WO2015118009A1

WO2015118009A1 - Preportioned cleaning product

Info

Publication number: WO2015118009A1
Application number: PCT/EP2015/052296
Authority: WO
Inventors: Volker Blank; Noelle Wrubbel; Martina Hutmacher; Matthias Sunder; Ulrich Pegelow; Oliver Kurth; von den Karl-Josef DRIESCH
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2014-02-06
Filing date: 2015-02-04
Publication date: 2015-08-13
Also published as: EP3102657A1; EP3102657B1; PL3102657T3; ES2675196T3; DE102014202225A1

Abstract

The invention relates to a preportioned cleaning product, in particular a machine dishwashing product, and the use thereof, said product containing at least one polyalkylene glycol having an average molecular weight of between 150 and 8000. The invention further relates to the use of the polyalkylene glycol for improving the storage stability of liquid cleaning products with a low content of water.

Description

Pre-portioned detergent

The present invention relates to pre-portioned 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 advantages of solid and liquid compositions mentioned above, into a pre-portioned form, the use of water-soluble films in the form of sachets or

Multichamber shaped articles, in particular those made of water-soluble material, such as e.g. Container made of PVA, produced by injection molding.

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 see one for the dosage of cleaning products

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 but sufficient quantities of different

Functional blocks of the dishwashing detergent formulation such as builder, alkalinity, enzymes, surfactants, etc. are provided. 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.

For this purpose, larger amounts of solid substances, in particular granular polymers have to be incorporated into the compositions. In the case of liquid, in particular water-poor, preferably anhydrous compositions, problems arise here with the separation of phases.

In particular, when such granular polymers which can be easily incorporated into hydrous products are incorporated into such low-to-anhydrous agents, these solid components usually sediment and do not leave one

satisfactory appearance, which are often associated by consumers with a loss of effectiveness of the agent.

Furthermore, in such low-water systems also frequently large amounts of surfactants, used for cleaning and in particular for a good rinse performance.

In addition to liquid at 25 to 30 ° C surfactants, waxy and solid surfactants are used, which lead to a phase separation within the low-water means, wherein the agent separates into two liquid phases.

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

This object has been achieved by a pre-portioned detergent, preferably

Machine dishwashing detergent, in a packaging with, comprising at least one liquid phase, characterized in that the liquid phase at least one polyalkylene glycol having an average molecular weight between about 1500 and about 8000, in particular between about 2000 and about 6000, in particular between about 3000 and about 4500 contains.

According to a preferred embodiment, the polyalkylene glycols are selected from

Polyethylene glycols, polypropylene glycols and polyalkylene glycols with alternating, random dispersed or blocky copolymers of ethylene glycol and propylene glycol, especially polyethylene glycols.

The liquid phase or the liquid phases of the cleaning agents according to the invention preferably contains a polyalkylene glycol which is selected from the polyalkylene glycols of the formula (I)

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 ) -0) zR ⁶

(Formula I)

With

R = 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.

According to a very particular embodiment, between 2 and 12% by weight, preferably between 4 and 10% by weight, in particular between 5.3 and 8% by weight, are present in the liquid phase.

(based on the weight of the individual liquid phase) polyalkylene glycols, especially those of the formula (i) with the abovementioned radicals, with an average molecular weight between about 1500 and about 8000, in particular between about 2000 and about 6000, in particular between about 3000 and about 4500, included. In particular, polyethylene glycols, in particular polyethylene glycols having an average molecular weight of about 4000 (INCI: PEG 4000), contained in the stated amount. In addition, other polyethylene glycols having other molecular weights may be included.

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 sufficiently high complexation of divalent cations To ensure the rinse water used, usually local tap water, which 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, substantially anhydrous or non-aqueous cleaning agents, in particular 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 containing at least one solid and one liquid phase optimized with respect to the dimensions of the metering chamber in dishwashers,

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 substantially free of water, the solid components must be finely distributed (as dispersion) in an organic matrix and also remain stable in storage in the dispersion and should not sediment. It is best in such liquid formulations, which are substantially free of water, the dried (freed from water)

Polycarboxylathaltige component and / or the sulfonic acid-containing polymers used in finely ground form.

