WO2019197315A1

WO2019197315A1 - Process for cleaning dishware

Info

Publication number: WO2019197315A1
Application number: PCT/EP2019/058763
Authority: WO
Inventors: Stephan Hueffer; Heike Weber; Alejandra Garcia Marcos; Frank Klippel; Juergen Tropsch
Original assignee: Basf Se
Priority date: 2018-04-13
Filing date: 2019-04-08
Publication date: 2019-10-17

Abstract

Process for cleaning dishware soiled with fatty residue, characterized in that said process is carried out at a temperature in the range of from 45 to 65°C and using at least one detergent composition, comprising (A) at least one graft copolymer comprising - as a graft base - a polyether that may be capped with Ci-C2o-alkyl or C6-C2o-2-hydroxyalkyl, and comprising side chains bearing C4-C2o-fatty acid groups or C6-C20-alkoholate groups, (B) at least one non-ionic surfactant according to general formula (I)

Description

Process for cleaning dishware

The present invention is directed towards a process for cleaning dishware by using a detergent composition comprising

(A) at least one graft copolymer comprising - as a graft base - a polyether that may be

capped with Ci-C2o-alkyl or C₆-C₂o-2-hydroxyalkyl, and comprising side chains bearing C4-C2o-fatty acid groups or C6-C20-alkoholate groups, and

(B) and at least one non-ionic surfactant according to general formula (I)

R¹-CH(0H)-CH₂-0-(A0)_X-R² (I) wherein:

R¹ being selected from C4-C3o-alkyl, straight-chain or branched, and from C4-C3o-alkylene, straight-chain or branched, with at least one C-C double bond,

R² being selected from Ci-C3o-alkyl, straight-chain or branched, and from C2-C3o-alkylene, straight-chain or branched, with at least one C-C double bond, x being selected from one to 100,

AO being identical or different alkylene oxides, selected from CH2-CH2-O, (CH₂)₃-0, (CH₂)₄-0, CH₂CH(CH₃)-0, CH(CH₃)-CH₂-0- and CH₂CH(n-C₃H₇)-0.

Furthermore, the present invention is directed towards detergent compositions that are useful for cleaning dishware, and towards a process for making such detergent compositions.

Detergent compositions, especially detergent compositions for automatic dishwashing, have to meet various requirements. When being used in automatic dishwashing, such detergent corn- positions need to enable a complete cleaning of china, polymer, metal, clay, and glassware and to remove all sorts of soil, like fat, proteins, starch, dyes, and more. The soils need to be dis persed in water during the cleaning and the water removal process, and the various soils should not deposit in the dishwashing machine in case of automatic dishwashing. Finally, during the drying process, the cleaned good should exhibit a good drying behavior, without spotting.

Making the respective detergent composition also needs to meet numerous requirements. Liq uid and solid detergent compositions should have a good storage stability. Shaped bodies - such as, but not limited to - tablets should not break upon manufacture. This is a particular chal- lenge in the case of detergent compositions that contain mixed hydroxymethyl ethers, so-called ΉME” or HME-ethers. In US 201 1/0259365 and EP 2 788 467 A, certain copolymers and their use in liquid detergent compositions is disclosed.

It has additionally been found that in many cases fatty residues are being accumulated in the fat filter or sieves of automatic dishwashing machines. Such residues usually contain surfactant and fat which has been removed from the dishware, or degradation products from soil. The deposition of residues is disadvantageous because such filters or sieves need cleaning when filled with surfactant and fat. Furthermore, such fatty residues may become smelly in case the machine is not in use for some time, and they may even become a hygiene hazard.

Mixed hydroxy ethers are particularly efficient non-ionic surfactants, especially when combined with certain polymers, see, e. g., WO 2008/095563. However, especially the use of mixed hy- droxy ethers in formulations disclosed in WO 2008/095563 in automatic dishwashers can lead to rather high amounts of surfactant and fat residues in the filters or sieves.

It was therefore an objective of the present invention to provide a method for cleaning dishware soiled with fat without having to cope with significant residues of surfactant and fat in the filters or sieves of the dishwashing machine but not loss on quality of the dishwashing process. Fur- thermore, it was an objective to provide detergent compositions useful for cleaning dishware soiled with fat without having to cope with significant residues of surfactant and fat in the filters or sieves of the dishwashing machine but not loss on quality of the dishwashing process. Fur- thermore, it was an objective to provide a method for making such detergent compositions.

It was also an objective of the present invention to provide a method for cleaning dishware with excellent quality of the dishwashing process. Furthermore, it was an objective to provide deter- gent compositions that can easily be converted into shaped bodies, for example tablets. Fur- thermore, it was an objective to provide a method for making suitable components for such compositions and methods of manufacture of such components.

Accordingly, the processes and compositions defined at the outset have been found. Firstly, the process defined in the outset, hereinafter also referred to as inventive process, will be defined in more detail.

The inventive process is a process for cleaning dishware. The inventive process can be carried out either manually (hand-dish-wash) or preferably with the help of a machine (machine dish- wash or automatic dish-wash). Dishes in the context of the present invention shall not only refer to plates from china but also to any kitchenware from china, metal, glass, clay or polymer, such as - but not limited to - cups, bowls and plates from china, flatware, drinking glasses such as wine glasses, champagne flutes, beer glasses and the like, and plastic kitchenware, furthermore pots, frying pans and Dutch ovens from metal such as iron, aluminum or stainless steel. Dish-ware is provided in soiled form, for example soiled with pigment(s), protein, carbohydrates such as starch or sugar, caramel, furthermore lecithin, dyestuff(s), or with fatty residue, also referred to as fat, that may stem from food itself or - for example in the case of frying pans - fat that stems from cooking or frying or baking food. The term“fat” may also include lard or oil, es- pecially oil like sunflower oil, olive oil or other oil that is used for cooking purposes.

Said fatty residue may be the sole soiling of dishware to be cleaned according to the inventive process. In another embodiment of the present invention, dish-ware to be cleaned according to inventive process may be soiled with a combination of fat and at least one substance other than fat, for example.

Most common are combinations of at least two of the foregoing soilings, for example lipstick residue on beakers or glassware.

On the dish-ware may a coherent layer of soiling, or - in other embodiments - only one or more spots or limited areas of the respective dish-ware may be soiled.

The inventive process may be carried out at temperatures in the range of from 30 to 65°C, pref- erably 45 to 60°C. Said temperature refers to the temperature of the water being used in the inventive process. The inventive process is being described in more detail below.

The inventive process is being carried out using water. In case of automatic dishwashing, the amount of water is influenced by the type of machine used and by the choice of the program.

Detergent compositions used in the inventive process comprise

(A) at least one graft copolymer, hereinafter also in brief“graft copolymer (A)”, comprising - as a graft base - a polyether that may be capped with Ci-C2o-alkyl or C₆-C₂o-2-hydroxyalkyl, and comprising side chains bearing C₄-C2o-fatty acid groups or C6-C20-alkoholate groups.

In the context of the present invention, polyethers bear at least 5 ether groups per mole and - if at all - only hydroxyl groups, for example one, two or three hydroxyl groups per molecule. Such hydroxyl groups may be primary or secondary hydroxyl groups, primary hydroxyl groups being preferred.

Polyethers in the context of the present invention may be non-capped. In such embodiments, polyethers may also be referred to as polyether polyols, and they have terminal hydroxyl groups. Examples are polyethylene glycols, for example with an average molecular weight M_n in the range of from 500 to 100,000 g/mole, preferably 1 ,000 to 25,000 g/mole and even more preferably 4,000 to 9,500 g/mol. Further examples of polyethers are copolymers of ethylene glycol and propylene glycols, for example random copolymers and preferably block copolymers, for example di-block copolymers and tri-block copolymers.

