detergent formulations

Abstract

Provided is a detergent composition comprising a detersive surfactant and a dispersant hydrophilic block copolymer comprising a carboxylic acid polymer segment comprising structural units of a monoethylenically unsaturated carboxylic acid monomer and a poly(alkylene oxide) diol polymer segment consisting of structural units of a poly(alkylene oxide) diol, wherein 90 to 100 weight percent of the poly(alkylene oxide) diol polymer segment is esterified with two structural units of the monoethylenically unsaturated carboxylic acid monomer present in the carboxylic acid polymer segment per poly(alkylene oxide) diol polymer segment.

Description

[Technical Field]

[0001] The present invention relates to detergent formulations, particularly detergent formulations comprising a detersive surfactant and a dispersant hydrophilic block copolymer comprising a carboxylic acid polymer segment comprising structural units of a monoethylenically unsaturated carboxylic acid monomer and a poly(alkylene oxide) diol polymer segment consisting of structural units of a poly(alkylene oxide) diol, wherein 90 to 100 weight percent of the poly(alkylene oxide) diol polymer segment is esterified with two structural units of the monoethylenically unsaturated carboxylic acid monomer present in the carboxylic acid polymer segment per poly(alkylene oxide) diol polymer segment.

[0002] Detergent applications use large amounts of ingredients. Because these ingredients may eventually enter the environment and be present in groundwater, it is desirable for such ingredients to be degradable to avoid any environmental concerns. Traditionally, detergents and cleaning agents have contained phosphates. Phosphates have been added to formulations as detergent builders that act to sequester alkaline earth metal hardness ions, as encrustation inhibitors, and as anti-redeposition agents. Despite the fact that well-known inorganic phosphorus compounds are highly effective and relatively non-toxic, their use in many applications has been discontinued.

[0003] The detergent industry continues to strive to convert from polyphosphates to materials such as polycarboxylic acid polymers, e.g., poly(acrylic acid). While the polycarboxylic acid polymers and copolymers currently used in detergent and water treatment formulations do not suffer from the same recognized problems as phosphorus-containing inorganic builders, it has been taught in the past that it may be desirable for ingredients used in high-volume applications that may enter the environment to be biodegradable. Unfortunately, most polycarboxylic acid polymers and copolymers useful in detergent and / or water treatment applications are not highly biodegradable.

[0004] Some efforts have been made to provide biodegradable, water-soluble poly(acrylic acid) copolymers. Notable in this regard is U.S. Pat. No. 5,318,719, in which Hughes et al. teach graft polymers as biodegradable detergent additives. In particular, Hughes et al. teach a class of biodegradable, water-soluble graft copolymers having builder, anti-filming, dispersing, and threshold crystallization-inhibiting properties, comprising (a) an acid-functional monomer and, optionally, (b) another water-soluble monoethylenically unsaturated monomer copolymerizable with (a), grafted to a biodegradable substrate comprising a polyalkylene oxide and / or a polyalkoxylated material. Nevertheless, the processing method taught in U.S. Pat. No. 5,318,719 is unable to produce poly(acrylic acid) / poly(alkylene oxide) copolymers at high concentrations.

[0005] Therefore, it would be desirable to have detergents, particularly automatic dishwashing detergents, formulated with high purity poly(acrylic acid) / poly(alkylene oxide) copolymers.

[0006] The present invention provides a detergent composition comprising a detersive surfactant and a dispersant hydrophilic block copolymer comprising a carboxylic acid polymer segment comprising structural units of a monoethylenically unsaturated carboxylic acid monomer and a poly(alkylene oxide) diol polymer segment consisting of structural units of a poly(alkylene oxide) diol, wherein 90 to 100 wt% of the poly(alkylene oxide) diol polymer segment is esterified with two structural units of the monoethylenically unsaturated carboxylic acid monomer present in the carboxylic acid polymer segment per poly(alkylene oxide) diol polymer segment.

[0007] The present invention provides a detergent composition comprising a detersive surfactant and a dispersant hydrophilic block copolymer comprising a carboxylic acid polymer segment comprising structural units of a monoethylenically unsaturated carboxylic acid monomer and a poly(alkylene oxide) diol polymer segment consisting of structural units of a poly(alkylene oxide) diol, wherein from 40 to 100 wt. % of the dispersant hydrophilic block copolymer is a copolymer of formula (I):

[0008] [ka] In the formula, z1 is 1, x1 is 0 to 139, r1 is 0 to 139, x1+z1+r1=7 to 140, z2 is 1, x2 is 0 to 139, r2 is 0 to 139, x2+z2+r2=7 to 140, and each R 1 are independently hydrogen and C 1~3 The alkyl group is selected from the group consisting of alkyl groups, and y is an average of 4 to 84.

[0009] The present invention provides a detergent composition comprising a detersive surfactant and a dispersant hydrophilic block copolymer comprising a carboxylic acid polymer segment comprising structural units of a monoethylenically unsaturated carboxylic acid monomer and a poly(alkylene oxide) diol polymer segment comprising structural units of a poly(alkylene oxide) diol, wherein 40 to 100 wt. % of the dispersant hydrophilic block copolymer is a poly(alkylene oxide) diol polymer segment comprising structural units of a poly(alkylene oxide) diol

[0010] [ka] wherein z1 is 1, x1 is 0 to 139, r1 is 0 to 139, x1+z1+r1=7 to 140, z2 is 1, x2 is 0 to 139, r2 is 0 to 139, x2+z2+r2=7 to 140, and each R 1 are independently hydrogen and C 1~3alkyl groups, y is an average of 4 to 84, the molar ratio of poly(alkylene oxide) diol polymer segments to carboxylic acid polymer segments in the dispersant hydrophilic block copolymer is 0.005 to 0.03, the dispersant hydrophilic block copolymer contains 0 to 60 wt. % residual carboxylic acid polymer segments that remain unesterified with the poly(alkylene oxide) diol polymer segments, and the dispersant hydrophilic block copolymer contains 0 to 1 wt. % residual poly(alkylene oxide) diol polymer segments that remain unesterified with the carboxylic acid polymer segments.

