CN116568758A - biodegradable polymer - Google Patents

Abstract

The present invention relates to biodegradable polymers, a process for producing such polyamines and alkoxylated polyamines, the use of such polyamines and alkoxylated polyamines and formulations and compositions comprising such polyamines and alkoxylated polyamines, the use of such polyamines and alkoxylated polyamines as ingredients of formulations and compositions in the fields of fabric and home care, industrial and institutional cleaning, cosmetics, personal care, agricultural formulations, industrial formulations and construction formulation applications.

Description

biodegradable polymer

The present invention relates to biodegradable polymers having structural units of polyamines or alkoxylated polyamines, a process for the production of such polymers, the use of such polymers as well as formulations and combinations comprising such polymers Use of such polymers as ingredients in formulations and compositions in the fields of fabric and home care, industrial and institutional cleaning, cosmetics, personal care, agricultural formulations, industrial formulations and construction formulations applications.

Certain polyamines and alkoxylated polyamines containing ethoxylate chains or chain moieties and their use in fabric care and home care applications are well known. A variety of such products are commercially available. There is a continuing desire to formulate more sustainable detergents and to further improve the biodegradability of ingredients including detergent polymers.

Therefore, there is a need to provide polyamines and polyamines which exhibit advantageous properties, such as wash performance in laundry, in detergents such as fabric and home care products and applications such as laundry, but at the same time provide enhanced biodegradation compared to known commercial products. Alkoxylated polyamine.

The invention further includes polymers as defined below.

The invention further comprises a process for the preparation of a polymer as defined below.

The invention further comprises polymers obtainable by or derived from the process of the invention as defined below.

The present invention further includes polymers having advantageous initial wash properties.

The invention further comprises the use of the polymers of the invention in the fields of fabric and home care, industrial and institutional cleaning, cosmetic and personal care applications, preferably in laundry applications, such formulations and compositions as improved wash performance, more preferably primary Use of ingredients for washing performance.

This object is achieved by the embodiments defined below:

implementation plan

In one embodiment of the invention, the polymer of the invention comprises:

a) 5-40% by weight of at least one amine having at least 2 amine groups, such as 1,4-bis(3-aminopropyl)piperazine, ethylenediamine, propylenediamine, butylenediamine, pentamethylene Diamine, hexamethylenediamine, heptanediamine, octanediamine, preferably polyethyleneimine (PEI), tris(2-aminoethyl)amine, tris(3-aminopropyl)amine,

1-(3-1,2-diaminocyclohexane, 1,2-diaminopropane, 1,2-propylenediamine, 1,3-diaminopropane, 2-(2-aminoethoxy)ethanol , 2-3-(2-aminoethylamino)propylamine, 3-(cyclohexylamino)propylamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'- Diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 4,7,10-tris Oxatridecane-1,13-diamine, 4,9-dioxadodecane-1,12-diamine, methylcyclohexane-2,4-diamine and 2,6-diamine Isomers, diethylenetriamine, dipropylenetriamine, ethylenediamine, isophoronediamine, N-(2-aminoethyl)ethanolamine, N,N'-bis(3-amino Propyl)ethylenediamine, N,N-bis(3-aminopropyl)methylamine, N,N-dimethylcadaverine, neopentyldiamine (2,2-dimethyl-1,3-propanediamine amine), octamethylenediamine, piperazine; polyetheramines such as methoxypolyethylene glycolamine, 3,3'-oxybis(ethyleneoxy)bis(propylamine), O,O '-bis(2-aminopropyl)polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol and similar structures with different polyoxyalkylene chain structures; amino acids such as particularly preferred histidine, lysine ; other amines such as histamine, citrulline, diaminopimelic acid; naturally occurring amines such as chitosan and zein;

More preferred are diethylenetriamine (DETA), triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tris(2-aminoethyl)amine, N,N'-bis(3 -aminopropyl)ethylenediamine (H ₂ N(CH ₂ ) ₃ NHCH ₂ CH ₂ NH((CH ₂ ) ₃ ) ₂ NH ₂ ="N4-amine"), most preferably N4-amine and tris(2- Aminoethyl)amine,

b) 10-65% by weight of at least one acrylate selected from glycerol propoxylate tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, trimethylolpropoxylate propane propoxylate tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta- or hexa(meth)acrylate Acrylates, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate and polyethylene glycol di(meth)acrylate, preferably the corresponding acrylates ,

c) 10-75% by weight of at least one monoacrylate, such as stearyl polyethylene glycol methacrylate 1100, hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and/or stearyl polyacrylate Ethylene glycol acrylate 1100, preferably polyethylene glycol methyl ether methacrylate [H ₂ C=CCH ₃ CO ₂

(CH ₂ CH ₂ O) _n CH ₃ ], polyethylene glycol methyl ether acrylate [H ₂ C=CHCO ₂ (CH ₂ CH ₂ O) _n CH ₃ ], stearyl polyethylene glycol methacrylate Ester 1100 (CAS No. 70879-51-5) and/or Stearyl Polyethylene Glycol Acrylate 1100, most preferably Polyethylene Glycol Methyl Ether Methacrylate [H ₂ C=CCH ₃ CO ₂ (CH ₂ CH ₂ O) _n CH ₃ ], where n is in the range from 5 to 40, with the proviso that the sum of components a), b) and c) add up to 100% by weight.

Other embodiments are listed in the dependent claims and they are explained in more detail below.

In one embodiment of the invention, the entirety of component b) consists of the abovementioned triacrylates and trimethacrylates. In another embodiment, the entirety of component b) consists of the abovementioned diacrylates and dimethacrylates. In one embodiment of the invention, the amount of component a) is 10-35% by weight, preferably 10-30% by weight, more preferably 10-28% by weight, even more preferably about 25% by weight, of the polymer of the invention, Most preferably about 20% by weight, the amount of component b) is 10-65% by weight, preferably 10-60% by weight, more preferably 15-55% by weight, even more preferably 20-50% by weight, most preferably Preferably 30-45% by weight, such as about 40% by weight and the amount of component c) is 10-75% by weight, preferably 10-60% by weight, more preferably 10-50% by weight, even more preferably 10- 45% by weight, such as 25-50% by weight, 20-45% by weight and about 40% by weight. In one embodiment of the invention, component b) consists of a combination of the abovementioned diacrylates and triacrylates or tetraacrylates, wherein the amount of triacrylates or tetraacrylates is at most 50 mol of the total amount of component b) %, preferably up to 30 mol%, more preferably up to 20 mol%, even more preferably up to 10 mol%, such as up to 5 mol%. The formulations or compositions according to the invention can be used in effective amounts for removing or releasing solid or water-insoluble substances from surfaces and/or dispersing such substances in liquids and/or solids.

Other embodiments of the present invention are as follows:

In another embodiment, such polymers comprise:

a) 5-40% by weight of at least one amine having at least 2 amine groups, such as 1,4-bis(3-aminopropyl)piperazine, ethylenediamine, propylenediamine, butylenediamine, pentamethylene Diamine, hexamethylenediamine, heptanediamine, octanediamine, preferably polyethyleneimine (PEI), tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, more preferably Diethylenetriamine (DETA), triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, most preferably N,N'-bis(3-aminopropyl)ethylenediamine,

b) 10-60% by weight of at least one acrylate selected from glycerol propoxylate (1PO/OH) triacrylate, di(trimethylolpropane) tetraacrylate, trimethylolpropane propoxylate Triacrylate, Trimethylolpropane Trimethacrylate, Trimethylolpropane Ethoxylate Triacrylate, Pentaerythritol Tetraacrylate, Dipentaerythritol Penta/Hexaacrylate, Trimethylolpropane Trimethacrylate ester [H ₂ C=C(CH ₃ )CO ₂ CH ₂ ] ₃ CC ₂ H ₅ ], trimethylolpropane triacrylate [H ₂ C=CHCO ₂ CH ₂ ] ₃ CC ₂ H ₅ ], trihydroxy Methylpropane ethoxylate triacrylate [H ₂ C=CHCO ₂ (CH ₂ CH ₂ O) _n CH ₂ ] ₃ CC ₂ H ₅ ] and/or diethylene glycol dimethacrylate [H ₂ C= C(CH ₃ )CO ₂ CH ₂ CH ₂ ] ₂ O, polyethylene glycol diacrylate [H ₂ C=CHCO(OCH ₂ CH ₂ ) _n OCOCH=CH ₂ ], more preferably trimethylolpropane ethoxylate triacrylate [H ₂ C=CHCO ₂ (CH ₂ CH ₂ O) _n CH ₂ ] ₃ CC ₂ H ₅ ], trimethylolpropane triacrylate and/or polyethylene glycol diacrylate, most Preference is given to trimethylolpropane ethoxylate triacrylate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate, and

c) 15-75% by weight of at least one monoacrylate, such as stearyl polyethylene glycol methacrylate 1100, hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and/or stearyl polyacrylate Ethylene glycol acrylate 1100, preferably polyethylene glycol methyl ether methacrylate [H ₂ C=CCH ₃ CO ₂ (CH ₂ CH ₂ O) _n CH ₃ ], polyethylene glycol methyl ether acrylate [ H ₂ C=CHCO ₂

(CH ₂ CH ₂ O) _n CH ₃ ], Stearyl Polyethylene Glycol Methacrylate 1100 (CAS No. 70879-51-5) and/or Stearyl Polyethylene Glycol Acrylate 1100, most preferably poly Ethylene glycol methyl ether methacrylate,

The proviso is that the sum of compounds a), b) and c) adds up to 100% by weight.

In one embodiment, the amount of component a) is 10-35% by weight, preferably 10-30% by weight, more preferably 10-25% by weight, even more preferably about 20% by weight, and the amount of component b) is 10% by weight - 60% by weight, preferably 15-55% by weight, more preferably 20-50% by weight, even more preferably 30-45% by weight, such as about 40% by weight and component c) in an amount of 15-75% by weight, preferably 20- 60% by weight, more preferably 25-50% by weight, even more preferably 20-45% by weight, such as about 40% by weight.

In one embodiment, the amount of the corresponding triacrylate or higher acrylate is at most 50 mol%, preferably at most 30 mol%, more preferably at most 20 mol%, even more preferably at most 10 mol%, such as at most 5 mol% of the total amount of component b) %.

In one embodiment, the amount of component a) is 15-35% by weight, preferably 10-33% by weight, more preferably 20-30% by weight, even more preferably about 25% by weight, and the amount of component b) is 10% by weight - 60% by weight, preferably 20-55% by weight, more preferably 25-53% by weight, even more preferably 30-50% by weight, most preferably 40-50% by weight, such as about 40% by weight and the amount of component c) is 15% by weight - 75% by weight, preferably 20-55% by weight, more preferably 23-50% by weight, even more preferably up to 45% by weight or even up to 40% by weight, such as up to 35% by weight, in particular about 40% by weight.