Further examples are polypropylene glycols, for example with an average molecular weight M_n in the range of from 500 to 20,000 g/mole, preferably 2,000 to 10,000 g/mole and even more preferably 4,000 to 9,000 g/mol.

Further examples are poly-tetrahydrofurans, also referred to as poly-THF, for example with an an average molecular weight M_n in the range of from 500 to 5,000 g/mole, preferably 800 to 4,000 g/mole.

In one embodiment of the present invention, the graft base of graft copolymer (A) is selected polyethylene glycol, polypropylene glycol and EO-PO block copolymers, each non-capped or capped with Ci-C₂o-alkyl or C₆-C₂o-2-hydroxyalkyl.

Examples of Ci-C₂o-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl, n-Ci₂H₂₅, n-C-i₄H₂9, n- C16H33 or n-Ci8H37, preferred are Ci-C₄-alkyl, for example methyl, ethyl, n-propyl, n-butyl, and in particular methyl.

Examples of C₆-C₂o-2-hydroxyalkyl are 2-hydroxy-n-hexyl, 2-hydroxy-n-octyl, 2-hydroxy-n-decyl, 2-hydroxy-n-dodecyl, 2-hydroxy-n-tetradecyl, 2-hydroxy-n-hexadecyl, 2-hydroxy-n-octadecyl, and 2-hydroxy-n-eicosyl.

In one embodiment of the present invention, the side chains of graft copolymer (A) contain in copolymerized form at least one of comonomers (II a) to (II c)

CH₂=CH-0-C(0)-R³ (II a)

CH₂=CH-CH₂-0-C(0)-R³ (II b)

CH₂=CZ-CO-OR⁴ (II c) wherein R³ is selected from C3-C_2i-alkyl, preferably with an odd number of carbon atoms, for example n-propyl, n-pentyl, n-heptyl, n-nonyl, iso-nonyl, n-undecyl, n-tridecyl, n-pentadecyl, n- heptadecyl, or n-nonadecyl.

R⁴ is selected from C₆-C_2o-alkyl, preferably with an even number of carbon atoms, for example n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl, n- CI₂H₂₅, n-Ci₄H₂₉, n-Ci6H33 or n-CieH37, and Z is selected from hydrogen and methyl, hydrogen bring preferred.

Comonomers of general formulae (II a) and (II c) are preferred.

Specific examples of comonomers according to formula (II a) are vinylbutyrate, vinyl-n- hexanoate, vinyl-n-octanoate, vinyl-2-ethylhexanoate, vinyllaurate, vinalstearate, vinylmyristate, and vinylpalmitate, preferred are vinylbutyrate, vinyl-2-ethylhexanoate, vinyllaurate, and vi- nylstearate.

Specific examples of comonomers according to formula (II b) are allylbutyrate, allyl-n- hexanoate, allyl-n-octanoate, allyl-2-ethylhexanoate, allyllaurate, vinalstearate, allylmyristate, and allylpalmitate, preferred are allylbutyrate, allyl-2-ethylhexanoate, allyllaurate, and allylstea- rate.

Specific examples of comonomers according to formula (II c) are 2-ethylhexyl(meth)acrylate, 2- n-propylheptyl(meth)acrylate, stearyl(meth)acrylate, lauryl(meth)acrylate, palmityl(meth)acrylate, and myristyl(meth)acrylate, preferred are 2-ethylhexylacrylate, lauryl(meth)acrylate and stear- yl(meth)acrylate.

In one embodiment of the present invention, graft copolymer (A) has a weight ratio of graft base to side chains in the range of from 95:5 to 1 :1 , preferably 95:5 to 3:2 and even more preferably 9:1 to 7:3.

In one embodiment of the present invention, graft copolymer (A) has an average molecular weight M_n in the range of from 2,250 to 200,000 g/mol, preferred are 2,250 to 25,000 g/mol, even more preferred are 2,500 to 10,000 g/mol. The average molecular weight M_n may be de- termined by gel permeation chromatography (GPC), with polyethylene glycol as comparison standard. The grafting as such may be confirmed by HPLC (High Pressure Liquid Chromatog- raphy).

In one embodiment of the present invention, graft copolymer (A) has a broad weight distribution. A broad weight distribution in the context of graft copolymer (A) means that such copolymers (A) have a polydispersity Q = M_w/M_n of at least 3.5, preferably from 3.5 to 10, more preferably from 4 to 9 and even more preferably from 4.0 to 5.5.

In another embodiment of the present invention, graft copolymer (A) has a narrow weight distri bution. A narrow weight distribution in the context of graft copolymer (A) means that such copol- ymers (A) have a polydispersity Q = M_w/M_n of at most 3.25, preferably from 1.5 to 3.0, more preferably from 2 to 2.5. In one embodiment of the present invention, the melting point of graft copolymer (A) is in the range of from 50 to 70°C. The melting point usually is a softening range of about 2 to 4°C. A suitable apparatus is the Melting Point M 560, commercially available from Buchi.

Detergent compositions used in the inventive process further comprise

(B) at least one non-ionic surfactant according to general formula (I)

R¹-CH(0H)-CH₂-0-(A0)_X-R² (I), hereinafter also being referred to as“surfactant (B)”, the variables being defined as follows:

R¹ is selected from C₄-C3o-alkyl, straight-chain or branched, and from C₄-C3o-alkylene,

straight-chain or branched, with at least one C-C double bond, preferred is C₄-C3o-alkyl, straight-chain or branched, more preferred is straight-chain C₄-C3o-alkyl and even more preferred is n-Cio-Ci2-alkyl.

R² is selected from Ci-C3o-alkyl, straight-chain or branched, and from C2-C3o-alkylene,

straight-chain or branched, with at least one C-C double bond, preferred is C6-C2o-alkyl, more preferred is C8-Ci2-alkyl, even more preferred Cio-Ci2-alkyl, x is selected from one to 100, preferably from 5 to 60, more preferably 10 to 50, and even more preferably 20 to 40,

AO is selected from identical or different alkylene oxides, selected from CH2-CH2-O, (CH₂)₃-0, (CH₂)₄-0, CH₂CH(CH₃)-0, CH(CH₃)-CH₂-0- and CH₂CH(n-C₃H₇)-0. Preferred example of AO is CH2-CH2-O (EO).

In one embodiment of the present invention, (AO)_x is selected from (ChhCI-hO^i, x1 being se- lected from one to 50.

In one embodiment of the present invention, (AO)_x is selected from

-(CH₂CH20)_X2-(CH2CH(CH3)-0)_x3 and -(CH₂CH20)_X2-(CH(CH3)CH2-0)_x3, x2 and x3 being identi- cal or different and selected from 1 to 30.

In one embodiment of the present invention, (AO)_x is selected from -(CH₂CH₂0)_x4, x4 = being in the range of from 10 to 50, AO being EO, and R¹ and R² each being independently selected from C₈-Ci₄-alkyl.

In the context of the present invention, x or x1 or x2 and x3 or x4 are to be understood as aver- age values, the number average being preferred. Therefore, each x or x1 or x2 or x3 or x4 - if applicable - can refer to a fraction although a specific molecule can only carry a whole number of alkylene oxide units.

Detergent compositions used in the inventive process may further comprise at least one com- plexing agent (C). Said complexing agent (C) is capable of removing water hardness. Examples of complexing agents (C) are the alkali metal salts of citric acid, from the alkali metal salts of aminocarboxylic acids and from sodium tripolyphosphate, with non-phosphate complexing agents (C) being preferred.

Preferred complexing agents (C) are selected from alkali metal salts of citric acid and aminocar- boxylic acids. Examples of alkali metal salts in the context of complexing agent (C) are the po- tassium salts and in particular the sodium salts.

Preferred alkali metal salts of citric acid are the sodium salts, especially the trisodium salt.