The cleaning agent according to the invention, in particular machine dishwashing detergent, contains a total of between 0.5 wt .-% and 30 wt .-%, preferably 1 to 20 wt .-%, in particular 2 to 10 wt .-% (based on the total weight of the composition) of polymeric or co-polymers

Polycarboxylates or sulfonic acid-containing polymers.

In particular, it contains in total between 0.5% by weight and 30% by weight, preferably 1 to 20% by weight, in particular 2 to 10% by weight (based on the total weight of the composition) of (co) polymeric polycarboxylates and sulfonic acid group-containing polymers.

The solid phase (or solid phases) of the cleaning agent according to the invention, in particular machine dishwashing detergent, contains less than 10% by weight, preferably less than 5% by weight, in particular less than 3% by weight (based on the weight of the solid phase ), polymeric or co-polymeric polycarboxylates.

The solid phase (or solid phases) of the cleaning agent according to the invention, in particular machine dishwashing detergent, contains less than 10% by weight, preferably less than 5% by weight, in particular less than 3% by weight (based on the weight of the solid phase )

Contains sulfonic acid-containing polymers.

Preferably, the solid phase (or solid phases) of the invention

Cleaning agent, in particular machine dishwashing detergent, less than 10 wt .-%, preferably less than 5 wt .-%, in particular less than 3 wt .-% (based on the weight of the solid phase), polymeric or co-polymeric polycarboxylates and sulfonic acid-containing polymers ,

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

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of from 1,000 to 20,000, in particular from 2,000 to 10,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 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 detergents according to the invention may further comprise 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 inventive cleaning agent is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight .-%, preferably 1, 0 to 15 wt .-%, very particularly preferably 2.0 to 14 wt .-%, in particular from 4 to 14 wt .-%, especially from 4.5 to 12% by weight The sulfopolymer is used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, wherein this may optionally additionally be ground.

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 sulfonic acid group-containing (s)

Monomer (s) at least one monomer from the group of unsaturated carboxylic acids. Unsaturated carboxylic acid (s) used are, with particular preference, unsaturated carboxylic acids of the formula R (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another represent -H, -CH 3, a straight-chain or branched one 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 defined above or for -COOH or -COOR ⁴ wherein 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 case of the monomers containing sulfonic acid groups, preference is given to those of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ independently of one another are -H, -CH 3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ in which R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from - (CH ₂ ) n - where 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 (0) -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

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 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 (0) -NH-C (CH ₃₎ 2 CH ₂ - and -C (0) -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-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, 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 inventively preferred.

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 share of

Carboxylic acid-containing monomers 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 \ preferably of 4000 to 25,000 gmol ^" and in particular of 5000 to 15,000 gmol ^-1 .

In another preferred embodiment, the copolymers include besides

Carboxyl-containing monomer and sulfonic acid-containing monomer further 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.

As nonionic monomers are preferably monomers of the general formula

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

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-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) acryl amide,

Octyl acrylate, octyl acrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof.

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.

According to a preferred embodiment, in the liquid phase between 5 wt .-% and 55 wt .-%, preferably 10 and 45 wt .-%, in particular 20 and 38 wt .-% (based on the Weight of the liquid phase) polymeric or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers, in particular acrylic acid and sulfopolymers.

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, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,

Maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for environmental reasons, and mixtures thereof. In addition to their builder effect, the free acids typically also have the property of a

Acidification and thus also serve to set a lower and milder pH of the automatic dishwashing detergent. In particular, here are citric acid,

Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

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 is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance. As Aminoalkanphosphonate are preferably

Ethylenediaminetetramethylenephosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. 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 respect to the proportion of the phosphonate unit (independently of the hydroxyalkane and / or

Aminoalkan portion) contain the agents of the invention from 0.01 to 25 wt .-%, preferably 5 to 20 wt .-%, 8 to 15 wt .-% 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. 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 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 invention are

Detergent "substantially free of water", ie each of the individual phases contains less than 7 wt .-%, in particular less than 5 wt .-%, preferably less than 3 wt%, more preferably less than 1 wt .-% Water (in each case based on the total weight of the respective phase).