In another embodiment of the present invention, the polymer disclosed above is prepared by a process comprising the steps of:

A) The following components are reacted by Michael addition:

a) 15-40% by weight of at least one amine having at least 2 amine groups, such as 1,4-bis(3-aminopropyl)piperazine, ethylenediamine, propylenediamine, butylenediamine, pentamethylene Diamine, hexamethylenediamine, heptanediamine, octyldiamine, preferably polyethyleneimine (PEI), tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, more preferably Diethylenetriamine (DETA), triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, more preferably N4-amine, and

b) 10-60% by weight of at least one acrylate selected from the group consisting of glycerol propoxylate (1PO/OH) triacrylate, di(trimethylolpropane) tetraacrylate, trimethylolpropane propoxylate trimethylolpropane trimethacrylate, trimethylolpropane ethoxylate triacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta/hexaacrylate, 1,1,1-tri Methylolpropane trimethacrylate [H ₂ C=C(CH ₃ )CO ₂ CH ₂ ] ₃ CC ₂ H ₅ ], 1,1,1-trimethylolpropane triacrylate, 1,1, 1-Trimethylolpropane ethoxylate triacrylate [H ₂ C=CHCO ₂ (CH ₂ CH ₂ O) _n CH ₂ ] ₃ CC ₂ H ₅ ], diethylene glycol dimethacrylate [H ₂ C=C(CH ₃ )CO ₂ CH ₂ CH ₂ ] ₂ O, polyethylene glycol diacrylate [H ₂ C=CHCO(OCH ₂ CH ₂ ) _n OCOCH=CH ₂ ], wherein n is in the range of 5-14 Within, more preferably 1,1,1-trimethylolpropane ethoxylate triacrylate, 1,1,1-trimethylolpropane triacrylate and polyethylene glycol diacrylate, even more preferably 1 ,1,1-Trimethylolpropane Ethoxylate Triacrylate, 1,1,1-Trimethylolpropane Trimethacrylate and 1,1,1-Trimethylolpropane Triacrylate,

to obtain amine-containing polyamines, and

B) reacting the polyamine obtained in step A) with the following components:

c) 15-75% by weight of at least one monoacrylate, such as stearyl polyethylene glycol methacrylate 1100, hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and/or stearyl polyacrylate Ethylene glycol acrylate 1100, preferably polyethylene glycol methyl ether methacrylate [H ₂ C=CCH ₃ CO ₂ (CH ₂ CH ₂ O)nCH ₃ ], polyethylene glycol methyl ether acrylate [H ₂ C=CHCO ₂ (CH ₂ CH ₂ O) _n CH ₃ ], Stearyl Polyethylene Glycol Methacrylate 1100 (CAS No. 70879-51-5) or Stearyl Polyethylene Glycol Acrylate 1100, Even more preferably polyethylene glycol methyl ether methacrylate [H ₂ C═CCH ₃ CO ₂ (CH ₂ CH ₂ O) _n CH ₃ ],

- provided that the sum of compounds a), b) and c) adds up to 100% by weight,

to obtain preferably biodegradable polymers,

wherein the reaction in step A) is preferably carried out substantially in bulk (i.e. substantially no solvent is added) and preferably to substantially all of the acrylate groups reacted, and wherein the reaction in step B) is preferably carried out substantially in bulk (i.e. substantially no solvent is added) and preferably proceeds until substantially all of the acrylate groups have reacted.

In one embodiment of the present invention, the reaction of steps A) and B) independently at 50-150°C and 0.5-5 bar pressure, preferably 50-110°C and ambient pressure, more preferably 70°C, even more preferably 80°C , such as 55°C, 60°C, 65°C, 75°C, 85°C, 90°C or 95°C for 3-15 hours, preferably 5-12 hours, more preferably 6-10 hours, such as 7, 8 or 9 hours time.

The polymers described above can be used in fabric and home care, industrial and institutional cleaning, cosmetics, personal care, industrial formulations such as paints and colours, formulations in the construction sector such as cements containing inorganic materials which need to be dispersed and/or stabilized and in formulations or compositions in the field of cement-containing formulations etc. and agricultural formulation applications, preferably as dispersants in the respective application to remove or release substances from surfaces and/or to disperse substances in liquids and/or solids.

General process description

A general process scheme of the process of the present invention is shown in Figure 1A excluding optional step B. Figure IB includes this optional process step B.

Figure 1 is intended to illustrate the general synthetic pathway; therefore, the residues R1, R2, R3, R4 and R5 are shown as placeholders for suitable chemical groups such as alkyl, aryl, alkaryl which may contain other heteroatom-containing substituents out.

In particular, R1, R2, R3, R4 and R5 as can - but usually preferably do not - contain other groups such as hydroxyl groups, amide groups, carboxylate groups, preferably only hydroxyl groups, most preferably free of such other groups Placeholders for alkyl, aryl, and alkaryl groups are shown.

Each of these residues can be selected independently of each other as further defined below in the description of the general process:

The process uses in principle two ways to obtain the polymers of the invention, either a linear polymer or a branched (or hyperbranched depending on the degree of branching) polymer:

The process begins by providing an amine compound having at least two amine groups (the "A2" monomer in Figure 1).

Linear polymers are obtained by reacting one or more A2 monomers (diamines) with one or more B2 monomers (diacrylate monomers) to give linear polymers. Further reaction of this linear polymer with a B4 monomer (monoacrylate, preferably a hydrophilic acrylate monomer) yields the functionalized polyamines of the present invention. This can be further modified by alkoxylation using standard procedures and conditions (not shown in Figure 1).

Branched polymers are obtained by combining one or more A2 monomers with at least a defined amount of one or more B3 monomers (acrylates having at least 3 polymerizable olefin units, such as triacrylates) and optionally some One or more B2 monomers (diacrylate monomers) are reacted to give branched polymers or - in relatively large amounts of B3 relative to B2 - hyperbranched polymers. The (hyper)branched polymer is further reacted with one or more B4 monomers (monoacrylates, preferably hydrophilic acrylate monomers) to obtain the functionalized polyamines of the invention. This can also be further modified by alkoxylation (not shown in Figure 1).

By choosing the relative amounts (ratio) of B2 to B3 monomers and also the relative amounts of B2 to B3 monomers to A2 monomers, the structure of the polyamine polymers of the invention can be varied to a large extent, resulting in linear polymers, slightly Branched polymers to highly branched polymers such as even hyperbranched polymers.

By further selecting not only diamines but also amines with more than 2 amine groups in the molecule as A2 monomers and also by selecting mixtures of various amines (which can have different numbers of amine groups in the corresponding molecules, that is, choosing diamines Adding mixtures of triamines), the present invention offers a further possibility of modifying the polymer structure of branched polymers.

The Michael reactions of the monomers of components a) and b) as defined above can be carried out in various orders to obtain linear polymers: one or more A2 can be combined with one or more B2 in a single reaction or Reaction in a stepwise reaction, such as one or more A2 plus one or more B2, then another or the same A2 monomer, then another or the same B2 monomer, etc., finally obtained by one or more A linear polymer composed of various A2 monomers and one or more B2 monomers.

The same is certainly true for the process route to obtain branched polymers: one or more A2 and B (can be one or more B2 and/or one or more B3, provided that there must be a certain amount of at least A B3) is reacted in a single reaction or in a stepwise reaction, such as one or more A2 plus one or more B2 and/or B3 (wherein at least one B3 is present in the required amount), followed by another and/or the same A2 monomer, then another or the same B2 monomer and/or B3 monomer, etc., finally obtained by one or more A2 monomers and one or more B2 monomers and/or A linear polymer of one or more B3 monomers (provided that at least one B3 is used in the required amount).

The invention includes all those changes and modifications generally described before to obtain polyamine polymers.

By further alkoxylation of these polyamines, further modification results in alkoxylated polyamines. Further modifications of this structure are readily obtained by appropriate choice of alkoxylates and mixtures of more than one alkoxylate. A block structure of polyalkoxylate chains attached to the polyamines according to the invention can be obtained, for example, by first reacting one alkoxylate and then reacting a second alkoxylate. By such selection of alkoxylates, the hydrophilicity/hydrophobicity of such polyalkoxy side chains can be adjusted to achieve the desired overall hydrophilic-hydrophobic balance of the alkoxylated polyamines of the invention.

Such polyalkoxy chains can of course also be introduced by using polyoxyalkylene-(meth)acrylate monomers such as Jeffamine type monomers as the monoacrylate component. Even when such polyoxyalkylene-(meth)acrylate monomers are used, further alkoxylation is still a possible reaction, and the present invention also includes polyoxyalkylene-(meth)acrylate monomers comprising Such further alkoxylated polyamines of "component c)" (as defined in embodiment 1, more particularly as defined in the other embodiments).

The invention includes all those changes and modifications generally described before obtaining polyamine polymers and alkoxylated polyamine polymers; the polyamines of the invention and thus also the alkoxylated polyamines are described in the following embodiments. General composition of amines.

The term "obtainable by" as used herein generally means that the corresponding product is generally not necessarily produced (that is, obtained) by the corresponding method or process described in the corresponding specific context, but includes the product having the ability to be produced by the corresponding method or process ( A product that has all the characteristics of a product obtained) that is not actually produced (obtained) by the method or process. However, the term "obtainable from" also includes the more restrictive term "obtained from", ie products that are actually produced (ie obtained) by the method or process described in the corresponding specific context.

"Branched"/"hyperbranched" is a colloquial differentiation of the degree of branching which depends on the raw materials used, ie the amount of raw materials and the functionalities therein and their relative ratio to each other. The term is not further differentiated in terms of chemical structure beyond this general distinction between "slightly branched" and "massively branched".

"Biodegradable", "biodegradable" with or without "as tested under standard conditions" means that the biodegradability test has been used according to ISO14851 or ISO14852 (both in water), OECD 301F test method or according to ASTM D. 6691 (in seawater) or according to ISO 17556 (in soil) biodegradation of said substance, compound or formulation and—if a percentage is given such as "30% biodegradable/biodegradable"; the test method— In the case of different results, and when two test conditions are feasible and can be used, the test according to OECD 301F shall be the decisive one.

The following terms—and other terms of art not listed below—have their ordinary meanings unless explicitly defined otherwise in this disclosure:

Molecular weight descriptors Mw, Mn and polydispersity of molecular weight (PDI as polydispersity index); pH value; ¹ H-NMR.

All percentages given are by weight based on the total weight of the composition, formulation, dispersion, feed, mixture, etc., unless expressly defined otherwise; abbreviated as "% by weight".