Preferred examples of aminocarboxylic acids are methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and iminodisuccinic acid (IDS). Preferred alkali metal salts of ami- nocarboxylic acids are the trisodium salt of MGDA, the tetrasodium salt of GLDA and the tetra- sodium salt of IDS.

In one embodiment of the present invention, said detergent composition may contain a combi- nation of at least two complexing agents (C), such as, for example, a combination of alkali metal salts of citric acid and MGDA, or of citric acid and GLDA, or combinations of alkali metal salts of citric acid and sodium tripolyphosphate. Preferred are combinations of the respective sodium salts, in particular combinations of the trisodium salts of citric acid and MGDA.

Preferably, detergent compositions used in the inventive process are phosphate-free. In the context of the present invention, the term phosphate-free refers to a combined phosphate and polyphosphate content of 0.01 or less up to 0.5% by weight of phosphate.

In one embodiment of the present invention, detergent compositions used in the inventive pro- cess contain

in the range of from 0.1 to 10% by weight, preferably 0.25 to 5% by weight and more preferably 0.5 to 2.5% weight of graft copolymer (A),

in the range of from 1 to 10 % by weight, preferably 2 to 8 % by weight and more preferably up to 6 % by weight of surfactant (B), and, optionally,

in the range of from 1 to 50% by weight, preferably 10 to 40 % by weight of complexing agent (C).

Percentages of graft copolymer (A), surfactant (B) and complexing agent (C) are percentages by weight and refer to the total solids content of the respective detergent composition. In one embodiment of the present invention, detergent compositions used in the inventive pro- cess may have a total solids content in the range of from 90 to 99.9%, preferably 95 to 99 % by weight. Such inventive detergent compositions are, e. g., in the form of powder or tablets.

In one embodiment of the present invention, detergent compositions used in the inventive pro- cess may have a total solids content in the range of from 15 to 40% by weight. Such inventive detergent compositions are, e. g., in the form of gels.

In one embodiment of the present invention, the inventive process comprises several steps, one of the steps being contacting the soiled dishware with a detergent composition as disclosed above, and also comprising at least one rinsing step and at least one drying step. Preferably, the detergent composition used in the inventive process can be used as 2-in-1 or 3-in-1 formu- lation, and no separate rinse agent is necessary. In another preferred embodiment, the ion ex- change does not need to be treated with regenerating salt. Even more preferably, the detergent composition used in the inventive process can be used as 2-in-1 or 3-in-1 formulation, and nei- ther a separate rinse agent nor a regenerating salt is necessary.

In one embodiment of the present invention, detergent compositions used in the inventive pro- cess may contain at least one further ingredient, also being referred to as ingredient (D). Ingre- dient (D) may be selected from one or more surfactants other than surfactant (B), one or more enzymes, one or more (co)polymers other than graft copolymer (A), in particular phosphorus- free builders, one or more cobuilders, one or more alkali carriers, one or more bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more antifoams, one or more corrosion inhibitors, one or more buffer or one or more dyes.

Examples of surfactants other than surfactant (B) are in particular nonionic surfactants other than surfactant (B) as well as mixtures of anionic or zwitterionic surfactants with nonionic surfac- tants other than surfactant (B). Preferred nonionic surfactants other than surfactant (B) are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (III)

in which the variables are defined as follows: R⁷ is selected from hydrogen and from Ci-Ci2-alkyl, for example methyl, ethyl, n-propyl, iso- propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,

1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n- nonyl, n-decyl, isodecyl, n-dodecyl or iso-dodecyl,

R⁵ is identical or different and selected from linear Ci-Ci2-alkyl, preferably in each case iden- tical and ethyl and particularly preferably methyl,

R⁶ is selected from C8-C22-alkyl, for example n-CsH^, n-C-ioHh-i, n-Ci2H25, n-Ci₄H29, n-Ci6H33 or n-Ci8H₃₇, m and n are in the range from zero to 300, where the sum of n and m is at least one. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

Compounds of the general formula (II) may be block copolymers or random copolymers, prefer- ence being given to block copolymers.

Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for exam- pie, compounds of the general formula (IV)

in which the variables are defined as follows:

R⁹ is identical or different and selected from linear Ci-C₄-alkyl, preferably identical in each case and ethyl and particularly preferably methyl,

R⁸ is selected from C6-C2o-alkyl, in particular n-CsH^, n-C-ioHh-i, n-Ci2H25, n-C-i₄H29, n-Ci6H33, n-CieH37, a is a number in the range from 1 to 6, b is a number in the range from 4 to 20, d is a number in the range from 4 to 25.

Compounds of the general formula (IV) may be block copolymers or random copolymers, pref- erence being given to block copolymers. Further suitable nonionic surfactants are selected from di- and multiblock copolymers, corn- posed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides are like- wise suitable. An overview of suitable further nonionic surfactants can be found in

EP-A 0 851 023 and in DE-A 198 19 187.

Mixtures of two or more different nonionic surfactants other than surfactant (B) may also be pre- sent.

Examples of anionic surfactants are C8-C2o-alkyl sulfates, C8-C2o-alkylsulfonates and C8-C20- alkyl ether sulfates with one to 6 ethylene oxide units per molecule.

In one embodiment of the present invention, detergent compositions used in the inventive pro- cess can comprise in the range from 3 to 20% by weight of surfactant other than surfactant (B).

Detergent compositions used in the inventive process can comprise one or more enzymes. Ex- amples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pecti- nases, lactases and peroxidases.

Detergent compositions used in the inventive process can comprise, for example, up to 5% by weight of enzyme, preference being given to 0.1 to 3% by weight, in each case based on the total solids content of the detergent composition according to the invention.

Over and above graft copolymer (A), detergent compositions used according to the invention can comprise one or more builders, in particular phosphate-free builders. Examples of suitable builders are fatty acid sulfonates, ohydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid.

In one embodiment of the present invention, builders are selected from polycarboxylates, for example alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.

Suitable comonomers of polycarboxylates are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.

A suitable (meth)acrylic acid homopolymer is in particular polyacrylic acid, which preferably has an average molecular weight M_w in the range from 2,000 to 40,000 g/mol, preferably 2,000 to 10,000 g/mol, in particular 3,000 to 8,000 g/mol. Also of suitability are copolymeric polycarbox- ylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid. Detergent compositions used according to the invention can comprise, for example, in the range from in total 2.5 to 20% by weight, preferably up to 10% by weight, of (co)polymers other than graft copolymer (A).

Useful (co)polymers are, for example, polyalkylenimines such as polyethylenimines and poly- propyleneimines, and polyalkoxylated polyalkylenimines.

In the context of the present invention, polyalkylenimines may be regarded as polyalkylenepoly- amines. They bear at least 12 N-atoms per molecule in the form of amino groups, e. g., as Nhh- groups, as secondary amino groups or as tertiary amino groups. In a preferred embodiment of the present invention, polyalkylenimines are selected from poly-C2-C4-alkylenimines, in particu- lar from polyethylenimines and polypropylenimines.

The term“polyethylenimine” in the context of the present invention does not only refer to poly- ethylenimine homopolymers but also to polyalkylenimines containing NH-CH₂-CH₂-NH structural elements together with other alkylene diamine structural elements, for example NH-CH₂-CH₂- CH₂-NH structural elements, NH-CH₂-CH(CH₃)-NH structural elements, NH-(CH₂)₄-NH structural elements, NH-(CH₂)₆-NH structural elements or (NH-(CH₂)₈-NH structural elements but the NH- CH₂-CH₂-NH structural elements being in the majority with respect to the molar share. Preferred polyethylenimines contain NH-CH₂-CH₂-NH structural elements being in the majority with re- spect to the molar share, for example amounting to 60 mol-% or more, more preferably amount- ing to at least 70 mol-%, referring to all alkylenimine structural elements. In a special embodi- ment, polyethylenimine refers to those polyalkylene imines that bear one or zero alkylenimine structural element per molecule that is different from NH-CH₂-CH₂-NH.

