Water-soluble grafted polymers, their preparation, use and compositions containing such polymers - Patents.com

Abstract

The present invention relates to a water-soluble graft polymer comprising a polysaccharide as polymer substrate and at least one water-soluble ethylenically unsaturated monomer as grafted side chain, the water-soluble ethylenically unsaturated monomer comprising at least one sodium carboxylate unit, produced by a radical initiated polymerization reaction, in which at least one organic compound is used during the polymerization, the organic compound comprising at least one carboxyl group capable of complexing with a metal ion, preferably iron, and which comprises in its structure at least one carboxyl group, which may be present in part or in full as an acid group or in deprotonated salt form, as well as to its preparation and use, for example in laundry or dishwashing, and to a method for stabilizing such a graft polymer, the graft polymer having a solids content of at least 20% after preparation and a solids content of at least 70%. Aqueous solutions of the graft polymer are characterized by a Gardner color value of less than 4.0 and a color stability of at most 1 unit increase in the Gardner color value at room temperature for at least 6 months.

Description

[Technical field]

[0001] The present invention relates to a water-soluble graft polymer (in the present invention, always referred to as "graft polymer" or "polymer of the present invention" or "polymer of the present invention" when referring to the polymer of the present invention), comprising a polysaccharide as polymer substrate and at least one water-soluble ethylenically unsaturated monomer as grafted side chain, the water-soluble ethylenically unsaturated monomer comprising at least one sodium carboxylate unit, produced by a radical initiated polymerization reaction, in which at least one organic compound is used during the polymerization, which comprises at least one carboxyl group capable of complexing with a metal ion, preferably iron, and which may be present in its structure partially or entirely as an acid group or in the form of a deprotonated salt, its preparation, its use, in particular for use in cleaning compositions, such as laundry and dishwashing detergent compositions. The graft polymer has a solids content of at least 20% after preparation and a solids content of at least 70%. Aqueous solutions of the graft polymer are characterized by a Gardner color of less than 4.0 and a color stability of at most 1 unit increase in the Gardner color value at room temperature for at least 6 months. [Background technology]

[0002] Detergent formulators are continually challenged to develop improved products for the removal of various soils and stains from fabrics and hard surfaces. Soils and stains are diverse and range in chemistry and physicochemical properties from polar soils such as proteinaceous materials, clays and inorganic soils to non-polar soils such as soot, carbon black, by-products of incomplete combustion of hydrocarbons and organic soils such as sebum. Recently, these challenges have been highlighted by the increasing interest and drive to reduce the amount of surfactants in cleaning detergents for environmental, sustainability and cost reasons. It has been found that reducing the amount of surfactants, especially oil-derived surfactants such as linear alkylbenzene sulfonates LAS, usually compromises the removal of oily / greasy stains. Furthermore, there is a global trend towards lowering the temperature of the washing conditions, further reducing the grease cleaning ability of typical detergents, as the performance of the stains classified as oily and greasy stains is most affected by the reduction in temperature.

[0003] Another global trend is the compactification of laundry and dishwashing detergents with the aim of improving their sustainability in terms of water usage and / or transportation costs as well as improving end-consumer convenience (e.g. individualized single mono dose products, tablets, sachets, etc.), which is driving market demand for new ingredients that are more weight-efficient and have a wider range of performance properties.

[0004] Another new and gaining momentum is the desire to improve the "footprint" of any product, either in terms of its origin, such as from natural or renewable resources, or its production, in terms of efficiency and therefore reduced energy use, both compared to conventional products, its efficiency of use, such as equal performance at reduced quantities or higher performance at equal quantities used, its persistence in the natural environment during and / or after its use, such as biodegradation.

[0005] Therefore, one of the most important goals today, for example in the detergent and cleaner (D&C) industry due to climate change, is to significantly reduce CO2 emissions per wash by improving cold water conditions and increasing wash efficiency at temperatures below 40, below 30 or below 20 or even lower, and to reduce the amount of chemicals used per wash and improve the weight efficiency of the washing technology. Another technical challenge is to reduce the corrosion of glass by automatic dishwashing (ADW), thus generally extending the life of dishes and thus contributing to improved sustainability overall. Another important goal of the D&C industry is to seek biodegradable polymers to improve the sustainability of detergent formulations and to avoid the accumulation in ecosystems of non-degradable polymers or polymer blocks resulting from incomplete biodegradation of polymers (persistent blocks), thereby reducing the material remaining in nature after use.

[0006] As a result of these trends, there is a strong need for new biodegradable cleaning polymers that provide excellent primary (i.e., stain removal) and secondary (i.e., whiteness maintenance) cleaning benefits for both hydrophobic and hydrophilic stains and do not contain residual blocks in their polymeric structure. The materials should exhibit good stain removal for oily / greasy and particulate stains, as well as improved whiteness maintenance and minimize the amount of suspended and emulsified oily / greasy and particulate stains redeposited on fabric or hard surfaces. Preferably, the new ingredients will also exhibit synergy with other cleaning polymers known to improve only the removal of oily / greasy or particulate stains and / or only the whiteness of fabrics and hard surfaces, thereby further improving the detergent composition.

[0007] As a result of these trends, there is an increasing need for new biodegradable polymers that do not contain persistent blocks within their polymeric structure.

[0008] Graft polymers of acrylic acid on polysaccharides are known per se, but they usually have a colour problem, being at least yellow to brown in colour, and have a very typical, often strong, odour, which is also hardly acceptable. Summary of the Invention

[0009] Therefore, there was a need to improve this class of polymers by providing polymers and polymer solutions that are colorless or nearly colorless and exhibit only a faint odor.

[0010] The object of the present invention is to provide a novel water-soluble graft polymer comprising a polysaccharide as polymer substrate and at least one water-soluble ethylenically unsaturated monomer as grafted side chain, the water-soluble ethylenically unsaturated monomer comprising at least one sodium carboxylate unit, which is produced by a radical initiated polymerization reaction, and furthermore, during this polymerization, at least one organic compound is used which comprises in its structure at least one carboxyl group capable of complexing with a metal ion, preferably iron, which may be present in part or in full as an acid group or in the form of a deprotonated salt. [Brief description of the drawings]

[0011] [Figure 1] 1 is a GPC chart of GL01924, GL01925 and MD240. [Diagram 2] 1 is a GPC chart of Examples 12 and 15. [Diagram 3] 1 is a GPC chart of Examples 12 and 15. [Figure 4] 1 shows the biodegradability of Example 12. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The following embodiments 1 to 43, together with the experiments detailed in the Experimental Section and the claims, define the present invention.

[0013] EMBODIMENT 1 A water-soluble graft polymer comprising a polysaccharide as the polymer substrate and at least one water-soluble ethylenically unsaturated monomer as a grafted side chain, the water-soluble ethylenically unsaturated monomer comprising at least one sodium carboxylate unit, which is produced by a radical initiated polymerization reaction, and further comprising, during the polymerization, at least one organic compound is used which comprises at least one carboxyl group in its structure, which can be complexed with a metal ion, preferably iron, and which may be present in part or in whole as an acid group or in deprotonated salt form.

[0014] EMBODIMENT 2 2. The graft polymer according to embodiment 1, wherein the polysaccharide consists of an average of up to n=30 glucose units.

[0015] EMBODIMENT 3 3. The graft polymer according to embodiment 2, wherein the polysaccharide consists of an average of up to n=2 to 20 glucose units.

[0016] EMBODIMENT 4 4. The graft polymer according to embodiment 3, wherein the polysaccharide consists of an average of up to n=3 to 10 glucose units.

[0017] EMBODIMENT 5 5. The graft polymer according to any one of the preceding embodiments, wherein the polysaccharide is selected from maltodextrin, corn syrup and / or corn syrup solids.

[0018] EMBODIMENT 6 6. The graft polymer according to any one of the preceding embodiments, wherein the ethylenically unsaturated monomers comprise at least 50 mol %, preferably at least 90 mol %, of sodium acrylate and / or sodium methacrylate, more preferably sodium acrylate, based on the total amount of monomers used, and optionally other monomers polymerizable with the aforementioned monomers.

[0019] EMBODIMENT 7 The graft polymer according to any one of embodiments 1 to 6, wherein the radical polymerization is a radical polymerization type, preferably a radical oxidation-reduction polymerization type.

[0020] EMBODIMENT 8 The graft polymer according to any one of the embodiments 1 to 7, wherein at least one organic compound is used to reduce or preferably prevent discoloration before, during and / or after polymerization, more preferably before and / or during polymerization, even more preferably before and during polymerization, and most preferably such at least one organic compound is still present in a sufficient amount after polymerization and post-polymerization; "sufficient amount" is defined as the molar ratio of the total amount of metal salts and the total amount of at least one organic compound is 1:1 to 1:10,000, preferably 1:2 to 1:1,000, most preferably 1:5 to 1:500, for example, 1:10 to 1:400, 1:30 to 1:200, 1:50 to 1:200 or about 1:80 to 1:120.

[0021] EMBODIMENT 9 The graft polymer according to any one of the first to eighth embodiments, wherein a polymerization system comprising at least one metal salt and a peroxide, preferably hydrogen peroxide, is used as a radical initiator at least in the main polymerization stage.

[0022] EMBODIMENT 10 10. The graft polymer according to any of the embodiments 9, wherein the at least one organic compound comprises at least one functional group that forms a metal complex with at least one metal salt used as part of the polymerization system.

[0023] EMBODIMENT 11 The metal salt preferably comprises, and preferably only comprises, a cation of a metal selected from Fenton catalyzing metals, more preferably from iron and / or copper, most preferably used as iron(II) sulfate, copper(II) sulfate and their hydrated derivatives, more preferably as iron(II) sulfate, and most preferably used as ferrous sulfate heptahydrate, the graft polymer according to any one of embodiments 9 to 10.

[0024] EMBODIMENT 12 The at least one water-soluble organic compound is preferably of natural origin, more preferably from renewable resources, and comprises at least one carboxylate group, such as gluconic acid and its salts, and preferably comprises at least two carboxylate groups (COOR), and if it comprises at least two carboxylate groups, these are more preferably separated by 1-3 other atoms, more preferably by 1-3 other atoms selected from the following types of atoms: C, Si, N, P, O, S, and more preferably the following chemical structures 1-4: [ka] (In all of Structures 1-4, the variables are selected from: R is H, Li, Na, K, Ca, preferably H or Na; A is O or S; R1, R2, R3 are: H and / or organic substituents containing 1 to 20 carbon atoms, optionally further comprising amino, hydroxy, carboxylic, sulfonic, sulfonate, phosphonate, keto, aldehyde and / or aromatic groups, preferably organic structures containing H and / or one or more further carboxylate groups selected from -COOR and -COOH, preferably -COOR; 12. The graft polymer according to any one of the preceding embodiments, wherein R4 is H, OH or an organic substituent containing 1 to 20 carbon atoms, optionally further comprising amino groups, hydroxy groups, carboxylic acid groups, sulfonic acid groups, sulfonate groups, phosphonate groups, keto groups, aldehyde groups and / or aromatic groups, preferably an organic structure containing H and / or one or more further carboxylate groups selected from -COOR and -COOH, preferably -COOR.

[0025] EMBODIMENT 13 13. The graft polymer of embodiment 12, wherein the organic compound has at least three carboxylate groups (COOR).

[0026] EMBODIMENT 14 The graft polymer according to embodiment 12 or 13, wherein the organic compound is selected from the group consisting of citric acid, methylglycidin diacetic acid, ethylenediaminetetraacetic acid, tetra N,N-bis(carboxylatomethyl)-glutamic acid, diethylenetriaminepentaacetic acid, tartaric acid, succinic acid or any salt thereof, such as the ammonium, alkali metal and / or alkaline earth metal salts, such as the sodium, potassium, calcium salts, preferably the sodium salts, more preferably citric acid, succinic acid and / or diethylenetriaminepentaacetic acid, most preferably citric acid and its salts, preferably citric acid.

[0027] EMBODIMENT 15 The graft polymer according to any one of embodiments 9 to 14, wherein the molar ratio of the total amount of the metal salt and the total amount of the at least one organic compound is between 1:1 and 1:10,000, preferably between 1:2 and 1:1,000, and most preferably between 1:5 and 1:500, for example, between 1:10 and 1:400, 1:30 and 1:200, 1:50 and 1:200, or between about 1:80 and 1:120.

[0028] EMBODIMENT 16 16. The graft polymer according to any one of embodiments 12 to 15, wherein the organic compound is a chelating agent that exhibits "readily biodegradable" according to the OCED guidelines (Test No. 301).

[0029] EMBODIMENT 17 17. The graft polymer according to any one of the preceding embodiments, in a dried form, such as by spray drying, freeze drying, vacuum drying, rotary drum drying, or in a granule or granulate form.

[0030] EMBODIMENT 18 The graft polymer according to any one of the preceding embodiments, which is in solution form, preferably as an aqueous solution, more preferably as a solution essentially in water.

[0031] EMBODIMENT 19 A graft polymer according to any one of the first to eighteenth embodiments, which satisfies at least one, preferably more than one of the following requirements, for example in the order of b>c>d>a, for example b+c, more preferably b+c+d, and even more preferably all of them: exhibiting ready biodegradability according to the tests defined by the OECD 301F and / or B guidelines, preferably with a biodegradability within 28 days according to OECD 301F and / or B of at least 50% by weight (based on the total solids content) based on the total weight of the polymer; and / or Gardner color scale is less than 4.0; and / or exhibiting color stability of no more than 3 units increase in Gardner color value for at least 6 months; and / or The polymers of the present invention form clear solutions in liquid detergent formulations with no observable cloudiness or precipitation in the liquid detergent formulation for at least 28 days when the liquid detergent formulation contains a minimum of 0.5% of the polymer of the present invention.

[0032] EMBODIMENT 20 A process for producing a graft polymer according to any one of the first to 19 embodiments, comprising the steps of: - a polymeric substrate which is at least one polysaccharide, preferably this polysaccharide comprises an average of up to 30 glycose units, more preferably comprises an average of up to 20 glycose units, preferably comprises between 2 and 20 glycose units, more preferably comprises maltodextrin, corn syrup and / or corn syrup solids, at least one water-soluble ethylenically unsaturated monomer comprising at least one sodium carboxylate unit, which may be neutralized in situ (in the reactor if polysaccharide is present) from the carboxylic acid form prior to addition to the reactor (i.e. if no polysaccharide is present at the time of neutralization), preferably the monomers used in the polymerization reaction are at least 50 mol %, preferably at least 90 mol %, of the total amount of sodium acrylate, and optionally at least one other polymerizable monomer, most preferably the sodium acrylate is prepared prior to addition to the reaction mixture, is polymerized by a radical initiated polymerization reaction, preferably by a radical redox polymerization type reaction, more preferably using a polymerization system comprising at least one metal salt and hydrogen peroxide as a radical initiator for at least this polymerization step, the metal salt comprising iron, preferably comprising iron as the only metal, more preferably used as ferrous sulfate heptahydrate; Furthermore, at least one organic compound containing at least two carboxyl groups, some or all of which may be present as acid groups or in the form of their deprotonated salts, is added at least before or during this polymerization reaction, and such organic compound is selected from the group defined in the above embodiments 12 to 14, preferably embodiments 13 to 14, more preferably embodiment 14; Such polymerization reactions are carried out in a suitable solvent or solvent mixture, such solvent being selected from polar protic or polar aprotic solvents, preferably acetone, ethanol, isopropanol or water, more preferably an aqueous solution, most preferably essentially water; Optionally, in a post-polymerization step following the main polymerization step, additional amounts of the same initiator or initiator system used in the main polymerization step or a different initiator or initiator system selected from azo initiators, redox initiators, peroxides, photoinitiators and mixtures thereof, preferably water soluble initiator systems, most preferably sodium persulfate and a combination of sodium persulfate and hydrogen peroxide, are added to further reduce the amount of unreacted monomer in the polymerization reaction mixture; Thereby, a polymer solution containing the graft polymer and the organic compound is obtained, Optionally, the polymer solution is subjected to a further treatment selected from steam stripping, steam distillation, thermal distillation and / or vacuum distillation, thereby obtaining a purified polymer solution compared to the polymer solution prior to this step; Optionally, to obtain the grafted polymer in solid form, the process wherein the polymer solution obtained in the previous step is dried using at least one spray dryer, freeze dryer, vacuum dryer, rotary drum dryer, paddle dryer, kneader as drying means or any agglomerate forming means such as fluidized bed agglomeration to obtain the polymer as agglomerates or granules or particulates, preferably by using a drying method such as agglomeration such as spray dryer, freeze dryer, vacuum dryer, fluidized bed agglomeration, which acts at low temperature on the polymer to prevent discoloration, thereby obtaining a polymer solid.

[0033] EMBODIMENT 21 21. The process according to embodiment 20, wherein the polymerization is carried out at a temperature of 70-150°C, preferably 80-120°C, more preferably 90-100°C, and the post-polymerization reaction is carried out at a temperature about 5-10 degrees lower compared to the temperature of the main polymerization reaction.