"Liquid" as used herein in reference to the cleaning agent of the present invention includes all flowable compositions and more particularly includes gels and pastes

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 in reference 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, in some cases compositions may also contain granules.

The detergent is 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 one

Dishwasher), before.

The cleaning agent according to the invention preferably comprises at least one solid, preferably pulverulent phase and at least one liquid phase.

It is particularly preferred if the water-soluble packaging at least two or more spatially separate compartments (chambers), in which spatially separated at least one solid, preferably powdery, 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 packaging (multi-chamber bag or

Mehrkammerformkörper) ,, which contain a powdery in at least one of the separated compartments and a liquid phase in at least one other compartments. A phase is here understood to mean a detergent (partial) composition which, in combination with the other phase (s), 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 has one, two or more chambers in addition to one, two or more liquid phases

(Compartments), containing solid 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 containing at least one solid, preferably at least one compressed phase and one liquid phase in separate

Have 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 cleaning agent, in particular in a multi-chamber bag, contains a solid, one of which is different powdery and two liquid phases in each case 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;

Essentially free of organic components, which is 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 included, which have an average molecular weight of less than 175 g / mol, preferably of less than 150 g / mol. In particular, according to the invention, the presence of usually short-chain organic solvents which a

average molecular weight of less than 175 g / mol, such as

Dipropylene glycol dimethyl ether, preferably of less than 150 g / mol, such as decane, octane, dipropylene glycols, glycerol, propanediols, monoethanolamine, diethanolamine are 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 content of the organic components contained in the liquid phase or phases, preferably organic solvents, which is an average

Molecular weight of less than 175 g / mol, preferably less than 150 g / mol, is at most 20 wt .-% (based on the total weight of the single 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 those mentioned under a)) components, since otherwise a migration of the components between the individual liquid phases in the separated

Compartments takes place.

According to a preferred embodiment, the liquid phase (are the liquid phases) of the cleaning agent according to the invention, in particular machine dishwashing, in

Substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol and liquid at 20 ° C and 1 bar.

According to a preferred embodiment, at least one is in the liquid phase

nonionic surfactant, which is liquid at 20 ° C and 1 bar, preferably in amounts between 5 and 60 wt .-%, in particular between 8 and 40 wt .-%, preferably between 10 and 30% by weight (based on the weight the liquid phase).

According to a preferred embodiment, at least one is in the liquid phase

nonionic surfactant which is waxy or solid at 20 ° C and 1 bar, preferably in amounts between 5 and 60 wt .-%, in particular between 10 and 50 wt .-%, preferably between 15 and 30 wt .-% (based on the weight of the liquid phase). In particular, it is preferred if at least one nonionic surfactant which is liquid at 20 ° C. and 1 bar and at least one nonionic surfactant which is waxy or solid at 20 ° C. and 1 bar are used together in the abovementioned amounts.

The pre-portioned detergents according to the invention, in particular machine dishwashing detergents, preferably additionally contain 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.

(Formula I)

in which

R is selected from -H, -CH ₃ , straight-chain or branched, saturated or mono- or polyunsaturated, C2-24-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 , Cs-24-alkyl or alkenyl, and

CH ₂ CH (OH) R ⁷

R ^{7 represents} 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).

According to a preferred embodiment, in the liquid phase additionally at least one polyalkylene glycol, preferably polyethylene glycols or polypropylene glycols, in particular

Polyethylene glycols) having an average molecular weight between 150 and 1000, preferably 200 to 800, in particular between 300 and 600, for example 400.