The term "obtainable by" as used herein generally means that the corresponding product is generally not necessarily produced (that is, obtained) by the corresponding method or process described in the corresponding specific context, but includes the product having the ability to be produced by the corresponding method or process ( A product that has all the characteristics of a product obtained) that is not actually produced (obtained) by the method or process. However, the term "obtainable from" also includes - and preferably refers to - the more restrictive term "obtainable from", i.e. actually produced by the method or process described in the corresponding specific context (i.e. obtained )The product.

The term "about" means that small deviations from the actual value given are intended to be included by the term. Thus, "about 50% by weight" shall also include +/- 10% deviations from the original value given in figures and thus the value of "45-55% by weight", but preferably +/- 5% deviations, more preferably +/- 3% deviation, even more preferably +/- 1% deviation, correspondingly within this category - as applies to the above range - includes all other numbers and values between 10 and 0 (zero), Most preferably should consist only of the given values.

The term "substantially" as used, for example, in "substantially in bulk", "substantially no added solvent" and "substantially all acrylate groups" shall mean, for example, that the reaction proceeds to near completion, i.e. close to/almost 100% or as the term Indicates that solvent or any other group is (or is not) nearly completely present/absent and similar uses of the term. In the preferred form, "substantially" shall include the small deviations normally present in commercial operations, for example when using technical grade ingredients such as solvents etc. which are by no means "100% pure" but "technical grade" or when measured values When certain descriptors are shown to be absent, eg "essentially all acrylate groups have reacted (according to method X)" means that no acrylate groups are detectable according to method X.

The polymers according to the invention can advantageously be used in formulations or compositions in the fields of fabric and home care, industrial and institutional cleaning, cosmetics, personal care, paint and color formulations, industrial applications, agricultural formulation applications, in various In applications preferably as a dispersant and/or soil release agent to release dirt and other stains from surfaces and/or to disperse dirt, stains, organic and/or inorganic solid particles in liquid or solid environments such as liquid formulations or powder formulations Or solids such as extruded particles or solid films.

In one embodiment of the invention, formulations or compositions according to the invention comprise from 0.2 to 10% by weight of the polymers according to the invention, relative to the total solids content of the formulation or composition. The total solids content is determined by drying to constant weight at 150-200°C with infrared light.

Compositions for fabric and home care

Such compositions and formulations include those designed for cleaning soiled materials or surfaces of any kind, including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric strengthening compositions, fabric refreshing compositions, Laundry pre-wash liquids, laundry pre-treatment liquids, laundry additives, spray products, dry-cleaning preparations or compositions, laundry rinse additives, washing additives, fabric after-rinse treatments, ironing aids, dishwashing compositions, hard Surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwovens and other suitable forms may be apparent to those skilled in the art in view of the teachings herein. Such compositions may be used as pre-wash treatments, post-wash treatments or may be added during the rinse or wash cycle of a laundry operation. The cleaning composition may have a form selected from liquid, powder, single or multi-phase unit dose, sachet, tablet, gel, paste, stick or flake. Specifically included are cleaning compositions as further defined below.

cleaning composition

As used herein, the phrase "cleaning composition" includes compositions and formulations designed for cleaning soiled materials. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric strengthening compositions, fabric freshening compositions, laundry pre-washes, laundry pre-treatments, laundry additives, spray products, Dry cleaning agent or composition, rinse additive for laundry, detergent additive, fabric after-rinse treatment, ironing aid, dishwashing composition, hard surface cleaning composition, unit dose formulation, delayed delivery formulation, contained in a porous base detergent on or in a fabric or nonwoven and other suitable forms that may be apparent to those skilled in the art in view of the teachings herein. Such compositions may be used as pre-wash treatments, post-wash treatments or may be added during the rinse or wash cycle of a laundry operation. The cleaning composition may have a form selected from liquid, powder, single or multi-phase unit dose, sachet, tablet, gel, paste, stick or flake.

Preferably the cleaning compositions of the present invention are laundry cleaning compositions and detergents for use in laundry, more preferably for a first wash in laundry applications, even more particularly for the removal of clay-based stains such as those on fabrics those in the field.

Industrial and Institutional Cleaning

Such compositions and formulations include those designed for cleaning soiled materials or surfaces of any kind, such as for use on surfaces of any kind including tiles, carpets, PVC surfaces, wooden surfaces, metal surfaces, painted surfaces Hard surface cleaner.

The cleaning compositions of the present invention preferably comprise a surfactant system in an amount sufficient to provide the desired cleaning performance. In some embodiments, the cleaning compositions comprise from about 1-70% surfactant system, based on the weight of the composition. In other embodiments, the liquid cleansing composition comprises about 2-60% of the surfactant system, based on the weight of the composition. In other embodiments, the cleaning composition comprises about 5-30% of the surfactant system, based on the weight of the composition. The surfactant system may comprise a cleansing surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, amphiphilic surfactants, and mixtures thereof . Those of ordinary skill in the art will understand that detersive surfactants include any surfactant or mixture of surfactants that provide cleaning, stain removal, or detergency benefits to soiled materials.

The cleaning compositions of the present invention can also - and preferably do - contain auxiliary cleaning additives (also abbreviated herein as "adjuvants"). Suitable auxiliary cleaning additives include builders, structurants or thickeners, clay stain removal/anti-redeposition agents, polymeric soil release agents, polymeric dispersants, polymeric grease cleaners, enzymes, enzyme stabilization systems, bleach Compounds, bleaches, bleach activators, bleach catalysts, brighteners, dyes, toners, dye transfer inhibitors, chelating agents, suds suppressors, softeners and fragrances.

Another subject of the present invention is at least one polymer according to the invention (also referred to herein as "polymer of the invention" or sometimes as "polymer (P1)" (without limiting "polymer of the invention" to the examples 1, that is, the term "polymer (P1)" does not mean "the polymer of Example 1", but includes the polymer of Example 1) in laundry detergents, fabric and home care products and/or In cosmetic formulations, the use in cleaning compositions and/or fabric and home care products is preferred.The embodiments and examples described herein further illustrate such claimed uses as well as compositions and formulations.

A further subject-matter of the present invention is therefore laundry detergents, cleaning compositions, fabric and home care products and/or cosmetic formulations comprising at least one polymer according to the invention as described above.

Preferably the compositions of the invention are laundry detergents, cleaning compositions and/or fabric and home care products comprising at least one polymer of the invention as described above, providing improved stain removal, dispersion and/or Emulsification and/or modification.

Laundry detergents, cleaning compositions and/or fabric and home care products are known per se to the person skilled in the art. For the respective use, any composition etc. known to the person skilled in the art can be used in the context of the present invention.

The composition may be in any form, i.e. in liquid form; solids such as powders, granules, agglomerates, pastes, tablets, sachets, sticks, gels; emulsions; types delivered in dual or multi-chambered containers; sprays or foam detergent; pre-moistened wipes (i.e. the cleaning composition combined with a nonwoven material such as those discussed in Mackey et al. US 6,121,165); dry wipes activated by consumer water (i.e. the cleaning composition combined with a nonwoven combinations of materials such as those discussed in Fowler et al. US 5,980,931); and other homogeneous or heterogeneous consumer cleaning product forms.

At least one inventive polymer as described herein is present in an amount of 0.05-20% by weight, preferably about 0.05-15% by weight, more preferably about 0.1-10% by weight, most preferably about 0.5-10% by weight, relative to the total weight of the composition or product. A concentration of 5% by weight is present in the composition according to the invention.

In a preferred embodiment, the cleaning compositions of the present invention are liquid or solid laundry detergent compositions. In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that can be used to clean various surfaces such as hardwood, tile, ceramic, plastic, leather, metal, glass. In another embodiment, the cleaning composition is designed for use in personal care and pet care compositions such as shampoo compositions, body washes, liquid or solid soaps.

In another embodiment, the cleaning composition of the present invention is a dishwashing composition, such as a tablet/unit dose of a liquid hand dishwashing composition, a solid automatic dishwashing composition, a liquid automatic dishwashing composition and an automatic dishwashing composition form.

Very typically, cleaning compositions herein such as laundry detergents, laundry detergent additives, hard surface cleaners, synthetic and soap based laundry bars, fabric softeners and fabric treatment liquids, solids and treatment articles of all kinds require Several auxiliaries.

Cleaning adjuncts common to cleaning compositions include surfactants, builders, secondary builders, dispersant polymers, dye transfer inhibitors, anti-redeposition agents, enzymes, suds boosters, suds suppressors (anti-foam Foaming agent), etc., stain agent, silver care agent, anti-tarnish agent and/or preservative, dye, pigment, source of alkalinity, hydrotrope, antioxidant, enzyme stabilizer, original fragrance, fragrance, solubilizer, carrier and processing aids.

Liquid compositions may additionally contain rheology control agents and solvents and solid compositions may additionally contain fillers, bleaches, bleach activators and catalytic materials.

Suitable examples and use levels of such cleaning adjuncts are found in WO 99/05242, US Patent Nos. 5,576,282, 6,306,812B1 and 6,326,348B1.

The laundry detergents, cleaning compositions and/or fabric and home care products according to the invention preferably additionally comprise a surfactant system and, if appropriate, further adjuvants as described above. The surfactant system may be composed of a surfactant or combination of surfactants selected from: anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, Amphiphilic surfactants and mixtures thereof. Those of ordinary skill in the art will understand that surfactant systems for use in detergents include any surfactant or mixture of surfactants that provide cleaning, stain removal or detergency benefits to soiled materials.

Non-limiting examples of anionic cosurfactants useful herein include C ₉ -C ₂₀ linear alkylbenzene sulfonates (LAS), C ₁₀ -C ₂₀ branched and random primary alkyl sulfates (AS); C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates; C ₁₀ -C ₁₈ alkyl alkoxy sulfates (AExS), where x is 1-30; C ₁₀ containing 1-5 ethoxy units - C ₁₈ alkyl alkoxy carboxylates; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy as discussed in US 6,008,181 and US 6,020,303 Sulfates; modified alkylbenzene sulfonates (MLAS) as discussed in WO 99/05243, WO 99/05242, and WO 99/05244; methyl ester sulfonate (MES); and alpha-olefin sulfonates (AOS). Preferred anionic surfactants are C ₁₀ -C ₁₅ linear alkylbenzene sulfonates, C ₁₀ -C ₁₈ alkyl ether sulfates and C ₁₀ -C ₁₈ alkyl sulfates with 1-5 ethyleneoxy units Salt.