The term“polypropylenimine” in the context of the present invention does not only refer to poly- propylenimine homopolymers but also to polyalkylenimines containing NH-CH₂-CH₂-CH₂-NH structural elements or NH-CH₂-CH(CH₃)-NH structural elements together with other alkylene diamine structural elements, for example NH-CH₂-CH₂-NH structural elements, NH-(CH₂)₄-NH structural elements, NH-(CH₂)₆-NH structural elements or (NH-(CH₂)₈-NH structural elements but the NH-CH₂-CH₂-CH₂-NH structural elements or NH-CH₂-CH(CH₃)-NH structural elements being in the majority with respect to the molar share. Preferred polypropylenimines contain NH- CH₂-CH₂-CH₂-NH structural elements being in the majority with respect to the molar share, for example amounting to 60 mol-% or more, more preferably amounting to at least 70 mol-%, re- ferring to all alkylenimine structural elements. In a special embodiment, polypropylenimine re- fers to those polyalkylene imines that bear one or zero alkylenimine structural element per mol- ecule that is different from NH-CH₂-CH₂-CH₂-NH.

Branches may be alkylenamino groups such as, but not limited to -CH2-CH2-NH2 groups or (CH2)3-NH2-groups. Longer branches may be, for examples, -(CH2)3-N(CH2CH2NH2)2 or -(Chhjs- N(CH2CH₂CH₂NH2)2 groups. In the context of the present invention, branched polyalkylenimines are characterized by their degree of branching (DB). The degree of branching can be determined, for example, by ¹³C- NMR spectroscopy, preferably in D₂0, and is defined as follows:

DB = D +T/D+T+L with D (dendritic) corresponding to the fraction of tertiary amino groups, L (linear) corresponding to the fraction of secondary amino groups and T (terminal) corresponding to the fraction of pri mary amino groups.

Within the context of the present invention, branched polyethylenimines are polyethylenimines (A) with DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, particularly preferably in the range from 0.30 to 0.80% and very particularly preferably at least 0.5. Polyethylenimine (A) may be monomodal, bimodal or multimodal with respect to the molecular weight distribution.

Within the context of the present invention, highly branched polypropylenimines are polypropyl- enimines with DB in the range from 0.25 to 0.95, particularly preferably in the range from 0.30 to 0.90% and very particularly preferably at least 0.5.

In the context of the present invention, d-h-groups are not being considered as branches.

Preferred polypropylenimine backbones are those that exhibit little or no branching, thus pre- dominantly linear or linear polypropylenimine backbones.

The synthesis of suitable polypropylenimines has been disclosed in WO 2014/131584.

In the context of the present invention, polyalkanolamines are polycondensates of alkanola- mines, alkanolamines are selected from monoalkanolamines, dialkanolamines and trialkanola- mines. Monoalkanolamines are selected from mono-C2-Cio-alkanolamines, preferably w-mono- C2-Cio-alkanolamines, preferably monoethanolamines, for example w-ethanolamine, N,N- dimethylethanolamine, N-methylethanolamine, and N-n-butylethanolamine. Examples of dialka- nolamines are di-(o-C2-Cio-alkanolamines, especially N,N-diethanolamine, hereinafter also re- ferred to as diethanolamine, N,N-di-n-propanolamine, N,N-diisopropanolamine, N,N-di-n- butanolamine, N,N'-C2-C8-(o-hydroxyalkylpiperidine N-methyl-N,N-diethanolamine, and N-n- butyl-N,N-diethanolamine.

In one embodiment of the present invention, polyalkanolamines are selected from trialkanola- mines. Preferred are tri-((o-C2-Cio-alkanolamines), for example triethanolamine, tripropanola- mine, triisopropanolamine and tributanolamine, most preferred being triethanolamine.

In polyalkoxylated polyalkylenimines and polyalkoxylated polyalkanolamines the polyalkoxylate chains are selected from polyethylenoxide chains, polypropylenoxide chains, mixed polyeth- ylenoxide/polypropylenoxide chains, especially with one propylenoxide unit directly attached to an N-atom and a subsequent polyethylenoxide chain.

Optionally, polyalkoxylated polyalkylenimines and polyalkoxylated polyalkanolamines may con- tain one or more alkylene oxide with 4 or more C-atoms per molecule in their polyalkylene oxide chains. Examples are 1 ,4-butylene oxide, 1 ,2-butylene oxide, 1 ,5-pentylene oxide and 1 ,2- hexylene oxide. Preferably, such alkylene oxide(s) with 4 or more C-atoms per molecule is/are present with up to 25 mol-%, referring to the total alkylene oxide content of the respective poly- alkoxylated polyalkylenime or polyalkoxylated polyalkanolamine, respectively.

In one embodiment of the present invention, polyalkoxylated polyalkylenimines are selected from polyalkoxylated polyalkylenimines with an average of at least 8 and up to 50 equivalents of alkylene oxide per NH group, even more preferably at least 12 and up to 30 equivalents. The expression“per NH group” refers to the respective polyalkylenimine that serves as backbone of the respective polyalkoxylated polyalkylenimine. Each NH₂ group of a polyalkylenimine bears two chains of polyalkylenoxide, each CH2-NH-CH2 group bears one chain of polyalkylenoxide, and tertiary amine groups may not be alkoxylated.

In one embodiment of the present invention, polyalkoxylated polyalkylenimine has a cationic charge density in the range of from 0.01 to 2 meq/g (milli-equivalent per gram), preferably 0.01 to 1 meq/g. The cationic charge density may be determined by titration. The cationic charge density can be determined, for example, by titration, for example with polyvinyl sulfate solution.

In one embodiment of the present invention, polyalkoxylated polyalkylenimines has an average molecular weight M_w in the range of from 2,500 to 100,000 g/mol, preferably 5,000 to 50,000 g/mol and even more preferably up to 25,000 g/mol. The average molecular weight M_w may be determined by gel permeation chromatography (GPC), with 1.5 % by weight aqueous formic acid as eluent and cross-linked poly-hydroxyethylmethacrylate as stationary phase.

In one embodiment of the present invention, polyalkoxylated polyalkylenimines have a HLB val- ue (hydrophilic-lipophilic balance) in the range of from at least 4 up to 8, preferably at least 3 up to 7. The HLB value is calculated as follows:

HLB = 20 (1 - ML/MG)

With M_L being the molecular weight of the lipophilic portion and M_G being the total molecular weight. Polypropylene oxide portions -and the respective higher alkylene oxide portions, if ap- plicable - are deemed lipophilic. Polypropylene imine unites, if applicable, are deemed lipo philic. Polyethylene imine backbone and ethylene oxide units, if applicable, are deemed hydro- philic. Details about the HLB value are disclosed in H.-D. Dorfer,“Grenzflachen und kolloid- disperse Systeme”, Springer 2002, Chapter 9.3. In one embodiment of the present invention, detergent compositions used according to the in- vention can comprise one or more cobuilders.

Examples of cobuilders are phosphonates, for example hydroxyalkanephosphonates and ami- noalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1 ,1- diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt giving a neutral reaction and the tetrasodium salt an alkaline re- action (pH 9). Suitable aminoalkanephosphonates are preferably ethylenediaminetetra- methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and higher homologs thereof. They are preferably used in the form of the neutrally reacting so- dium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octasodium salt of DTPMP.

Moreover, amphoteric polymers can also be used as cobuilders.

Detergent compositions used in the inventive process can comprise one or more alkali carriers. Alkali carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired. Of suitability are, for example, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydrox- ides and alkali metal metasilicates. A preferred alkali metal is in each case potassium or sodi- um, particular preference being given to sodium.

Detergent compositions used in the inventive process can comprise one or more bleach cata- lysts. Bleach catalysts can be selected from bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum- salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also co- bait-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.