It is particularly preferred that the additional polyalkylene glycol in an amount of 10 to 40 wt .-%, preferably from 15 to 35 wt .-%, in particular (based on the weight of the liquid n phase) is included. In particular, it is particularly preferred if the liquid phase (s) is at least one polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, in particular a PEG having an average molecular weight of approx. PEG 4000 (INCI: PEG 4000).

It is particularly preferred if the liquid phase (the liquid phases) is a PEG having an average molecular weight of about 400, in particular in amounts of 15 to 35 wt.%, And a PEG having an average molecular weight of about 4000, in particular in amounts from 4 to 10 wt .-% (each based on the amount in the liquid phase).

Under the o.g. Formula (I) are also a large part of the nonionic surfactants to grasp. Preference is given to weakly foaming alkoxylated nonionic surfactants, in particular ethoxylated,

low-foaming nonionic surfactants preferably used. In preferred embodiments, the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.

According to a further preferred embodiment, the inventive

Cleaning agent in the liquid phase at least one nonionic surfactant, in particular selected from surfactants according to formula (I).

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-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 ) -0) zR ⁶ in which R 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 -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6. Thus, particularly preferred are nonionic surfactants having a C9-alkyl group with 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.

Further preferred nonionic surfactants here are those of the general formula

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 ) -0) zR ⁶ With

R 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, -Chta, -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

with R ⁷ for a straight-chain or branched, saturated or on or

polyunsaturated C6-26 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, hereinafter also referred to as "hydroxy mixed", the

Cleaning performance of the preparations according to the invention are 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

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

R 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

with R ⁷ for a straight-chain or branched, saturated or on or

polyunsaturated C6-26 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 C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.

Also preferred are also surfactants of the formula (I)

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 ) -0) z R ⁶ in which R 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 include, for example, the C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,

Preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula

With y, z = 0 and R ² = H, R ⁶ = -CH ₂ CH (OH) R ⁷

in the R independently of R ⁷ for a linear or branched, saturated or on 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 is -CH 3, and w and x independently represent values are between 1 and 32, with 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) being very particularly preferred.

According to a particular embodiment, in the case of the cleaning agent, in particular machine dishwashing detergent, in the liquid phase 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 particular <20 ° C.

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-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 ) -0) zR ⁶ in which R is a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ -C 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 with a melting point of <30 ° C, preferably <25 ° C, in particular <20 ° C (at 1 bar) additionally contain other components according to a), which have a higher melting point, in particular at least one of the above is particularly preferred said ethoxylated hydroxy mixed ethers.

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

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

in which

R is selected from straight-chain or branched, saturated Ce-alkyl radicals;

R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,

CH 2 CH ₃ , -CH 2 CH (CH ₃ ) 2, -C (CH ₃ ) 3, Cs-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.

According to a preferred embodiment, at least one nonionic surfactant is selected from those nonionic surfactants which are liquid at 20 ° C and 1 bar.

Particularly preferred are, for example, the aforementioned preferred

Fatty alcohol alkoxylates, these are preferably in amounts between 5 and 60 wt .-%, in particular between 8 and 40 wt .-%, preferably between 10 and 30 wt .-% (based on the weight of the liquid phase).

These components according to a) are particularly advantageous, since they (possibly in addition to liquid polyalkylene glycols) can provide a basis for the liquid phase, without thereby organic components, in particular organic solvents which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, must be used.

It is particularly preferred in this case if, in addition, a polyalkylene glycol, preferably at least one polyethylene glycol, which has an average molecular weight between 300 and 4000 g / mol, is used.

It is particularly preferred if the liquid phase (s) comprises a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having a middle molecular weight

Molecular weight of about 4000 (INCI: PEG 4000) have.

It is particularly preferred if, in addition to the abovementioned

Components used as further component according to a) is at least one ethoxylated hydroxy mixed ether of the formula (I)

R 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

with R ⁷ for a straight-chain or branched, saturated or on or

polyunsaturated C6-26 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 fatty alcohol (EO) io-8o-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) 4-alcohols. 8o-2-hydroxyalkyl ethers.

