dishwashing detergents, in particular automatic dishwashing detergents, bleaching agents can also be used. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. 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. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Preference is given to detergents, preferably dishwashing agents, in particular automatic dishwasher detergents, which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 25% by weight, very particularly preferably 4.0 to 20 wt .-% and in particular 5 to 18 wt .-% (based on the total weight of the cleaning agent) bleach, preferably sodium percarbonate.
According to a particularly preferred embodiment, in the solid phase (or in one of the solid phases) is bleach, preferably sodium percarbonate, preferably in an amount of 5 to 40 wt .-%, preferably from 10 to 20 wt .-% (based on the total weight of the solid phases).

Furthermore, the cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, may contain bleach catalysts. Useful bleach catalysts include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo complexes, more preferably from the group of manganese and / or cobalt salts and / or or complexes, in particular the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate and the complexes of manganese with 1,4,7- trimethyl-1,4,7-triazacyclononane (Mn ₃ -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Mn ₄ -TACN).

Preference is given to detergents, preferably dishwashing agents, in particular automatic dishwasher detergents, which contain from 0.001 to 1% by weight, preferably from 0.01 to 0.1% by weight (based in each case on the total weight of the cleaning agent) of bleach catalyst, preferably a Mn complex. in particular a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mn ₃ -TACN) or 1,2,4,7-tetramethyl-1,4,7-tri-azacyclononane (Mn ₄ -TACN).

In various embodiments of the invention, the cleaning agents, preferably dishwashing agents, in particular automatic dishwasher detergents, additionally comprise at least one bleach activator. 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. Of all the bleach activators known to the person skilled in the art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of the detergents used.

The bleaching agent and also bleach catalysts and / or bleach activators are preferably contained in the solid phase (s).

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix are} four identical or different, in particular two long and two short-chain, alkyl radicals and X ^{- are} an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.

The enzymes 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 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 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, or further developed, Humicola lanuginosa ( Thermomyces lanuginosus ), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, most 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, 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. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or Gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or other auxiliaries.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those 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, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.

The enzymes, in particular the amylase (s) and / or protease (s), are preferably present in (one) of the solid phase (s), preferably as granules or granules.

Glass corrosion inhibitors used are metal salts, in particular zinc salts or bismuth salts, preferably zinc salts, in particular zinc acetate. Polyethyleneimines and polyvinylamines, which are obtainable for example under the name Lupasol® or Lupamin® from BASF, in particular non-alkoxylated polyethyleneimines, are also preferably used as glass corrosion inhibitors. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.

The cleaning agents according to the invention are characterized in that they are stable on storage and even after a prolonged period, no phase separation occurs.

A further subject of the present invention is also a machine dishwashing process in which a cleaning agent according to the invention is used.

In yet another aspect, the invention also relates to the use of the cleaning agent according to the invention as a dishwashing detergent, in particular automatic dishwashing detergent.

embodiments

The inventive detergent formulation E1 (E1 according to Table 1, 2) and a corresponding comparative formulation V1 (V1 according to Table 1, 2) were prepared. The amounts indicated in the tables are in% by weight of active substance. In each case, 15 g of the solid phase were sealed into a first chamber and 5 g each of the liquid phase (E1 or V1) in a chamber next to the first chamber in a two-chamber bag made of polyvinyl alcohol.

As the bulk density of the powder phases, the weight of 1 liter of powder was determined.

The density of the liquid phases was determined by a pycnometer. From both values, the mean density of the composite product is calculated. Table 1: Formulation of the solid phase (15 g) Fixed phase E1 V1 Sodium carbonate peroxyhydrate 20 20 Sodium citrate dihydrate 18 13 Sodium carbonate (anhydrous) 20 20 Methylglycinediacetic acid, sodium salt 18 13 Bleach catalyst (containing MnTACN) 2.5 2.5 Bleach activator (TAED) 2.5 2.5 Enzyme preparation (amylase, protease) 4 4 Perfume, dye, auxiliaries 5 5 HEDP 10 10 Sulfopolymer, (partially neutralized) Na salt - 7 Polyacrylate, Na salt - 3 total quantity 100 100 Bulk density of the powder phase (in g / l) 950 800 E1 V1 PEG 400 (Mr = about 400) 20 20 PEG 4000 (Mr = approx. 4000) 6 6 C ₁₀ -C ₁₄ fatty alcohol alkoxylate (EO + 10 PO) 17 17 C ₁₀ -C _{14 end} caps capped C ₈ -C ₁₀ fatty alcohol ethoxylate (18-30 EO) 20 20 Sodium citrate dihydrate - 16 methylglycine 4 20 Sulfopolymer, (partially neutralized) Na salt 24 - Polyacrylate, Na salt 8th - Perfume, dye, auxiliaries, 1 1 total quantity 100 100 Density of the liquid phase in g / l 1150 1200 Average product density in g / l 1000 900