[0034] EMBODIMENT 22 22. The process according to embodiment 20 or 21, wherein the polymerization is carried out at a solids concentration of 20 to 60, preferably 25 to 50 wt.-%, based on the total amount of polysaccharide and monomers used together.

[0035] EMBODIMENT 23 The graft polymer is produced by reacting an aqueous solution of corn syrup consisting of an average of 3-8 glycose units with a mixture of acrylic acid and sodium acrylate, the mixture having a degree of neutralization of 90-96%, using hydrogen peroxide initiator and ferrous sulfate heptahydrate redox catalyst, using citric acid or its salts, preferably citric acid monohydrate or aqueous citric acid during polymerization and post polymerization to chelate metal ions, and using sodium persulfate in combination with hydrogen peroxide during post polymerization to consume residual acrylate monomers; 23. The process according to any one of embodiments 20 to 22, wherein the polymerization temperature is 90-100°C, the post-polymerization temperature is 85-95°C, and the solids content of the graft polymer after completion of the polymerization is 20-60, preferably 25-50 wt%.

[0036] EMBODIMENT 24 Use of at least one grafted polymer according to any one of embodiments 1 to 19 or obtained or obtainable by the process according to any one of embodiments 20 to 23 in a composition which is a cleaning composition, a fabric care and home care product, an institutional cleaning product, a cosmetic or personal care product or an agrochemical formulation.

[0037] EMBODIMENT 25 The use according to embodiment 24 in a fabric care and home care composition, a cleaning composition or an institutional cleaning product.

[0038] EMBODIMENT 26 The use according to any one of embodiments 24 or 25, wherein the composition comprises at least one grafted polymer in a concentration by weight of about 0.05% to about 10% by weight, based on the total weight of such composition or product.

[0039] EMBODIMENT 27 Use according to any one of embodiments 24 to 26, At least one enzyme and / or about 1% to about 70% by weight of a surfactant system and / or and / or In such a composition, when the sodium polyacrylate polymer having a Fikentscher K value of 15 is replaced with the present graft polymer, it shows improved cleaning performance in red clay dispersion. use.

[0040] EMBODIMENT 28 A laundry detergent composition, cleaning composition or fabric care and home care product comprising at least one grafted polymer as defined in any one of embodiments 1 to 19 or obtained or obtainable by the process as defined in any one of embodiments 20 to 23, preferably a laundry detergent composition, more preferably a liquid or semi-liquid or multi-component laundry detergent composition, most preferably a liquid laundry detergent composition, comprising the at least one grafted polymer in a concentration, by weight based on the total weight of such composition or product, preferably from about 0.05% to about 10%, and optionally at least one enzyme and / or from about 1% to about 70% by weight of a surfactant system and / or an effective amount of at least one additional cleaning adjunct The composition further comprises:

[0041] EMBODIMENT 29 A dishwashing detergent composition, preferably a liquid dishwashing detergent composition or a solid automatic dishwashing detergent composition, more preferably a liquid hand dishwashing detergent composition, comprising at least one grafted polymer as described in any one of embodiments 1 to 19 or obtained or obtainable by the process as described in any one of embodiments 20 to 23, the at least one grafted polymer being present in a concentration, by weight based on the total weight of such composition, of about 0.05% to about 10%, and optionally at least one enzyme and / or from about 1% to about 70% by weight of a surfactant system and / or an effective amount of at least one additional cleaning adjunct and / or at least one chelating agent and / or At least one anionic surfactant The composition further comprises:

[0042] EMBODIMENT 30 A method for stabilizing a graft polymer according to any one of embodiments 1 to 19, or obtained or obtainable by a process according to any one of embodiments 20 to 23, by adding at least one organic compound according to any one of embodiments 12 to 14, to the graft polymer after polymerization, in such a way that the molar ratio of the total amount of the at least one organic compound to the total amount of the graft polymer is 1:100 to 1:1, more preferably 1:500 to 1:100,000, and most preferably 1:1,000 to 1:10,000 (boundary values ​​included).

[0043] Use of at least one graft polymer and compositions containing same Part of the invention is also the use of the polymers of the invention for various fields of application, where they can replace similar structures currently known, but with an improved rate of biodegradation compared to these already known structures.

[0044] EMBODIMENT 31 Use of at least one graft polymer as defined in any one of embodiments 1 to 19 or obtained or obtainable by the process as defined in any one of embodiments 20 to 23, comprising: a) as an additive in cleaning compositions, preferably for liquid, solid or semi-solid detergent formulations, in particular for liquid detergent formulations, preferably for concentrated liquid detergent formulations or individualized single dose laundry detergent formulations or liquid hand dishwashing detergent formulations or solid automatic dishwashing formulations; b) In fabric care and home care products, c) in electroplating formulations; d) in cementitious compositions; e) in agrochemical formulations, preferably as dispersants; f) as adhesion promoter, e.g. for printing inks for laminating films; g) as an auxiliary (adhesive), for example for blending not only different polymer layers but also metal foils to produce multilayer composite films; h) as adhesion promoters in adhesives, for example in combination with polyvinyl alcohol, butyric and acetate esters and styrene copolymers, or as cohesion promoters in label adhesives; i) As a primer to improve adhesion to substrates such as glass, wood, plastics and metals in coating applications; j) To improve wet adhesion, e.g. in standard emulsion paints, and to improve the instantaneous rain resistance of paints, e.g. road markings; k) as a complexing agent, especially as a complexing agent with high binding capacity for heavy metals such as Hg, Pb, Cu, Ni; l) flocculants, for example as flocculants in water treatment / water processing; m) as a penetration aid, e.g. for active metal salt formulations in wood protection; n) as corrosion inhibitors, for example for ferrous and non-ferrous metals and in the fields of oil production and secondary oil production; o) proteins and enzymes; for the immobilization of microorganisms or as immobilization carriers for enzymes and microorganisms; p) for blocking and sealing, e.g. in the mineral oil and natural gas industries; q) as fixative, for example in the textile industry, in particular as formaldehyde-free cofixers; r) as an additive in cosmetic formulations, for example in hair styling compositions and hair rinses; s) as an auxiliary in the paper industry, for example for facilitating drainage, removing impurities, neutralizing charges and as a general-purpose auxiliary for paper coating; t) To separate oil and water, e.g. in the metalworking industry; u) As an additive for landfill seals; v) as a flocculant; w) as an algaecide in swimming pools; x) to produce bitumen chemicals by reacting with fatty acids; y) as an anti-swelling agent to retard water absorption in clays; z) as an emulsifier or emulsion breaker; aa) as surfactants in the industrial cleaning (IC) sector; bb) as a wood preservative; cc) for preparing complexing agents (polycarboxylates); dd) To manufacture mineral mining and processing auxiliaries; ee) as dispersants for pigments, ceramics, carbon black, carbon, carbon fibre, metal powders, e.g. as emulsifiers or dispersants for inks, e.g. for ink jet printing; ff) as CO2, NOX, SOX, Cl2 and aldehyde adsorbents for gas cleaning and for neutralizing acidic components; gg) for water softening; hh) as crystal growth inhibitors, e.g. in agrochemical formulations, oil field applications; ii) As a rheology modifier (thickener); jj) as an auxiliary or component for oil, coal and natural gas extraction and processing aids; kk) for the manufacture of synthetic rubber and rubber chemicals; ll) as an additive in coolants, lubricants and cooling lubricants; mm) as an auxiliary in the field of construction chemicals; nn) as a component of zinc plating baths; or oo) for the production of non-viral genetic vectors; Use of.

[0045] Another subject of the present invention is the use of the above mentioned polymers (including modified polymers) in fabric care and home care products, in cosmetic formulations, as emulsion breakers for crude oils, in pigment dispersions for inkjet inks, in electroplating formulations, in cement-based compositions and / or as dispersants for agrochemical formulations, preferably in cleaning compositions and / or in fabric care and home care products, in particular in cleaning compositions for improving the removal of oily and greasy stains, which cleaning compositions are preferably laundry detergent formulations and / or hand dishwashing detergent formulations, more preferably liquid laundry detergent formulations and / or liquid hand dishwashing detergent formulations.

[0046] The polymers of the present invention can be added to cosmetic formulations, as crude oil emulsion breakers, to pigment dispersions for inkjet inks, to electroplating formulations, to cementitious compositions, while the compounds of the present invention can also be added (used) in washing or cleaning compositions.

[0047] Other subjects of the present invention are therefore cleaning compositions, fabric and home care products, institutional cleaning products, cosmetic formulations, crude oil emulsion breakers, pigment dispersions for inkjet inks, electroplating formulations, dispersants for cement-based compositions and / or agrochemical formulations, comprising at least one polymer as defined above.

[0048] Preferably, this is a cleaning composition and / or a fabric care and home care product, preferably a laundry detergent formulation and / or a hand dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid hand dishwashing detergent formulation, preferably for improving the removal of oily and greasy stains, comprising at least one polymer as defined above.

[0049] In another preferred embodiment of the present invention, the cleaning composition can be used for soil removal of particulate stains and / or oily and greasy stains as well as preferably for whiteness maintenance in laundry care.

[0050] In another embodiment, the cleaning compositions of the present invention are hard surface cleaning compositions that can be used to clean a variety of surfaces, such as hardwood, tile, ceramic, plastic, leather, metal, glass, and the like.

[0051] In another embodiment, the cleaning composition of the present invention is a liquid or solid automatic dishwashing detergent composition, preferably a solid automatic dishwashing detergent composition that can be used to clean dishes, such as dishes, such as glasses, and the inventive polymer prevents corrosion of the glass surface.

[0052] In other embodiments, the cleaning compositions are designed for use in personal care and pet care compositions, such as shampoo compositions, personal wash formulations, liquid or bar soaps, etc.

[0053] In the present invention, the preferred application fields for the use of the polymers are in the field of fabric care and home care products and cleaning compositions, preferably cleaning compositions for institutional and consumer domestic use.

[0054] EMBODIMENT 32 Use according to embodiment 31 in cleaning compositions and / or fabric care and home care products, preferably liquid and solid detergent compositions, such detergent compositions preferably comprising: a) hand dishwashing and automatic dishwashing detergent compositions comprising at least one polymer and at least one chelating agent and / or at least one surfactant, more preferably hand dishwashing and automatic dishwashing detergent compositions comprising a chelating agent in the case of liquid or solid automatic dishwashing compositions and a surfactant system in the case of liquid hand dishwashing detergent compositions, respectively; and / or b) a laundry detergent composition comprising at least one polymer and at least one surfactant, preferably a surfactant system; That is, use.

[0055] In the preferred application fields of such uses, typical tasks must be fulfilled, all of which are encompassed under the general term "cleaning", but which in reality include different tasks, such as the removal of oily and fatty residues, solid residues, amphoteric residues and hydrophilic residues. Another task is to protect the article to be cleaned from deterioration, such as protecting glass from corrosion, protecting silverware from oxidation, protecting against fading, etc. Another task is to improve the overall appearance of the article to be cleaned, such as enhancing or restoring color, whiteness, imparting or increasing shine. In many of these applications, additional ingredients are usually added, important for cleaning applications are, for example, enzymes that aid in the biological decomposition of the residues.

[0056] Embodiment 33: The use according to embodiment 32, i) to improve the removal of oily / greasy stains, and / or ii) to remove clay; and / or iii) To remove dirt caused by particle stains; and / or iv) To disperse and / or emulsify dirt; and / or v) To modify the treated surface to improve removal of subsequent recontamination; and / or vi) to prevent or reduce, preferably prevent, corrosion of glass; and / or vii) to improve whiteness; and / or viii) additionally at least one enzyme selected from the list consisting of lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, pectinase, lactase and peroxidase, and combinations of at least two of the above mentioned types, when present, for improving oily / greasy stain removal, food stain removal and / or combination stain removal, The use of Most preferred is the use in a cleaning composition for i) improving the removal of oily / greasy stains, The above mentioned options i) to viii) respectively relate to the use in preferably laundry detergent formulations and / or dishwashing detergent formulations, more preferably in liquid laundry detergent formulations and / or automatic dishwashing detergents or liquid hand dishwashing detergent formulations, preferably solid.

[0057] Embodiment 34: Use according to embodiments 32-33 in cleaning compositions and / or fabric care and home care products, preferably cleaning compositions for fabric care and home care, wherein the cleaning composition is preferably a laundry detergent formulation or a dishwashing detergent formulation.

[0058] Such ingredients are typically combined with other ingredients into formulations and compositions, which may also be referred to as "products" (as such formulations are provided by the supplier to other customers, either as formulations to be used as such, such as for cleaning purposes, or to make other formulations which in turn can be sold to consumers as consumer "products").

[0059] EMBODIMENT 35 A composition comprising at least one grafted polymer according to any one of embodiments 1 to 19 or obtained or obtainable by the process according to any one of embodiments 20 to 23, respectively, which is a fabric care and home care product, a cleaning composition, an institutional cleaning product, a cosmetic or personal care product, an oil field formulation such as a crude oil emulsion breaker, a pigment dispersion for inks such as inkjet inks, an electroplating product, a cementitious composition, a lacquer, a paint, an agrochemical formulation, preferably a laundry detergent, a dishwashing composition, a cleaning composition and / or a fabric care and home care product.

[0060] EMBODIMENT 36 The composition according to embodiment 35, which is a solid or liquid laundry detergent composition or a solid or liquid hand dishwashing detergent composition, preferably a liquid laundry detergent or hand dishwashing detergent composition, more preferably a liquid laundry detergent composition, comprising at least one polymer, preferably at least one grafted polymer, according to embodiments 5-15; optionally further comprising at least one enzyme, preferably at least one enzyme selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, mannanases and peroxidases, and a combination of at least two of the above mentioned types, preferably the at least one enzyme is selected from proteases, Optionally, at least one antimicrobial agent; The at least one polymer is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to about 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, based on the total weight of such composition or product; Such products or compositions further comprise from about 1% to about 70% by weight of a surfactant system comprising at least one surfactant, preferably an anionic surfactant, and more preferably at least one anionic surfactant, of the composition.

[0061] EMBODIMENT 37 The composition according to embodiment 35, which is a solid or liquid automatic dishwashing detergent composition, preferably a solid automatic dishwashing detergent composition, comprising at least one grafted polymer, Optionally, at least one enzyme is further included, preferably at least one enzyme selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, mannanases and peroxidases, and combinations of at least two of the above mentioned types, preferably the at least one enzyme is selected from proteases and amylases; Optionally, at least one antimicrobial agent; Optionally, at least one compound selected from an alkali metal percarbonate, an alkali metal perborate, and an alkali metal persulfate; Optionally, at least one zinc salt; At least one grafted polymer is present in a total amount ranging from about 0.001% to about 10%, preferably from about 0.005% to about 5%, more preferably from about 0.01% to about 3%, and most preferably from about 0.1% to about 2%, and such products or compositions further comprise at least one chelating agent present in a total amount ranging from about 1% to about 70%, preferably from 10% to about 60%, and even more preferably from 30% to about 50%, Optionally, further comprising at least one surfactant, more preferably a surfactant system, in a total amount of from about 1% to about 70% by weight; All weight percentages are based on the total weight of such composition.

[0062] Embodiment 38: The composition of embodiment 37, which is a solid automatic dishwashing detergent composition comprising at least one grafted polymer, At least one chelating agent selected from methylglycine diacetate (MGDA), glutamic acid diacetate (GLDA), citric acid, and salts thereof; At least one enzyme selected from a protease and / or an amylase; at least one bleaching agent selected from alkali metal percarbonates, alkali metal perborates and alkali metal persulfates, preferably an alkali metal percarbonate; at least one nonionic surfactant; Optionally, at least one disintegrant, preferably a superdisintegrant, more preferably PVPP; Optionally, at least one zinc salt; The composition further comprises:

[0063] Superdisintegrants are known to the skilled artisan from, for example, EP 1004661, EP 1263814 and EP 1036839 and are also described in Pharmaceutical Technology, Volume 2006 Supplement, Issue 5, "A Comparative Study of Current Superdisintegrants", October 1, 2006.

[0064] Embodiment 39: The composition according to any one of embodiments 35 to 36, which is a detergent composition comprising at least one anionic surfactant as a surfactant, and further comprising water.

[0065] Embodiment 40: 39. The composition of any one of embodiments 37 and 38, which is a detergent composition comprising at least one nonionic surfactant as a surfactant and further comprising water.

[0066] EMBODIMENT 41 41. The composition of any one of embodiments 35-40, which is a detergent composition comprising at least one further polymer selected from a multifunctional polyethyleneimine or a multifunctional diamine, or a mixture thereof.

[0067] Embodiment 42: 42. The composition of any one of embodiments 35-41, which is a liquid detergent composition comprising, as a surfactant, at least one 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation from 3 to 5.

[0068] Further, the present invention may have the following features.