[0011] The present invention provides an automatic dishwashing detergent composition comprising: 50 to 85 wt. % of a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof, based on the weight of the automatic dishwashing detergent composition; 0.75 to 7 wt. % of a phosphonate, based on the weight of the automatic dishwashing detergent composition; 1.5 to 7.5 wt. % of a nonionic surfactant, based on the weight of the automatic dishwashing detergent composition; and 4 to 7 wt. % of a dispersant hydrophilic block copolymer, based on the weight of the automatic dishwashing detergent composition, comprising a carboxylic acid polymer segment comprising structural units of a monoethylenically unsaturated carboxylic acid monomer and a poly(alkylene oxide) diol polymer segment consisting of structural units of a poly(alkylene oxide) diol, wherein 90 to 100 wt. % of the poly(alkylene oxide) diol polymer segment are esterified with two structural units of the monoethylenically unsaturated carboxylic acid monomer present in the carboxylic acid polymer segment per poly(alkylene oxide) diol polymer segment.

[0012] The present invention provides an automatic dishwashing detergent composition comprising 50 to 85 wt. % of a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof, based on the weight of the automatic dishwashing detergent composition; 0.75 to 7 wt. % of a phosphonate, based on the weight of the automatic dishwashing detergent composition; 1.5 to 7.5 wt. % of a nonionic surfactant, based on the weight of the automatic dishwashing detergent composition; and 4 to 7 monoethylenically unsaturated carboxylic acid monomer structural units, based on the weight of the automatic dishwashing detergent composition. and a dispersant hydrophilic block copolymer comprising a dispersant hydrophilic block copolymer comprising a poly(alkylene oxide) diol polymer segment consisting of structural units of a poly(alkylene oxide) diol, wherein 40 to 100 wt % of the dispersant hydrophilic block copolymer is a copolymer of formula (I), wherein z1 is 1, x1 is 0 to 139, r1 is 0 to 139, x1+z1+r1=7 to 140, z2 is 1, x2 is 0 to 139, r2 is 0 to 139, x2+z2+r2=7 to 140, and each R 1 are independently hydrogen and C 1~3 alkyl groups, and y is an average of 4 to 84.

[0013] The present invention provides a method of cleaning items in an automatic dishwashing machine, the method comprising providing at least one item, providing an automatic dishwashing detergent composition of the present intention, and applying the automatic dishwashing detergent composition to the at least one item in the automatic dishwashing machine. DETAILED DESCRIPTION OF THE INVENTION

[0014] It has surprisingly been found that detergent compositions comprising the dispersant hydrophilic block copolymers of the present invention, comprising carboxylic acid polymer segments comprising structural units of monoethylenically unsaturated carboxylic acid monomers and poly(alkylene oxide) diol polymer segments consisting of structural units of poly(alkylene oxide) diol, wherein 90 to 100 wt. % of the poly(alkylene oxide) diol polymer segments are esterified with two structural units of monoethylenically unsaturated carboxylic acid monomers present in the carboxylic acid polymer segments per poly(alkylene oxide) diol polymer segment, when incorporated into automatic dishwashing detergent compositions, particularly phosphate-free automatic dishwashing detergent compositions, provide surprisingly good spotting and filming performance on a variety of surfaces relative to conventional dispersant polymers, while at the same time potentially having more favorable biodegradability than the conventional dispersant polymers.

[0015] Unless otherwise indicated, ratios, percentages, parts, etc. are by weight. Weight percentages (or wt %) in a composition are percentages by weight, i.e., excluding any water that may be present in the composition. Percentages of monomer units in a polymer are percentages by solids weight, i.e., excluding any water that may be present in the polymer emulsion.

[0016] As used herein, unless otherwise indicated, the terms "weight average molecular weight" and "Mw" are used interchangeably to refer to weight average molecular weight measured in a conventional manner using gel permeation chromatography (GPC) (sometimes referred to as size exclusion chromatography (SEC)) and conventional standards such as polyethylene glycol standards. GPC techniques are discussed in detail in Striegel, AM et al., "Modem Size Exclusion Liquid Chromatography," Practice of Gel Permeation and Gel Filtration (2 ed.) John Wiley & Sons, Inc. (2009) and Podzimek, S., "Light Scattering, Size Exclusion Chromatography and Asymmetric Flow Field Flow Fractionation: Powerful Tools for the Characterization of Polymers, Proteins and Nanoparticles," John Wiley & Sons, Inc. (2011). Weight average molecular weights are reported herein in units of Daltons.

[0017] As used herein and in the appended claims, the term "phosphate-free" means a composition containing 1% by weight or less (preferably, 0.5% by weight or less, more preferably, 0.2% by weight or less, even more preferably, 0.01% by weight or less, still more preferably, 0.001% by weight or less, and most preferably below the detection limit) of phosphate (measured as elemental phosphorus).

[0018] Preferably, the detergent composition of the present invention is selected from the group consisting of laundry detergent compositions and dish detergent compositions. More preferably, the detergent composition of the present invention is a laundry detergent composition. Most preferably, the detergent composition of the present invention is an automatic dishwashing detergent composition.

[0019] Preferably, the detergent composition (preferably an automatic dishwashing detergent composition) of the present invention comprises a detersive surfactant (preferably 0.5 to 15 wt % (more preferably 0.75 to 10 wt %, even more preferably 1 to 8 wt %, and most preferably 1.5 to 7.5 wt %) of the detersive surfactant, based on the weight of the detergent composition), and a dispersant hydrophilic block copolymer (preferably 0.5 to 15 wt % (more preferably 1 to 10 wt %, even more preferably 1.5 to 8 wt %, and most preferably 2 to 7 wt %) of the dispersant hydrophilic block copolymer, based on the weight of the detergent composition), comprising carboxylic acid polymer segments comprising structural units of a monoethylenically unsaturated carboxylic acid monomer and poly(alkylene oxide) diol polymer segments comprising structural units of a poly(alkylene oxide) diol, wherein 90 to 100 wt % of the poly(alkylene oxide) diol polymer segments are composed of structural units of a poly(alkylene oxide) diol, and wherein 90 to 100 wt % of the poly(alkylene oxide) diol polymer segments are composed of two monoethylenically unsaturated carboxylic acid monomers present in the carboxylic acid polymer segments per poly(alkylene oxide) diol polymer segment. and optionally a builder (preferably 0 to 99 wt. % (more preferably 10 wt. % or more, even more preferably 20 wt. % or more, even more preferably 25 wt. % or more, most preferably 50 wt. % or more, preferably 95 wt. % or less, more preferably 90 wt. % or less, even more preferably 85 wt. % or less, most preferably 80 wt. % or less) of the builder, based on the weight of the detergent composition (preferably the builder is at least one and at least one citrate salt), and optionally a phosphonate (preferably 0 to 15 wt % (more preferably 0.05 to 10 wt %, even more preferably 0.5 to 8 wt %, most preferably 0.75 to 7 wt %) of the phosphonate based on the weight of the detergent composition), and optionally a poly(acrylic acid) homopolymer (preferably 0 to 15 wt % (more preferably 0.05 to 10 wt %, even more preferably 0.5 to 8 wt %, most preferably 0.75 to 7 wt %) of the phosphonate based on the weight of the detergent composition).75 to 7% by weight of a poly(acrylic acid) homopolymer), and optionally a bleaching agent (preferably 0 to 35% by weight (more preferably 0 to 30% by weight, even more preferably 1 to 25% by weight, and most preferably 5 to 20% by weight) of the bleaching agent, based on the weight of the detergent composition of the present invention).