According to a particularly preferred embodiment, at least one nonionic surfactant which is waxy or solid at 20 ° C. and 1 bar is present in the liquid phase.

Particularly suitable are the fatty alcohol hydroxy mixed ethers specified hereinbefore. These are preferably used in amounts of between 5 and 60% by weight, in particular between 10 and 50% by weight, preferably between 15 and 30% by weight (based on the weight of the liquid phase). 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 to 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase) ,

In all the aforementioned embodiments, in particular the particular

highlighted combinations, it is preferred that the amount of all the components mentioned in accordance with 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) ,

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 (single) liquid phase:

0-40% by weight of at least one component according to formula (I)

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 ) -0) zR ^e where

R is selected from straight-chain or branched, saturated Ce-alkyl radicals;

R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,

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 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

o R ² = H,

o R ^{6 is} selected from -CH ₂ CH (OH) R ⁷

with R ⁷ for a straight-chain or branched, saturated or on or

polyunsaturated C6-26 alkyl or alkenyl radical; and

w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0.

And 2-12 wt .-% polyalkylene glycols, preferably polyethylene glycol, having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500, is contained.

It is preferred that the amount of all of those mentioned above as preferred

Components in the liquid phase between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).

Total weight of (single) liquid phase:

0 to 40% by weight, preferably 1 to 30% by weight, of at least one component of the formula (I)

R is selected from straight-chain or branched, saturated Ce-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, Cs -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 to 40% by weight, preferably 1 to 30% by weight, of at least one ethoxylated hydroxy mixed ether of the formula (I)

R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

o R ² = H,

o R ^{6 is} selected from -CH ₂ CH (OH) R ⁷

with R ⁷ for a straight-chain or branched, saturated or on or

polyunsaturated C6-26 alkyl or alkenyl radical; and

w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0. and 4-10 wt .-% polyalkylene glycols preferably polyethylene glycol, having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500, is contained.

It is preferred that the amount of all of those mentioned above as preferred

Total weight of (single) liquid phase:

R is selected from straight-chain or branched, saturated Ce-alkyl radicals;

R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,

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,

R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

o R ² = H,

o R ^{6 is} selected from -CH ₂ CH (OH) R ⁷

with R ⁷ for a straight-chain or branched, saturated or on or

polyunsaturated C6-26 alkyl or alkenyl radical; and

w = 1 to 120, preferably 10 to 80, in particular 15 to 40; and x, y, z = 0. and 5.3-8% by weight of polyalkylene glycols, preferably polyethylene glycol, having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500.

It is preferred that the amount of all of those mentioned above as preferred

Total weight of (single) liquid phase:

R is selected from straight-chain or branched, saturated Ce-alkyl radicals;

R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,

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,

R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

o R ² = H,

o R ^{6 is} selected from -CH ₂ CH (OH) R ⁷

with R ⁷ for a straight-chain or branched, saturated or on or

polyunsaturated C6-26 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 to 30% by weight of polyethylene glycols, preferably polyethylene glycol, with a middle

Molecular weight between 300 and 600 g / mol as well 2 to 12 wt .-% polyalkylene glycols, preferably polyethylene glycol, having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500, having.

It is preferred that the amount of all of those mentioned above as preferred

Total weight of (single) liquid phase:

R is selected from straight-chain or branched, saturated Ce-alkyl radicals;

R ² and R ⁴ are -H, R ³ and R ⁵ are -CH ₃ ,

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,

R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

o R ² = H,

o R ^{6 is} selected from -CH ₂ CH (OH) R ⁷

with R ⁷ for a straight-chain or branched, saturated or on or

polyunsaturated C6-26 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 to 30 wt.% Polyalkylenglycole, preferably polyethylene glycol, having an average molecular weight between 300 and 600 g / mol and

4 to 10 wt .-% polyalkylene glycols preferably polyethylene glycol, with a middle

Molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500, has.