Non-limiting examples of nonionic cosurfactants include C ₈ -C ₁₈ alkyl ethoxylates, such as ® from Shell Nonionic surfactants; ethylene oxide/propylene oxide block alkoxylates such as ® from BASF C ₁₄ -C ₂₂ mid-chain branched alkyl alkoxylates, BAEx, where x is 1-30 as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; Alkyl polysaccharides in question; specifically alkyl polyglycosides as discussed in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides as discussed in US 5,332,528; and ether terminated polysaccharides as discussed in US 6,482,994 and WO 01/42408 (Oxyalkylated) alcohol surfactants.

Preferred nonionic surfactants are C _12/14 and C _16/18 fatty alcohol alkoxy groups with 3-15 ethoxy units or 1-3 propoxy units and 2-15 ethoxy units compound, C _13/15 oxo alcohol alkoxylate, C ₁₃ alcohol alkoxylate and 2-propylheptanol alkoxylate.

Non-limiting examples of semi-polar nonionic surfactants include one alkyl moiety having about 8-18 carbon atoms and two alkyl moieties selected from about 1-3 carbon atoms and hydroxyalkanes The water-soluble amine oxide of the moiety of the radical moiety; and containing an alkyl moiety having about 10-18 carbon atoms and being selected from the group consisting of an alkyl moiety and a hydroxyalkyl moiety having about 1-3 carbon atoms The structural part of the water-soluble sulfoxide. See WO 01/32816, US 4,681,704 and US 4,133,779.

Preferred semi-polar nonionic cosurfactants are C ₈ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₈ alkyl bis(hydroxyethyl) amine oxides.

Non-limiting examples of cationic co-surfactants include quaternary ammonium surfactants which may have up to 26 carbon atoms, including alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; as discussed in US 6,004,922 Dimethyl hydroxyethyl quaternary ammonium surfactant; Dimethyl hydroxyethyl lauryl ammonium chloride; The polyamine cationic surfactants discussed; the cationic ester surfactants as discussed in US Pat. Propyldimethylamine (APA).

In one embodiment, the polymers of the present invention may be used in laundry detergent or cleaning compositions comprising a surfactant system comprising C ₁₀ -C ₁₅ alkylbenzene sulfonate (LAS) as A primary surfactant and one or more co-surfactants selected from nonionic, cationic, other anionic surfactants or mixtures thereof.

In a second embodiment, the polymers of the invention can be used to comprise C ₈ -C ₁₈ linear or branched alkyl ether sulfates having 3-10 ethyleneoxy units as primary surfactant and one or more A laundry detergent or cleaning composition as a cosurfactant selected from nonionic, cationic, other anionic surfactants or mixtures thereof.

In a third embodiment, the polymers of the present invention may be used to comprise C ₁₀ -C ₁₈ alkyl ethoxylate surfactants as primary surfactants and one or more surfactants selected from other nonionic, cationic, anionic surfactants Active agent or mixture thereof as a co-surfactant in a laundry detergent or cleaning composition.

The choice of co-surfactant in these embodiments can depend on the application and desired benefit.

Laundry formulations according to the invention may be liquid, gel or solid compositions, where solid embodiments include, for example, powders and tablets. Liquid compositions are preferred and may be packaged as unit doses.

In one embodiment of the invention, the polymers according to the invention are the group of laundry formulations (also referred to in this description as laundry care compositions) additionally comprising at least one surfactant, preferably at least one anionic surfactant. point.

Examples of suitable anionic surfactants are C ₈ -C ₁₂ alkyl sulfuric acid, C ₁₂ -C ₁₈ fatty alcohol ether sulfuric acid, C ₁₂ -C ₁₈ fatty alcohol polyether sulfuric acid, ethoxylated C ₄ -C ₁₂ alkylphenol (ethoxylated: 3-50 mol ethylene oxide/mol) sulfuric acid half esters, C ₁₂ -C ₁₈ alkyl sulfonic acids, C ₁₂ -C ₁₈ sulfo fatty acid alkyl esters - e.g. C ₁₂ -C ₁₈ sulfo fatty acids Methyl esters, C ₁₀ -C ₁₈ alkylaryl sulfonic acids - preferably n-C ₁₀ -C ₁₈ alkylbenzene sulfonic acids, C ₁₀ -C ₁₈ alkyl alkoxy carboxylic acids and soaps such as C ₈ -C ₂₄ Alkali metal and ammonium salts of carboxylic acids. The alkali metal salts of the aforementioned compounds are preferred, the sodium salts being particularly preferred.

In one embodiment of the present invention, the anionic surfactant is selected from n-C ₁₀ -C ₁₈ alkylbenzene sulfonic acids and fatty alcohol polyether sulfates, which in the context of the present invention are especially ethoxylated C ₁₂ - Sulfate half esters of C ₁₈ alkanols (ethoxylation: 1-50 mol ethylene oxide/mol), preferably n-C ₁₂ -C ₁₈ alkanols.

In one embodiment of the invention, it is also possible to use alcohol polyether sulfates derived from branched (ie synthetic) C ₁₁ -C ₁₈ alkanols (ethoxylation: 1-50 mol ethylene oxide/mol).

Preferably the alkoxylation groups of the two types of alkoxylated alkyl sulfates based on C ₁₂ -C ₁₈ fatty alcohols or based on branched (i.e. synthetic) C ₁₁ -C ₁₈ alcohols are ethoxylated groups and The average degree of ethoxylation of any alkoxylated alkyl sulfate is 1-5, preferably 1-3.

Preferably, the laundry detergents of the present invention comprise at least 1% by weight to 50% by weight, preferably greater than or equal to about 2 to equal to or less than about %, more preferably greater than or equal to 3 to less than or equal to 25% by weight, most preferably greater than or equal to 5 to less than or equal to 25% by weight of one or more anionic surfactants as described above.

The compositions of the present invention may comprise at least one builder. In the context of the present invention, no distinction is made between builders and components of this type referred to elsewhere as "secondary builders". Examples of builders are complexing agents - also referred to below as complexing agents, ion exchange compounds and precipitants. Builders are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates and polycarboxylates.

In the context of the present invention, the term citrate includes the mono- and dialkali metal salts of citric acid, especially the mono- and preferably trisodium salt, the ammonium or substituted ammonium salts of citric acid and citric acid. Citrates can be used as anhydrous compounds or as hydrates, for example as sodium citrate dihydrate. The amount of citrate is calculated with reference to anhydrous trisodium citrate.

The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate. However, it is preferred that the compositions of the present invention be free of phosphates and polyphosphates, including hydrogen phosphates, eg, free of trisodium phosphate, pentasodium triphosphate and hexasodium metaphosphate ("phosphate free"). In the context of phosphates and polyphosphates, "free" is understood in the context of the present invention to mean that the content of phosphates and polyphosphates in total is in the range from 10 ppm to 0.2% by weight of the corresponding composition, which is determined gravimetrically Determination.

The term "carbonate" includes alkali metal carbonates and alkali metal bicarbonates, preferably sodium salts. Particular preference is given to Na ₂ CO ₃ .

Examples of phosphonates are hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a builder. It is preferably used as the sodium salt, where the disodium salt is neutral and the tetrasodium salt is basic (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and also higher homologues thereof. They are preferably used in the form of neutrally reacting sodium salts, for example as the hexa-sodium salt of EDTMP or as the hepta- and octasodium salts of DTPMP.

Examples of aminocarboxylates and polycarboxylates are nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, triethylenetetraminehexaacetate, propane Diaminetetraacetic acid, ethanol diglycine, methylglycine diacetate, and glutamine diacetate. The terms aminocarboxylates and polycarboxylates also include the corresponding unsubstituted or substituted ammonium salts and especially the corresponding alkali metal salts, such as sodium salts, of the fully neutralized compounds.

Silicates in the context of the present invention include especially sodium disilicate and sodium metasilicate, aluminosilicates such as zeolites and phyllosilicates, especially of the formula α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ and those of δ-Na ₂ Si ₂ O ₅ .

The compositions of the present invention may contain one or more builders selected from materials not mentioned above. Examples of builders are alpha-hydroxypropionic acid and oxidized starch.

In one embodiment of the invention the builder is selected from polycarboxylates. The term "polycarboxylate" includes non-polymeric polycarboxylates such as succinic acid, C ₂ -C ₁₆ alkyl disuccinates, C ₂ -C ₁₆ alkenyl disuccinates, ethylenediamine-N,N '-disuccinic acid, tartrate diacetate, alkali metal malonate, tartrate monoacetate, propanetricarboxylate, butanetetracarboxylate and cyclopentanetetracarboxylate.

Oligomeric or polymeric polycarboxylates are, for example, the alkali metal salts of polyaspartic acid or especially (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.

Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. Suitable polymers are especially polyacrylic acids, which preferably have a weight-average molecular weight M _w in the range of 2000-40 000 g/mol, preferably 2000-10 000 g/mol, especially 3000-8000 g/mol. Further suitable copolymeric polycarboxylates are especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid.

It is also possible to use at least one selected from monoethylenically unsaturated C ₃ -C ₁₀ mono- or C ₄ -C ₁₀ dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid Copolymers of monomers of acid, itaconic acid and citraconic acid with at least one of the hydrophilically or hydrophobically modified comonomers listed below.

Suitable hydrophobic comonomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with 10 or more carbon atoms or mixtures thereof, e.g. 1-decene, 1-decene Didecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-dococene, 1-tetradecene and 1- Hexadecene, C ₂₂ -α-olefins, mixtures of C ₂₀ -C ₂₄ -α-olefins and polyisobutenes having an average of 12 to 100 carbon atoms per molecule.

Suitable hydrophilic comonomers are monomers having sulfonate or phosphonate groups, and also nonionic monomers having hydroxyl functions or oxyalkylene groups. Mention may be made, by way of example, of allyl alcohol, isoprenyl alcohol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (methoxy base) acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate , ethoxylated polytetramethylene glycol (meth)acrylate and ethoxylated poly(oxypropylene-co-oxyethylene) (meth)acrylate. The polyalkylene glycols here can contain 3 to 50, in particular 5 to 40, especially 10 to 30 alkylene oxide units per molecule.

Particularly preferred monomers containing sulfonic acid groups here are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid , 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxy Benzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, Vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as sodium, potassium or ammonium salts thereof.

Particularly preferred monomers containing phosphonate groups are vinylphosphonic acid and salts thereof.

In addition, amphoteric polymers can also be used as builders.

The compositions according to the invention may comprise, for example, a total of 0.1-70% by weight, preferably 10-50% by weight, preferably up to 20% by weight, of builders, especially in the case of solid formulations. The liquid formulations according to the invention preferably comprise builders in the range from 0.1 to 8% by weight.

Formulations according to the invention may comprise one or more base carriers. Alkaline carriers, for example, ensure a pH of at least 9, if an alkaline pH is desired. Suitable are, for example, alkali metal carbonates, alkali metal bicarbonates and the abovementioned alkali metal metasilicates and additionally alkali metal hydroxides. The preferred alkali metal is in each case potassium, particularly preferably sodium. In one embodiment of the invention the pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

In one embodiment of the invention, the laundry formulations according to the invention additionally comprise at least one enzyme.