[0069] Also preferred according to the invention, the cleaning composition further comprises (besides the at least one polymer as defined above) at least one enzyme, preferably chosen from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the abovementioned types.

[0070] Preferably, such inventive cleaning composition is a fabric and home care product or an institutional (I&I) cleaning product, preferably a fabric and home care product, more preferably a laundry detergent or a hand dish detergent, comprising at least one inventive polymer and optionally further comprising at least one surfactant or surfactant system, for improved soil removal, dispersion and / or emulsification, and / or modifying treated surfaces and / or maintaining the whiteness of the treated surfaces.

[0071] At least one polymer as described herein (such polymers as defined above, in particular as obtained or obtainable by the process according to any one of embodiments 1 to 19 or embodiments 20 to 23, are also referred to in the following paragraphs as "polymer of the invention") is present in said cleaning composition of the invention at a concentration of 0.001 to 10, preferably about 0.005% to 5%, more preferably about 0.01% to about 5%, most preferably about 0.1% to about 3%, based on the total weight of such composition; such cleaning composition may further comprise, and preferably does comprise, about 1% to about 70% by weight of a surfactant system.

[0072] More preferably, the cleaning compositions of the present invention comprising at least one inventive polymer and optionally further comprising at least one surfactant or surfactant system are intended for primary cleaning (i.e., removal of stains) in laundry and hand dishwashing applications, more particularly for the removal of oily and fatty stains, such as fabric and dish stains, and further comprise at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the above mentioned types of enzymes.

[0073] In one preferred embodiment, the cleaning compositions of the present invention are liquid or solid laundry detergent compositions.

[0074] In other preferred embodiments, the cleaning compositions of the present invention are liquid or solid (e.g., powder or tablet / unit dose) detergent compositions for manual dishwashing or automatic dishwashing, preferably either liquid hand dishwashing detergent compositions or solid automatic dishwashing compositions.

[0075] In one embodiment, the inventive polymers may be utilized in cleaning compositions comprising a surfactant system comprising C10-C15 alkyl benzene sulfonate (LAS) as the surfactant base and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0076] In a further embodiment, the polymers of the present invention can be utilized in cleaning compositions, such as any type of laundry detergent, comprising a C8 to C18 linear or branched alkyl ether sulfate salt containing 1 to 5 ethoxy units as the surfactant base and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0077] In a further embodiment, the polymers of the present invention can be utilized in cleaning compositions, such as any type of laundry detergent, comprising a C12-C18 alkyl ethoxylate surfactant containing 5-10 ethoxy units as the surfactant base, and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants, or mixtures thereof.

[0078] In one embodiment of the present invention, the inventive polymer is a component of a cleaning composition, preferably a laundry or dishwashing formulation, more preferably a liquid laundry or hand dishwashing detergent formulation, respectively, further comprising at least one surfactant, preferably at least one anionic surfactant.

[0079] The selection of the additional surfactant in these embodiments can depend on the application and the benefit desired.

[0080] Description of cleaning compositions, formulations and their ingredients As used herein, the phrase "cleaning composition" includes compositions and formulations designed for cleaning soiled materials, including those designed to clean any type of soiled material or surface.

[0081] "Industrial cleaning" compositions include those types of cleaning compositions designed for use in industrial cleaning, for example, for use in cleaning any type of soiled material or surface, such as hard surface cleaners for any type of surface, including tiles, carpets, PVC surfaces, wood surfaces, metal surfaces, lacquered surfaces.

[0082] "Fabric care and home care compositions" include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, laundry pre-wash detergents, laundry pre-treatments, laundry aids, spray products, dry cleaning agents or compositions, laundry rinsing additives, rinse-off additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, cleaning compositions such as detergents contained on or within porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions may be used as laundry pre-treatments, laundry post-treatments, or may be added during the rinse or rinse cycle of a laundry operation, preferably during the rinse cycle of a laundry or dishwashing operation.

[0083] The cleaning compositions of the present invention can be in any form, i.e., liquid form; solids such as powders, granules, aggregates, pastes, tablets, sachets, bars, gels, etc.; emulsions; the type delivered in containers having two or more compartments; single or multi-phase unit dose articles; spray or foam cleaners; wet wipes (i.e., the cleaning composition is combined with a nonwoven material such as those described in U.S. Pat. No. 6,121,165 to Mackey et al.); dry wipes that are activated by the user or consumer by wetting with water (i.e., the cleaning composition is combined with a nonwoven material such as those described in U.S. Pat. No. 5,980,931 to Fowler et al.); or other homogeneous, heterogeneous, or single or multi-phase cleaning products.

[0084] The liquid cleaning compositions of the present invention preferably have a viscosity of 50 to 10,000 mPa·s, the liquid manual dish wash cleaning compositions (also referred to as liquid "dish wash compositions") preferably have a viscosity of 100 to 10,000 mPa·s, more preferably 200 to 5,000 mPa·s, and most preferably 500 to 3,000 mPa·s, at 20 1 / s and 20°C, and the liquid laundry cleaning compositions preferably have a viscosity of 50 to 3,000 mPa·s, more preferably 100 to 1,500 mPa·s, and most preferably 200 to 1,000 mPa·s, at 20 1 / s and 20°C.

[0085] The liquid cleaning composition of the present invention may have any suitable pH value. Preferably, the pH of the composition is adjusted to 4-14. More preferably, the pH of the composition is 6-13, even more preferably 6-10, and most preferably 7-9. The pH of the composition may be adjusted using pH adjusting ingredients known in the art, measured at a product concentration of 10% in demineralized water at 25°C. For example, NaOH may be used, the actual weight % of NaOH may vary, and a desired pH, such as pH 8.0, may be achieved. In one embodiment of the present invention, the pH may be adjusted to above 7 by using amines, preferably alkanolamines, more preferably triethanolamine.

[0086] Detergent compositions, such as fabric care and home care products and commercial cleaning formulations, more specifically laundry and hand dish detergents, are known to those skilled in the art. Any compositions related to the respective applications, such as those known to those skilled in the art, can be used within the context of the present invention by including at least one of the inventive polymers, preferably at least one polymer, in an amount suitable for developing specific properties in such compositions, especially when such compositions are used in their field of use.

[0087] An aspect of the present invention is also the use of the polymers of the present invention as additives in detergent formulations, especially liquid detergent formulations, preferably concentrated liquid detergent formulations or single dose laundry detergent formulations.

[0088] The cleaning compositions of the present invention may, and preferably do, contain cleaning adjuncts (sometimes abbreviated herein as "adjuncts"), such adjuncts preferably being in addition to the surfactant system defined above.

[0089] Suitable cleaning adjuncts include builders, co-builders, structurants or thickeners, clay soil removal / anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersants, polymeric degreasers, solubilizers, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, optical brighteners, malodor control agents, pigments, dyes, opacifying agents, color correctors, color transfer inhibitors, chelating agents, foam boosters, foam suppressors (defoamers), color speckles, silver care agents, anti-tarnish and / or corrosion inhibitors, alkalizing agents, pH adjusters, pH buffers, hydrotropes, scrubbing particles, antimicrobial agents, antioxidants, softening agents, carriers, processing aids, fragrance precursors, and fragrances.

[0090] The liquid cleansing composition may additionally comprise, and preferably does comprise, at least one of a rheology control / regulator, an emollient, a moisturizer, a skin rejuvenation active, and a solvent.

[0091] The solid composition may additionally comprise, and preferably does comprise, at least one of a filler, a bleaching agent, a bleach activator, and a catalytic material.

[0092] Suitable examples of such cleaning auxiliaries and amounts used are described in WO 99 / 05242, US Pat. No. 5,576,282, US Pat. No. 6,306,812 B1 and US Pat. No. 6,326,348 B1.

[0093] Those skilled in the art will appreciate that a detersive surfactant includes any surfactant or mixture of surfactants that is useful in cleaning, removing stains or laundering soiled materials.

[0094] Thus, cleaning compositions of the present invention, such as fabric care and home care products and institutional cleaning formulations, more particularly laundry and hand dish detergents, preferably additionally comprise a surfactant system as described above and in more detail below, and more preferably also further adjuvants.

[0095] The surfactant system can be composed of one surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those skilled in the art will appreciate that a detergent surfactant system includes any surfactant or mixture of surfactants that is beneficial for cleaning, removing stains, or laundering soiled materials.

[0096] The cleaning compositions of the present invention preferably comprise a surfactant system in an amount sufficient to impart the desired cleaning properties. In some embodiments, the cleaning composition comprises from about 1% to about 70% of the surfactant system by weight of the composition. In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% of the surfactant system by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% of the surfactant system by weight of the composition. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof.

[0097] (a) Laundry composition In laundry formulations, anionic surfactants usually make up the largest and by far the largest proportion of surfactants contained in such formulations.Thus, preferably, the cleaning composition of the present invention for use in laundry comprises at least one anionic surfactant and, optionally, further surfactants selected from any of the surfactant classes described herein, preferably from nonionic surfactants and / or amphoteric surfactants and / or zwitterionic surfactants and / or cationic surfactants.

[0098] Non-limiting examples of useful anionic surfactants, which may also be used in combination with more than one surfactant herein, include C9-C20 linear alkylbenzene sulfonates (LAS), C10-C20 primary, branched and random alkyl sulfates (AS); C10-C18 These include secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) (x is 1-30); C10-C18 alkyl alkoxy carboxylates containing 1-5 ethoxy units; internally branched alkyl sulfates as described in U.S. Pat. Nos. 6,020,303 and 6,060,443; internally branched alkyl alkoxy sulfates as described in U.S. Pat. Nos. 6,008,181 and 6,020,303; modified alkylbenzene sulfonates (MLAS) as described in WO 99 / 05243, WO 99 / 05242 and WO 99 / 05244; methyl ester sulfonates (MES); and α-olefin sulfonates (AOS).

[0099] In a preferred embodiment of the present invention, the anionic surfactant is selected from C10-C15 linear alkylbenzene sulfonate, C10-C18 alkyl ether sulfate containing 1-5 ethoxy units, and C10-C18 alkyl sulfate.

[0100] Non-limiting examples of nonionic surfactants that can be used in combination with one or more other surfactants include: C8-C18 alkyl ethoxylates, such as NEODOL®, a nonionic surfactant from Shell; ethylene oxide / propylene oxide block alkoxylates, such as PLURONIC® from BASF; C14-C22 internally branched alkyl alkoxylates, such as those described in U.S. Pat. Nos. 6,153,577, 6,020,303, and 6,093,856; Silylates BAEx (x is 1-30); alkyl polysaccharides as described in U.S. Pat. No. 4,565,647, issued Jan. 26, 1986 to Llenado; alkyl polyglycosides as described in U.S. Pat. Nos. 4,483,780 and 4,483,779; polyhydroxy fatty acid amides as described in U.S. Pat. No. 5,332,528; and ether-terminated poly(oxyalkylated) alcohol surfactants as described in U.S. Pat. No. 6,482,994 and WO 01 / 42408.

[0101] In a preferred embodiment of the invention, the non-ionic surfactants are selected from C12 / 14 and C16 / 18 fatty alcohol alkoxylates, C13 / 15 oxoalcohol alkoxylates, C13 alcohol alkoxylates and 2-propylheptyl alcohol alkoxylates, each of which contains 3 to 15 ethoxy units, preferably 5 to 10 ethoxy units or 1 to 3 propoxy units and 2 to 15 ethoxy units.

[0102] Non-limiting examples of amphoteric surfactants that may be used in combination with more than one other surfactant include: water-soluble amine oxides containing one alkyl moiety having about 8 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties having about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety having about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties having about 1 to about 3 carbon atoms. See WO 01 / 32816, U.S. Pat. No. 4,681,704 and U.S. Pat. No. 4,133,779. Thus, suitable surfactants include so-called amine oxides, such as lauryl dimethylamine oxide ("lauramine oxide").

[0103] In a preferred embodiment of the present invention, the amphoteric surfactant is selected from C8-C18 alkyl-dimethylamine oxide and C8-C18 alkyl-di(hydroxyethyl)amine oxide.

[0104] The cleaning composition may also include zwitterionic surfactants, which may also be used in combination with one or more other surfactants.

[0105] Suitable zwitterionic surfactants include betaines, such as alkyl betaines, alkyl amido betaines, amido azolinium betaines, sulfobetaines (INCI: Sultaine), as well as phosphobetaines. do.

[0106] Preferred betaines are, for example, C12-C18 alkyl betaines and sulfobetaines. The zwitterionic surfactant is preferably a betaine surfactant, more preferably a cocamidopropyl betaine surfactant.

[0107] Non-limiting examples of cationic surfactants that may be used in combination with one or more other surfactants include: quaternary ammonium surfactants that may have up to 26 carbon atoms, such as the alkoxylated quaternary ammonium (AQA) surfactants described in U.S. Pat. No. 6,136,769; dimethylhydroxyethyl quaternary ammonium, described in U.S. Pat. No. 6,004,922; dimethylhydroxyethyl lauryl ammonium chloride, described in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005, WO 98 / 35006, WO 98 / 35007, WO 98 / 35009, WO 98 / 35010, WO 98 / 35011, WO 98 / 35012, WO 98 / 35013, WO 98 / 35014, WO 98 / 35015, WO 98 / 35016, WO 98 / 35017, WO 98 / 35018, WO 98 / 35019 ... Polyamine cationic surfactants as described in WO 98 / 35004, WO 98 / 35005 and WO 98 / 35006; cationic ester surfactants as described in U.S. Pat. Nos. 4,228,042, 4,239,660, 4,260,529 and 6,022,844; and amino surfactants as described in U.S. Pat. No. 6,221,825 and WO 00 / 47708, particularly amidopropyldimethylamine (APA).

[0108] The compositions according to the invention may contain at least one builder. In the context of the present invention, no distinction is to be made between builders and components elsewhere called "cobuilders". Examples of builders are complexing agents, also called complexing agents hereinafter, ion exchange compounds and precipitating agents. The builders are selected from citrates, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarboxylates.

[0109] The term citrate in the context of the present invention includes mono- and di-alkali metal salts of citric acid, in particular the monosodium salt and preferably the trisodium salt, ammonium salts or substituted ammonium salts of citric acid, as well as citric acid. Citrate can be used as anhydrous compound or as a hydrate, for example as sodium citrate dihydrate. The amount of citrate is calculated based on trisodium citrate anhydrous.

[0110] The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogen phosphate, sodium pyrophosphate and polyphosphates, such as sodium tripolyphosphate. However, preferably, the compositions according to the invention are free of phosphates and polyphosphates, including hydrogen phosphates, such as trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate ("phosphate-free"). "Free" in relation to phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphates and polyphosphates, determined by gravimetric analysis, is in the range of 10 ppm to 0.2% by weight of the respective composition.

[0111] The term carbonate includes alkali metal carbonates and alkali metal hydrogen carbonates, with the sodium salts being preferred, Na2CO3 being particularly preferred.

[0112] The compositions according to the invention, in particular solid formulations, may contain builders, for example in a total amount of 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably up to 20% by weight. Liquid formulations according to the invention preferably contain builders in the range of 0.1 to 8% by weight.

[0113] The formulation according to the invention may contain one or more alkali carriers. The alkali carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired. For example, in addition to the above-mentioned alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal metasilicates, alkali metal hydroxides are also suitable. In each case, the preferred alkali metal is potassium, with sodium being particularly preferred. In one embodiment of the invention, the pH is adjusted to above 7 using an amine, preferably an alkanolamine, more preferably triethanolamine.

[0114] In one embodiment of the invention, the laundry formulation according to the invention further comprises at least one enzyme.

[0115] Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the above mentioned types.

[0116] Such enzymes can be incorporated in an amount sufficient to provide an effective amount for cleaning. A preferred amount is that in which the active enzyme ranges from 0.001% to 5% by weight of the detergent composition according to the invention. Enzyme stabilizing systems can also be used together with the enzymes, such as, for example, calcium ions, boric acid, boronic acid, propylene glycol and short chain carboxylic acids. The short chain carboxylic acids relevant to the present invention are selected from monocarboxylic acids having 1 to 3 carbon atoms per molecule and from 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 above mentioned, as well as the respective sodium and potassium salts.

[0117] The compositions according to the invention may also contain one or more bleaching agents.

[0118] Preferred bleaching agents are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or as the so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, the term "persulfate" including in each case also peroxodisulfates in addition to salts of the peracid H2SO5.

[0119] In this connection, the alkali metal salts can also in each case be alkali metal hydrogen carbonates, alkali metal hydrogen perborates and alkali metal hydrogen persulfates, however, the dialkali metal salts are preferred in each case.

[0120] The formulation according to the invention comprises one or more bleach catalysts. The bleach catalysts may be selected from oxaziridinium bleach catalysts, bleach boosting transition metal salts or transition metal complexes such as manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes. In addition to manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, cobalt, iron, copper and ruthenium amine complexes can also be used as bleach catalysts.