[0020] Preferably, the detergent composition of the present invention (preferably, automatic dishwashing detergent composition) comprises 0.5 to 15 wt % (preferably, 0.75 to 10 wt %, more preferably, 1 to 8 wt %, and most preferably, 1.5 to 7.5 wt %) of a cleaning surfactant based on the weight of the detergent composition. More preferably, the detergent composition of the present invention (preferably, automatic dishwashing detergent composition) comprises 0.5 to 15 wt % (preferably, 0.75 to 10 wt %, more preferably, 1 to 8 wt %, and most preferably, 1.5 to 7.5 wt %) of a cleaning surfactant based on the weight of the detergent composition, the cleaning surfactant being selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof. Even more preferably, the detergent composition (preferably an automatic dishwashing detergent composition) of the present invention comprises 0.5 to 15 wt % (preferably 0.75 to 10 wt %, more preferably 1 to 8 wt %, most preferably 1.5 to 7.5 wt %) of a detersive surfactant based on the weight of the detergent composition, and the detersive surfactant comprises a nonionic surfactant. Most preferably, the detergent composition (preferably an automatic dishwashing detergent composition) of the present invention comprises 0.5 to 15 wt % (preferably 0.75 to 10 wt %, more preferably 1 to 8 wt %, most preferably 1.5 to 7.5 wt %) of a detersive surfactant based on the weight of the detergent composition, and the detersive surfactant comprises a nonionic alcohol ethoxylate.

[0021] Anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, alkyl polyethoxy sulfates, alkoxylated alcohols, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, alpha-sulfocarboxylates, esters of alpha-sulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, sulfates of fatty acids, sulfonates of fatty acids, sulfonates of fatty acid esters, alkyl phenols, alkylphenol polyethoxy ether sulfates, 2-acryloxy-alkane-1-sulfonic acids, 2-acryloxy-alkane-1-sulfonates, beta-alkyloxyalkane sulfonic acids, beta-alkyloxyalkane sulfonates, amine oxides, and mixtures thereof. Preferred anionic surfactants include C 8~20 Alkylbenzene sulfate, C 8~20 Alkylbenzene sulfonic acid, C 8~20 Alkylbenzene sulfonates, paraffin sulfonic acids, paraffin sulfonates, alpha-olefin sulfonic acids, alpha-olefin sulfonates, alkoxylated alcohols, C 8~20 Alkylphenols, amine oxides, sulfonates of fatty acids, sulfonates of fatty acid esters, C 8~10 alkyl polyethoxy sulfates, and mixtures thereof. More preferred anionic surfactants include C 12~16 Alkylbenzene sulfonic acid, C 12~16 Alkylbenzene sulfonate, C 12~18 Paraffin sulfonic acid, C 12~18 Paraffin sulfonate, C 12~16 Alkyl polyethoxy sulfates, and mixtures thereof.

[0022] Nonionic surfactants include alkoxylates (e.g., polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, fatty acid polyglycol esters, and mixtures thereof. Preferred nonionic surfactants include fatty alcohol polyglycol ethers. More preferred nonionic surfactants include secondary alcohol ethoxylates, ethoxylated 2-ethylhexanol, ethoxylated seed oil, butanol capped ethoxylated 2-ethylhexanol, and mixtures thereof. Most preferred nonionic surfactants include secondary alcohol ethoxylates.

[0023] Preferably, the nonionic surfactants used in the automatic dishwashing detergent compositions of the present invention are: ROM) x -(N) y -OH, and ROM) x -(N) y -(P) z -OH wherein M represents an ethylene oxide structural unit and N represents a C 3~18 Represents the structural unit of 1,2-epoxyalkane, and P is C 6~18 where x is 5 to 40, y is 0 to 20, z is 0 to 3, and R is C 6~22 represents a straight or branched chain alkyl group).

[0024] Preferably, the nonionic surfactants used in the automatic dishwashing detergent compositions of the present invention are: ROM) x -(N) y -OH, and ROM) x -(N) y -O-R' wherein M and N are structural units derived from alkylene oxide (one of which is ethylene oxide), x is 5 to 40, y is 0 to 20, and R is C 6~22 represents a linear or branched alkyl group, and R' is an alcohol precursor and C 6~22 represents a group derived from the reaction of a linear or branched alkyl halide, an epoxyalkane, or a glycidyl ether.

[0025] Preferably, the nonionic surfactant used in the automatic dishwashing detergent compositions of the present invention is a surfactant of the formula ROM) x -OH wherein M represents an ethylene oxide structural unit and x is at least 3 (preferably at least 5, preferably no more than 10, more preferably no more than 8). Preferably, wherein R and R' each have at least 8 (more preferably at least 10) carbon atoms.

[0026] The cationic surfactant includes quaternary surfactant compounds.Preferred cationic surfactants include quaternary surfactant compounds having at least one of ammonium group, sulfonium group, phosphonium group, iodonium group, and arsonium group.More preferred cationic surfactants include at least one of dialkyldimethylammonium chloride and alkyldimethylbenzylammonium chloride.Even more preferred cationic surfactants include C 16~18 Dialkyldimethylammonium chloride, C 8~18 The most preferred cationic surfactants include at least one of alkyldimethylbenzylammonium chloride and dimethylditallow ammonium chloride.

[0027] Examples of amphoteric surfactants include betaine, amine oxide, alkylamidoalkylamine, alkyl-substituted amine oxide, acylated amino acid, derivatives of aliphatic quaternary ammonium compounds, and mixtures thereof. Preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds. More preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds having a long chain group with 8 to 18 carbon atoms. Even more preferred amphoteric surfactants include C 12~14 The most preferred amphoteric surfactants include at least one of alkyl dimethylamine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonio)propane-1-sulfonate, and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate. 12~14 At least one of alkyl dimethyl amine oxides may be mentioned.