Useful enzymes are, for example, one or more enzymes selected from the group consisting of lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases and the aforementioned types A combination of at least two hydrolases.

Such enzymes can be incorporated at levels sufficient to provide an effective amount for cleaning. Preferred amounts range from 0.001 to 5% active enzyme by weight of the detergent compositions herein. Enzyme stabilizing systems such as calcium ions, boric acid, organoboric acid, propylene glycol and short chain carboxylic acids can also be used with the enzyme. In the context of the present invention, short-chain carboxylic acids are selected from monocarboxylic acids having 1 to 3 carbon atoms per molecule and dicarboxylic acids having 2 to 6 carbon atoms per molecule. Preferred examples are formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, HOOC( _CH2 ) _3COOH , adipic acid and mixtures of at least two of the foregoing and the corresponding sodium and potassium salts.

In one embodiment of the invention the laundry formulation comprises lipase and the polymers of the invention are used in combination with lipase to achieve even further improvement in the removal of oily/fatty stains.

In another embodiment of the invention the laundry formulations according to the invention do not comprise lipase.

The compositions of the present invention may contain one or more bleaching agents. Preferred bleaching agents are selected from the group consisting of anhydrous sodium perborate or sodium perborate e.g. as monohydrate or tetrahydrate or so-called dihydrate, anhydrous sodium percarbonate or sodium percarbonate e.g. Sodium sulfate, where _the term "sodium persulfate" includes in each case the salts of the peracids _H2SO5 and also peroxodisulfates.

Alkali metal salts in this context are also alkali metal hydrogencarbonates, alkali metal hydrogenperborates and alkali metal hydrogenpersulfates in each case. However, dialkali metal salts are preferred in each case.

Formulations according to the invention may comprise one or more bleach catalysts. The bleach catalyst may be selected from oxaziridine Based bleach catalysts, bleach enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper and also cobalt, iron, copper and ruthenium-amine complexes with nitrogen-containing tripod ligands can also be used as bleach catalysts.

Formulations according to the invention may contain one or more bleach activators, for example tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluril, tetraacetylhexamethylenediamine, acylated phenol sulfonates such as n-nonyl Acyl- or isononanoyloxybenzenesulfonate, N-methylmorpholine - acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acyl imides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexa Hydrogen-1,3,5-triazine ("DADHT") or nitrile quaternary ammonium salt (trimethylammonium acetonitrile).

The formulations according to the invention may comprise one or more corrosion inhibitors. In this case, this is understood to include those compounds which inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, especially benzotriazoles, dibenzotriazoles, aminotriazoles, alkylaminotriazoles, but also phenol derivatives such as hydroquinone, phthalate Phenol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In one embodiment of the invention, the formulations according to the invention comprise corrosion inhibitors in total in the range from 0.1 to 1.5% by weight.

The formulations according to the invention may also comprise further cleaning and/or soil-release polymers.

Additional cleaning polymers may include, without limitation, polyfunctional polyethyleneimines (such as BASF's HP20) and/or polyfunctional diamines (such as BASF's /> HP96).

The multifunctional polyethyleneimine of the present invention usually has a weight average molecular weight M _w of 3000-250000g/mol, preferably 5000-200000g/mol, more preferably 8000-100000g/mol, more preferably 8000-50000g/mol, more preferably 10000- 30000 g/mol, most preferably ethoxylated polyethyleneimine in the range 10000-20000 g/mol. The polyfunctional polyethyleneimine has 80-99 wt%, preferably 85-99 wt%, more preferably 90-98 wt%, most preferably 93-97 wt% or 94-96 wt% ethylene oxide side chains based on the total weight of the material . The ethoxylated polyethyleneimines of the invention are based on a polyethyleneimine core and a polyoxyethylene shell. Suitable polyethyleneimine core molecules are polyethyleneimines with a weight-average molecular weight _Mw in the range of 500-5000 g/mol. Preferred molecular weights are 500-1000 g/mol, even more preferred M _w are 600-800 g/mol. The ethoxylated polymer then has on average 5-50, preferably 10-35, even more preferably 20-35 ethylene oxide (EO) units per NH functional group.

The polyfunctional diamines according to the invention are generally ethoxylated C ₂ -C ₁₂ alkylenediamines, preferably hexamethylenediamine, which are further quaternized and optionally sulphated. The polyfunctional diamines have a weight average molecular weight M _w in the range of 2000-10000 g/mol, more preferably 3000-8000 g/mol, most preferably 4000-6000 g/mol. In a preferred embodiment of the invention, ethoxylated hexamethylenediamine can be used - additionally quaternized and sulphated, containing on average 10-50, preferably 15-40, even more preferably 20-30 ethylene oxide (EO) groups/NH functional groups and preferably with two cationic ammonium groups and 2 anionic sulfate groups.

In a preferred embodiment of the present invention, polyfunctional polyethyleneimines or polyfunctional diamines according to the above description can be used to improve the soil removal power of laundry detergents, especially the primary detergency of particulate stains on polyester fabrics .

In another embodiment of the present invention, mixtures of polyfunctional polyethyleneimines and polyfunctional diamines according to the above description can be used to improve the soil removal performance of laundry detergents, especially the primary removal of particulate stains on polyester fabrics. Detergency.

The polyfunctional polyethyleneimines or polyfunctional diamines or mixtures thereof according to the above descriptions can be used in an amount of generally 0.05-15% by weight, preferably 0.1- Amounts of 10% by weight, more preferably 0.25-5% by weight are added to laundry detergent and cleaning compositions.

Accordingly, one aspect of the present invention is a laundry detergent composition, especially a liquid laundry detergent, comprising (i) at least one polymer according to the invention and (ii) at least one polyfunctional polyethyleneimine or polymers of polyfunctional diamines or mixtures thereof.

In one embodiment of the invention, the ratio of the at least one polymer according to the invention and (ii) the at least one polymer selected from polyfunctional polyethyleneimines or polyfunctional diamines or mixtures thereof is 10:1 - 1:10, preferably 5:1-1:5, more preferably 3:1-1:3.

Laundry formulations comprising polymers according to the invention may also comprise at least one antimicrobial agent.

The antimicrobial agent may be selected from the list consisting of 2-phenoxyethanol (CAS No. 122-99-6) and 4,4'-dichloro-2-hydroxydiphenylether (CAS: 3380-30-1) and its combination.

4,4'-Dichloro-2-hydroxydiphenyl ether can be used as a solution, for example a 30% by weight solution of 4,4'-dichloro-2-hydroxydiphenyl ether in 1,2-propanediol.

Laundry formulations according to the invention may comprise at least one antimicrobial agent selected from the above list and/or combinations thereof and/or in combination with at least one other antimicrobial agent not listed here.

The antibacterial agents can be added to the laundry formulations according to the invention in concentrations of 0.0001 to 10% by weight, relative to the total weight of the composition.

Preferably the formulation contains 2-phenoxyethanol in a concentration of 0.01-5% by weight, more preferably 0.1-2% by weight and/or 4,4' in a concentration of 0.001-1% by weight, more preferably 0.002-0.6% by weight - dichloro-2-hydroxydiphenyl ether (in each case relative to the total weight of the composition).

The formulations according to the invention may comprise at least one additional surfactant selected from nonionic and amphoteric surfactants and zwitterionic surfactants:

Nonionic and Amphoteric Surfactants

Examples of (additional) surfactants are especially nonionic surfactants. Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multi-block copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, in addition Also alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides). Examples of (additional) amphoteric surfactants are so-called amine oxides.

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

where the variables are defined as follows:

R ¹ is selected from linear C ₁ -C ₁₀ alkyl groups, preferably ethyl and particularly preferably methyl,

R ² is selected from C ₈ -C ₂₂ alkyl groups, such as nC ₈ H ₁₇ , nC ₁₀ H ₂₁ , nC ₁₂ H ₂₅ , nC ₁₄ H ₂₉ , nC ₁₆ H ₃₃ or nC ₁₈ H ₃₇ ,

^R is selected from C ₁ -C ₁₀ alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl or isodecyl,

m and n are in the range 0-300, where the sum of n and m is at least 1. Preferably m is in the range of 1-100 and n is in the range of 0-30.

The compounds of the general formula (I) here can be block copolymers or random copolymers, preferably block copolymers.

Further preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II):

where the variables are defined as follows:

R ¹ are identical or different and are selected from linear C ₁ -C ₄ alkyl, preferably in each case identical and are ethyl and particularly preferably methyl,

R ⁴ is selected from C ₆ -C ₂₀ alkyl groups, especially nC ₈ H ₁₇ , nC ₁₀ H ₂₁ , nC ₁₂ H ₂₅ , nC ₁₄ H ₂₉ , nC ₁₆ H ₃₃ , nC ₁₈ H ₃₇ ,

a is a number in the range of 0-6, preferably 1-6,

b is a number in the range of 0-20, preferably 4-20,

d is a number in the range of 4-25.

Preferably at least one of a and b is greater than 0.

The compounds of the general formula (II) here can be block copolymers or random copolymers, preferably block copolymers.

Other suitable nonionic surfactants are selected from di- and multi-block copolymers composed of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. A review of suitable further nonionic surfactants can be found in EP-A 0 851 023 and DE-A 198 19 187 .

Mixtures of two or more different nonionic surfactants may also be present.

Suitable amphoteric surfactants are so-called amine oxides, such as lauryldimethylamine oxide ("laurylamine oxide").

zwitterionic surfactant

Examples of zwitterionic surfactants are C ₁₂ -C ₁₈ alkyl betaines and sultaines.

The formulations according to the invention may also comprise water and additional organic solvents, such as ethanol or propylene glycol.

Other optional ingredients may be, but are not limited to, viscosity modifiers, cationic surfactants, foam boosters or antifoam agents, fragrances, dyes, optical brighteners, and dye transfer inhibitors.

(b) Hand dishwashing detergent

A further aspect of the invention is also a hand dishwashing detergent formulation comprising at least one polymer according to the invention as described above.

Accordingly, an aspect of the present invention is also the use of the polymers of the invention as described above in hand dishwashing applications.

The hand dishwashing detergents of the present invention may be in the form of liquids, semi-liquids, cleansers, lotions, gels or solid compositions, where solid embodiments include powders and tablets, for example. Liquid compositions are preferred. Detergents are intended to be applied directly or indirectly to dishware in liquid form.

In one embodiment of the invention, the polymers according to the invention are a component of hand dishwashing formulations which additionally comprise at least one surfactant, preferably at least one anionic surfactant.