Detergent compositions used in the inventive process can comprise, for example, 0.5 to 15% by weight of bleaching agents, hereinafter also referred to as bleach (D). Bleach (D) can be select- ed from oxygen bleaches and chlorine-containing bleaches.

Examples of suitable oxygen bleaches are sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylau- ric acid, peroxystearic acid, peroxy-a-naphthoic acid, 1 ,12-diperoxydodecanedioic acid, per- benzoic acid, peroxylauric acid, 1 ,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as free acid or as alkali metal salt, in particular as sodium salt, also sulfonylperoxy acids and cationic peroxy acids.

Detergent compositions used in the inventive process can comprise, for example, in the range from 0.5 to 15% by weight of oxygen bleach. Suitable chlorine-containing bleaches are, for example, 1 ,3-dichloro-5,5-dimethylhydantoin, N- N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

Detergent compositions used in the inventive process can preferably comprise, for example, in the range from 3 to 10% by weight of chlorine-containing bleach.

Detergent compositions used in the inventive process can comprise one or more bleach activa- tors, for example N-methylmorpholinium-acetonitrile salts (“MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1 ,5-diacetyl-2,2- dioxohexahydro-1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).

Other examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

Detergent compositions used in the inventive process can comprise one or more corrosion in- hibitors. In the present case, this is to be understood as including those compounds that inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular ben- zotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In one embodiment of the present invention, detergent compositions used in the inventive pro- cess comprise in total in the range from 0.1 to 1.5% by weight of corrosion inhibitor.

Detergent compositions used in the inventive process can comprise one or more fillers, for ex- ample sodium sulfate.

Detergent compositions used in the inventive process can comprise one or more antifoams, selected for example from silicone oils and paraffin oils.

In one embodiment of the present invention, detergent compositions used in the inventive pro- cess comprise in total in the range from 0.05 to 0.5% by weight of antifoam.

Dishware cleaned according to the inventive process exhibits excellent properties, such as very good removal of soiling, especially of fat. Furthermore, dishware cleaned according to the in- ventive process show excellent values for spotting, filming and residues. In addition, when modern dishwashing machines are used, the filter(s) and/or sieves will contain only very low amounts of surfactant and fat after operation. A further aspect of the present invention are detergent compositions, hereinafter also being re- ferred to as inventive detergent compositions, with whom the inventive process can advanta- geously be carried out. Inventive detergent compositions may be unit doses, such as tablets, or as gel or powder, as granules or compactate. In a preferred embodiment, such a unit dose comprises 10 to 30 g of inventive detergent composition.

Inventive shaped bodies, hereinafter also referred to as inventive shaped bodies, contain a de- tergent composition, hereinafter also referred to as inventive detergent composition. Inventive shaped bodies may be disk-like, spherical, or cuboids, especially with rounded corners. Pre- ferred shaped bodies are tablets. Inventive shaped bodies contain a detergent composition, preferably as mono-dose. Such a mono-dose may have a weight of from 10 to 30 g, preferably 15 to 25 g.

Inventive detergent compositions may be solid, and in such embodiments they may contain some residual humidity, such as 0.01 to 10 % by weight, water. In other embodiments, deter- gent compositions may be liquids or gels and stored in a container made from a water-soluble polymer, for example in a pouch. Preferred water-soluble polymers are polyvinylalcohols (PVA), for example with an average molecular weight M_w in the range of from 50,000 to 150,000 g/mol and with a degree of saponification in the range of from 87 to 89 mole-%. The degree of saponi- fication can be determined in accordance with the determination of the ester value, for example according to DIN EN ISO 3681 (2007-10).

Inventive detergent compositions comprise

(A) at least one graft copolymer (A),

(B) at least one non-ionic surfactant according to general formula (I), and, optionally,

(C) at least one complexing agent (C).

Preferably, inventive detergent compositions are phosphate-free. In the context of the present invention, the term phosphate-free refers to a combined phosphate and polyphosphate content of 0.01 or less up to 0.5% by weight of phosphate.

Graft copolymers comprise - as a graft base - a polyether that may be capped with Ci-C2o-alkyl or C₆-C₂o-2-hydroxyalkyl, and comprising side chains bearing C₄-C2o-fatty acid groups or C6-C20- alkoholate groups

Further details of graft copolymers (A) have been described above.

Inventive detergent compositions further comprise

(B) at least one surfactant (B) R¹-CH(0H)-CH₂-0-(A0)_X-R² (I), the variables being defined as follows:

straight-chain or branched, with at least one C-C double bond, preferred is C6-C2o-alkyl, more preferred is C8-Ci2-alkyl, even more preferred Cio-Ci2-alkyl. x is selected from one to 100, preferably from 5 to 60, more preferably 10 to 50, and even more preferably 20 to 40,

In one embodiment of the present invention, (AO)_x is selected from -(ChhCI-hO)^- (CH₂CH(CH₃)-0)_X3, X2 and x3 being identical or different and selected from 1 to 30.

Optionally, detergent compositions further comprise (C) at least one complexing agent (C).

Complexing agent (C) has been described in more detail above. Most preferred complexing agent is MGDA-Na3.

In one embodiment of the present invention, inventive detergent compositions contain in the range of from 0.1 to 10% by weight, preferably 0.25 to 5% by weight and more preferably

0.5 to 4% by weight of graft copolymer (A),

in the range of from 1 to 10 % by weight, preferably 2 to 8 % by weight and more preferably up to 6 % by weight of surfactant (B), and, optionally, in the range of from 1 to 50 % by weight, preferably 10 to 40 % by weight of complexing agent(s) (C).

Percentages of graft copolymer (A), surfactant (B) and complexing agent(s) (C) are percentages by weight and refer to the total solids content of the respective detergent composition.

In one embodiment of the present invention, inventive detergent compositions have a total sol- ids content in the range of from 90 to 99.9%, preferably 95 to 99 % by weight. Such inventive detergent compositions are, e. g., in the form of powder or tablets.

In one embodiment of the present invention, inventive detergent compositions have a total sol- ids content in the range of from 15 to 40% by weight. Such inventive detergent compositions are, e. g., in the form of gels.

In one embodiment of the present invention, inventive detergent compositions may contain at least one further ingredient, also being referred to as ingredient (D). Ingredient (D) may be se- lected from one or more surfactants other than surfactant (B), one or more enzymes, one or more builders other than graft copolymer (A), in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more antifoams, one or more corrosion inhibitors, one or more buffer or one or more dyes. Ingredients (D) have been explained in more detail above.

Inventive detergent compositions are excellently suitable for carrying out the inventive process.

A further aspect of the present invention is related to a method of making an inventive detergent composition, hereinafter also referred to as inventive process or process according to the pre- sent invention. The inventive process comprises the step of mixing graft copolymer (A), surfac- tant (B) and - if applicable complexing agent (C) and - if applicable - further ingredients.

In a preferred embodiment of the present invention, in one step of the inventive process, a pre- mix of graft copolymer and surfactant (B) is made. Said premix is then mixed with further com- ponents. Preferably, said premix has a melting point or softening point of at least 40°C, prefera- bly at least 45°C and even more preferably of at least 50 to 55°C. The melting point - or soften- ing point - of said premix is preferably not higher than 100°C, more preferably not higher than 70°C.

A further aspect of the present invention is a process for making inventive detergent composi- tions, hereinafter also being referred to as inventive manufacturing process. The inventive man- ufacturing process comprises mixing graft copolymer (A), surfactant (B) and, optionally, com- plexing agent (C) and, if applicable, one or more further ingredient (D), in one or more steps. Such mixing can be performed in the absence or presence of water, preferably mixing is being performed in the absence of water. In other embodiments, at least one of the components graft copolymer (A), surfactant (B) and complexing agent (C) or, if applicable, one or more further ingredient (D), is added as aqueous solution to other components that are powdery or in the form of granules, and the water is being removed during or after mixing. Mixing can be per- formed at a temperature in the range of from 5 to 100°C, preferably 20 to 70°C or at ambient temperature.