[0121] Formulations according to the invention may include one or more bleach activators, such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluril, tetraacetylhexylenediamine, acylated phenolsulfonates such as n-nonanoyl- or isononanoyloxybenzenesulfonates, N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts).

[0122] The formulation according to the invention can contain one or more corrosion inhibitors. In this case, this is understood to include compounds that inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, especially benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, as well as phenol derivatives, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

[0123] In one embodiment of the invention, the formulation according to the invention comprises a total amount of corrosion inhibitors in the range of 0.1-1.5 wt.%.

[0124] The formulations according to the invention may also comprise further detersive and / or soil release polymers.

[0125] Additional detergent polymers include, but are not limited to, "multifunctional polyethyleneimines" (e.g., BASF's Sokalan® HP20) and / or "multifunctional diamines" (e.g., BASF's Sokalan® HP96). Such multifunctional polyethyleneimines are typically ethoxylated polyethyleneimines having a weight average molecular weight Mw in the range of 3,000 to 250,000 g / mol, preferably in the range of 5,000 to 20,0000 g / mol, more preferably in the range of 8,000 to 10,0000 g / mol, more preferably in the range of 8,000 to 50,000 g / mol, more preferably in the range of 10,000 to 30,000 g / mol, and most preferably in the range of 10,000 to 20,000 g / mol. Suitable polyfunctional polyethyleneimines have 80% to 99% by weight, preferably 85% to 99% by weight, more preferably 90% to 98% by weight, most preferably 93% to 97% by weight or 94% to 96% by weight of ethylene oxide side chains, based on the total weight of the material. Ethoxylated polyethyleneimines are typically based on a polyethyleneimine core and a polyethylene oxide shell. Suitable polyethyleneimine core molecules are polyethyleneimines with a weight average molecular weight Mw in the range of 500 to 5,000 g / mol. Preferably, those with a molecular weight of 500 to 1,000 g / mol are used, more preferably Mw is 600 to 800 g / mol. In that case, the ethoxylated polymer has an average of 5 to 50, preferably 10 to 35, more preferably 20 to 35 ethylene oxide (EO) units per NH functionality.

[0126] Suitable polyfunctional diamines are typically ethoxylated C2-C12 alkylenediamines, preferably hexamethylenediamine, which are further quaternized and optionally sulfated. The weight average molecular weight Mw of typical polyfunctional diamines is in the range of 2,000-10,000 g / mol, more preferably in the range of 3,000-8,000 g / mol, most preferably in the range of 4,000-6,000 g / mol. In a preferred embodiment of the present invention, an ethoxylated hexamethylenediamine, which is further quaternized and sulfated, can be used, which contains an average of 10-50, preferably 15-40, more preferably 20-30 ethylene oxide (EO) groups per NH functional group, preferably having two cationic ammonium groups and two anionic sulfate groups.

[0127] In a preferred embodiment of the present invention, the cleaning composition may contain at least one polyfunctional polyethyleneimine and / or at least one polyfunctional diamine to improve the cleaning performance of the laundry detergent, for example, preferably to improve the stain removal ability, especially the primary cleaning power of particle stains on polyester fabrics. The above-described polyfunctional polyethyleneimine or polyfunctional diamine or mixtures thereof may be added to the laundry detergent and cleaning composition in small amounts of generally 0.05 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.25 to 5% by weight, and even up to 2% by weight, based on the total specific composition including other components and water and / or solvent.

[0128] Thus, one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one inventive polymer and (ii) at least one compound selected from multifunctional polyethyleneimines and multifunctional diamines, and mixtures thereof.

[0129] In one embodiment of the present invention, the ratio of at least one of the polymers of the present invention to (ii) at least one compound selected from polyfunctional polyethyleneimines and polyfunctional diamines, and mixtures thereof, is 10:1 to 1:10, preferably 5:1 to 1:5, and more preferably 3:1 to 1:3.

[0130] Laundry formulations containing the polymers of the present invention may also contain at least one antimicrobial agent (sometimes referred to as a "preservative").

[0131] The composition may contain one or more antimicrobial agents and / or preservatives described on pages 35-39 of WO 2021 / 115912 A1.

[0132] In particular, the following antimicrobial and / or antiseptic agents are of interest: 4,4'-Dichloro-2-hydroxydiphenyl ether (CAS number 3380-30-1), also known as 5-chloro-2-(4-chlorophenoxy)phenol, sold under the trade name Diclosan, DCPP, Tinosan® HP 100 (BASF) as a 30% by weight solution of 4,4'-dichloro-2-hydroxydiphenyl ether in 1,2-propylene glycol; 2-phenoxyethanol (CAS number 122-99-6, also known as phenoxyethanol, methylphenyl glycol, phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, Protectol® PE); 2-bromo-2-nitropropane-1,3-diol (CAS number 52-51-7, also known as 2-bromo-2-nitro-1,3-propanediol, Bronopol®, Protectol® BN, Myacide AS); glutaraldehyde (CAS number 111-30-8, also known as: 1-5-pentanedial, pentane-1,5-dial, glutaral, glutaric dialdehyde, Protectol® GA, Protectol® GA 50, Myacide® GA); Glyoxal (CAS No. 107-22-2; Alternative names: Ethanedial, Oxylaldehyde, 1,2-Ethanedial, Protectol® GL); 2-Butyl-benzo[d]isothiazol-3-one (BBIT, CAS No. 4299-07-4); 2-Methyl-2H-isothiazol-3-one (MIT, CAS No. 2682-20-4); 2-Octyl-2H-isothiazol-3-one (OIT, CAS No. 26530-20-1); 5-Chloro-2-methyl-2H-isothiazol-3-one (CIT, CMIT, CAS No. 26172-55-4); 5-Chloro-2-methyl-2H-isothiazol-3-one (CMIT, EINECS 247-500-7) and 2-methyl-2H-isothiazol-3-one (MIT, EINECS 220-239-6) (mixture of CMIT / MIT, CAS no. 55965-84-9);1,2-benzisothiazol-3(2H)-one (BIT, CAS no. 2634-33-5);Hexa-2,4-dienoic acid (sorbic acid, CAS number 110-44-1) and its salts, such as calcium sorbate, sodium sorbate, potassium (E,E)-hexa-2,4-dienoate (potassium sorbate, CAS number 24634-61-5); lactic acid and its salts; L-(+)-lactic acid (CAS number 79-33-4); benzoic acid and its sodium salts (CAS number 65-85-0, CAS number 532-32-1) and its salts, such as ammonium benzoate, calcium benzoate, magnesium benzoate, MEA benzoate, potassium benzoate; salicylic acid and its salts, such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate , TEA salicylate; benzalkonium chloride, bromide and saccharinates, such as benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate (CAS numbers 8001-54-5, 63449-41-2, 91080-29-4, 68989-01-5, 68424-85-1, 68391-01-5, 61789-y71-7, 85409-22-9); didecyldimethylammonium chloride (DDAC, CAS number 68424-95-3 and CAS number 7173-51-5); N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (diamine, CAS number 2372-82-9); peracetic acid (CAS number 79-21-0); hydrogen peroxide (CAS number 7722-84-1). ;

[0133] The antibacterial agent is added to the composition at a concentration of 0.001 to 10% by weight of the total composition.

[0134] Preferably, the composition contains 2-phenoxyethanol at a concentration of 0.1 to 2% or 4,4'-dichloro 2-hydroxydiphenyl ether (DCPP) at a concentration of 0.005 to 0.6%.

[0135] The present invention therefore also includes a method of protecting an aqueous composition according to the present invention from bacterial contamination or growth, which method comprises the addition of 2-phenoxyethanol.The present invention therefore also includes a method of imparting antimicrobial benefit to textiles after treatment with a solid laundry detergent (e.g., powder, granules, capsules, tablets, bars, etc.), liquid laundry detergent, fabric softener or post-rinse treatment agent containing 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP).

[0136] Formulations according to the invention may also contain water and / or additional organic solvents, such as ethanol or propylene glycol.

[0137] Further optional ingredients can be, but are not limited to, viscosity modifiers, cationic surfactants, suds boosters or suppressors, fragrances, dyes, optical brighteners and dye transfer inhibitors.

[0138] (b) Dishwashing compositions Another aspect of the invention is also a dishwashing composition comprising at least one polymer as described above (any of the embodiments herein, particularly those described in embodiments 1 to 18; the polymers in this section are also referred to as "polymers of the invention").

[0139] Thus, an aspect of the present invention is also the use of the inventive polymers described above in dishwashing applications, such as hand dishwashing or automatic dishwashing applications.

[0140] The dishwashing compositions according to the invention can be in the form of liquids, semi-liquids, creams, lotions, gels or solid compositions, with solid embodiments including, for example, powders and tablets. Liquid compositions are typically preferred for hand dishwashing applications, while solid and sachet formulations (sachets may contain solids in addition to liquid components) are typically preferred for automatic dishwashing compositions, although in some parts of the world liquid automatic dishwashing compositions are also used and therefore are of course encompassed by the term "dishwashing composition".

[0141] Dishwashing compositions are intended for direct or indirect application to dishware and metal and glass surfaces, including drinking glasses and other glasses, cups, dishes and cookware such as pots and pans, and cutlery such as forks, spoons and knives.

[0142] The method of the present invention for cleaning dishware, metal and / or glass surfaces comprises the step of applying the dishwashing composition, preferably in liquid form, directly or by means of a cleaning implement, i.e. undiluted, to the surface. The composition is applied directly to the surface to be treated without significant dilution (neat) prior to application and / or to a cleaning implement or implement, such as a dish cloth, sponge or dishwashing brush. The cleaning implement or implement is preferably moistened before or after delivering the composition thereto. In the method of the present invention, the composition can also be applied in diluted form.

[0143] The formulations of the invention, which contain at least one inventive polymer, exhibit excellent cleaning performance, i.e., excellent degreasing properties, whether applied neat or diluted. The presence of the inventive polymer reduces the effort required to remove greasy and / or oily soils from dishware, metal and / or glass surfaces, even if less surfactant is used than in conventional compositions.

[0144] Preferably, the compositions are formulated to provide excellent grease cleaning (degreasing) performance, foam retention and / or ease of viscosity control upon exposure to low temperatures, preferably at least two and more preferably all three of these performance attributes are present in the dishwashing compositions of the present invention. Optional but preferably present additional benefits of the hand dishwashing compositions of the present invention include stain removal, shine and / or hand protection, more preferably at least two and most preferably all three of these additional benefits are present in the dishwashing compositions of the present invention.

[0145] In a preferred embodiment of the invention, the inventive polymer is a component of an automatic dishwashing formulation, preferably a solid automatic dishwashing formulation. Formulations containing the inventive polymer have significantly reduced glass corrosivity.

[0146] In one embodiment of the invention, the inventive polymer is a component of a hand dishwashing formulation additionally comprising at least one surfactant, preferably at least one anionic surfactant.

[0147] In another embodiment of the present invention, the inventive polymer is a component of a hand dishwashing formulation additionally comprising at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric and / or zwitterionic surfactants. In a preferred embodiment of the present invention, the hand dishwashing formulation comprises at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or a mixture thereof, to aid in the foaming, cleaning power and / or mildness of the detergent composition.

[0148] Examples of suitable anionic surfactants are those already described above in relation to the laundry compositions.

[0149] Preferred anionic surfactants for hand dishwashing compositions are selected from C10-C15 linear alkyl benzene sulfonates, C10-C18 alkyl ether sulfates containing 1-5 ethoxy units, and C10-C18 alkyl sulfates.

[0150] Preferably, the hand dishwashing detergent formulation of the present invention contains one or more of the above-mentioned anionic surfactants in an amount of at least 1% to 50% by weight, preferably in the range of from about 3% to about 35% by weight, more preferably in the range of from 5% to 30% by weight, and most preferably in the range of from 5% to 20% by weight, based on the total specific composition including other ingredients and water and / or solvent.

[0151] The dishwashing compositions, preferably hand dishwashing compositions, of the present invention may comprise at least one amphoteric surfactant.

[0152] Examples of suitable amphoteric surfactants for dishwashing compositions are those already described above for laundry compositions.

[0153] Preferred amphoteric surfactants for dishwashing compositions are selected from C8-C18 alkyl-dimethylamine oxides and C8-C18 alkyl-di(hydroxyethyl)amine oxides.

[0154] The hand dishwashing detergent composition of the present invention preferably contains an amphoteric surfactant, preferably an amine oxide surfactant, in an amount of 1% to 15% by weight of the composition, preferably 2% to 12% by weight, more preferably 3% to 10% by weight. Preferably, the composition of the present invention contains a mixture of an anionic surfactant and an 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.

[0155] The addition of an amphoteric surfactant imparts good foaming properties to the dishwashing composition.

[0156] Dishwashing compositions, preferably hand dishwashing compositions, according to the present invention may comprise at least one zwitterionic surfactant.

[0157] Examples of zwitterionic surfactants suitable for dishwashing compositions are as already described above for laundry compositions.

[0158] Preferred zwitterionic surfactants for dishwashing compositions are selected from betaine surfactants, more preferably from cocamidopropyl betaine surfactants.

[0159] In a preferred embodiment of the present invention, the zwitterionic surfactant is cocamidopropyl betaine.

[0160] The hand dishwashing detergent of the present invention optionally comprises from 1% to 15%, preferably from 2% to 12%, more preferably from 3% to 10% by weight of the composition of a zwitterionic surfactant, preferably a betaine surfactant.

[0161] The dishwashing composition, preferably the hand dishwashing composition, according to the present invention may comprise at least one cationic surfactant.

[0162] Examples of cationic surfactants suitable for dishwashing compositions are those already described above for laundry compositions.

[0163] When a cationic surfactant is present in the composition, it is present in an effective amount, more preferably from 0.1% to 5%, preferably from 0.2% to 2% by weight of the composition.

[0164] Dishwashing compositions according to the present invention, preferably both hand dishwashing and automatic dishwashing compositions, may contain at least one nonionic surfactant.

[0165] Examples of suitable nonionic surfactants for dishwashing compositions are already described above for laundry compositions. Nonionic surfactants generally improve the rinseability of automatic dishwashing formulations.

[0166] Preferred nonionic surfactants for automatic dishwashing compositions are C8 to C18 alkyl ethoxylate and ether-terminated poly(oxyalkylated) alcohol surfactants, such as those described in U.S. Pat. No. 6,482,994 and WO 01 / 42408.

[0167] Examples of suitable non-ionic surfactants for dishwashing compositions are already described above for laundry compositions. Non-ionic surfactants generally improve sudsing in hand dishwashing formulations.

[0168] Preferred nonionic surfactants for hand dishwashing formulations are the condensation products of Guerbet alcohols with 2 to 18 moles, preferably 2 to 15 moles, more preferably 5 to 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.

[0169] The detergent composition for hand dishwashing of the present invention may contain 0.1% to 10% by weight, preferably 0.3% to 5% by weight, more preferably 0.4% to 2% by weight of a linear or branched C10 alkoxylated nonionic surfactant having an average alkoxylation degree of 2 to 6, preferably 3 to 5. Preferably, the linear or branched C10 alkoxylated nonionic surfactant is a branched C10 ethoxylated nonionic surfactant having an average ethoxylation degree of 2 to 6, preferably 3 to 5. Preferably, the composition contains 60% to 100% by weight, preferably 80% to 100% by weight, more preferably 100% by weight of the branched C10 ethoxylated nonionic surfactant based on the total linear or branched C10 alkoxylated nonionic surfactant. The linear or branched C10 alkoxylated nonionic surfactant is preferably a 2-propylheptyl ethoxylated nonionic surfactant having an average ethoxylation degree of 3 to 5. A suitable 2-propylheptyl ethoxylated nonionic surfactant with an average degree of ethoxylation of 4 is Lutensol® XP40, available from BASF SE, Ludwigshafen, Germany. The use of 2-propylheptyl ethoxylated nonionic surfactants with an average degree of ethoxylation of 3 to 5 improves foam height and foam retention.

[0170] Thus, one aspect of the present invention is a hand dishwashing detergent composition, in particular a liquid hand dishwashing detergent composition, comprising (i) at least one inventive polymer and (ii) further at least one 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation between 3 and 5.

[0171] In one embodiment of the invention, the inventive polymer is a component of a dishwashing formulation, preferably an automatic dishwashing formulation, additionally comprising at least one builder, preferably at least one chelating agent.

[0172] Examples of suitable builders are as already described above in relation to the laundry compositions.

[0173] Preferred builders for dishwashing compositions are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates and polycarboxylates. The builders are more preferably selected from citrates, silicates, carbonates, phosphonates, aminocarboxylates and polycarboxylates (i.e. phosphate-free compositions).