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) ,

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

R ⁸ 0 [CH ₂ CH (R ⁹ ) O] h [CH ₂ ] kCH (OH) [CH 2] jOR °,

be contained, in particular poly (oxyalkylated) nonionic surfactants of formula II

in which R ⁸ and R ^{0 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. If the value h> 2, then any R ⁹ in the formula above can

R ⁸ 0 [CH ₂ CH (R ⁹ ) 0] h [CH ₂ ] kCH (OH) [CH 2] jOR ° be different. R ⁸ and R ⁰ 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, -Chta 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 together in any order, for example (EO) (PO ) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO),

(PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for h has been selected here by way of example and may well be greater, with the range of variation 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, so that the above formula zu

R ⁸ 0 [CH ₂ CH (R ⁹ ) 0] hCH ₂ CH (OH) CH ₂ OR ° simplified. In the latter formula, R ⁸ , R ⁰ and R ^{9 is} 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 ⁸ and R ^{0 have} 9 to 14 carbon atoms, R ⁹ stands for 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 and 80% by weight, preferably between 20 and 70% by weight (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 detergents, essentially 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).

The water-soluble coating of the detergent, the package, 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 preferred that the water-soluble coating be polyvinyl alcohol or a

Contains 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 gmor, 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 comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath

(Meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. 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 include, 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, detackifiers, 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 cleaning agents according to the invention are preferably a

Dishwashing agent, in particular a machine dishwashing detergent.

According to a preferred embodiment, the invention is pre-portioned

Cleaning agent, in particular machine dishwashing detergent, is substantially free of phosphates.

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. As phosphates or too

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.

When silicates are, in particular crystalline layered silicates of general formula NaMSix02x + i ^■ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 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 are preferably delayed in dissolution and secondary wash 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 ° C, 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 12th

The agents 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, perfumes, bitter substances, and antimicrobial agents.

In the detergents, preferably dishwashing detergents, in particular machine

Dishwashing agents can also be used bleaching agents. Among the compounds which serve as bleaching agents in water H2O2, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic agents known to the person skilled in the art

Peroxy.

As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine releasing materials

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 into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

There are cleaning agents, preferably dishwashing detergents, in particular machine

Dishwashing agents 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% by weight and in particular 5 up to 18% by weight (based on the total weight of the cleaning agent) of bleaching agent,

preferably sodium percarbonate.

According to a particularly preferred embodiment, in the solid phase bleach, 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 (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane (Mm-TACN).

Dishwashing agent preferably, the 0.001 to 1 wt .-%, preferably 0.01 to 0, 1 wt .-% (each based on the total weight of the cleaning agent) bleach catalyst, preferably a Mn complex, in particular a complex of manganese with 1, 4 , 7-trimethyl-1, 4,7-triazacyclononane (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-tri-azacyclononane (Mm-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. All of the bleach activators known to the person skilled in the art are acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) 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 0.1% to 8% by weight, especially 2 to 8% by weight and more preferably 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 ^{i 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 as well R ^v like or various alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula

(R ^VI ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^" , in which R ^vi to R ^ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X ^" for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Other suitable cationic surfactants are the quaternary

surface-active compounds, in particular with 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 contain enzymes

preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% 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 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 obtain peracids in situ from suitable precursors produce. 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 termed hemicellulases

be summarized. 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 preferable to add organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the

Stains to ensure the flow of electrons (mediators).

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 can be encapsulated for both the solid and liquid dosage forms, 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 entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core with a water, air and / or

Chemical-impermeable protective layer is coated. 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 former, low-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, more preferably between 0.4 and 20% by weight and

in particular between 0.8 and 10% by weight of the enzyme protein.

Preference is given in particular to those detergents which, in each case based on their

Total weight, 0, 1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% 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. Also preferred as glass corrosion inhibitors are polyethyleneimines and polyvinylamines, for example those obtainable under the name Lupasol® or Lupamin® from BASF, in particular nonalkoxylated

Polyethyleneimines used. 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.