The compositions are preferably formulated to provide excellent grease cleaning (degreasing) performance, long-lasting foam and improved viscosity control at reduced temperature exposure. Optional additional benefits include stain removal, shine and hand care.

Examples of suitable anionic surfactants are C ₈ -C ₁₂ alkyl sulfuric acid, C ₁₂ -C ₁₈ fatty alcohol ether sulfuric acid, C ₁₂ -C ₁₈ fatty alcohol polyether sulfuric acid, ethoxylated C ₄ -C ₁₂ alkylphenol (ethoxylated: 3-50 mol ethylene oxide/mol) sulfuric acid half esters, C ₁₂ -C ₁₈ alkyl sulfonic acids, C ₁₂ -C ₁₈ sulfo fatty acid alkyl esters - e.g. C ₁₂ -C ₁₈ sulfo fatty acids Methyl esters, C ₁₀ -C ₁₈ alkylaryl sulfonic acids - preferably n-C ₁₀ -C ₁₈ alkylbenzene sulfonic acids, C ₁₀ -C ₁₈ alkyl alkoxy carboxylic acids and soaps such as C ₈ -C ₂₄ Alkali metal and ammonium salts of carboxylic acids. The alkali metal salts of the aforementioned compounds are preferred, the sodium salts being particularly preferred.

In one embodiment of the present invention, the anionic surfactant is selected from n-C ₁₀ -C ₁₈ alkylbenzene sulfonic acids and fatty alcohol polyether sulfates, the latter being especially ethoxylated C ₁₂ in the context of the present invention Sulfate half esters of -C ₁₈ -alkanols (ethoxylation: 1-50 mol ethylene oxide/mol), preferably n-C ₁₂ -C ₁₈ -alkanols.

In one embodiment of the invention, it is also possible to use alcohol polyether sulfates derived from branched (ie synthetic) C ₁₁ -C ₁₈ alkanols (ethoxylation: 1-50 mol ethylene oxide/mol).

Preferably the alkoxylation groups of the two types of alkoxylated alkyl sulfates based on C ₁₂ -C ₁₈ fatty alcohols or based on branched (i.e. synthetic) C ₁₁ -C ₁₈ alcohols are ethoxylated groups and The average degree of ethoxylation of any alkoxylated alkyl sulfate is 1-5, preferably 1-3.

Preferably, the hand dishwashing detergent formulations of the present invention comprise at least 1% by weight to 50% by weight, based on the specified total composition including other components and water and/or solvents, preferably between greater than or equal to about 3 to equal to or less than about 35% by weight, more preferably greater than or equal to 5 to less than or equal to 30% by weight, most preferably greater than or equal to 5 to less than or equal to 20% by weight of one or more anionic surfactants as described above.

Compositions of the invention may comprise at least one amphoteric surfactant.

Examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyldimethylamine oxides or alkylamidopropyldimethylamine oxides, more preferably alkyldimethylamine oxides and especially cocodimethylamine oxides. Amine oxides can have linear or mid-chain branched alkyl moieties. Typical linear amine oxides include one R ¹ =C _8-18 alkyl moiety and two R ² and R ³ moieties selected from C ₁ -C ₃ alkyl and C ₁ -C ₃ hydroxyalkyl. Sexual amine oxide. Preferably the amine oxide is characterized by the formula R ¹ -N(R ² )(R ³ )-O, wherein R ¹ is C _8-18 alkyl and R ² and R ³ are selected from methyl, ethyl, propyl, iso Propyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants may include, inter alia, linear C ₁₀ -C ₁₈ alkyl dimethyl amine oxide and linear C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxide. Preferred amine oxides include linear C ₁₀ , linear C ₁₀ -C ₁₂ and linear C ₁₂ -C ₁₄ alkyl dimethyl amine oxides. As used herein, "mid-chain branching" means that the amine oxide has an alkyl moiety having n1 carbon atoms and an alkyl branch having n2 carbon atoms on the alkyl moiety. The alkyl branch is located on the carbon alpha to the nitrogen on the alkyl moiety. This type of branching of the amine oxide is also known in the art as internal amine oxide. The sum of n1 and n2 is 10-24, preferably 12-20, more preferably 10-16 carbon atoms. The number of carbon atoms (n1) of the one alkyl moiety should be approximately the same as the number of carbon atoms (n2) of the one alkyl branch such that the one alkyl moiety and the one alkyl branch are symmetrical. "Symmetrical" as used herein means at least 50%, more preferably at least 75% to 100% by weight of (n1-n2) less than or equal to 5, preferably 4, most preferably 0-4 carbons in the medium chain amine oxides used herein atom. The amine oxide further comprises two moieties independently selected from C ₁ -C ₃ alkyl, C ₁ -C ₃ hydroxyalkyl, or polyoxyethylene groups containing on average about 1-3 ethylene oxide groups. Preferably both moieties are selected from C ₁ -C ₃ alkyl, more preferably both are methyl.

The hand dishwashing detergent compositions of the invention preferably comprise 1-15% by weight, preferably 2-12% by weight, more preferably 3-10% by weight of amphoteric surfactants, preferably amine oxide surfactants, based on the composition. Preferably, the compositions of the present invention comprise a mixture of anionic surfactant and alkyldimethylamine oxide in a weight ratio of less than about 10:1, more preferably less than about 8:1, more preferably from about 5:1 to about 2:1.

The addition of amphoteric surfactants provides good sudsing performance in the detergent compositions.

Compositions of the invention may comprise at least one zwitterionic surfactant.

Suitable zwitterionic surfactants include betaines such as alkyl betaines, alkylamide betaines, imidazoline Betaine, sultaine (INCI sultaine) and phosphobetaine. Examples of suitable betaines and sultaines are the following (according to INCI nomenclature): almond oleamidopropyl betaine, apricot oleamidopropyl betaine, avocado oleamidopropyl betaine, babassu oleamidopropyl betaine Betaine, Betaine, Behenyl Betaine, Canolamidopropyl Betaine, Caprylyl/Caprylamidopropyl Betaine, Carnitine, Cetyl Betaine, Coconut Oleamidoethyl Betaine, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco Betaine, Coco Hydroxysultaine, Coco/Oleamidopropyl Betaine, Coconut Oleosulfobetaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Siloxanepropyl PG-Betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Betaine Hydroxyl sultaine, Lauryl sultaine, Cramidopropyl betaine, Mink amidopropyl betaine, Myristyl amidopropyl betaine, Myristyl betaine, Oleamidopropyl betaine, Oleamidopropyl Hydroxysultaine, Oleyl Betaine, Oleamidopropyl Betaine, Palm Oleamidopropyl Betaine, Palmimidopropyl Betaine, Palmitoyl Carnitine, Palm Kernel Amidopropyl Betaine Alkaline, Teflon Acetoxypropyl Betaine, Ricinoyl Amidopropyl Betaine, Sesame Oleamidopropyl Betaine, Soybetaine Amidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine Alkaline, tallow amidopropyl betaine, tallow amidopropyl hydroxy sultaine, tallow betaine, tallow betaine, tallow betaine, undecyl amidopropyl betaine and wheat germ amidopropyl betaine .

A preferred betaine is eg cocamidopropyl betaine. The zwitterionic surfactant is preferably a betaine surfactant, more preferably a cocamidopropyl betaine surfactant.

The hand dishwashing detergent compositions of the present invention optionally comprise from 1 to 15% by weight, preferably from 2 to 12% by weight, more preferably from 3 to 10% by weight of a zwitterionic surfactant, preferably a betaine surfactant, based on the composition .

In a preferred embodiment of the invention, the hand dishwashing formulation contains at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or a mixture thereof, to facilitate the washing Foaming, cleansing and/or mildness of the agent composition.

The compositions of the present invention may comprise at least one cationic surfactant.

Examples of cationic surfactants are quaternary ammonium surfactants, preferably selected from mono-C ₆ -C ₁₆ , more preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are replaced by Methyl, hydroxyethyl or hydroxypropyl substitution. Another preferred cationic surfactant is a _C6-18 alkyl or alkenyl ester of a quaternary ammonium alcohol, such as a quaternary chloride ester.

When present in the composition, the cationic surfactant is present in an effective amount, more preferably 0.1-5%, preferably 0.2-2% by weight of the composition.

Compositions of the invention may comprise at least one nonionic surfactant.

Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multi-block copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, in addition Also alkylphenol ethoxylates, alkyl glycosides and polyhydroxy fatty acid amides (glucamides).

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

where the variables are defined as follows:

R ¹ is selected from linear C ₁ -C ₁₀ alkyl groups, preferably ethyl and particularly preferably methyl,

R ² is selected from C ₈ -C ₂₂ alkyl groups, such as nC ₈ H ₁₇ , nC ₁₀ H ₂₁ , nC ₁₂ H ₂₅ , nC ₁₄ H ₂₉ , nC ₁₆ H ₃₃ or nC ₁₈ H ₃₇ ,

^R is selected from C ₁ -C ₁₀ alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl or isodecyl,

m and n are in the range 0-300, where the sum of n and m is at least 1. Preferably m is in the range of 1-100 and n is in the range of 0-30.

The compounds of the general formula (I) here can be block copolymers or random copolymers, preferably block copolymers.

Further preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II):

where the variables are defined as follows:

R ¹ are identical or different and are selected from linear C ₁ -C ₄ alkyl, preferably in each case identical and are ethyl and particularly preferably methyl,

R ⁴ is selected from C ₆ -C ₂₀ alkyl groups, especially nC ₈ H ₁₇ , nC ₁₀ H ₂₁ , nC ₁₂ H ₂₅ , nC ₁₄ H ₂₉ , nC ₁₆ H ₃₃ , nC ₁₈ H ₃₇ ,

a is a number in the range of 0-6, preferably 1-6,

b is a number in the range of 0-20, preferably 4-20,

d is a number in the range of 4-25.

Preferably at least one of a and b is greater than 0.

The compounds of the general formula (II) here can be block copolymers or random copolymers, preferably block copolymers.

Other suitable nonionic surfactants are selected from di- and multi-block copolymers composed of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. A review of suitable further nonionic surfactants can be found in EP-A 0 851 023 and DE-A 198 19 187 .

Mixtures of two or more different nonionic surfactants may also be present.

Highly preferred nonionic surfactants are the condensation products of Guerbet alcohols with 2-18 moles, preferably 2-15 moles, more preferably 5-12 moles of ethylene oxide per mole of alcohol. Other preferred nonionic surfactants for use herein include fatty alcohol polyglycol ethers, alkyl polyglucosides and fatty acid glucamides.