[0174] Na2CO3 and sodium citrate are particularly preferred. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a builder. Preferred aminocarboxylates are methylglycine diacetate (MGDA) and glutamine diacetate (GLDA). The terms aminocarboxylates and polycarboxylates also include their respective unsubstituted or substituted ammonium and alkali metal salts, for example the sodium salts, in particular the respective fully neutralized compounds. Preferred polycarboxylates are, for example, polyaspartic acid or, in particular, the alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers. Suitable polymers are, in particular, polyacrylic acids, preferably with weight-average molecular weights Mw in the range of 2,000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol.

[0175] Silicates relevant to the present invention include in particular sodium disilicate and sodium metasilicate, alumosilicates, such as zeolites and sheet silicates, in particular those of the formulae α-Na2Si2O5, β-Na2Si2O5 and δ-Na2Si2O5.

[0176] The compositions according to the invention, in particular solid formulations, may contain builders, for example in a total amount of 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably up to 20% by weight. Liquid formulations according to the invention preferably contain builders in the range of 0.1 to 8% by weight.

[0177] Dishwashing compositions, preferably automatic dishwashing compositions, according to the present invention comprise one or more bleaching agents.

[0178] Examples of suitable bleaching agents are as already described above in relation to the laundry compositions.

[0179] A preferred bleaching agent for dishwashing compositions is sodium percarbonate, either anhydrous or, for example, monohydrate.

[0180] In one embodiment of the invention, the inventive polymer is a component of an automatic dishwashing formulation that additionally contains one or more bleach catalysts.

[0181] Examples of suitable bleach catalysts are as already described above in relation to the laundry compositions.

[0182] Dishwashing compositions according to the present invention, particularly automatic dishwashing compositions, comprise one or more bleach activators.

[0183] Examples of suitable bleach activators are as already described above for the laundry compositions.

[0184] A preferred bleach activator for dishwashing compositions is tetraacetylethylenediamine.

[0185] The dishwashing formulation according to the invention may contain one or more corrosion inhibitors. In this case, this should be understood to include compounds that inhibit corrosion of metals and / or glass. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, as well as phenol derivatives, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol, etc., or zinc salts, in particular zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnCl2, ZnSO4, zinc acetate, zinc citrate, Zn(NO3)2, Zn(CH3SO3)2, zinc gallate, zinc oxide, zinc hydroxide and zinc carbonate.

[0186] In one embodiment of the invention, the dishwashing formulation according to the invention further comprises at least one enzyme.

[0187] Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the abovementioned types, preferably at least one protease and one amylase.

[0188] Such enzymes can be incorporated at a level sufficient to provide an effective amount for cleaning. A preferred amount is that in which the active enzyme ranges from 0.001% to 5% by weight of the detergent composition according to the invention. Enzyme stabilizing systems can also be used together with the enzymes, such as, for example, calcium ions, boric acid, boronic acid, propylene glycol and short chain carboxylic acids. In the context of the present invention, short chain carboxylic acids are selected from monocarboxylic acids containing 1 to 3 carbon atoms per molecule and dicarboxylic acids containing 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 above mentioned, as well as the respective sodium and potassium salts.

[0189] The dishwashing formulation according to the invention may contain one or more alkali sources. The alkali source ensures, for example, a pH of at least 9 if an alkaline pH is desired. For example, in addition to the above-mentioned alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal metasilicates, alkali metal hydroxides are also suitable. In each case, potassium is preferred as the alkali metal, and sodium is particularly preferred. In one embodiment of the invention, an amine, preferably an alkanolamine, more preferably triethanolamine, is used to adjust the pH to above 7.

[0190] The hand dishwashing compositions according to the present invention may include an effective amount of at least one hydrotrope to ensure compatibility of the liquid hand dishwashing detergent composition with water.

[0191] Suitable hydrotropes for use herein include anionic hydrotropes, particularly sodium, potassium and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium, potassium and ammonium cumene sulfonate and mixtures thereof and related compounds disclosed in U.S. Pat. No. 3,915,903.

[0192] The liquid dishwashing detergent composition of the present invention typically comprises from 0.1% to 15% by weight of the total liquid detergent composition of a hydrotrope agent or mixtures thereof, preferably from 1% to 10% by weight of the total liquid hand dishwashing composition, most preferably from 2% to 5% by weight.

[0193] The dishwashing composition according to the present invention may comprise at least one organic solvent.

[0194] Examples of organic solvents are C4-C14 ethers and diethers, glycols, alkoxylated glycols, C6-C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons and mixtures thereof.

[0195] When a solvent is present, the liquid dishwashing composition will contain from 0.01% to 20%, preferably from 0.5% to 15%, more preferably from 1% to 10%, and most preferably from 1% to 5% by weight of the liquid detergent composition. The solvent can be used in combination with an aqueous liquid carrier such as water or in the absence of an aqueous liquid carrier. In systems with higher amounts of solvent, the absolute viscosity may decrease, but there will be a local maximum in the viscosity profile.

[0196] The dishwashing compositions herein may further comprise 30% to 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 compositions of the present invention comprise 45% to 85% by weight, and even more preferably 60% to 80% by weight of the aqueous liquid carrier. However, the aqueous liquid carrier may also comprise other materials that are liquid at room temperature (25° C.) or that can be dissolved in the liquid carrier and that can perform some function other than that of an inert extender.

[0197] The dishwashing composition according to the present invention may comprise at least one electrolyte.

[0198] Suitable electrolytes are preferably selected from inorganic salts, more preferably from monovalent salts, most preferably from sodium chloride.

[0199] The dishwashing composition according to the present invention may contain from 0.1% to 5% by weight, preferably from 0.2% to 2% by weight of the composition, of an electrolyte.

[0200] Liquid dishwashing formulations containing the polymers of the present invention may also contain at least one antimicrobial agent.

[0201] Examples of antimicrobial agents suitable for dishwashing compositions are as already described above for laundry compositions.

[0202] The antimicrobial agent may be added to the liquid dishwashing formulation of the invention in a concentration of 0.0001% to 10% by weight relative to the total weight of the composition. Preferably, the formulation comprises 2-phenoxyethanol in a concentration of 0.01% to 5%, more preferably 0.1% to 2%, and / or 4,4'-dichloro-2-hydroxydiphenyl ether in a concentration of 0.001% to 1%, more preferably 0.002% to 0.6% by weight (in all cases relative to the total weight of the composition).

[0203] Further additional ingredients include, but are not limited to, conditioning polymers, detersive polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, cyclic diamines, structurants, emollients, moisturizers, skin rejuvenation actives, carboxylic acids, scrubbing particles, fragrances, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, disintegrants, pH adjusters such as NaOH, alkanolamines such as monoethanolamine, buffering means, and the like.

[0204] (c) General cleaning compositions and formulations In a preferred embodiment, at least one polymer (as defined in any of the embodiments herein, in particular in embodiments 1 to 18; the polymer is also referred to in this section as the "polymer of the invention") is used in a laundry detergent.

[0205] The liquid laundry detergent according to the present invention comprises: 0.05 to 20% of at least one polymer of the present invention; 1 to 50% surfactant, 0.1 to 40% of a builder, cobuilder and / or chelating agent; With 0.1-50% of other auxiliary substances, Water, which adds up to 100% It consists of:

[0206] Preferred liquid laundry detergents according to the present invention include 0.2 to 6% of at least one polymer of the present invention; 5-40% of an anionic surfactant selected from C10-C15-LAS and C10-C18 alkyl ether sulfates containing 1-5 ethoxy units; 1.5-10% of a non-ionic surfactant selected from C10-C18 alkyl ethoxylates containing 3-10 ethoxy units; 2-20% of a soluble organic builder / cobuilder selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids and polycarboxylic acids; an enzyme system comprising 0.05-5% of at least one enzyme suitable for detergent applications, preferably further comprising an enzyme stabilisation system; 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol; With 0.1-20% of other adjuvants, Water, which adds up to 100% It consists of:

[0207] The solid laundry detergent according to the present invention (e.g. powder, granule or tablet) comprises: 0.05 to 20% of at least one polymer of the present invention; 1 to 50% surfactant, 0.1 to 80% of a builder, cobuilder and / or chelating agent; 0-50% bulking agent and 0-40% bleaching active substance, 0.1 to 30% of other auxiliary substances and / or water, It is composed of The sum of the ingredients equals 100%.

[0208] Preferred solid laundry detergents according to the present invention include 0.2 to 6% of at least one polymer of the present invention; 5-30% of an anionic surfactant selected from C10-C15-LAS, C10-C18 alkyl sulfates and C10-C18 alkyl ether sulfates containing 1-5 ethoxy units; 1.5-7.5% of a non-ionic surfactant selected from C10-C18 alkyl ethoxylates containing 3-10 ethoxy units; 5-50% of an inorganic builder selected from sodium carbonate, sodium bicarbonate, zeolites, soluble silicates, and sodium sulfate; 0.5 to 15% of a cobuilder selected from C10 to C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids and polycarboxylic acids; an enzyme system comprising 0.1-5% of at least one enzyme suitable for detergent applications, preferably further comprising an enzyme stabilisation system; 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol; With 0.1-20% of other adjuvants, Water, which adds up to 100% It consists of:

[0209] In a preferred embodiment, the polymers according to the present invention are used in hand dish detergents.

[0210] The liquid hand dishwashing detergent according to the present invention comprises: 0.05 to 10% of at least one polymer of the present invention; 1 to 50% surfactant, With 0.1-50% of other auxiliary substances, Water, which adds up to 100% It consists of:

[0211] Preferred liquid hand dishwashing detergents according to the present invention include: 0.2 to 5% of at least one polymer of the present invention; 5-40% of an anionic surfactant selected from C10-C15-LAS, C10-C18 alkyl ether sulfate salts containing 1-5 ethoxy units, and C10-C18 alkyl sulfate salts; 2-10% cocamidopropyl betaine, 0-10% lauramine oxide, 0-2% of a non-ionic surfactant, preferably a C10 Guerbet alcohol alkoxylate; 0-5% of an enzyme, preferably an amylase, and preferably also an enzyme stabilization system; 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol; With 0.1-20% of other adjuvants, Water, which adds up to 100% It consists of:

[0212] The following tables show certain types of typical cleaning compositions, corresponding to typical compositions correlated with typical cleaning conditions commonly employed in different regions and countries of the world. At least one of the polymers of the present invention can be added to such formulations in the appropriate amounts as outlined herein.

[0213] [Table 1]

[0214] [Table 2]

[0215] [Table 3]

[0216] [Table 4]

[0217] [Table 5]

[0218] [Table 6]

[0219] The present invention is further illustrated by the following examples which should not be construed as limiting the scope of the invention. EXAMPLES

[0220] raw material DI Water DI water is deionized water containing NH3 and has the following characteristics: - pH 9~10 - Conductivity before treatment (as is) <15μS / cm - Conductivity <0.5μS / cm after removing the conditioning chemical ammonia (NH3) using a cation exchanger - Hardness (Ca+Mg) 0.0005mmol / l or less - Sodium (Na) 0.01mg / l or less - Ammonium (NH4)* 3mg / l or less, *adjuster ammonia (NH3) - Iron, total (Fe) 1mg / l or less - Dissolved silica (SiO2) 0.05mg / l or less - Dissolved organic carbon (DOC) 0.5mg / l or less NaAA-DN95 NaAA-DN95 is an aqueous solution of sodium acrylate with a degree of neutralization of 95% and a solid content of 38.2% by weight. NaAA-DN95 is produced by neutralizing acrylic acid with a 50% by weight aqueous solution of sodium hydroxide. The pH of NaAA-DN95 is in the range of 6.2 to 6.4. Fe(II)SO4 Fe(II)SO4 is iron(II) sulfate heptahydrate with a purity of ≧99.0%. H2O2(5%) H2O2(5%) is an aqueous solution of hydrogen peroxide with an active substance concentration of 5% by weight. NaPS (7%) NaPS(7%) is an aqueous solution of sodium persulfate with an active substance concentration of 7% by weight.

[0221] Catalytic additive ("organic compound") a) MGDA-Na3 is an aqueous solution of dicarboxymethylalanine trisodium with a solids content of 40% by weight. b) DTPA-Na5 is an aqueous solution of pentasodium diethylenetriaminepentaacetic acid with a solids content of 50% by weight. c) EDDS-Na3 is an aqueous solution of trisodium ethylenediamine-N,N'-disuccinate with a solids content of 35% by weight. d) CA-40% is an aqueous solution of citric acid with a solids content of 40% by weight.

[0222] Low molecular weight poly-α-glucose Low molecular weight poly-α-glucose is a poly-α-glucose having an average of 2 to 30, preferably 2 to 20, most preferably 3 to 10 glycose units, which is produced, for example, from vegetable starches, such as those from corn, wheat, tapioca and potato, and from cellulose, for example by partial hydrolysis, by acid hydrolysis or enzymatic hydrolysis, and is available as a syrup or dry powder.

[0223] For example, the following corn syrups and corn syrup solids are preferred: 1. GL01924 is Dry GL™ 01924E from Cargill, China, a spray-dried glucose corn syrup obtained by enzymatic conversion of corn starch, with dextrose equivalent (DE) 25-30, pH 4.5-6.5, moisture content ≦6 wt.%, and carbohydrate profile (dry basis) of dextrose 2 wt.%, maltose 10 wt.%, maltotriose 13 wt.% and higher polysaccharides 75 wt.%. 2. GL01925 is Dry GL™ 01925 from Cargill, USA, a spray-dried glucose corn syrup obtained by enzymatic conversion of corn starch, with a dextrose equivalent (DE) of 23-27, pH 4.5-5.5, moisture content ≦6 wt.% and carbohydrate constituents (dry basis) of dextrose 4.5 wt.%, maltose 8.5 wt.% and higher polysaccharides 87 wt.%. 3. MD240 is STAR-DRI 240 from Tate & Lyle, USA, a corn syrup powder with dextrose equivalent (DE) 22-30, pH 4.0-6.5, moisture content ≦6 wt.% and carbohydrate constituents (dry basis) as follows: dextrose 5.5 wt.%, maltose 9.5 wt.%, maltotriose 11 wt.% and higher polysaccharides 74 wt.%. 4. C_Dry™ GL 01921 from Cargill, France is a spray-dried glucose corn syrup obtained by enzymatic conversion of corn starch, with a dextrose equivalent (DE) of 20-24, pH 3.5-5.5, moisture content ≦6 wt.% and carbohydrate constituents (dry basis) of dextrose 2 wt.%, maltose 7 wt.%, maltotriose 10 wt.% and higher polysaccharides 81 wt.%. 5. C_Dry™ GL 01924 from Cargill, France is a spray-dried glucose corn syrup obtained by enzymatic conversion of corn starch, with a dextrose equivalent (DE) of 25.5-30.5, a pH of 3.5-5.5, a moisture content of ≦6 wt.% and carbohydrate constituents (dry basis) of 3 wt.% dextrose, 11 wt.% maltose, 16.5 wt.% maltotriose and 69.5 wt.% higher polysaccharides. 6. C_Dry™ GL 01932 from Cargill, France is a spray-dried glucose corn syrup obtained by enzymatic conversion of corn starch, with a dextrose equivalent (DE) of 32-36, a pH of 3.5-5.5, a moisture content of ≦6 wt.% and carbohydrate constituents (dry basis) of 1 wt.% dextrose, 25 wt.% maltose, 22 wt.% maltotriose and 52 wt.% higher polysaccharides. 7. Cleardex™ 25-42 from Cargill, USA is an aqueous solution of corn syrup obtained by enzymatic conversion with a dextrose equivalent (DE) of 23-27, a pH of 4.5-5.3, a solids content of 77.4-78.6% by weight and carbohydrate constituents (dry basis) of 6% by weight dextrose, 7% by weight maltose, 9% by weight maltotriose and 78% by weight higher polysaccharides. 8. C*LMD 10982 from Cargill, Netherland is a liquid maltodextrin syrup solution obtained from wheat by enzymatic conversion, with a dextrose equivalent (DE) of 16.5-19.9, pH 3.5-5.5, and solids content of 66.3-67.7% by weight.

[0224] Equipment - Glass reactor A 2.5 liter glass reactor equipped with a three-stage cross bean tutor Magnet-driven diaphragm pump for supplying NaAA-DN95 (gamma / L from ProMinent®, Germany) HPLC pump (PLM 707-1 from FLUSYS GmbH, Germany) to deliver H2O2 (5%) and NaPS (7%) ·Cooling / heating circulation device (Julabo FP 50)

[0225] Equipment - Steel Reactor 6L steel mixer with 3-stage cross-blade agitator Two magnet-driven diaphragm pumps (gamma / 4 from ProMinent®, Germany) to deliver NaPS (7%) and CA-40% Cooling / heating circulation unit FP 50 from JULABO GmbH, Germany Two HPLC pumps (HPLC Compact pump 3350 from BISCHOFF Analysentechnik u.-geraete GmbH, Germany) to deliver H2O2 (5%) and NaAA-DN95

[0226] method pH value The pH of the polymer solution with a solids content of 10% by weight is determined in accordance with DIN 19268 (pH-measurement - pH-measurement of aqueous solutions with pH measuring chains with pH glass electrodes and evaluation of measurement uncertainty).