Example E1 according to the invention (combination of 15 g of solid phase E1 and 5 g of liquid phase E1) shows a higher average product density compared to comparative formulation V1 (combination of 15 g of solid phase V1 and 5 g of liquid phase V1). This means that the pre-portioned cleaning agent according to the invention fills a smaller volume with the same amount of active substances and thus can also be used in volume-limited metering chambers. Alternatively, such a pre-proportioned detergent with the same volume of the portion as in the comparison substance, a pre-portioned detergent with a higher weight (and thus a higher content of active ingredient per wash) can be used.

Also suitable are pre-portioned detergents of the following composition (E2). To this end, 12 g of the solid phase (E2) were sealed in a first bag of polyvinyl alcohol and 4 g of the liquid phase (E2) were sealed in a second bag of polyvinyl alcohol. Table 3: Formulation of the solid phase Fixed phase E2 Sodium carbonate peroxyhydrate 22 Sodium citrate dihydrate 8th Sodium carbonate (anhydrous) 22 Methylglycinediacetic acid, sodium salt 20 Bleach catalyst (containing MnTACN) 2.5 Enzyme preparation (amylase, protease) 4 Perfume, dye, auxiliaries 7.5 HEDP Na salt 11 C ₁₀ -C _{14 end} caps capped C ₈ -C ₁₀ fatty alcohol ethoxylate (18-30 EO) 3 total quantity 100 E2 PEG 400 (Mr = approx. 400) 20 PEG 4000 (Mr = approx. 4000) 6 C ₁₀ -C ₁₄ fatty alcohol alkoxylate (EO + 10 PO) 16 C ₁₀ -C _{14 end} caps capped C ₈ -C ₁₀ fatty alcohol ethoxylate (18-30 EO) 20 methylglycine 5 Sulfopolymer, (partially neutralized) Na salt 22 Polyacrylate, Na salt 8th Perfume, dye, auxiliaries, 3 total quantity 100

Claims (11)

1. A pre-portioned cleaning agent, preferably an automatic dishwashing agent, in a packaging having at least two compartments, comprising at least one solid, preferably powdered, phase and at least one liquid phase, characterized in that the cleaning agent contains from 2 to 20 wt.%, in particular from 2 to 10 wt.% (based on the total weight of the agent), of polymeric or co-polymeric polycarboxylates and/or sulfonic acid group-containing polymers, and the solid phase (or solid phases) contains less than 1 wt.% (based on the total weight of the solid phase) of the polymeric or co-polymeric polycarboxylates and/or sulfonic acid group-containing polymers, the cleaning agent containing less than 1 wt.% of phosphate, based on the total weight of the cleaning agent.
2. The cleaning agent according to claim 1, characterized in that the ratio of the weight of the solid phase, optionally of all the solid phases, to the weight of the liquid phase, optionally of all the liquid phases, is from 1:10 to 10:1, preferably from 1:5 to 5:1.
3. The cleaning agent according to one of the preceding claims, characterized in that at least one polyalkylene glycol, preferably polyethylene glycol, having an average molecular weight of between 160 and 6000, preferably between 200 and 5000, in particular between 300 and 4000, for example 400, is contained in the liquid phase.
4. The cleaning agent according to one of the preceding claims, characterized in that a bleaching agent, preferably in an amount of from 5 to 40 wt.%, more preferably from 10 to 20 wt.% (based on the total weight of the solid phases) is contained in the solid phase.
5. The cleaning agent according to one of the preceding claims, characterized in that the liquid phase is substantially free of water.
6. The cleaning agent according to one of the preceding claims, characterized in that at least one, preferably two or more, nonionic surfactants are contained in the liquid phase.
7. The cleaning agent according to one of the preceding claims, characterized in that the cleaning agent contains phosphonate in amounts of from 0.01 to 25 wt.%, preferably from 5 to 20 wt.%, 8 to 15 wt.% (in each case based on the total weight of the agent).
8. The cleaning agent according to one of the preceding claims, characterized in that it is a water-soluble packaging, in particular a multi-chamber pouch, in particular having two, three, four or more chambers.
9. The cleaning agent according to one of claims 1 to 8, characterized in that it is a water-soluble or water-dispersible packaging consisting of a polyvinyl alcohol-containing film.
10. The use of a cleaning agent according to one of the preceding claims 1 to 9 in a cleaning process in an automatic dishwasher.
11. A method for cleaning dishes, preferably in an automatic dishwasher, characterized in that a cleaning agent according to one of claims 1 to 9 is used.