[0028] Preferably, the detergent composition of the present invention (preferably an automatic dishwashing detergent composition) contains from 0.5 to 15 wt % (preferably, 1 to 10 wt %, even more preferably, 1.and 5 to 8 wt. %, most preferably 2 to 7 wt. %, of a dispersant hydrophilic block copolymer, the dispersant hydrophilic block copolymer comprising a carboxylic acid polymer segment comprising structural units of a monoethylenically unsaturated carboxylic acid monomer (preferably, the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of (meth)acrylic acid, (meth)acryloxypropionic acid, itaconic acid, aconitic acid, maleic acid, fumaric acid, crotonic acid, citraconic acid, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, and mixtures thereof; more preferably, the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and mixtures thereof; even more preferably, the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof; and most preferably, the monoethylenically unsaturated carboxylic acid monomer is acrylic acid) (most preferably, the monoethylenically unsaturated carboxylic acid monomer is acrylic acid). and a poly(alkylene oxide) diol polymer segment comprising structural units of a poly(alkylene oxide) diol (preferably, the structural units of the poly(alkylene oxide) diol are residues formed from an esterification reaction of a poly(alkylene oxide) diol according to Formula A).

[0029] [ka] In the formula, each R 1 are independently hydrogen and C 1~3 Alkyl groups (preferably hydrogen and C 1~2 alkyl groups, more preferably hydrogen and methyl groups, and most preferably hydrogen), y is an average of 4 to 84 (preferably 5 to 75, more preferably 10 to 70, and most preferably 12 to 67), and 90 to 100% by weight (preferably 92 to 100% by weight, more preferably 95 to 100% by weight, even more preferably 97.5 to 100% by weight, still more preferably 98 to 100% by weight, and most preferably 99 to 100% by weight) of the poly(alkylene oxide) diol polymer segment is a poly(alkylene oxide) diol polymer. Two per segment are esterified with structural units of monoethylenically unsaturated carboxylic acid monomers present in the carboxylic acid polymer segments. (Preferably, the poly(alkylene oxide) diol polymer segments form crosslinks within the dispersant hydrophilic block copolymer, the crosslinks being selected from the group consisting of intracrosslinks and intercrosslinks.) (Intracrosslinks occur when esterifications are formed on the same carboxylic acid polymer segment, and intercrosslinks occur when esterifications are formed on two separate carboxylic acid polymer segments.)

[0030] More preferably, the detergent composition (preferably an automatic dishwashing detergent composition) of the present invention contains from 0.5 to 15 wt % (preferably, 1 to 10 wt %, even more preferably, 1.and 5 to 8 wt. %, most preferably 2 to 7 wt. %, of a dispersant hydrophilic block copolymer, the dispersant hydrophilic block copolymer comprising a carboxylic acid polymer segment comprising structural units of a monoethylenically unsaturated carboxylic acid monomer (preferably, the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of (meth)acrylic acid, (meth)acryloxypropionic acid, itaconic acid, aconitic acid, maleic acid, fumaric acid, crotonic acid, citraconic acid, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, and mixtures thereof; more preferably, the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and mixtures thereof; even more preferably, the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof; and most preferably, the monoethylenically unsaturated carboxylic acid monomer is acrylic acid) (most preferably, the monoethylenically unsaturated carboxylic acid monomer is acrylic acid). and a poly(alkylene oxide) diol polymer segment comprising structural units of a poly(alkylene oxide) diol (preferably, the structural units of the poly(alkylene oxide) diol are residues formed from an esterification reaction of a poly(alkylene oxide) diol according to Formula A).

[0031] [ka] In the formula, each R 1 are independently hydrogen and C 1~3 Alkyl groups (preferably hydrogen and C 1~2 alkyl groups, more preferably hydrogen and methyl groups, most preferably hydrogen), y is on average 4 to 84 (preferably 5 to 75, more preferably 10 to 70, most preferably 12 to 67), and 40 to 100 wt% (preferably 50 to 100 wt%, more preferably 55 to 100 wt%, even more preferably 60 to 100 wt%, still more preferably 75 to 100 wt%, most preferably 90 to 100 wt%) of the dispersant hydrophilic block copolymer is a compound of formula (I):

[0032] [ka] wherein z1 is 1 to 2 (preferably 1), x1 is 0 to 139 (preferably 0 to 140, more preferably 0 to 104, most preferably 0 to 83), r1 is 0 to 139 (preferably 0 to 140, more preferably 0 to 104, most preferably 0 to 83), x1+z1+r1=7 to 140 (preferably 21 to 140, more preferably 28 to 104, most preferably 48 to 83), and z2 is x2 is 1 to 2 (preferably 1) (preferably, z1 = z2), x2 is 0 to 139 (preferably 0 to 140, more preferably 0 to 104, most preferably 0 to 83), r2 is 0 to 139 (preferably 0 to 140, more preferably 0 to 104, most preferably 0 to 83), x2 + z2 + r2 = 7 to 140 (preferably 21 to 140, more preferably 28 to 104, most preferably 48 to 83), and each R 1 are independently hydrogen and C 1~3 Alkyl groups (preferably hydrogen and C 1~2alkyl groups, more preferably hydrogen and methyl groups, most preferably hydrogen), and y is an average of 4 to 84 (preferably 5 to 75, more preferably 10 to 70, most preferably 12 to 67) (preferably, the poly(alkylene oxide) diol copolymer segments are esterified at random positions along the carboxylic acid copolymer segments) (optionally, some of the carboxylic acid copolymer segments corresponding to x1, z1, r1, and x2, z2, r2 form a single carboxylic acid copolymer segment, and the poly(alkylene oxide) diol copolymer segments esterified thereto form internal crosslinks within the single carboxylic acid copolymer segment). forming bridges) (preferably, the carboxylic acid copolymer segments corresponding to each x1, z1, r1, and x2, z2, r2 in the dispersant hydrophilic block copolymer are separate carboxylic acid copolymer segments joined together only by poly(alkylene oxide) diol copolymer segments) (preferably, the dispersant hydrophilic block copolymer comprises less than 5 wt. % (preferably, 0-3 wt. %, more preferably, 0-2 wt. %, even more preferably, 0-1 wt. %, still more preferably, 0-0.5 wt. %, and most preferably, 0-0.1 wt. %) of the dispersant hydrophilic block copolymer having internal crosslinks of poly(alkylene oxide) diol copolymer segments).