[0227] Hazen and Gardner color scales The Hazen and Gardner colour indices of the undiluted polymer solutions are determined at 23° C. in accordance with DIN EN 1557 (Surface active agents - Colorimetric characterization of optically clear coloured liquids (products) as X,Y,Z tristimulus values ​​in transmission).

[0228] Concentration (dry) The concentration of the polymer solution is measured using a Halogen Moisture Analyzer HR73 from Mettler-Toledo GmbH. 3.0 g of neat polymer are heated below 120° C. for 15 minutes.

[0229] K value (1%) The K value of a polymer solution with a solids content of 5% by weight is determined in accordance with DIN EN ISO 1628-1 (Plastics - Determination of the viscosity of polymers in dilute solution using capillary viscometers - Part 1).

[0230] Residual Acrylate Content: The concentration of residual acrylic acid or sodium acrylate during or after the polymerization is determined by HPLC measurement.

[0231] Size Exclusion Chromatography (SEC) / Gel Filtration Chromatography Number average molar mass M n and mass average molar mass M w is given by the following formula:

number

number

number

[0232] Size Exclusion Chromatography (SEC) / Gel Permeation Chromatography (GPC) of Corn Syrup To determine the molecular weight, narrow polymer standards of known molecular weight are used and the hydrodynamic volume of the chain is set relative to its molecular weight. The accuracy of the results for a sample depends on the similarity between the sample and the standards used for the calibration. Calibration was performed using dextran with molecular weights between M = 180 g / mol and M = 21,400 g / mol. Values ​​outside this elution range were extrapolated. SEC / GPC measurement parameters: Eluent: Dimethylacetamide + 1% LiCl Detector: DRI Agilent 1200 Column temperature: 35℃ Flow rate: 0.5mL / min Injection volume: 100μL Concentration: 4mg / mL Sample filtration: Sartorius Minisart RC 25 (0.2 μm)

[0233] The following separation column combination (Plgel 3 μm) from Agilent Technologies, Inc, Santa Clara, CA, is used for the SEC / GPC measurements: HPLC guard precolumn, inner diameter 8.0 mm x length 5 cm Plgel 3μm, inner diameter 7.5mm x length 30cm Plgel 3μm, inner diameter 7.5mm x length 30cm Plgel 3μm, inner diameter 7.5mm x length 30cm

[0234] FIG. 1 shows the GPC charts of GL01924, GL01925 and MD240.

[0235] [Table 7]

[0236] Size Exclusion Chromatography (SEC) / Gel Permeation Chromatography (GPC) of Polymers Method A: To calibrate the SEC / GPC measurements of the polymers of the invention, pyridine with molecular weights M=79 g / mol and poly(2-vinylpyridine) in the range M=620 g / mol to M=256,000 g / mol from PSS GmbH, Mainz, Germany are used as calibration standards.

[0237] SEC / GPC measurement parameters: Eluent: 0.1% (w / w) trifluoroacetic acid / 0.1M NaCl in distilled water Column temperature: 35℃ Flow rate: 0.8mL / min Injection volume: 100μL Concentration: 1.5mg / mL Sample filtration: Sartorius Minisart RC 25 (0.2 μm)

[0238] The following separation column combinations from Tosoh Bioscience GmbH, Griesheim, Germany are used for the SEC / GPC measurements: TSK G3000 PWxl, inner diameter 7.8mm x length 30cm TSK G3000 PWxl, inner diameter 7.8mm x length 30cm TSKgel G4000PWXL, inner diameter 7.8mm x length 30cm

[0239] Method B: To calibrate the SEC / GPC measurements of the polymers of the invention, polyethylene glycols (PEGs) ranging from M=106 g / mol to M=1,378,000 g / mol from PSS GmbH, Mainz, Germany are used as calibration standards.

[0240] SEC / GPC measurement parameters: Eluent: 0.01 mol / l phosphate buffered saline, pH = 7.4 (= 10Na2HPO4 + 1.8KH2PO4 + 2.7KCl + 137NaCl (unit: mmol / L)) / 0.1M NaN3 in distilled water Column temperature: 35℃ Flow rate: 0.5mL / min Injection volume: 100μL Concentration: 1.5mg / mL Sample filtration: Sartorius Minisart RC 25 (0.2 μm)

[0241] The following separation column combinations from Tosoh Bioscience GmbH, Griesheim, Germany are used for the SEC / GPC measurements: TSK G3000 PWxl, inner diameter 7.8mm x length 30cm TSK G3000 PWxl, inner diameter 7.8mm x length 30cm

[0242] Examples 1 to 6 (non-inventive) Preparation of water-soluble graft polymers without using catalytic additives Example 1 (non-inventive): A 2.5 liter glass reactor is precharged with 1100 g DI water. 596 g GL01924 and 0.018 g Fe(II)SO4 are added with stirring (150 rpm). The reaction mixture is heated under N2 atmosphere with stirring (150 ppm) until the internal temperature is 95 °C. When the temperature reaches 92 °C, the parallel addition of 498 g NaAA-DN95 over 240 min and 443 g H2O2 (5%) over 255 min is started, followed by 30 min of postpolymerization with stirring. During polymerization and postpolymerization, the reaction temperature is kept constant in the range of 94-96 °C. Then, it is cooled to room temperature over 30 min. The product characteristics are summarized in Table 6.

[0243] Example 2 (non-inventive): This example is carried out similarly to Example 1, except that GL01925 was used instead of GL01924. Product properties are summarized in Table 6.

[0244] Example 3 (non-inventive): A 2.5 liter glass reactor is precharged with 1100 g DI water. 596 g GL01925 and 0.018 g Fe(II)SO4 are added with stirring (150 rpm). The reaction mixture is heated under N2 atmosphere with stirring (150 ppm) until the internal temperature is 90 °C. When the temperature reaches 87 °C, the parallel addition of 498 g NaAA-DN95 over 240 min and 443 g H2O2 (5%) over 255 min is started, followed by 30 min of postpolymerization with stirring. During polymerization and postpolymerization, the reaction temperature is kept constant in the range of 89-91 °C. Then, it is cooled to room temperature over 30 min. The product characteristics are summarized in Table 6.

[0245] Example 4 (non-inventive): This example is carried out similarly to Example 2, except that no Fe(II)SO4 was added. The product properties are summarized in Table 6.

[0246] Example 5 (non-inventive): This example is carried out similarly to Example 1, except that SD240 was used instead of GL01924. Product properties are summarized in Table 6.

[0247] Example 6 (non-inventive): This example is carried out similarly to Example 1, except for the post-polymerization step. After polymerization is complete, the mixture is cooled from 95° C. to 90° C. and parallel addition of 159.0 g NaPS (7%) over 75 min and 79.5 g H2O2 (5%) over 90 min is started. After H2O2 addition is complete, the reaction mixture is stirred for an additional 30 min at 90° C. and cooled to room temperature over approximately 30 min. Product properties are summarized in Table 6.

[0248] Example 7 (non-inventive): A 2.5 liter glass reactor is precharged with 1100 g DI water. 596 g GL01925, 6.619 g MGDA-Na3 and 0.018 g Fe(II)SO4 are added with stirring (150 rpm). The reaction mixture is heated under N2 atmosphere with stirring (150 ppm) until the internal temperature is 95°C. Once the temperature reaches 92°C, start the parallel addition of NaAA-DN95 over 240 min and 443 g H2O2 (5%) over 255 min. 3 hours after the addition of NaAA-DN95 and H2O2 (5%) the reaction mixture strongly discolors and the polymerization is stopped after 3 hours. The Gardner color of the reaction mixture is >16.

[0249] Example 8 (present invention): A 2.5 liter glass reactor is precharged with 1100 g DI water. 596 g GL01925, 50.655 g DTPA-Na, and 0.018 g Fe(II)SO4 are added with stirring (150 rpm). The molar ratio of Fe:catalyst additive is 1:10. The reaction mixture is heated under N2 atmosphere with stirring (150 ppm) until the internal temperature is 95°C. When the temperature reaches 92°C, parallel additions of NaAA-DN95 are started for 240 min and 443 g H2O2 (5%) are started for 255 min. After polymerization is complete, the mixture is cooled from 95°C to 90°C and parallel additions of 159.0 g NaPS (7%) are started for 75 min and 79.5 g H2O2 (5%) are started for 90 min. After H2O2 addition is complete, the reaction mixture is stirred for another 30 min at 90°C and cooled to room temperature for about 30 min. The product properties are summarized in Table 7.

[0250] Example 9 (Invention): This example is carried out similarly to Example 8, except that 36.6 g of EDDS-Na was used instead of 5 g of DTPA-Na. The molar ratio of Fe:catalyst additive is 1:100. The product properties are summarized in Table 8.

[0251] Example 10 (Invention): A 2.5 liter glass reactor is precharged with 1100 g DI water. 596 g GL01925, 3.42 g CA-40% and 0.018 g Fe(II)SO4 are added with stirring (150 rpm). The molar ratio of Fe:catalyst additive is 1:100. The reaction mixture is heated under N2 atmosphere with stirring (150 ppm) until the internal temperature is 95°C. When the temperature reaches 92°C, parallel additions of 498 g NaAA-DN95 over 240 min and 443 g H2O2 (5%) over 255 min are started. After the polymerization is complete, the mixture is cooled from 95°C to 90°C and parallel additions of 159.0 g NaPS (7%) over 75 min and 79.5 g H2O2 (5%) over 90 min are started. The product properties are summarized in Table 8.

[0252] Example 11 (Invention): This example is carried out similarly to Example 10, except that 34.2 g of CA-40% is added before the start of the post-polymerization step. The molar ratio of Fe:catalyst additive during polymerization is 1:100 and 1:1100 in the final product. The product properties are summarized in Table 8.

[0253] Example 12 (Invention): This example is carried out similarly to Example 11, except that the content of precharged DI water is reduced from 1100 g to 492 g. The molar ratio of Fe:catalyst additive during polymerization is 1:100 and in the final product is 1:1100. The product properties are summarized in Table 8.

[0254] 2 and 3 show the GPC charts of Example 12.

[0255] Example 13 (invention): This example is carried out similarly to Example 11, except that SD240 is used instead of GL01925 and the precharged DI water content is reduced from 1100 g to 827 g. Product properties are summarized in Table 8.

[0256] Example 14 (Invention): A 6 L steel vessel is precharged with 1264 g DI water. 911 g GL01925, 5.2 g CA-40% and 0.028 g Fe(II)SO4 are added over 1 h with stirring (150 rpm). The molar ratio of Fe:catalyst additive is 1:100. The reactor is inerted with 2 x 2.5 bar nitrogen gas. After the second depressurization, 0.3 bar of excess pressure remains. The reactor is sealed and heated with stirring (150 ppm) until the internal temperature is 95°C. Once the temperature reaches 95°C, the internal pressure is increased to 2.4 bar and the parallel addition of 762 g NaAA-DN95 over 240 min and 678 g H2O2 (5%) over 255 min is started. After the polymerization is complete, the internal pressure is increased to 2.9 bar. After polymerization, 52.3 g of CA-40% is added to the reaction mixture. The reaction mixture is cooled from 95° C. to 90° C. and parallel addition of 243 g of NaPS (7%) over 75 min and 121 g of H2O2 (5%) over 90 min is started. After H2O2 addition is complete, the reaction mixture is stirred for an additional 30 min at 90° C. and cooled to room temperature over approximately 30 min. Product properties are summarized in Table 8.

[0257] Example 15 (Invention): A 6 L steel vessel is precharged with 790 g DI water. 1055 g GL01925, 6.0 g CA-40% and 0.032 g Fe(II)SO4 are added over 1 h with stirring (150 rpm). The molar ratio of Fe:catalyst additive is 1:100. The reactor is inerted with 2 x 2.5 bar nitrogen. After the second depressurization, 0.3 bar of nitrogen overpressure remains. The reactor is sealed and heated with stirring (150 ppm) until the internal temperature is 95°C. Once the temperature reaches 95°C, the internal pressure is increased to 2.4 bar and the parallel addition of 883 g NaAA-DN95 over 240 min and 785 g H2O2 (5%) over 255 min is started. After the polymerization is complete, the internal pressure is increased to 3.1 bar. After polymerization, 60.5 g of CA-40% is added to the reaction mixture. The reaction mixture is cooled from 95° C. to 90° C. and parallel addition of 281 g of NaPS (7%) over 75 min and 140 g of H2O2 (5%) over 90 min is started. After H2O2 addition is complete, the reaction mixture is stirred for an additional 30 min at 90° C. and cooled to room temperature over approximately 30 min. Product properties are summarized in Table 8.

[0258] 2 and 3 show the GPC charts of Example 15.

[0259] Example 16 (Invention): A 6 L steel vessel is precharged with 669 g DI water. 1461 g Cleardex™ 25-42, 5.3 g anhydrous citric acid and 0.036 g Fe(II)SO4 are added over 1 hour with stirring (150 rpm). The molar ratio of Fe:catalyst additive is 1:100. The reactor is inerted with 2×2.5 bar nitrogen. After the second depressurization, 0.3 bar of nitrogen overpressure remains. The reactor is sealed and heated with stirring (150 ppm) until the internal temperature is 95° C. Once the temperature reaches 95° C., the internal pressure is increased to 2.4 bar and the parallel addition of 1015 g NaAA-DN95 over 240 min and 449 g H2O2 (10%) over 255 min is started. After the polymerization is complete, the internal pressure is increased to 3.1 bar. After polymerization, 63 g of CA-40% is added to the reaction mixture. The reaction mixture is cooled from 95° C. to 90° C. and parallel addition of 319 g of NaPS (7%) over 75 min and 20 g of H2O2 (10%) over 90 min is started. After H2O2 addition is complete, the reaction mixture is stirred at 90° C. for an additional 30 min and cooled to room temperature over approximately 30 min. Product properties are summarized in Table 8.

[0260] Example 17 (Invention): A 2.5 liter glass reactor is precharged with 995.4 g of C*LMD 10982. 6.4 g of CA-40% and 0.021 g of Fe(II)SO4 are added with stirring (150 rpm). The reaction mixture is heated under N2 atmosphere with stirring (150 ppm) until the internal temperature is 95°C. When the temperature reaches 92°C, parallel additions of 564 g of NaAA-DN95 and 502 g of H2O2 (5%) are started over 240 min and 255 min, respectively. After polymerization is complete, the mixture is cooled from 95°C to 90°C and the addition of 180.0 g of NaPS (7%) is started over 75 min. After the addition of NaPS is complete, the reaction mixture is stirred at 90°C for another 30 min and cooled to room temperature over approximately 30 min. This experiment is repeated twice and the average product properties of the three runs are summarized in Table 8.

[0261] Example 18 (Granulation of Example 17 of the present invention) A laboratory-scale granulator commercially available as "WFP-Mini" from DMR is charged with 300 g of solid Sokalan PA 15 particles finely ground at 4000 rpm (revolutions per minute) using a Kinetatica Polymix PX-MFL 90D with a 2 mm mesh. 3 Nitrogen in an amount of 0.1 liter / h is blown in from the bottom at a temperature of 106-110°C. A fluidized bed of particles of Sokalan PA 15 is obtained. The polymer solution of Example 17 is then introduced into the fluidized bed by spraying through a three-fluid nozzle at about 11 g / min of liquid (feed temperature about 20°C). The pressure of the atomizing gas is 1.5-2 bar. Granules are formed and the bed temperature, which corresponds to the surface temperature of the solids of the fluidized bed, is 75-80°C.

[0262] Approximately every 25 minutes, the granules are removed from the container (180-220 g) and sieved. Three fractions are obtained: coarse particles (diameter >1 mm), a value fraction (diameter 0.35-1 mm) and fine particles (diameter <0.35 mm). The coarse particles are finely ground using a hammer mill (Kinetatica Polymix PX-MFL 90D) with a 2 mm mesh at 4000 rpm (revolutions per minute). The powder and fine particles thus obtained are returned to the fluidized bed. The value fraction is removed from the process and recovered without fine grinding.

[0263] After 4 kg of liquid is sprayed, a steady state is reached. The important fraction is then collected as the inventive granules. The product characteristics are summarized in Table 9.

[0264] Compatibility testing of liquid detergent formulations To carry out the compatibility test of liquid detergent formulations, 1 or 3% by weight of the polymer (calculated as dry matter) is stirred into the liquid detergent formulation. The appearance of the liquid detergent formulation is visually classified into 4 levels a) after preparation (0 d), after 7 days (7 d) and after 28 days (28 d). C: clear / ST: slightly cloudy / T: cloudy / SP: separated.

[0265] PA1 PA1 is an aqueous solution of polyacrylic acid sodium salt with a pH of 7, a K value of about 15, and a weight average molecular weight of 1200 g / mol.