In various embodiments, the detergent immediately after production has a viscosity above 4000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 5000 and 20,000 mPas. After storage, the viscosity may be higher, for example greater than 20,000 mPas, for example in the range 10000-50000 mPas, (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C). It is preferred that the agent is at least substantially fluid at room temperature.

The cleaning agents according to the invention are characterized in that they are stable in 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.

Another object is the use of polyalkylene glycols (in particular as described above) having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500 to improve the storage stability of liquid low-water detergents or cleaners, preferably machine dishwashing detergents.

The abovementioned properties also apply in particular to the invention

Use too.

embodiments

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

Table 1: Formulations of liquid phases (5 g)

The comparative formulation shows a visible phase separation within 4 weeks when stored at 40 ° C, the inventive examples E1 and E2 are stable under these conditions and have a higher color brilliance and viscosity.

Claims

claims

1. Pre-portioned detergent, preferably machine dishwashing, in one

Packaging comprising at least one liquid phase,

characterized in that the liquid phase contains at least one polyalkylene glycol having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500.

2. Cleaning agent according to claim 1, characterized in that the polyalkylene glycols are selected from polyethylene glycols, polypropylene glycols and polyalkylene glycols with alternating, randomly distributed or blocky copolymers of

Ethylene glycol and propylene glycol, especially polyethylene glycols.

3. Cleaning agent according to one of the preceding claims, characterized in that in the liquid phase between 2 and 12 wt .-%, preferably between 4 and 10 wt .-%, in particular between 5.3 and 8 wt .-% (based on the weight of the liquid phase) polyalkylene glycols having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500, is included.

4. Cleaning agent according to one of the preceding claims, characterized in that in the liquid phase at least one nonionic surfactant which is liquid at 20 ° C and 1 bar, preferably in amounts of between 5 and 60 wt .-%, in particular between 8 and 40 Wt .-%, preferably between 10 and 30 wt .-% (based on the weight of the liquid phase) are included.

5. Cleaning agent according to one of the preceding claims, characterized in that in the liquid phase at least one nonionic surfactant, which is waxy or solid at 20 ° C and 1 bar, preferably in amounts between 5 and 60 wt .-%, in particular between 10 and 50% by weight, preferably between 15 and 30% by weight (based on the weight of the liquid phase).

6. Cleaning agent according to one of the preceding claims, characterized in that in the liquid phase additionally at least one polyalkylene glycol, preferably

Polyethylene glycols or polypropylene glycols, in particular polyethylene glycols) having an average molecular weight between 150 and 1000, preferably 200 to 800, in particular between 300 and 600, for example 400 is included.

7. Cleaning agent according to claim 6, characterized in that the additional polyalkylene glycol in an amount of 10 to 40 wt .-%, preferably from 15 to 35 wt .-%, in particular (based on the weight of the liquid phase) is included.

8. Cleaning agent according to one of the preceding claims, characterized in that in the liquid phase between 5 wt .-% and 55 wt .-%, preferably 10 and 45 wt .-%, in particular 20 and 38 wt .-% (based on the weight of the liquid phase) comprises polymeric or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers, in particular acrylic acid and sulfopolymers.

9. Cleaning agent according to one of the preceding claims, characterized in that the weight of the solid (or all solid) phases to the weight of the liquid phase (or all liquid phases) 1: 10 to 10: 1, preferably 1: 5 to 5: 1.

10. Cleaning agent according to one of the preceding claims, characterized in that the cleaning agent are substantially free of water.

1 1. Cleaning agent according to one of the preceding claims, characterized in that the cleaning agent are substantially free of phosphates.

12. Cleaning agent according to one of the preceding claims, characterized in that the packaging has at least two compartments and the cleaning agent comprises at least one solid, preferably pulverulent phase and at least one liquid phase.

13. Use of polyalkylene glycols having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500, to improve the storage stability of liquid low-water washing or

Cleaning agents, preferably machine dishwashing detergents.