In one embodiment of the present invention, the inventive manufacturing process is being car- ried out in the presence of water, and such water is at least partially removed at the end of the inventive manufacturing process, for example by spray-drying or by making compactates of granules of different components or of premixed components.

Furthermore, a process for making graft copolymers (A) is disclosed, hereinafter also referred to as manufacturing process. The manufacturing process comprises grafting a polyether that may be capped with Ci-C2o-alkyl or C₆-C₂o-2-hydroxyalkyl, or non-capped, with at least one comon- omer with an ethylenically unsaturated group and bearing C₄-C2o-fatty acid groups or C6-C20- alkoholate groups.

In a preferred version, the manufacturing process comprises the steps - hereinafter also re- ferred to as step (a), step (b) or step (c) - of

(a) providing a polyether that may be capped with Ci-C2o-alkyl or C₆-C₂o-2-hydroxyalkyl,

(b) adding a comonomer selected from at least one of comonomers (II a) to (II c)

CH₂=CH-0-C(0)-R³ (II a)

CH₂=CH-CH₂-0-C(0)-R³ (H b)

CH₂=CZ-CO-OR⁴ (M e) wherein R³ is selected from C3-C2i-alkyl,

R⁴ is selected from C6-C2o-alkyl, and Z is selected from hydrogen and methyl, and, optionally, at least one further comonomer with a polymerizable C=C bond, (c) performing a radical copolymerization.

Said step (b) may also be termed a grafting reaction. Steps (a), (b) and (c) may be performed simultaneously. It is preferred to perform step (b) and step (c) simultaneously.

Suitable polyethers have been described above. In step (a), said polyether is provided in bulk or in solution ethylene glycol and propylene glycol are suitable solvents. However, providing a polyether as graft base in bulk is preferred.

In step (b), at least one comonomer that bears a C₄-C2o-fatty acid group or a C6-C20-alkoholate group is added, preferably at least one comonomer according to formula (II a), (II b) or (II c).

Preferred embodiments of comonomers (II a), (II b) and (II c) have been described above.

In step (b), comonomer that bears a C₄-C2o-fatty acid group or a C6-C20-alkoholate group may be added in bulk or in solution, preferably in bulk. In embodiments wherein said comonomer is solid at ambient temperature it is preferred to add comonomer in molten form.

In step (c), a radical copolymerization is performed. By said radical copolymerization, the comonomer(s) that bear a C₄-C2o-fatty acid group or a C6-C20-alkoholate group is grafted on the graft base, preferably at least one comonomer according to formula (II a), (II b) or (II c). The radical copolymerization is preferably performed by adding a radical starter and then allowing the comonomer added in step (b) to react with graft base provided in step (a).

In one variant, the procedure involves firstly adding of some of comonomers (II a), (II b) or (II c) and some radical starter to the graft base provided in step (a), and then adding the remainder of radical starter and comonomer (II a), (II b) or (II c).

In a particularly preferred variant, firstly graft base is introduced and heated to 60 to 120°C. Then, a part amount of comonomers (II a), (II b) or (II c) is added, preferably continuously, to- gether with a radical starter. After the reaction with the graft base (a) has subsided, a mixture of comonomer (II a), (II b) or (II c) are added, preferably continuously, together with further radical starter.

Examples of suitable radical starters are: azodiisobutyronitrile (AIBN), peroxides such as e.g. benzoyl peroxide, also hydroperoxides and peresters. Particular preference is given to using sodium peroxodisulfate and tert-butyl hydroperoxide or hydrogen peroxide, which can be used in the standard commercial concentrations and preparations, e.g. as aqueous or alcoholic solu- tions. In another embodiment, a mixture of H2O2 with iron(ll) salts can be used. The hydrogen peroxide here is preferably used in the form of aqueous solutions. Free-radical initiators are preferably used in amounts of from 0.001 to 30 mol%, preferably from 0.1 to 25 mol% and in particular from 1 to 20 mol%, in each case based on the sum of molar amounts of graft base and comonomers. The manufacturing process may be carried out at a temperature in the range from 60 to 120°C, preferably 65 to 100°C, very particularly preferably at 70 to 100°C.

The manufacturing process may be carried out at atmospheric pressure. In another embodi- ment, the process according to the invention is carried out at a pressure in the range from 1.2 to 20 bar.

A further aspect of the present invention is related to premixes, hereinafter also referred to as inventive premixes - that are excellently useful for making inventive compositions. Inventive premixes comprise

(A) at least one graft copolymer (A) and

(B) at least one non-ionic surfactant according to general formula (I)

R¹-CH(0H)-CH₂-0-(A0)_X-R² (I) wherein:

R¹ selected from C₄-C3o-alkyl, straight-chain or branched, and from C₄-C3o-alkylene, straight-chain or branched, with at least one C-C double bond,

R² selected from Ci-C3o-alkyl, straight-chain or branched, and from C2-C3o-alkylene, straight-chain or branched, with at least one C-C double bond, x being selected from one to 100,

AO identical or different alkylene oxides, selected from CH2-CH2-O, (CH₂)₃-0, (CH₂)₄-0, CH₂CH(CH₃)-0, CH(CH₃)-CH₂-0- and CH₂CH(n-C₃H₇)-0 in a weight ratio in the range of from 10:1 to 1 :100, preferably 1 :1 to 1 :75.

Inventive premixes may be made by mixing graft copolymer (A) and surfactant according to formula (B), preferably in bulk. It is even more preferred to mix graft copolymer (A) and surfac- tant according to formula (B) in liquid form, for example in molten form.

Inventive premixes preferably essentially comprise graft copolymer (A) and surfactant according to formula (B). In one embodiment of the present invention, inventive premixes comprise 0.1 to 50% by weight components other than graft copolymer (A) and surfactant according to formula (B), referring to the sum of graft copolymer (A) and surfactant according to formula (B). In this context, residual moisture is not deemed a component.

In a preferred embodiment of the present invention, inventive premixes are solid at ambient temperature. Their melting - or softening - point may be at least 40°C, preferably at least 45°C and even more preferably of at least 50 to 55°C. The melting point - or softening point - of said premix is preferably not higher than 100°C, more preferably not higher than 70°C.

When making inventive compositions - especially as shaped body - the use of inventive pre- mixes leads to a low breakage rate.

The invention is further explained by the following working examples.

General remarks:

As radical starter, tert.-butyl-peroctoate was used as a 25 % by weight solution in tripropylene glycol (“solution of radical starter”).

Comonomers for grafting: vinyl butyrate (n-butyric acid vinyl ester) (II a.1 ), vinyl 2- ethylhexanoate (II a.2), vinyl laurate (II a.3);

2-ethylhexylacrylate (II c.1 ), lauryl acrylate (II c.2), lauryl methacrylate (II c.3)

The following ingredients were used:

Surfactant (B.1 ): n-C₈Hi7-CH(OH)-CH2-0-(EO)22-CH(CH3)-CH₂-0-n-CioH2i

Surfactant (B.2): n-CioH2i-CH(OH)-CH2-0-(EO)4o-n-CioH2i

(C.1 ): trisodium salt of methyl glycine diacetic acid, MGDA-Na3

Percentages refer to weight percent unless expressly noted otherwise.

I. Syntheses of inventive graft copolymers (A) and comparison copolymers

1.1 Synthesis of inventive graft copolymer (A.1 )

A 4-l-vessel with stirrer and three feeds was charged with 1987 g polyethylene glycol (M_n: 4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 851 g 2-ethylhexylacrylate (II. c.1 ) was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71 .5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile compo- nents were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.1 ) was obtained as a white solid, 2,960 g. 1.2 Synthesis of inventive graft copolymer (A.2)

A 4-l-vessel with stirrer and three feeds was charged with 1987 g polyethylene glycol (M_n: 4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 851 g laurylacrylate (II c.2) was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g of solution of radical starter) com- menced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.2) was obtained as a white solid, 2,970 g.