The hand dishwashing detergent composition according to the invention may comprise 0.1-10% by weight, preferably 0.3-5% by weight, more preferably 0.4-2% by weight, based on the composition, of an average degree of alkoxylation of 2-6, preferably 3 -5 linear or branched alkoxylated nonionic C ₁₀ alkyl surfactants. Preferably the linear or branched _C10 alkoxylated nonionic surfactant is a branched _C10 alkyl ethoxylated nonionic surfactant having an average degree of ethoxylation of 2-6, preferably 3-5. Preferably the composition comprises 60-100 wt%, preferably 80-100 wt%, more preferably 100 wt% branched _C10 ethoxylated nonionic surfactants based on total linear or branched C10 _alkoxylated nonionic surfactants. Nonionic surfactant. The linear or branched _C10 alkoxylated nonionic surfactant is preferably a 2-propylheptyl ethoxylated nonionic surfactant with an average degree of ethoxylation of 3-5. The use of 2-propylheptyl ethoxylated nonionic surfactants with an average degree of ethoxylation of 3-5 resulted in improved suds levels and long-lasting suds.

Accordingly, one aspect of the present invention is a hand dishwashing detergent composition, especially a hand dishwashing detergent composition comprising (i) at least one polymer according to the invention and (ii) at least one average ethoxylated Other 2-propylheptylethoxylated nonionic surfactants of degree 3-5.

The compositions of the present invention may comprise at least one hydrotrope in an amount effective to ensure the compatibility of the liquid hand dishwashing detergent composition with water.

Hydrotropes suitable for use herein include anionic hydrotropes, especially sodium, potassium and ammonium xylene sulfonates, sodium, potassium and ammonium toluene sulfonates, sodium, potassium and ammonium cumene sulfonates and mixtures thereof and such as Related compounds disclosed in US Patent No. 3,915,903.

The liquid hand dishwashing detergent composition of the present invention generally comprises 0.1-15% by weight based on the whole liquid detergent composition, preferably 1-10% by weight based on the whole liquid hand dishwashing composition, most preferably 2-5% by weight of water soluble Accelerators or mixtures thereof.

The compositions of the invention may comprise at least one organic solvent.

Examples of organic solvents are _C4 - _C14 ethers and diethers, diols, alkoxylated diols, _C6 - _C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatically branched Alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C ₁ -C ₅ alcohols, linear C ₁ -C ₅ alcohols, amines, C ₈ -C ₁₄ alkyl and cycloalkyl hydrocarbons and halogens Hydrocarbons and their mixtures.

When present, the liquid detergent composition contains from 0.01 to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 1 to 10% by weight, even more preferably from 1 to 5% by weight of solvent, based on the liquid detergent composition . These solvents can be used in combination with an aqueous liquid carrier such as water, or they can be used in the absence of any aqueous liquid carrier. In more advanced solvent systems, the absolute value of the viscosity may decrease, but there is a local maximum point in the viscosity curve.

The compositions herein may further comprise 30-90% by weight of an aqueous liquid carrier comprising water in which other essential and optional ingredients are dissolved, dispersed or suspended. More preferably the composition of the invention comprises 45-85%, even more preferably 60-80% by weight, of an aqueous liquid carrier. However, the aqueous liquid carrier may contain other materials that are liquid at ambient temperature (25°C) or are soluble in the liquid carrier and may also serve some other function than an inert filler.

The compositions of the invention may comprise at least one electrolyte.

Suitable electrolytes are preferably selected from inorganic salts, even more preferably monovalent salts, most preferably sodium chloride.

Liquid hand dishwashing compositions according to the invention may comprise 0.1-5% by weight, preferably 0.2-2% by weight, of electrolytes, based on the composition.

Hand dishwashing formulations comprising polymers according to the invention may also comprise at least one antimicrobial agent.

The antimicrobial agent may be selected from the list consisting of 2-phenoxyethanol (CAS No. 122-99-6) and 4,4'-dichloro-2-hydroxydiphenylether (CAS: 3380-30-1) and its combination.

4,4'-Dichloro-2-hydroxydiphenyl ether is available as a solution, for example a 30% by weight solution of 4,4'-dichloro-2-hydroxydiphenyl ether in 1,2-propanediol, e.g. from BASF HP 100 used.

Hand dishwashing formulations according to the invention may comprise at least one antimicrobial agent selected from the above list and/or combinations thereof and/or in combination with at least one other antimicrobial agent not listed here.

The antimicrobial agent can be added to the hand-dishwashing formulations according to the invention in concentrations of 0.0001 to 10% by weight, relative to the total weight of the composition. Preferably the formulation contains 2-phenoxyethanol in a concentration of 0.01-5% by weight, more preferably 0.1-2% by weight and/or 4,4' in a concentration of 0.001-1% by weight, more preferably 0.002-0.6% by weight - dichloro-2-hydroxydiphenyl ether (in each case relative to the total weight of the composition).

Compositions of the invention may comprise at least one additional ingredient.

Examples of additional ingredients are, but are not limited to, conditioning polymers, cleaning polymers, surface modifying polymers, stain flocculants, rheology modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, Structurants, emollients, humectants, skin rejuvenation actives, carboxylic acids, scrubbing particles, bleaches and bleach activators, fragrances, malodor control agents, pigments, dyes, sunscreens, beads, pearlescent particles, microcapsules, Antimicrobials, pH adjusters including NaOH and alkanolamines such as monoethanolamine, buffers and divalent salts including divalent salts including magnesium and calcium cations.

The liquid hand dishwashing detergent composition can have any suitable pH. Preferably the pH of the composition is adjusted to 4-14. More preferably the composition has a pH of 6-13, even more preferably 6-10, most preferably 7-9. The pH of the composition can be adjusted using pH adjusting ingredients known in the art and measured as a 10% by weight product concentration in demineralized water at 25°C. For example NaOH can be used and the actual weight % of NaOH can be varied and fine tuned up to the desired pH such as pH 8.0. In one embodiment of the invention the pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

The composition of the invention preferably has a viscosity at 20 1/s and 20°C of 50-4000 mPa*s, more preferably 100-2000 mPa*s, most preferably 500-1500 mPa*s.

The compositions of the invention can be used for dishwashing. Said method of dishwashing comprises the step of applying the composition, preferably in liquid form, to the surface of the dish, either directly or with the aid of a cleaning implement, ie in neat form. The composition is applied directly onto the surface to be treated and/or onto the cleaning device or utensil, such as a dishcloth, sponge or dish brush, without a main dilution (immediately) prior to application. The cleaning device or implement is preferably wetted before or after delivering the composition thereto. In the method of the invention, the composition may also be applied in diluted form.

Both neat and diluted application lead to excellent cleaning performance, ie the formulations according to the invention which contain the polymers according to the invention show excellent degreasing properties. The effort to remove fatty and/or oily stains from tableware is reduced by the presence of the polymers of the invention even when lower levels of surfactant are used than in conventional compositions.

In a preferred embodiment, the polymers of the invention are used in laundry detergents. The liquid laundry detergent of the present invention consists of the following components:

0.05-20% of at least one polymer of the invention

1-50% surfactant

0.1-40% builder, second builder and/or chelating agent

0.1-50% other auxiliary agents

Add to 100% water.

Preferred liquid laundry detergents of the present invention consist of the following components:

0.2-6% of at least one polymer of the invention

5-40% anionic surfactants selected from C ₁₀ -C ₁₅ LAS and C ₁₀ -C ₁₈ alkyl ether sulfates containing 1-5 ethyleneoxy units

1.5-10% nonionic surfactants selected from _C10 - _C18 alkyl ethoxylates containing 3-10 ethyleneoxy units

2-20% Soluble organic builders/secondary builders selected from _C10 - _C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids and polycarboxylic acids

0.05-5% enzyme system containing at least one enzyme suitable for detergent applications and preferably also an enzyme stabilization system

0.5-20% monoalcohol or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol

0.1-20% other auxiliaries

Add to 100% water

The solid laundry detergent (e.g. powder, granule or tablet) of the present invention consists of the following components:

0.05-20% of at least one polymer of the invention

1-50% surfactant

0.1-80% builder, second builder and/or chelating agent

0-50% filler

0-40% bleach actives

0.1-30% other auxiliaries and/or water

Wherein the sum of each composition adds up to 100%.

Preferred solid laundry detergents of the present invention consist of the following components:

0.2-6% of at least one polymer of the invention

5-30% anionic surfactants selected from C ₁₀ -C ₁₅ LAS, C ₁₀ -C ₁₈ alkyl sulfates and C ₁₀ -C ₁₈ alkyl ether sulfates containing 1-5 ethyleneoxy units

1.5-7.5% nonionic surfactants selected from C ₁₀ -C ₁₈ alkyl ethoxylates containing 3-10 ethyleneoxy units

5-50% inorganic builders selected from sodium carbonate, sodium bicarbonate, zeolite, soluble silicate, sodium sulfate

0.5-15% of a second builder selected from C ₁₀ -C ₁₈ fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids and polycarboxylic acids

0.1-5% enzyme system comprising at least one enzyme suitable for detergent applications and preferably also an enzyme stabilization system

0.5-20% monoalcohol or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol

0.1-20% other auxiliaries

Add to 100% water

Table 1: General Formulations of Detergent Compositions of the Invention

Element Range of ingredients in liquid frame formulations linear alkylbenzene sulfonic acid 0-30% Coconut Fatty Acid 1-12% Fatty Alcohol Ether Sulfate 0-25% NaOH or mono or triethanolamine until pH 7.5-9.0 Alcohol Ethoxylates 3-10% 1,2-propanediol 1-10% ethanol 0-4% Sodium citrate 0-8% water until 100%

The at least one polymer according to the invention may be added to such formulations in suitable amounts as described herein.