[0033] Preferably, the carboxylic acid copolymer segment comprises 0 to 30 mol % (preferably 0 to 20 mol %, more preferably 0 to 10 mol %, even more preferably 0 to 5 mol %, even more preferably 0 to 3 mol %, even more preferably 0 to 2 mol %, even more preferably 0 to 1 mol %, and most preferably 0 mol %) of structural units selected from the group consisting of structural units of monoethylenically unsaturated nonionic monomers, structural units of sulfonated monomers, and mixtures thereof. More preferably, the carboxylic acid copolymer segment comprises 0 to 30 mol % (preferably 0 to 20 mol %, more preferably 0 to 10 mol %, even more preferably 0 to 5 mol %, even more preferably 0 to 3 mol %, even more preferably 0 to 2 mol %, even more preferably 0 to 1 mol %, and most preferably 0 mol %) of structural units selected from the group consisting of structural units of monoethylenically unsaturated nonionic monomers, structural units of sulfonated monomers, and mixtures thereof, wherein the monoethylenically unsaturated nonionic monomer is C 1~4The alkyl (meth)acrylate (preferably, the monoethylenically unsaturated nonionic monomer is selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, and mixtures thereof, more preferably, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and mixtures thereof, even more preferably, ethyl (meth)acrylate, n-butyl (meth)acrylate, and mixtures thereof, most preferably, ethyl acrylate, butyl acrylate, and mixtures thereof), and the sulfonated monomer is selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 4-styrenesulfonic acid, vinylsulfonic acid, 3-allyloxysulfonic acid, 2-hydroxy-1-propanesulfonic acid (HAP), S), 2-sulfoethyl(meth)acrylic acid, 2-sulfopropyl(meth)acrylic acid, 3-sulfopropyl(meth)acrylic acid, 4-sulfobutyl(meth)acrylic acid, and salts thereof (preferably, the sulfonated monomer is 2-acrylamido-2-methylpropanesulfonic acid (AMPS) monomer (preferably, the sulfonated monomer is selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methylacrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, and salts thereof; more preferably, the sulfonated monomer is selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methylacrylamido-2-methylpropanesulfonic acid, and salts thereof; most preferably, the sulfonated monomer is selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and salts thereof).

[0034] Preferably, the dispersant hydrophilic block copolymer has a carboxylic acid copolymer segment weight average molecular weight of 500 to 10,000 daltons (preferably, 1,500 to 10,000 daltons, more preferably, 2,000 to 7,500 daltons, and most preferably, 2,500 to 6,000 daltons) per dispersant hydrophilic block copolymer molecule, and the dispersant hydrophilic block copolymer has a poly(alkylene oxide) diol copolymer segment weight average molecular weight of 250 to 5,000 daltons (preferably, 300 to 4,650 daltons, more preferably, 600 to 4,200 daltons, and most preferably, 720 to 4,020 daltons) per dispersant hydrophilic block copolymer molecule.

[0035] Preferably, the dispersant hydrophilic block copolymer has a molar ratio of poly(alkylene oxide) diol polymer segments to carboxylic acid polymer segments of 0.01 to 0.03 (preferably 0.01 to 0.03, more preferably 0.01 to 0.029, most preferably 0.0125 to 0.0285).

[0036] Preferably, the dispersant hydrophilic block copolymer of the present invention comprises 0 to 60 wt % (preferably 0 to 50 wt %, more preferably 0 to 45 wt %, even more preferably 0 to 40 wt %, still more preferably 0 to 25 wt %, and most preferably 0 to 10 wt %) of residual carboxylic acid polymer segments that remain unesterified with poly(alkylene oxide) diol polymer segments.

[0037] Preferably, the dispersant hydrophilic block copolymer of the present invention comprises 0 to 1 wt % (preferably 0 to 0.5 wt %, more preferably 0 to 0.25 wt %, even more preferably 0 to 0.1 wt %, still more preferably 0 to 0.01 wt %, and most preferably 0 to 0.001 wt %) of residual poly(alkylene oxide) diol polymer segments that remain unesterified with carboxylic acid polymer segments.

[0038] The dispersant hydrophilic block copolymers can be made using the syntheses described in Syntheses S2-S5 below.

[0039] The automatic dishwashing detergent compositions of the present invention optionally further comprise additives. Preferably, the automatic dishwashing detergent compositions of the present invention further comprise an additive selected from the group consisting of a builder, an alkaline source, a bleaching agent (e.g., sodium percarbonate, sodium perborate), a bleach activator (e.g., tetraacetylethylenediamine (TAED)), a bleach catalyst (e.g., manganese(II) acetate, cobalt(II) chloride, bis(TACN) magnesium trioxide diacetate), an enzyme (e.g., protease, amylase, lipase, or cellulase), a suds suppressor, a colorant, a fragrance, an additional builder, an antimicrobial agent, a filler, a deposit control polymer, and mixtures thereof. More preferably, the automatic dishwashing detergent compositions of the present invention further comprise an additive selected from the group consisting of a builder, a carrier (e.g., an aqueous liquid), a bleaching agent, a bleach activator, an enzyme, a filler, and mixtures thereof. Even more preferably, the automatic dishwashing detergent compositions of the present invention further comprise additives, including a builder, a bleaching agent (e.g., sodium percarbonate, sodium perborate), a bleach activator (e.g., tetraacetylethylenediamine (TAED)), and an enzyme (e.g., a protease, an amylase, a lipase, or a cellulase). Most preferably, the automatic dishwashing detergent compositions of the present invention further comprise additives, including a builder comprising a carbonate and a citrate, a bleaching agent comprising sodium percarbonate, a bleach activator comprising tetraacetylethylenediamine (TAED), and an enzyme comprising a protease and an amylase.

[0040] Preferably, the automatic dishwashing detergent composition of the present invention further comprises 0 to 99 wt. % (more preferably 10 wt. % or more, even more preferably 20 wt. % or more, even more preferably 25 wt. % or more, most preferably 50 wt. % or more, preferably 95 wt. % or less, more preferably 90 wt. % or less, even more preferably 85 wt. % or less, most preferably 80 wt. % or less) of a builder based on the weight of the automatic dishwashing detergent composition. More preferably, the automatic dishwashing detergent composition comprises 0 to 99 wt. % (more preferably 10 wt. % or more, even more preferably 20 wt. % or more, even more preferably 25 wt. % or more, most preferably 50 wt. % or more, preferably 95 wt. % or less, more preferably 90 wt. % or less, even more preferably 85 wt. % or less, most preferably 80 wt. % or less) of a builder based on the weight of the automatic dishwashing detergent composition, the builder comprising a mixture of at least one carbonate salt and at least one citrate salt. More preferably, the automatic dishwashing detergent compositions of the present invention comprise 0 to 99 wt. % (more preferably, 10 wt. % or more, even more preferably, 20 wt. % or more, even more preferably, 25 wt. % or more, most preferably, 50 wt. % or more, preferably, 95 wt. % or less, more preferably, 90 wt. % or less, even more preferably, 85 wt. % or less, and most preferably, 80 wt. % or less) of a builder, based on the weight of the automatic dishwashing detergent composition, the builder comprising a mixture of at least one carbonate, at least one citrate, and at least one silicate. Most preferably, the automatic dishwashing detergent compositions of the present invention comprise 0 to 99 wt. % (more preferably, 10 wt. % or more, even more preferably, 20 wt. % or more, even more preferably, 25 wt. % or more, most preferably, 50 wt. % or more, preferably, 95 wt. % or less, more preferably, 90 wt. % or less, even more preferably, 85 wt. % or less, and most preferably, 80 wt. % or less) of a builder, based on the weight of the automatic dishwashing detergent composition, the builder comprising a mixture of sodium carbonate, sodium citrate, and sodium silicate. The weight percentages of carbonate, citrate, and silicate builders are based on the actual weight of the salt containing the metal ion.