[0266] The following polymers are tested in a liquid detergent formulation (Formulation A): PA1, sodium salt (molar mass 1200 g / mol), Examples 1 and 3 (non-inventive examples) and 8 to 15 (inventive examples)

[0267] Formulation A An aqueous solution containing Sodium laureth sulfate (2EO), sodium salt 19.6% by weight C12-C14 fatty alcohol + 7EO 6.7% by weight Linear C10C13 Alkylbenzenesulfonic acid 5.0% by weight Coconut oil fatty acid 2.7% by weight Sodium hydroxide 2.2% by weight Sodium citric acid salt 4.1% by weight Propylene glycol 2.7% by weight Ethanol 0.8% by weight Glycerin 0.4% by weight Water remaining up to 100%.

[0268] Formulation B A commercial / premium quality liquid laundry detergent is specially formulated to be free of anti-redeposition / anti-darkening polymers. The test polymer is added to this detergent base at the time of use.

[0269] The stability studies of the liquid detergent formulations are summarized in Table 3.

[0270] Cleaning performance test based on Formulation A: Blackening prevention test using red clay fabric The anti-darkening performance of selected polymers was determined as follows: Several test white cloths are washed at 40°C in liquid detergent formulation A containing the selected polymer together with a combination of 0.75g of red soiled cloth and 1.25g of SBL 2004 and 20 steel balls. After washing, the test cloths are rinsed, spun dry and dried. This washing cycle is repeated twice with new soiled cloths and new washing liquid. After the third wash, the test cloths are rinsed, spun dry and dried in air.

[0271] The dark stain resistance was determined by measuring the reflectance values ​​of the soiled fabrics before and after washing at 460 nm using a spectrometer (Elrepho 2000) from Fa. Datacolor: the higher this value, the better the performance.

[0272] [Table 8]

[0273] Cleaning performance test based on formulation B: Anti-redeposition test method using Georgia red clay The anti-redeposition performance of selected polymers was determined as follows: Several test white fabrics are washed at 30° C. in the presence of liquid detergent formulation B containing the selected test polymer (1% active by weight) together with 0.5 g red soil (solid particles). After washing, the test fabrics are rinsed and squeezed out by hand. This washing cycle is repeated three times (four times in total) with fresh red soil and fresh washing liquid. After the fourth wash, the test fabrics are rinsed, spun out in a wringing machine and dried in a dryer at medium heat setting for 30 minutes.

[0274] The anti-redeposition performance is determined by measuring the L, a, and b values ​​of a white test cloth before (i) and after (f) washing using a Konica Minolta portable spectrophotometer. The dE value is then calculated from the L, a, and b values ​​as shown below:

number

[0275] The lower the dE value, the higher the anti-redeposition performance for red soil. The results are shown in the table.

[0276] [Table 9]

[0277] Test methods for accelerated aging and performance of chelating agents The chelator-iron binding capacity of selected polymer systems was determined as shown below.

[0278] Using Example 1, the chelating agent ( Table 14 Various loadings of chelant (see Table 1) were added to 20 g of graft copolymer samples (0.025, 0.05, 0.1 or 0.2 wt % based on sample). Hydrogen peroxide was then added to achieve the target loading (0.05, 0.1 or 0.2 wt % based on sample). The pH of each system was adjusted to 6.0-6.5 to remain in the intended range for the grafted biopolymer. The resulting aqueous polymer, chelating agent and peroxide samples were stored at 90°C and monitored for change in Gardner color for 4-6 hours. An ideal chelating agent-iron-peroxide system would maintain a low Gardner color (<4 units) for an extended period of time, i.e. the longer this time the better the performance. The reported values ​​( Table 14 ) is the inflection point time when the sample begins to develop color and the Gardner exceeds 4.

[0279] The following stained materials and test cloths were obtained from wfk Testgewebe GmbH, Brueggen, Germany. SBL2004: Soil Ballast wfk, 100% cotton, approx. 8g of dirt / sheet WFK 10 A: 100% cotton fabric DIN 53919 / ISO 2267 WFK 12 A: 100% cotton terry cloth, bleached with optical brightener WFK 80 A: 100% cotton knit, Ponte de Roma WFK 20 A: Polyester / cotton (65 / 35) woven fabric WFK 30 A: 100% polyester fabric

[0280] The following test fabrics were obtained from Swissatest Testmaterialien AG, St. Gallen, Switzerland. EMPA 221: Cotton, cretonne, bleached, no optical brighteners EMPA 406: Spun polyamide 6.6, type 200, plain weave, ISO 105-F03

[0281] The following soiled materials and test cloths were obtained from the Center for Test materials (CFT) BV, Vlaardingen, Netherland. SBL Red Clay: Cotton-loaded fabric stained with red clay

[0282] Determination of "ready biodegradability" according to OECD 301F guideline Biodegradation in wastewater was tested in triplicate using the manometric respirometry method of OECD 301F, an aerobic test that measures the biodegradation of samples by measuring oxygen consumption. A measured amount of medium is added with 100 mg / L of Example 14, nominally the only carbon source, together with an inoculum (aerated sludge taken from the municipal sewage treatment plant in Mannheim). This is stirred in a closed flask at constant temperature (25°C) for 28 days. The oxygen consumption is determined by measuring the change in pressure in the closed flask using an Oxi TopC. The released carbon dioxide is absorbed in a sodium hydroxide solution. A nitrification inhibitor is added to the flask to prevent the use of oxygen by nitrification. The amount of oxygen taken up by the microbial population during the biodegradation of the test substance (corrected for the amount taken up by a blank inoculum run in parallel) is expressed as a percentage of ThOD (theoretical oxygen demand measured by elemental analysis of the compound). For each cabinet, a test sample is run along with a positive control of glucose / glutamic acid.

[0283] Calculation: Theoretical oxygen demand: The amount of oxygen required to oxidize a compound to its final oxidation product.

[0284] This amount is determined using elemental analysis data.

number

[0285] Validity: According to OECD guidelines, a test is valid if: 1. The reference material reaches 60% within 14 days. 2. The difference in extreme values ​​between replicate tests by the end of the study is less than 20%. 3. The oxygen uptake of the blank containing only the inoculum should be 20-30 mg O2 / L and should not exceed 60 mg O2 / L. 4. The pH value measured at the end of the test is between 6.0 and 8.5.

[0286] Example 12 has a biodegradability of 70% and can be classified as "readily biodegradable", meeting the effectiveness criteria detailed by the OECD (see FIG. 4).

[0287] [Table 10]

[0288] [Table 11]

[0289] [Table 12]

[0290] [Table 13]

[0291] [Table 14]

[0292] [Table 15]

[0293] [Table 16]

[0294] [Table 17]

[0295] [Table 18] The present invention includes, for example, the following embodiments. [Section 1] 1. A water-soluble graft polymer comprising a polysaccharide as the polymer substrate and at least one water-soluble ethylenically unsaturated monomer as a grafted side chain, the water-soluble ethylenically unsaturated monomer comprising at least one sodium carboxylate unit, the water-soluble graft polymer being produced by a radical initiated polymerization reaction, wherein during said polymerization at least one organic compound is used which comprises at least one carboxyl group capable of complexing with a metal ion, preferably iron, and which may be present in its structure in part or in whole as an acid group or in deprotonated salt form. [Section 2] Item 2. The graft polymer according to item 1, wherein the polysaccharide consists of an average of up to n=30 glucose units. [Section 3] Item 3. The graft polymer according to item 2, wherein the polysaccharide comprises an average of n=2 to 20 glucose units. [Section 4] Item 4. The graft polymer according to item 3, wherein the polysaccharide comprises an average of n=3 to 10 glucose units. [Section 5] Item 5. The graft polymer according to any one of items 1 to 4, wherein the polysaccharide is selected from maltodextrin, corn syrup and / or corn syrup solids. [Section 6] The at least one water-soluble ethylenically unsaturated monomer comprises sodium acrylate and / or sodium methacrylate, more preferably sodium acrylate, in an amount of at least 50 mol%, preferably at least 90 mol%, based on the total amount of monomers used, and optionally other polymerizable monomers. The graft polymer according to any one of items 1 to 5. [Section 7] Item 7. The graft polymer according to any one of items 1 to 6, wherein the radical polymerization is a radical oxidation-reduction polymerization type. [Section 8] At least one organic compound is used to reduce or preferably prevent discoloration before, during and / or after polymerization, more preferably before and / or during polymerization, even more preferably before and during polymerization, and most preferably, at least one such organic compound is used so that it is still present in sufficient amount after the polymerization and post-polymerization. The graft polymer according to any one of items 1 to 7. [Section 9] Item 9. The graft polymer according to item 8, wherein a polymerization system containing at least one metal salt and a peroxide, preferably hydrogen peroxide, is used as a radical initiator at least in this polymerization stage. [Section 10] Item 8 or 9, wherein the at least one organic compound comprises at least one functional group that forms a metal complex with the at least one metal salt used as part of the polymerization system. [Section 11] The metal salt preferably comprises a cation of a metal selected from metals that catalyze the Fenton reaction, more preferably from iron and / or copper, and preferably comprises only said cations, which are most preferably used as iron(II) sulfate, copper(II) sulfate and hydrated derivatives thereof, more preferably as iron(II) sulfate, and most preferably used as ferrous sulfate heptahydrate. The graft polymer according to any one of items 8 to 10. [Section 12] The at least one organic compound is preferably water-soluble, preferably of natural origin, more preferably from renewable resources, and comprises at least one carboxylate group, such as gluconic acid and its salts, preferably comprising at least two carboxylate groups (COOR), and if comprising at least two carboxylate groups, these are more preferably separated by 1-3 other atoms, more preferably by 1-3 other atoms selected from the following types of atoms: C, Si, N, P, O, S, and more preferably the following chemical structures 1-4: [ka] (In all of Structures 1-4, the variables are selected from: R is H, Li, Na, K, Ca, preferably H or Na; A is O or S; R1, R2, R3 are: H and / or organic substituents containing 1 to 20 carbon atoms, optionally further comprising amino, hydroxy, carboxylic, sulfonic, sulfonate, phosphonate, keto, aldehyde and / or aromatic groups, preferably organic structures containing H and / or one or more further carboxylate groups selected from -COOR and -COOH, preferably -COOR; Item 12. The graft polymer according to any one of items 1 to 11, wherein R4 is H, OH or an organic substituent containing 1 to 20 carbon atoms, optionally further containing an amino group, a hydroxy group, a carboxylic acid group, a sulfonic acid group, a sulfonate group, a phosphonate group, a keto group, an aldehyde group and / or an aromatic group, preferably an organic structure containing H and / or one or more further carboxylate groups selected from -COOR and -COOH, preferably -COOR. [Section 13] Item 13. The graft polymer according to item 12, wherein the organic compound has at least three carboxylate groups (COOR). [Section 14] The organic compound is selected from citric acid, methylglycidin diacetic acid, ethylenediaminetetraacetic acid, tetra-N,N-bis(carboxylatomethyl)-glutamic acid, diethylenetriaminepentaacetic acid, tartaric acid, succinic acid or any salt thereof, for example, ammonium, alkali metal and / or alkaline earth metal salts, for example, sodium, potassium, calcium salts, preferably sodium salts, more preferably citric acid, succinic acid and / or diethylenetriaminepentaacetic acid, most preferably citric acid and its salts, preferably its citric acid. The graft polymer according to item 12 or 13. [Section 15] Item 15. The graft polymer according to any one of items 12 to 14, wherein the molar ratio of the total amount of the metal salt to the total amount of the at least one organic compound is between 1:1 to 1:10,000, preferably 1:2 to 1:1,000, most preferably 1:5 to 1:500, for example, 1:10 to 1:400, 1:30 to 1:200, 1:50 to 1:200, or about 1:80 to 1:120. [Section 16] Item 16. The graft polymer according to any one of Items 12 to 15, wherein the organic compound is a chelating agent that exhibits "readily biodegradable" according to the OCED guidelines (Test No. 301F). [Section 17] Item 17. The graft polymer according to any one of items 1 to 16, which is in a form dried by spray drying, freeze drying, vacuum drying, rotary drum drying or the like, or in the form of a granule or particulate. [Section 18] Item 17. The graft polymer according to any one of items 1 to 16, which is in the form of a solution, preferably as an aqueous solution, more preferably as a solution essentially in water. [Section 19] Item 19. The graft polymer according to any one of items 1 to 18, which satisfies at least one of the following requirements, preferably more than one of the following requirements, for example, in the order of b>c>d>a, for example, b+c, more preferably b+c+d, and further preferably all of these requirements: a. exhibits ready biodegradability according to the tests defined by the OECD 301F and / or B guidelines, preferably a biodegradability according to OECD 301F and / or B, preferably 301F, of at least 50% by weight (based on the total solids content) within 28 days, based on the total weight of the polymer; and / or b. Gardner color scale is less than 4.0; and / or c. exhibits color stability with an increase in Gardner color scale of no more than 3 units for at least 6 months; and / or d. The polymers of the present invention form clear solutions in liquid detergent formulations for at least 28 days when the formulation contains a minimum of 0.5% of the polymer of the present invention, and no turbidity or precipitation is observed in the liquid detergent formulation, particularly in liquid hand dishwashing formulations. [Section 20] A process for producing the graft polymer according to any one of items 1 to 19, a) as a reactant, i) at least one polysaccharide polymeric substrate, preferably said polysaccharide comprising an average of up to 30 glucose units, more preferably comprising an average of up to 20 glucose units, preferably 2 to 20 glucose units, more preferably 3 to 10 glucose units, maltodextrin, corn syrup and / or corn syrup solids; ii) at least one water-soluble ethylenically unsaturated monomer comprising at least one sodium carboxylate unit which may be neutralized in situ (within the reactor if the polysaccharide is present) from the carboxylic acid form prior to addition to the reactor (i.e. if the polysaccharide is not present at the time of neutralization), preferably the monomers used in the polymerization reaction are at least 50 mol %, preferably at least 90 mol %, of the total amount of sodium acrylate, and optionally at least one other polymerizable monomer, most preferably the sodium acrylate is prepared prior to addition to the reaction mixture; is polymerized by a radical initiated polymerization reaction, preferably by a radical redox polymerization type reaction, more preferably using a polymerization system comprising at least one metal salt and hydrogen peroxide as a radical initiator for at least said main polymerization step, said metal salt comprising iron, preferably comprising iron as the only metal, more preferably used as ferrous sulfate heptahydrate; b) further, at least one organic compound containing at least two carboxyl groups, some or all of which may be present as acid groups or in the form of a deprotonated salt thereof, is added at least before or during the main polymerization reaction, and such an organic compound is selected from the group described in items 12 to 14, preferably items 13 to 14, more preferably item 14; c) such polymerization reaction is carried out in a suitable solvent or solvent mixture, such solvent being selected from polar protic or polar aprotic solvents, preferably acetone, ethanol, isopropanol or water, more preferably an aqueous solution, most preferably essentially water; d) optionally, an additional amount of the same initiator or initiator system used in the main polymerization stage or a different initiator or initiator system selected from azo initiators, redox initiators, peroxides, photoinitiators and mixtures thereof, preferably water soluble initiator systems, most preferably sodium persulfate and a combination of sodium persulfate and hydrogen peroxide, is added after the main polymerization step to further reduce the amount of unreacted monomer in the polymerization reaction mixture; Thereby, a polymer solution containing the graft polymer and the organic compound is obtained, e) optionally, the polymer solution is subjected to a further treatment selected from steam stripping, steam distillation, thermal distillation and / or vacuum distillation, thereby obtaining a purified polymer solution compared to the polymer solution prior to this step; f) optionally, to obtain the grafted polymer in solid form, the polymer solution obtained in the previous step is dried using at least one spray dryer, freeze dryer, vacuum dryer, rotary drum dryer, paddle dryer, kneader as drying means, or any agglomeration means such as fluidized bed agglomeration to obtain the polymer as agglomerates or granules or particulates, preferably by using a drying method such as agglomeration such as spray dryer, freeze dryer, vacuum dryer, fluidized bed agglomeration, which acts on the polymer at low temperature to prevent discoloration, thereby obtaining a polymer solid, process. [Section 21] Item 21. The process according to item 20, wherein the polymerization is carried out at a temperature of 70 to 150°C, preferably 80 to 120°C, more preferably 90 to 100°C, and the post-polymerization reaction is carried out at a temperature about 5 to 10 degrees lower than the temperature of the main polymerization reaction. [Section 22] Item 22. The process according to item 20 or 21, wherein the polymerization is carried out at a solids concentration of 20 to 60, preferably 25 to 50 wt.%, based on the total amount of polysaccharide and monomer used. [Section 23] The graft polymer is produced by reacting an aqueous solution of corn syrup consisting of an average of 3 to 8 glucose units with a mixture of acrylic acid and sodium acrylate, the mixture having a degree of neutralization of 90 to 96%, using a hydrogen peroxide initiator and a ferrous sulfate heptahydrate redox catalyst, using citric acid or a salt thereof, preferably citric acid monohydrate or an aqueous citric acid solution, during the polymerization and post-polymerization to chelate metal ions, and using sodium persulfate in combination with hydrogen peroxide to consume the remaining acrylate monomer during post-polymerization, the polymerization temperature is 90 to 100 ° C, the post-polymerization temperature is 85 to 95 ° C, and the solids content of the graft polymer after the polymerization is completed is 20 to 60, preferably 25 to 50 wt%. The process according to any one of items 20 to 22. [Section 24] Use of at least one graft polymer according to any one of claims 1 to 19 or obtained or obtainable by the process according to any one of claims 20 to 23 in a composition which is a cleaning composition, a fabric care and home care product, an institutional cleaning product, a cosmetic or personal care product or an agrochemical formulation. [Section 25] 25. Use according to item 24 in fabric care and home care compositions, cleaning compositions or institutional cleaning products. [Section 26] Item 26. The use according to item 24 or 25, wherein the composition comprises at least one graft polymer in a concentration of about 0.05% by weight to about 10% by weight based on the total weight of such composition or product. [Section 27] The use according to any one of items 24 to 26, a. at least one enzyme and / or b. from about 1% by weight to about 70% by weight of a surfactant system and / or c. containing an effective amount of at least one additional cleaning adjunct; and / or d. In such a composition, when a sodium polyacrylate polymer having a Fikentscher K value of 15 is replaced by the graft polymer, it shows improved cleaning performance in red clay dispersions. The use preferably includes at least one of a) to c), more preferably at least a) and b), and even more preferably a), b) and c). [Section 28] A laundry detergent composition, cleaning composition or fabric care and home care product comprising at least one grafted polymer according to any one of claims 1 to 19 or obtained or obtainable by the process according to any one of claims 20 to 23, preferably a laundry detergent composition, more preferably a liquid or semi-liquid or multi-component laundry detergent composition, most preferably a liquid laundry detergent composition, comprising said at least one grafted polymer in a concentration of preferably about 0.05% to about 10% by weight based on the total weight of such composition or product, and optionally a. at least one enzyme and / or b. from about 1% to about 70% by weight of a surfactant system, and / or c. an effective amount of at least one additional cleaning adjunct The composition further comprises: [Section 29] A dishwashing detergent composition, preferably a liquid dishwashing detergent composition or a solid automatic dishwashing detergent composition, more preferably a liquid hand dishwashing detergent composition, comprising at least one grafted polymer obtained or obtainable by the process according to any one of claims 1 to 19 or 20 to 23, wherein the at least one grafted polymer is present in a concentration of about 0.05% to about 10% by weight based on the total weight of such composition, and optionally a. at least one enzyme and / or b. from about 1% to about 70% by weight of a surfactant system, and / or c. an effective amount of at least one additional cleaning adjunct; and / or d. at least one chelating agent and / or e. at least one anionic surfactant The composition further comprises: [Section 30] A method for stabilizing a graft polymer according to any one of items 1 to 19, or obtained or obtainable by the process according to any one of items 20 to 23, by adding at least one organic compound according to any one of items 10 to 14, which is a method by additionally adding the at least one organic compound according to any one of items 10 to 14 to the graft polymer after polymerization that already contains the at least one organic compound according to any one of items 10 to 14, and such an organic compound already contained is added before or during the polymerization to obtain such a graft polymer so that the molar ratio of the total amount of the at least one organic compound after the addition to the total amount of the graft polymer is 1:100 to 1:1, more preferably 1:500 to 1:100,000, and most preferably 1:1,000 to 1:10,000.