Table 2: Liquid framework formulations of the invention

active substance (Number: % Active Matter) F1 F2 F3 F4 F5 F6 Alcohol Ethoxylate 7EO 5.40 10.80 12.40 7.30 1.60 7.60 Coconut Fatty Acid K12-18 2.40 3.10 3.20 3.20 3.50 6.40 Fatty Alcohol Ether Sulfate 5.40 8.80 7.10 7.10 5.40 14.00 linear alkylbenzene sulfonic acid 5.50 0.00 14.50 15.50 10.70 0.00 1,2-propanediol 6.00 3.50 8.70 8.70 1.10 7.80 Triethanolamine Monoethanolamine 4.00 4.30 0.30 NaOH 2.20 1.10 1.00 glycerin 0.80 3.00 2.80 ethanol 2.00 0.38 0.39 Sodium citrate 3.00 2.80 3.40 2.10 7.40 5.40 Polymers of the invention (total) 0-5 0-5 0-5 0-5 0-5 0-5 protease 0-1 0-1 0-1 0-1 0-1 0-1 Amylase 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 Lipase 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 Mannanase 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 pectin lyase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 water to 100 to 100 to 100 to 100 to 100 to 100

Table 2 - Continued: Liquid framework formulations of the invention

active substance (Number: % Active Matter) F7 F8 F9 F10 F11 F12 F13 F14 Alcohol Ethoxylate 7EO 3.80 0.30 13.30 8.00 5.70 20.00 9.20 29.00 Coconut Fatty Acid K12-18 2.80 3.00 1.70 1.80 2.50 5.00 8.60 10.40 Fatty Alcohol Ether Sulfate 2.80 4.50 3.90 4.10 10.00 22.20 linear alkylbenzene sulfonic acid 6.30 5.43 11.45 5.90 10.10 10.00 28.00 27.00 1,2-propanediol 0.50 2.50 0.40 6.00 10.00 7.00 7.00 Triethanolamine 8.10 Monoethanolamine 0.40 1.80 8.00 7.00 NaOH 2.20 3.30 1.50 glycerin 0.60 0.20 1.90 7.00 10.00 ethanol 1.84 Sodium citrate 4.60 3.30 3.30 1.40 1.50 Polymers of the invention (total) 0-5 0-5 0-5 0-5 0-5 0-5 0-5 0-5 protease 0-1 0-1 0-1 0-1 0-1 0-3 0-3 0-3 Amylase 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 Lipase 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 Mannanase 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 0-0.2 pectin lyase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 water to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100

Table 3: Powder framework formulations of the invention

Table 3 - Continued: Powder framework formulations of the invention

Other fields of application for which the polymers of the invention are suitable include the following:

Cosmetics, Personal Care

Such compositions and formulations include shampoos, lotions, gels, sprays, soaps, cosmetic powders, lipsticks, hairsprays.

Paint and colorant formulations

Such compositions and formulations include non-water-based and preferably water-based paints and stains, paints, finishes.

industrial application

Such compositions and formulations include glues of any kind, non-aqueous and preferably water-based liquid formulations or solid formulations.

Agricultural formulations

Such compositions and formulations include formulations and compositions containing the active in a liquid or solid environment.

The following examples shall further illustrate the present invention without limiting the scope of the present invention.

Example

synthesis

Example 1: (hyper)branched polymer, polymer P1:

Step A.1: Into a four-neck round bottom flask was charged trimethylolpropane ethoxylate triacrylate (average molecular weight M _n 692 g/mol; CAS 28961-43-5; 32.5 g, 0.04697 mol). N,N'-bis(3-aminopropyl)ethylenediamine (CAS 10563-26-5; 16.37 g, 0.09393 mol) was slowly added to the reaction mixture, stirred at about 100° C. for 17 hours, and then cooled. No acrylate peak signal could be detected in ¹ H-NMR and the acrylate was therefore reacted as detectably as possible by this method.

Step B.1: Polyethylene glycol methyl ether methacrylate (average M _n 950 g/mol; CAS 26915-72-0; 22.31, 0.02348 mol) was then added to the reaction mixture and allowed to cool at about 100°C React for 17 hours. The inventive polymer P1 is obtained. K value (water): 16.6, GPC of 0.05% by weight ammonium acetate in HFIP (hexafluoroisopropanol): M _n = 6440 g/mol, M _w = 26700 g/mol, PDI (M _w /M _n ) = 4.1 .

Example 2: Linear polymer, Polymer P2:

Step A.2: Into a four-neck round bottom flask was added polyethylene glycol diacrylate (average molecular weight M _n 575 g/mol, CAS 26570-48- 9; 18.5 g, 0.03217 mol). N,N'-bis(3-aminopropyl)ethylenediamine (CAS 10563-26-5; 8.4 g, 0.04826 mol) was slowly added to the reaction mixture, stirred at 100° C. for 17 hours, and then cooled. No acrylate peak signal could be detected in ¹ H-NMR and the acrylate was therefore reacted as detectably as possible by this method.

Step B.2: Polyethylene glycol methyl ether methacrylate (average M _n 950 g/mol; CAS 26915-72-0; 15.28 g, 0.01609 mol) was then added to the reaction mixture and allowed to react under reflux 17 hours. The inventive polymer P2 is obtained. K value (water): 17.0, GPC of 0.05% by weight ammonium acetate in HFIP: M _n =9210 g/mol, M _w =30200 g/mol, PDI (M _w /M _n ) =3.3.

The general composition and analytical data (and thus also stability) of the polymers obtained are shown in Table 5.

Similar inventive polymers were synthesized following the same synthetic procedure above (as described in Example 1 and Example 2) and using the amounts indicated in Table 4 (Table 4). These polymers also performed in a similar manner for the Laundry Test, Biodegradability Test and Hydrolytic Stability Test shown below for Examples 1 and 2 respectively.

Table 4: Other inventive polymers

Table 5: Analytical data for P1 and P2

name K value (measured immediately after synthesis) K value (measured after 6 months) Polymer P1 16.6 16.6 Polymer P2 17.0 17.5

Polymer P1: solids content 34% by weight; final product solution pH 9.6. K values did not change over the 6-month period. Polymer P2 showed the least change over time (slight increase in deviation within the measurement error of the measured values).

application test

The detergency performance of selected polymers was determined as follows.

L*, a*, b* values of individual stains were measured with MACH 5 from CFT/Color Advisory before washing. The fabric was then washed with cotton ballast fabric and 20 steel balls at 30°C in a detergent formulation with the selected polymer. After washing the fabrics are rinsed, spin-dried and air-dried.

The wash performance on individual stains is determined by measuring the L*, a*, b* values after drying with the MACH 5 from CFT/Color Consulting. dE values were calculated from individual values before and after washing. The higher the value, the better the performance.

Table 6: Washing conditions (for clay removal):

Test Equipment Bottle Detergency Tester, Model LP2, SDL Atlas Inc., USA detergent 250ml Washing Time/Temperature 20 minutes at 30°C dose 2g detergent/L fabric/liquid ratio 1:12.5 washing cycle 1 water hardness 2.5mmol/l Ca ²⁺ :Mg ²⁺ :HCO ₃ ^- 4:1:8 ballast fabric 2.5g cotton fabric 283 Sum of ballast fabric + fouling fabric 20g soiled fabric CFT-PH 145 ¹⁾ or CFT-KC-H 018 ²⁾

¹⁾ CFT-PH 145, Tennis Court Clay Stained Polyester Fabric

²⁾ CFT-KC-H 018, Cotton Fabrics Stained by Site Soil

^{1) 2)} Manufacturer: Center for Testmaterials BV, NL-3130AC Vlaardingen

Table 7: Washing results for 4g detergent/L (* or 2g/L), polymer dosage: 3%

ΔΔE (polymer-containing detergent-detergent)

polymer P-H145 KC-H018 Ethoxylated polyethyleneimine 4.5 3.1; 4.3* (of Example 1) "Polymer 1" 0.8 3.4* (of Example 2) "Polymer 2" 1.5 2.7*

Tests for Biodegradation

Polymers P1 and P2 were analyzed for biodegradability in wastewater. The results show that polymer P1 is biodegradable to 63% and polymer P2 is biodegradable to -72% after 28 days using the OECD 301F test method (see also Figure 3).

Samples were tested in triplicate and compared to glucose (greater than 60%) as a positive control.

Hydrolytic stability

Hydrolytic stability was analyzed via reaction IR at 5% aqueous polymer solution with pH adjusted to about 7 with citric acid and monitored with FTIR for 24 hours. As can be seen from Figure 4, the IR spectrum showed no evidence of ester hydrolysis.

Description of drawings:

Figure 1 - General Reaction Pathway

Figure 2—GPC of Polymer P1 and Polymer P2

(Calibrated with PMMA standards from PSS with molecular weights from M=800 to M=2,200,000. Extrapolate values outside this elution range.)

Figure 3—Biodegradability tests of polymers P1 and P2

Figure 4 - Overlay of IR spectra of 10 exemplary runs of polymer P1 (Example 1) over a 24 hour time frame

Claims (13)

1. A polymer comprising the following components: a) 5-40% by weight of at least one amine having at least 2 amino groups, b) 10-65% by weight of at least one acrylate selected from glycerol propoxylate tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, trihydroxy Methylpropane propoxylate tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta- or hexa(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate and polyethylene glycol di(meth)acrylate, c) 10-75% by weight of at least one monoacrylate, Wherein the sum of components 0, 0 and c) is 100. 2. The polymer according to claim 1, wherein the acrylates b) carry two acrylate groups per molecule. 3. The polymer according to claim 1 or 2, wherein the amount of component a) is from 10 to 35% by weight. 4. The polymer according to any one of the preceding claims, wherein the acrylates of component b) are selected from acrylates with at least 3 C-C double bonds. 5. The polymer according to claim 4, wherein component b) is selected from acrylates having two C-C double bonds and acrylates having at least 3 C-C double bonds per molecule and wherein each molecule has at least 3 C-C double bonds The amount of acrylates is up to 50 mol % of the total amount of component b). 6. The polymer according to any one of claims 1-5, wherein the amount of component a) is 20-30% by weight, the amount of component b) is 25-53% by weight and the amount of component c) is 23-50% by weight. 7. Process for preparing a polymer according to any one of the preceding claims, wherein said process comprises the steps of: A) Reacting the following components in one or two substeps: a) 5-40% by weight of at least one amine having at least 2 amine groups, and b) 10-65% by weight of at least one acrylate selected from the group consisting of glycerol propoxylate tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, trimethylolpropoxylate Propane propoxylate tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta- or hexa(meth)acrylate esters, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate and polyethylene glycol di(meth)acrylate, to obtain amino-containing polymers, B) optionally reacting the polymer obtained in step A) with the following components: c) 10-75% by weight of at least one monoacrylate. 8. The method according to claim 7, wherein the method is performed in bulk. 9. Process according to claim 7 or 8, wherein the reaction of step A) or step B) is carried out independently of each other at 50-150° C. and a pressure of 0.5-5 bar for a period of 3-15 hours. 10. The method according to any one of claims 7-9, wherein steps A) and B) are carried out in bulk. 11. Formulations of the polymers according to any one of claims 1 to 6 in the fields of fabric and home care, industrial and institutional cleaning, cosmetics, personal care, industrial formulations such as paints and pigments, construction, if containing and/or the use in cement and cement-containing formulations etc. of inorganic materials stabilizing them and in formulations or compositions in the field of agricultural formulation applications, preferably as a dispersant in each application to remove or release substances from surfaces and/or Or disperse substances in liquids and/or solids. 12. Use of polymers according to any one of claims 1 to 6 as dispersants in fabric care applications to remove or release solid or water-insoluble substances from surfaces and/or to disperse such substances in liquids and/or solids the use of. 13. A formulation or composition comprising a polymer according to any one of claims 1-6.