[0041] The term "carbonate" as used herein and in the appended claims refers to alkali metal or ammonium carbonate, bicarbonate, and / or sesquicarbonate. Preferably, the carbonate (if present) used in the automatic dishwashing detergent composition is selected from the group consisting of sodium, potassium, and lithium carbonate (more preferably, sodium or potassium salts, most preferably, sodium salts). Most preferably, the carbonate (if present) used in the automatic dishwashing detergent composition comprises at least one of sodium carbonate and sodium bicarbonate. Preferably, when the builder used in the automatic dishwashing detergent composition of the present invention comprises a carbonate, the automatic dishwashing detergent composition preferably comprises 0 to 99 wt. % (preferably, 10 to 75 wt. %, more preferably, 25 to 60 wt. %, most preferably, 40 to 50 wt. %) of the carbonate, based on the weight of the automatic dishwashing detergent composition.

[0042] The term "citrate" as used herein and in the appended claims refers to an alkali metal citrate. Preferably, the citrate salt (if present) used in the automatic dishwashing detergent composition is selected from the group consisting of sodium, potassium, and lithium citrate salts (more preferably, the sodium or potassium salts, and most preferably, the sodium salt). More preferably, the citrate salt (if present) used in the automatic dishwashing detergent composition is sodium citrate. Preferably, when the builder used in the automatic dishwashing detergent composition of the present invention comprises a citrate salt, the automatic dishwashing detergent composition preferably comprises 0 to 99 wt. % (preferably, 5 to 75 wt. %, more preferably, 10 to 60 wt. %, and most preferably, 20 to 40 wt. %) of the citrate salt, based on the weight of the automatic dishwashing detergent composition.

[0043] The term "silicate" as used in this specification and the appended claims refers to an alkali metal silicate. Preferably, the silicate used in the automatic dishwashing detergent composition (if present) is selected from the group consisting of sodium, potassium, and lithium silicates (more preferably, the sodium or potassium salts, most preferably, the sodium salts). More preferably, the silicate used in the automatic dishwashing detergent composition (if present) is sodium disilicate. Preferably, the builder used in the automatic dishwashing detergent composition of the present invention includes a silicate. Preferably, when the builder used in the automatic dishwashing detergent composition of the present invention includes a silicate, the automatic dishwashing detergent composition preferably includes 0 to 99 wt. % (preferably 0.1 to 10 wt. %, more preferably 0.5 to 7.5 wt. %, most preferably 0.75 to 3 wt. %) of the silicate, based on the weight of the automatic dishwashing detergent composition.

[0044] Preferably, the automatic dishwashing detergent composition of the present invention further comprises 0 to 15 wt % (more preferably 0.05 to 10 wt %, even more preferably 0.5 to 8 wt %, and most preferably 0.75 to 7 wt %) of a phosphonate based on the weight of the automatic dishwashing detergent composition. More preferably, the automatic dishwashing detergent composition of the present invention further comprises 0 to 15 wt % (more preferably 0.05 to 10 wt %, even more preferably 0.5 to 8 wt %, and most preferably 0.75 to 7 wt %) of a phosphonate based on the weight of the automatic dishwashing detergent composition, and the phosphonate has a low molecular weight having a weight average molecular weight of 1,000 daltons or less. Even more preferably, the automatic dishwashing detergent composition of the present invention comprises 0 to 15 wt. % (more preferably, 0.05 to 10 wt. %, even more preferably, 0.5 to 8 wt. %, and most preferably, 0.75 to 7 wt. %) of a phosphonate, based on the weight of the automatic dishwashing detergent composition, the phosphonate comprising at least one of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and a salt of 1-hydroxyethylidene-1,1-diphosphonic acid. Most preferably, the automatic dishwashing detergent composition of the present invention comprises 0 to 15 wt. % (more preferably, 0.05 to 10 wt. %, even more preferably, 0.5 to 8 wt. %, and most preferably, 0.75 to 7 wt. %) of a phosphonate, based on the weight of the automatic dishwashing detergent composition, the phosphonate being selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts thereof.

[0045] Preferably, the automatic dishwashing detergent composition of the present invention further comprises 0 to 15 wt. % (preferably 0.05 to 10 wt. %, more preferably 0.5 to 8 wt. %, most preferably 0.75 to 7 wt. %) of a poly(acrylic acid) homopolymer, based on the weight of the detergent composition. Preferably, the automatic dishwashing detergent composition of the present invention further comprises 0 to 15 wt. % (preferably 0.05 to 10 wt. %, more preferably 0.5 to 8 wt. %, and most preferably 0.75 to 7 wt. %) of a poly(acrylic acid) homopolymer, based on the weight of the detergent composition, the polyacrylic acid homopolymer having a weight average molecular weight of 1,000 to 10,000 daltons (preferably 1,500 daltons or more, more preferably 2,000 daltons or more, even more preferably 3,000 daltons or more, most preferably 4,000 daltons or more, preferably 7,500 daltons or less, more preferably 7,000 daltons or less, even more preferably 6,000 daltons or less, and most preferably 5,000 daltons or less).

[0046] Preferably, the automatic dishwashing detergent composition of the present invention further comprises 0 to 35 wt. % (more preferably 0 to 30 wt. %, even more preferably 1 to 25 wt. %, and most preferably 5 to 20 wt. %) of a bleaching agent (e.g., sodium percarbonate) based on the weight of the automatic dishwashing detergent composition. The amount of bleaching agent (if present) in the automatic dishwashing detergent composition of the present invention is preferably at a concentration of 1 to 25 wt. % (more preferably 5 to 20 wt. %) based on the weight of the automatic dishwashing detergent composition.