1.3 Synthesis of inventive graft copolymer (A.3)

A 4-l-vessel with stirrer and three feeds was charged with 2,270 g polyethylene glycol (M_n:

4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 567 g (II c.2) was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g of solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient tempera- ture. Inventive graft copolymer (A.3) was obtained as a white solid, 2,961 g.

1.4 Synthesis of inventive graft copolymer (A.4)

A 4-l-vessel with stirrer and three feeds was charged with 2,553 g polyethylene glycol (M_n:

4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 283.5 g (II c.2) was fed continuously through feed 2 within 6 hours. After feed 1 was finished, feed 3 (3 hours, 71.5 g of solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.4) was obtained as a white solid, 2,971 g.

1.5 Synthesis of inventive graft copolymer (A.5)

4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (46 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 283.5 g (II c.2) was fed continuously through feed 2 within 5 hours. After addition feed 1 was completed, feed 3 (3 hours, 36 g of solution radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient tempera- ture. Inventive graft copolymer (A.5) was obtained as a white solid, 2,944 g.

1.6 Synthesis of inventive graft copolymer (A.6)

A 4-l-vessel with stirrer and three feeds was charged with 1987 g polyethylene glycol (M_n: 4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 851 g vinylbutyrate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient tempera- ture. Inventive graft copolymer (A.6) was obtained as a white solid, 2,964 g.

1.7 Synthesis of inventive graft copolymer (A.7)

4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 567 g vinylburyrate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g of solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient tempera- ture. Inventive graft copolymer (A.7) was obtained as a white solid, 2,957 g.

1.8 Synthesis of inventive graft copolymer (A.8)

4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 567 g vinyl-2-ethylhexanoate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g of solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile compo- nents were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.8) was obtained as a white solid, 2,961 g. 1.9 Synthesis of inventive graft copolymer (A.9)

A 4-l-vessel with stirrer and three feeds was charged with 1987 g polyethylene glycol (M_n: 4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 851 g vinyl laurate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient tempera- ture. Inventive graft copolymer (A.9) was obtained as a white solid, 2,954 g.

1.10 Synthesis of inventive graft copolymer (A.10)

4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 567 g vinyl laurate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient tempera- ture. Inventive graft copolymer (A.10) was obtained as a white solid, 2,964 g.

1.1 1 Synthesis of inventive graft copolymer (A.11 )

4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 283.5 g vinyl laurate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) com- menced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.11 ) was obtained as a white solid, 2,968 g.

1.12 Synthesis of inventive graft copolymer (A.12)

A 4-l-vessel with stirrer and three feeds was charged with 2,695 g polyethylene glycol (M_n:

4,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (46 g) was fed through feed 1 over a period of 5 hours. 15 minutes after the commencement of feed 1 , an amount of 141.9 g vinyl laurate was fed continuously through feed 2 within 6 hours. After addi- tion of feed 1 was completed, feed 3 (3 hours, 36 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient tempera- ture. Inventive graft copolymer (A.12) was obtained as a white solid, 2,947 g.

1.13 Synthesis of inventive graft copolymer (A.13)

9,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (46 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 283.5 g vinyl laurate was fed continuously through feed 2 within 5 hours. After addi- tion of feed 1 was completed, feed 3 (3 hours, 36 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient tempera- ture. Inventive graft copolymer (A.13) was obtained as a white solid, 2,947 g.

1.14 Synthesis of inventive graft copolymer (A.14)

9,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 283.5 g vinyl laurate was fed continuously through feed 2 within 6 hours. After addi- tion of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.14) was obtained as a white solid, 2,968 g.

1.15 Synthesis of inventive graft copolymer (A.15)

The protocol of 1.11 was followed, but instead of vinyl laurate, an identical amount of lauryl methacrylate was used. Inventive graft copolymer (A.14) was obtained as a white solid, 2,971 g.

1.16 Synthesis of inventive graft copolymer (A.16)

A 4-l-vessel with stirrer and three feeds was charged with 2,270 g of a di-block copolyether pol- yethylene/propylene glycol (weight ratio EO/PO: 1 :1 , M_n: 3,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 567 g lauryl acrylate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stir- ring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.16) was obtained as a white solid, 2,969 g.

1.17 Synthesis of inventive graft copolymer (A.17)

A 4-l-vessel with stirrer and three feeds was charged with 2,553 g of a di-block copolyether pol- yethylene/propylene glycol (weight ratio EO/PO: 2:3, M_n: 5,800 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 283.5 g lauryl acrylate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stir- ring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.17) was obtained as a white solid, 2,966 g.

1.18 Synthesis of inventive graft copolymer (A.18)

A 4-l-vessel with stirrer and three feeds was charged with 2,553 g of a di-block copolyether polyethylene/propylene glycol (weight ratio EO/PO: 1 :1 , M_n: 9,500 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 283.5 g lauryl acrylate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.18) was obtained as a white solid, 2,966 g.

1.19 Synthesis of inventive graft copolymer (A.19)

A 4-l-vessel with stirrer and three feeds was charged with 2,41 1 g of a di-block copolyether polyethylene/propylene glycol (weight ratio EO/PO: 1 :1 , M_n: 1 ,500 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 425 g lauryl acrylate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.19) was obtained as a white solid, 2,962 g.

1.20 Synthesis of inventive graft copolymer (A.20)

A 4-l-vessel with stirrer and three feeds was charged with 2,270 g of a di-block copolyether polyethylene/propylene glycol (weight ratio EO/PO: 2:3, M_n: 2,900 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 567 g vinyl laurate was added continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pres- sure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copoly- mer (A.20) was obtained as a white solid, 2,964 g.

1.21 Synthesis of inventive graft copolymer (A.21 )

A 4-l-vessel with stirrer and three feeds was charged with 2,270 g of polypropylene glycol (M_n: 2,000 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 567 g vinyl-2-ethylhexanoate was added continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) com- menced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.21 ) was obtained as a waxy solid, 2,972 g.

1.22 Synthesis of inventive graft copolymer (A.22)

A 4-l-vessel with stirrer and three feeds was charged with 2,270 g of surfactant (B.1) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 425 g vinyl laurate was added continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer (A.22) was obtained as a waxy solid, 2,967 g. Further graft copolymers were synthesized following the above protocols but with the following modifications. The properties of inventive graft copolymers (A.1) to (A.22) and of comparative copolymers (C) are summarized in Table 1.

1.23 Synthesis of comparative copolymer C-(A.23)

The protocol of 1.4 was followed, but instead of lauryl acrylate, the identical amount of vinyl ace- tate was used. After removal of the volatiles, comparative copolymer C-(A.23) was obtained as a white waxy solid.

1.24 Synthesis of comparative copolymer C-(A.24)

The protocol of 1.1 was followed, but instead of 2-ethylhexanoate, the identical amount of vinyl acetate was used. After removal of the volatiles, comparative copolymer C-(A.24) was obtained as a white waxy solid.

1.25 Synthesis of comparative copolymer C-(A.25)

The protocol of 1.7 was followed, but instead of lauryl acrylate, the identical amount of n-propyl acrylate was used. After removal of the volatiles, comparative copolymer C-(A.25) was obtained as a white waxy solid.