Claims

1. A water-soluble graft polymer comprising a polysaccharide as a polymer substrate and at least one water-soluble ethylenically unsaturated monomer as a grafted side chain, the water-soluble ethylenically unsaturated monomer comprising at least one sodium carboxylate unit, the water-soluble graft polymer being produced by a radical initiated polymerization reaction, and further comprising, during said polymerization, at least one organic compound comprising at least one carboxyl group capable of complexing with a metal ion, preferably iron, in its structure, which may be present in part or in whole as an acid group or in deprotonated salt form.

2. 2. The graft polymer according to claim 1, wherein the polysaccharide consists of an average of up to n=30 glucose units.

3. The graft polymer according to claim 2, wherein the polysaccharide consists of an average of n=2 to 20 glucose units.

4. The graft polymer according to claim 3, wherein the polysaccharide consists of an average of n=3 to 10 glucose units.

5. The graft polymer according to any one of claims 1 to 4, wherein the polysaccharide is selected from maltodextrin, corn syrup and / or corn syrup solids.

6. 6. The graft polymer according to any one of claims 1 to 5, wherein the at least one water-soluble ethylenically unsaturated monomer comprises at least 50 mol %, preferably at least 90 mol %, of sodium acrylate and / or sodium methacrylate, more preferably sodium acrylate, based on the total amount of monomers used, and optionally other polymerizable monomers.

7. The graft polymer according to any one of claims 1 to 6, wherein the radical polymerization is a radical oxidation-reduction polymerization type.

8. The graft polymer according to any one of claims 1 to 7, wherein at least one organic compound is used to reduce or preferably prevent discoloration before, during and / or after polymerization, more preferably before and / or during polymerization, even more preferably before and during polymerization, and most preferably such at least one organic compound is used such that it is still present in sufficient amount after said polymerization and post-polymerization.

9. The graft polymer according to claim 8, wherein a polymerization system comprising at least one metal salt and a peroxide, preferably hydrogen peroxide, is used as a radical initiator at least in the present polymerization stage.

10. 10. The graft polymer of claim 8 or 9, wherein the at least one organic compound contains at least one functional group that forms a metal complex with the at least one metal salt used as part of the polymerization system.

11. The graft polymer according to any one of claims 8 to 10, wherein the metal salt comprises a cation of a metal, preferably selected from metals that catalyze the Fenton reaction, more preferably from iron and / or copper, preferably comprising only said cations, most preferably used as iron(II) sulfate, copper(II) sulfate and their hydrated derivatives, more preferably as iron(II) sulfate, most preferably used as ferrous sulfate heptahydrate.

12. The at least one organic compound is preferably water-soluble, preferably of natural origin, more preferably from renewable resources, and comprises at least one carboxylate group, such as gluconic acid and its salts, preferably comprising at least two carboxylate groups (COOR), and if comprising at least two carboxylate groups, these are more preferably separated by 1 to 3 other atoms, more preferably by 1 to 3 other atoms selected from the following types of atoms: C, Si, N, P, O, S, and more preferably the following chemical structures 1 to 4: 【Chemistry 1】 (In all of Structures 1-4, the variables are selected from: R is H, Li, Na, K, Ca, preferably H or Na; A is O or S; R1, R2, R3 are: H and / or organic substituents containing 1 to 20 carbon atoms, optionally further comprising amino, hydroxy, carboxylic, sulfonic, sulfonate, phosphonate, keto, aldehyde and / or aromatic groups, preferably organic structures containing H and / or one or more further carboxylate groups selected from -COOR and -COOH, preferably -COOR, 12. The graft polymer according to claim 1, wherein R4 is H, OH or an organic substituent containing from 1 to 20 carbon atoms and optionally further comprising amino groups, hydroxy groups, carboxylic acid groups, sulfonic acid groups, sulfonate groups, phosphonate groups, keto groups, aldehyde groups and / or aromatic groups, preferably an organic structure containing H and / or one or more further carboxylate groups selected from -COOR and -COOH, preferably -COOR.

13. The graft polymer of claim 12, wherein the organic compound has at least three carboxylate groups (COOR).

14. The graft polymer according to claim 12 or 13, wherein the organic compound is selected from citric acid, methylglycidinediacetic acid, ethylenediaminetetraacetic acid, tetra N,N-bis(carboxylatomethyl)-glutamic acid, diethylenetriaminepentaacetic acid, tartaric acid, succinic acid or any salt thereof, such as the ammonium, alkali metal and / or alkaline earth metal salts, such as the sodium, potassium, calcium salts, preferably the sodium salts, more preferably citric acid, succinic acid and / or diethylenetriaminepentaacetic acid, most preferably citric acid and its salts, preferably citric acid.

15. The molar ratio of the total amount of said metal salts and the total amount of said at least one organic compound is between 1:1 and 1:10,000, preferably between 1:2 and 1:1,000, most preferably between 1:5 and 1:500, for example between 1:10 and 1:400, 1:30 and 1:200, 1:50 and 1:200 or between about 1:80 and 1:

120.

16. The graft polymer according to any one of claims 12 to 15, wherein the organic compound is a chelating agent exhibiting "readily biodegradable" according to the OCED guidelines (Test No. 301F).

17. The graft polymer according to any one of claims 1 to 16, in a form that has been dried by spray drying, freeze drying, vacuum drying, rotary drum drying, etc., or in the form of granules or particulates.

18. The graft polymer according to any one of claims 1 to 16, which is in solution form, preferably as an aqueous solution, more preferably as a solution essentially in water.

19. A graft polymer according to any one of claims 1 to 18, which satisfies at least one, preferably more than one of the following requirements, for example in the order of b>c>d>a, for example b+c, more preferably b+c+d, and even more preferably all of them: a. exhibits ready biodegradability according to the tests defined by the OECD 301F and / or B guidelines, preferably a biodegradability within 28 days according to OECD 301F and / or B, preferably 301F, of at least 50% by weight (based on the total solids content) based on the total weight of the polymer; and / or b. Gardner color scale is less than 4.0; and / or c. exhibiting color stability of no more than 3 units increase in Gardner color value over a period of at least 6 months; and / or d) The polymers of the present invention form clear solutions in liquid detergent formulations for at least 28 days when the formulation contains a minimum of 0.5% of the polymers of the present invention, and no cloudiness or precipitation is observed in the liquid detergent formulation, particularly in liquid hand dishwashing formulations.

20. A process for producing the graft polymer according to any one of claims 1 to 19, comprising the steps of: a) as a reactant, i) at least one polysaccharide polymeric substrate, preferably said polysaccharide consisting of an average of up to 30 glucose units, more preferably consisting of an average of up to 20 glucose units, preferably 2 to 20 glucose units, more preferably 3 to 10 glucose units, maltodextrin, corn syrup and / or corn syrup solids; ii) at least one water-soluble ethylenically unsaturated monomer comprising at least one sodium carboxylate unit which may be neutralized in situ (in the reactor if the polysaccharide is present) from the carboxylic acid form prior to addition to the reactor (i.e. if the polysaccharide is not present at the time of neutralization), preferably the monomers used in the polymerization reaction are at least 50 mol %, preferably at least 90 mol %, of the total amount of sodium acrylate, and optionally at least one other polymerizable monomer, most preferably the sodium acrylate is prepared prior to addition to the reaction mixture; is polymerized by a radical initiated polymerization reaction, preferably by a radical redox polymerization type reaction, more preferably using a polymerization system comprising at least one metal salt and hydrogen peroxide as a radical initiator for at least said main polymerization step, said metal salt comprising iron, preferably comprising iron as the only metal, more preferably used as ferrous sulfate heptahydrate; b) further, at least before or during said main polymerization reaction, at least one organic compound is added which contains in its structure at least two carboxyl groups, some or all of which may be present as acid groups or in the form of their deprotonated salts, said organic compound being selected from the group as described in claims 12 to 14, preferably claims 13 to 14, more preferably claim 14; c) such polymerization reaction is carried out in a suitable solvent or solvent mixture, such solvent being selected from polar protic or polar aprotic solvents, preferably acetone, ethanol, isopropanol or water, more preferably an aqueous solution, most preferably essentially water; d) optionally, an additional amount of the same initiator or initiator system used in the main polymerization stage or a different initiator or initiator system selected from azo initiators, redox initiators, peroxides, photoinitiators and mixtures thereof, preferably water soluble initiator systems, most preferably sodium persulfate and a combination of sodium persulfate and hydrogen peroxide, is added after the main polymerization step to further reduce the amount of unreacted monomer in the polymerization reaction mixture; Thereby, a polymer solution containing the graft polymer and the organic compound is obtained, e) optionally, the polymer solution is subjected to a further treatment selected from steam stripping, steam distillation, thermal distillation and / or vacuum distillation, thereby obtaining a purified polymer solution compared to the polymer solution prior to this step; f) optionally, to obtain the grafted polymer in solid form, the polymer solution obtained in the previous step is dried using at least one spray dryer, freeze dryer, vacuum dryer, rotary drum dryer, paddle dryer, kneader as drying means, or any agglomeration means such as fluidized bed agglomeration to obtain the polymer as agglomerates or granules or particulates, preferably by using a drying method such as agglomeration such as spray dryer, freeze dryer, vacuum dryer, fluidized bed agglomeration, which acts on the polymer at low temperature to prevent discoloration, thereby obtaining a polymer solid, process.

21. 21. The process of claim 20, wherein the polymerization is carried out at a temperature of 70-150°C, preferably 80-120°C, more preferably 90-100°C, and the post-polymerization reaction is carried out at a temperature about 5-10 degrees lower compared to the temperature of the main polymerization reaction.

22. 22. The process according to claim 20 or 21, wherein the polymerization is carried out at a solids concentration of 20 to 60, preferably 25 to 50 wt. %, based on the total amount of polysaccharide and monomers used together.

23. 23. The process according to any one of claims 20 to 22, wherein the graft polymer is produced by reacting an aqueous solution of corn syrup consisting of 3 to 8 glucose units on average with a mixture of acrylic acid and sodium acrylate, the degree of neutralization of the mixture being 90 to 96%, using hydrogen peroxide initiator and ferrous sulfate heptahydrate redox catalyst, using citric acid or its salts, preferably citric acid monohydrate or aqueous citric acid during the polymerization and post polymerization to chelate metal ions, and using sodium persulfate in combination with hydrogen peroxide during post polymerization to consume residual acrylate monomers, the polymerization temperature is 90 to 100°C, the post polymerization temperature is 85 to 95°C, and the solids content of the graft polymer after the polymerization is completed is 20 to 60, preferably 25 to 50% by weight.

24. Use of at least one grafted polymer according to any one of claims 1 to 19 or obtained or obtainable by the process according to any one of claims 20 to 23 in a composition which is a cleaning composition, a fabric care and home care product, an institutional cleaning product, a cosmetic or personal care product or an agrochemical formulation.

25. 25. Use according to claim 24 in fabric care and home care compositions, cleaning compositions or institutional cleaning products.

26. The use according to claim 24 or 25, wherein said composition comprises at least one grafted polymer in a concentration by weight of about 0.05% to about 10% by weight, based on the total weight of such composition or product.

27. Use according to any one of claims 24 to 26, a. at least one enzyme and / or b. from about 1% to about 70% by weight of a surfactant system, and / or c. an effective amount of at least one additional cleaning adjunct; and / or d. In such a composition, when a sodium polyacrylate polymer having a Fikentscher K value of 15 is replaced by the graft polymer, it shows improved cleaning performance in red clay dispersions. The use preferably comprises at least one of a) to c), more preferably at least a) and b), and even more preferably a), b) and c).

28. A laundry detergent composition, cleaning composition or fabric care and home care product comprising at least one grafted polymer according to any one of claims 1 to 19 or obtained or obtainable by the process according to any one of claims 20 to 23, preferably a laundry detergent composition, more preferably a liquid or semi-liquid or multi-component laundry detergent composition, most preferably a liquid laundry detergent composition, said at least one grafted polymer being present in a concentration, in weight % based on the total weight of such composition or product, preferably from about 0.05% to about 10%, and optionally a. at least one enzyme and / or b. from about 1% to about 70% by weight of a surfactant system, and / or c. an effective amount of at least one additional cleaning adjunct The composition further comprises:

29. A dishwashing detergent composition, preferably a liquid dishwashing detergent composition or a solid automatic dishwashing detergent composition, more preferably a liquid hand dishwashing detergent composition, comprising at least one grafted polymer according to claims 1 to 19 or obtained or obtainable by the process according to any one of claims 20 to 23, said at least one grafted polymer being present in a concentration, in weight % based on the total weight of such composition, of from about 0.05% to about 10%, and optionally a. at least one enzyme and / or b. from about 1% to about 70% by weight of a surfactant system, and / or c. an effective amount of at least one additional cleaning adjunct; and / or d. at least one chelating agent and / or e. at least one anionic surfactant The composition further comprises:

30. A method for stabilizing a graft polymer according to any one of claims 1 to 19 or obtained or obtainable by a process according to any one of claims 20 to 23 by adding at least one organic compound according to any one of claims 10 to 14 additionally to the polymerized graft polymer already containing at least one organic compound according to any one of claims 10 to 14, said organic compound already contained being added before or during said polymerization to obtain such a graft polymer in such a way that the molar ratio of the total amount of said at least one organic compound and the total amount of said graft polymer after addition is from 1:100 to 1:1, more preferably from 1:500 to 1:100,000, most preferably from 1:1,000 to 1:10,000.

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