[0047] Fillers included in tablets or powders are inert, water-soluble materials, typically sodium or potassium salts (e.g., sodium sulfate, potassium sulfate, sodium chloride, potassium chloride). In tablets and powders, fillers are typically present in amounts ranging from 0% to 75% by weight. Fillers included in gel formulations typically include those mentioned for use in tablets and powders, as well as water. Fragrances, dyes, suds suppressors, enzymes, and antimicrobial agents typically total no more than 10% by weight, alternatively no more than 5% by weight, of the automatic dishwashing detergent composition.

[0048] The automatic dishwashing detergent compositions of the present invention optionally further comprise an alkaline source. Suitable alkaline sources include, but are not limited to, alkali metal carbonates and alkali metal hydroxides, such as sodium or potassium carbonate, bicarbonates, sesquicarbonates, sodium hydroxide, lithium or potassium hydroxide, or mixtures thereof. Sodium hydroxide is preferred. The amount of alkaline source (if present) in the automatic dishwashing detergent compositions of the present invention is at least 1 wt. % (preferably at least 20 wt. %) and at most 80 wt. % (preferably at most 60 wt. %) based on the weight of the automatic dishwashing detergent composition.

[0049] The automatic dishwashing detergent compositions of the present invention optionally further comprise a bleach activator (e.g., tetraacetylethylenediamine (TAED)). The amount of bleach activator (if present) in the automatic dishwashing detergent compositions of the present invention is preferably at a level of 1 to 10 wt. % (more preferably, 2.5 to 7.5 wt. %) based on the weight of the automatic dishwashing detergent composition.

[0050] Preferably, the automatic dishwashing detergent compositions of the present invention comprise 1 wt. % or less (preferably 0.5 wt. % or less, more preferably 0.2 wt. % or less, even more preferably 0.1 wt. % or less, even more preferably 0.01 wt. % or less, and most preferably below the detection limit) of phosphate (measured as elemental phosphorus) based on the weight of the automatic dishwashing detergent composition. Preferably, the automatic dishwashing detergent compositions of the present invention are phosphate-free.

[0051] Preferably, the automatic dishwashing detergent compositions of the present invention contain 1% by weight or less (preferably, 0.5% by weight or less, more preferably, 0.2% by weight or less, even more preferably, 0.1% by weight or less, even more preferably, 0.01% by weight or less, and most preferably below the limit of detection) of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycine-N,N-diacetic acid, methylglycine-N,N-diacetic acid, 2-hydroxybenzoates, benzoates, benzoyl alcohols, benzoates ... The composition contains a builder selected from the group consisting of hydroxyethyl iminodiacetate, glutamic acid-N,N-diacetate, 3-hydroxy-2,2'-iminodisuccinate, S,S-ethylenediaminedisuccinate aspartic acid-diacetate, N,N'-ethylenediaminedisuccinate, iminodisuccinic acid, aspartic acid, aspartic acid-N,N-diacetate, beta-alanine diacetate, polyaspartic acid, salts thereof, and mixtures thereof. Most preferably, the automatic dishwashing detergent compositions of the present invention contain 0% by weight of a builder selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycine-N,N-diacetic acid, methylglycine-N,N-diacetic acid, 2-hydroxyethyliminodiacetic acid, glutamic acid-N,N-diacetic acid, 3-hydroxy-2,2'-iminodissuccinate, S,S-ethylenediaminedisuccinic acid aspartic acid-diacetic acid, N,N'-ethylenediaminedisuccinic acid, iminodisuccinic acid, aspartic acid, aspartic acid-N,N-diacetic acid, beta-alaninediacetic acid, polyaspartic acid, salts thereof, and mixtures thereof.

[0052] Preferably, the automatic dishwashing detergent compositions of the present invention have a pH (at 1% by weight in water) of at least 7 (preferably 9 or more, more preferably 9.5 or more). Preferably, the automatic dishwashing detergent compositions of the present invention have a pH (at 1% by weight in water) of 13 or less.

[0053] Preferably, the automatic dishwashing detergent composition of the present invention can be formulated in any typical form, such as a tablet, a powder, a block, a single dose, a sachet, a paste, a liquid, or a gel. More preferably, the automatic dishwashing detergent composition of the present invention is formulated as one of a tablet, a powder, a block, a paste, or a gel. Most preferably, the automatic dishwashing detergent composition of the present invention is formulated as a powder.

[0054] Preferably, the automatic dishwashing detergent compositions of the present invention are useful for cleaning items such as dishes and cookware, plates, and the like in automatic dishwashing detergent machines.

[0055] Preferably, the automatic dishwashing detergent composition of the present invention is suitable for use under typical operating conditions. For example, when used in an automatic dishwashing detergent machine, the typical water temperature during the washing process is preferably 20°C to 85°C, preferably 30°C to 70°C. The typical concentration of the automatic dishwashing detergent composition is preferably 0.1 to 1% by weight, preferably 0.2 to 0.7% by weight, as a total percentage of the liquid in the dishwasher. By selecting the appropriate product form and addition time, the automatic dishwashing detergent composition of the present invention can be present in the pre-wash, main wash, penultimate rinse, final rinse, or any combination of these cycles.

[0056] Preferably, the method of cleaning articles in an automatic dishwashing detergent machine of the present invention comprises providing at least one article (e.g., cookware, bakeware, tableware, dishware, flatware, and / or glassware, preferably, the at least one article comprises glassware), providing an automatic dishwashing detergent composition of the present invention, and applying the automatic dishwashing detergent composition to the at least one article (preferably in an automatic dishwashing machine).

[0057] Preferably, the method of cleaning articles in an automatic dishwashing detergent machine of the present invention includes (i) providing at least one article (e.g., cookware, bakeware, tableware, cutlery, flatware, and / or glassware, preferably, the at least one article comprises glassware); and (ii) providing an automatic dishwashing detergent composition of the present invention, the automatic dishwashing detergent composition comprising 50 to 85% by weight of a builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof, the builder comprising a mixture of at least one carbonate and at least one citrate, 0.75 to 7% by weight of a phosphonate, 1.5 to 7.5% by weight of a nonionic surfactant, and 4 to 85% by weight of a nonionic surfactant. and a dispersant hydrophilic block copolymer comprising 7% by weight of carboxylic acid polymer segments comprising structural units of a monoethylenically unsaturated carboxylic acid monomer and poly(alkylene oxide) diol polymer segments consisting of structural units of a poly(alkylene oxide) diol, wherein 90 to 100% by weight of the poly(alkylene oxide) diol polymer segments are esterified with two structural units of the monoethylenically unsaturated carboxylic acid monomer present in the carboxylic acid polymer segments per poly(alkylene oxide) diol polymer segment. [Example]

[0058] Some embodiments of the present invention will now be described in detail in the following examples.