1.26 Synthesis of comparative copolymer C-(A.26)

A 4-l-vessel with stirrer and three feeds was charged with 1 ,987 g of a di-block copolyether pol- yethylene/propylene glycol (weight ratio EO/PO: 2:3, M_n: 5,800 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (91 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 851 g -propyl acrylate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 71.5 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. After removal of the volatiles, comparative copolymer C-(A.26) was obtained as a creamy waxy solid. Table 1

The base detergent composition according to Table 2 was used for making detergent composi- tions according to the invention and comparison detergent compositions. Table 2: Base detergent composition

All data in g. Firstly, base mixtures were prepared from the feed materials according to Table 2. The feed materials as well as the respective complexing agent (C) or comparative complexing agent (C) were mixed in dry state apart from (B.1), which was finally added in molten form.

General remarks about the dish-wash process:

Fat residue tests:

All dish-wash experiments were carried out in Miele automatic dish wash machines, type G1222 SCL. The program 50°C (“R-time 2”, for washing) and 65° for rinsing was selected. No separate rinsing agent was added, no regenerating salt was used. Before the tests started the sieves of the dishwashers were weighed. The dish-wash experiments were carried out with water, 21 ° dH (German hardness), Ca/Mg:HC0₃ (3:1 ): 1.35. In each experiment three knives (stainless steel), three blue melamine resin plates, eleven drinking glasses and fourteen plates from china were placed in the dishwasher. Before each cycle, 5 g of Biskin Gold®, a solid vegetable fat, and 5 g of margarine were added. In each cycle of an experiment according to the invention, 18 g of a detergent composition according to table 3 were added. In each comparison experiment accord- ing to the invention, 18 g of a detergent composition according to table 3 but excluding graft copolymer (A) were added.

5 cycles were run without drying times between cycles. After the 5^th cycles the sieve was taken out of the machine and dried for 16 hours. Then weights of the sieves were determined and the differences to their weights before the first cycle were calculated. The results are summarized in Table 3. Table 3: Results of weight differences of sieves before and after 5 cycles

The addition of only minor amounts of inventive graft copolymer (A) significantly reduced the fat residue in the test.

Premixes comprising inventive graft copolymers (A) and non-ionic surfactants mixtures and the effect on melting points/range. Inventive graft copolymers (A) in accordance with Table 4 were mixed with non-ionic surfactant (B.1 ) (mp 33-35°C) or (B.2) (mp 31 -33°C) and homogenized at 95°C. Table 4 shows the recipe and resulting melting temperatures as determined with a Melting Point M-560, Fa. Buchi. Table 4: Automatic Dishwashing tests

Surfactant (B.1 ): n-C₈Hi7-CH(OH)-CH2-0-(EO)22-CH(CH3)-CH₂-0-n-CioH2i

Surfactant (B.2): n-CioH2i-CH(OH)-CH2-0-(EO)4o-n-CioH2i

Surfactant (B.3): n-C5Hii-CH(n-C3H₇)-CH2-(EO)32-n-Ci2H25

The combined action solves the issues with respect to processing temperature with a minimum demand of 45°C to enable tableting of ADW formulations. At the same time the fatty residues in the machine keep to be very low.

Claims

Patent claims:

1. Process for cleaning dishware by using at least one detergent composition, comprising

(A) at least one graft copolymer comprising - as a graft base - a polyether that may be capped with Ci-C₂o-alkyl or C₆-C₂o-2-hydroxyalkyl, and comprising side chains bearing C₄-C₂o-fatty acid groups or C₆-C₂o-alkoholate groups, and

(B) at least one non-ionic surfactant according to general formula (I)

R¹-CH(0H)-CH₂-0-(A0)_X-R² (I) wherein:

R² selected from Ci-C3o-alkyl, straight-chain or branched, and from C₂-C3o-alkylene, straight-chain or branched, with at least one C-C double bond, x being selected from one to 100,

AO identical or different alkylene oxides, selected from CH₂-CH₂-0, (CH₂)₃-0, (CH₂)₄-0, CH₂CH(CH₃)-0, CH(CH₃)-CH₂-0- and CH₂CH(n-C₃H₇)-0.

2. Process according to claim 1 , wherein said detergent composition contains

in the range of from 0.1 to 10 % by weight graft copolymer (A),

in the range of from 1 to 10% by weight of non-ionic surfactant (B),

percentages being based on the total solids content of said detergent composition.

3. Process according to claim 1 or 2, wherein said detergent composition additionally corn- prises at least one complexing agent (C) selected from the alkali metal salts of methyl gly cine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA).

4. Process according to any of claims 1 to 3, wherein graft copolymer (A) has an average molecular weight M_n in the range of from 2,250 to 10,000 g/mol.

5. Shaped body containing a detergent composition, comprising

(A) at least one graft copolymer comprising - as a graft base - a polyether that may be capped with Ci-C₂o-alkyl or C₆-C₂o-2-hydroxyalkyl, and comprising side chains bear- ing chains bearing C₄-C₂o-fatty acid groups or C₆-C₂o-alkoholate groups, and

(B) at least one non-ionic surfactant according to general formula (I)

R¹-CH(0H)-CH₂-0-(A0)_X-R² (I) wherein:

R² selected from Ci-C3o-alkyl, straight-chain or branched, and from C₂-C3o-alkylene, straight-chain or branched, with at least one C-C double bond, x selected from one to 100,

6. Shaped body according to claim 5, wherein said detergent composition contains

in the range of from 0.1 to 10% by weight graft copolymer (A),

in the range of from 1 to 10% by weight of non-ionic surfactant (B),

percentages being based on the total solids content of said composition.

7. Shaped body according to claim 5 or 6, wherein the graft base of graft copolymer (A) is selected polyethylene glycol, polypropylene glycol and EO-PO block copolymers, each non-capped or capped with Ci-C₂o-alkyl or C₆-C₂o-2-hydroxyalkyl.

8. Shaped body according to any of claims 5 to 7, wherein the side chains of copolymer (A) contain in copolymerized form at least one of comonomers (II a) to (II c)

CH₂=CH-0-C(0)-R³ (II a)

CH₂=CH-CH₂-0-C(0)-R³ (H b)

CH₂=CZ-CO-OR⁴ (li e) wherein R³ is selected from C3-C_2i-alkyl,

R⁴ is selected from C₆-C₂o-alkyl, and Z is selected from hydrogen and methyl.

9. Shaped body according to any of claims 5 to 8 wherein said detergent composition is solid at ambient temperature.

10. Detergent composition according to any of claims 5 to 9 wherein graft copolymer (A) has an average molecular weight M_w in the range of from 2,250 to 10,000 g/mol.

1 1 . Premix comprising

(A) at least one graft copolymer (A) comprising - as a graft base - a polyether that may be capped with Ci-C₂o-alkyl or C₆-C₂o-2-hydroxyalkyl, and comprising side chains bearing chains bearing C₄-C₂o-fatty acid groups or C₆-C₂o-alkoholate groups, and

(B) at least one non-ionic surfactant according to general formula (I)

R¹-CH(0H)-CH₂-0-(A0)_X-R² (I) wherein:

AO identical or different alkylene oxides, selected from CH₂-CH₂-0, (CH₂)₃-0, (CH₂)₄-0, CH₂CH(CH₃)-0, CH(CH₃)-CH₂-0- and CH₂CH(n-C₃H₇)-0 in a weight ratio in the range of from 10:1 to 1 :100.

12. Premix according to claim 1 1 wherein the side chains of graft copolymer (A) contain in copolymerized form at least one of comonomers (II a) to (II c)

CH₂=CH-0-C(0)-R³ (II a)

CH₂=CH-CH₂-0-C(0)-R³ (H b)

CH₂=CZ-CO-OR⁴ (li e) wherein R³ is selected from C3-Ci9-alkyl,

R⁴ is selected from C₆-C₂o-alkyl, and Z is selected from hydrogen and methyl,

13. Premix according to claim 11 or 12 wherein graft copolymer (A) has an average molecular weight M_n in the range of from 2,250 to 10,000 g/mol.

14. Premix according to any of claims 1 1 to 13 wherein said graft copolymer (A) has a weight ratio of graft base to side chains in the range of from 95:5 to 3:2