[0059] Synthesis S1: Preparation of poly(acrylic acid) Deionized water (312.50 g) was added to a 2-liter, four-neck round-bottom reactor equipped with an overhead stirrer, thermocouple, heating mantle, adapter inlet, Claisen head fitter with water condenser, and nitrogen inlet. The reactor contents were heated to 95°C under nitrogen. A monomer mixture was prepared by combining deionized water (158.00 g) with acrylic acid (1,090.91 g). A cofeed catalyst solution was prepared by combining sodium persulfate (21.6 g) and deionized water (133.06 g). A chain regulator mixture was prepared by combining sodium bisulfite monohydrate (105.98 g) with deionized water (347 g). The chain regulator mixture (168 g) was charged to the reactor over 10 minutes using an addition funnel. The temperature setpoint was adjusted to 85°C. Once the reactor contents reached 85°C, the catalyst cofeed solution was started and continued for 93 minutes. One minute after the catalyst cofeed solution was started, the monomer mixture and chain regulator feeds were simultaneously started and continued for 90 minutes. An initial exotherm was observed reaching 95°C, but the temperature stabilized and was maintained at 93°C for the duration of the reactant feeds. The reactor contents were maintained at 93°C for an additional 15 minutes to terminate the reaction. The reactor was then vented and cooled to 70°C. Deionized water (19.98 g) was then added to the reactor contents. The reactor contents were allowed to continue cooling to ambient temperature. After the temperature of the reactor contents had decreased to below 40°C, the product was recovered. The product had a solids level of 57.13 wt. %, a pH of 2.47, and a Tg of 77.05°C. Based on aqueous gel permeation chromatography (GPC) analysis, the product had a weight average molecular weight of 1,899 daltons and a number average molecular weight of 660 daltons.

[0060] Synthesis S2-S5: Poly(acrylic acid) / poly(ethylene oxide) diol copolymers Poly(acrylic acid) / poly(ethylene oxide) diol copolymers, S2 to S5, were prepared according to the following procedure. (A) Polyacrylic acid homopolymer (57.13 wt % in water, 18.42 g) with a weight-average molecular weight of 1,800 daltons, prepared according to S1, was added to a 25 mL scintillation vial equipped with a small magnetic stirrer. Then, poly(ethylene oxide) diol (7.02 g) with a weight-average molecular weight listed in Table 1 was added. The contents of the vial were then heated to 70 °C with stirring at 500 rpm for at least 1 hour. After the mixture became clear and was thoroughly mixed, the contents of the vial were poured into a small aluminum pan. The pan was then covered with a piece of aluminum foil, and the edges of the foil were secured by folding over the pan. The aluminum foil was then punctured with a syringe to create a small hole. The aluminum pan was then placed overnight in a vacuum oven at 30 mmHg vacuum with a set-point temperature of 120 °C. The aluminum pan was then removed from the oven and allowed to cool. Once cooled, the product was removed from the aluminum pan and collected.

[0061] [Table 1]

[0062] Synthetic S6:AA / mPEG copolymer Poly(acrylic acid) / poly(ethylene glycol) methyl ether (mPEG) monol copolymer was prepared according to synthesis S2, replacing poly(ethylene oxide) diol with poly(ethylene glycol) methyl ether (mPEG) monol with a weight-average molecular weight of 2,000 daltons.

[0063] Synthetic S7:AA / MPEGMA copolymer A 2-liter, four-neck, round-bottom reactor equipped with an overhead stirrer, thermocouple, heating mantle, adapter inlet, Claisen head fitted with a water condenser, and a nitrogen inlet was charged with deionized water (499.80 g) and phosphoric acid (2.2 g). The reactor contents were heated to 100°C under nitrogen. A monomer mixture containing acrylic acid (174.12 g) and a 50% aqueous solution of methoxypolyethylene glycol methacrylate (MPEGMA) having a weight-average molecular weight of 2,000 (335.24 g) were metered into the reactor over a 5-hour period, followed by a deionized water rinse. A catalyst cofeed solution of ammonium persulfate (18.37 g) and deionized water (96.90 g) was prepared. A 40% aqueous solution of sodium bisulfite chain regulator (46.24 g) was prepared. While the reactor temperature was maintained at 100°C, the catalyst cofeed solution and chain regulator solution were added simultaneously to the reactor over a 5-hour period while the monomer mixture was being added. After the reactant feeds were completed, the reactor contents were stirred for 2 hours while the temperature was maintained at 100°C. The reactor contents were then cooled to room temperature and the pH was adjusted to 7.2 by adding 190.40 g of a 50% aqueous solution of sodium hydroxide over 1 hour. The reactor contents were transferred to a storage bottle after rinsing the reactor with 190.40 g of deionized water. The product polymer had a solids content of 25.91 wt% and a pH of 7.78.

[0064] Based on gel permeation chromatography (GPC) analysis, the product polymer had a weight average molecular weight of 4,336 daltons and a number average molecular weight of 1,195 daltons. The product polymer was determined to consist primarily of a copolymer of acrylic acid and MPEGMA by two-dimensional liquid chromatography analysis.

[0065] Synthesis S8: Poly(acrylic acid) polymerized in the presence of poly(ethylene glycol) (following the process illustrated in U.S. Patent No. 5,318,719) A 2-liter, four-neck flask equipped with a mechanical stirrer, a reflux condenser, and inlets for the gradual addition of the monomer, caustic solution, and initiator solution was charged with deionized water (380.0 g), 0.15 wt % aqueous copper(II) sulfate pentahydrate solution (25.3 g), and polyethylene glycol (152.0 g) having a weight-average molecular weight of 3,350 Daltons. The contents of the reactor were heated to reflux. Then, glacial acrylic acid (383.84 g), a 30% hydrogen peroxide initiator solution (126.67 g), and a 50% aqueous sodium hydroxide solution (316.92 g) were added linearly and separately to the contents of the flask over a 2-hour period. Upon completion of the addition, the system was maintained at reflux for an additional 20 minutes. The system was then cooled to 60°C. Then, 50% aqueous sodium hydroxide solution (76.0 g) was added dropwise to the contents of the flask as a post-neutralization.

[0066] Based on gel permeation chromatography (GPC) analysis, the product has a weight-average molecular weight of 18,067 daltons and a number-average molecular weight of 3,370 daltons. The product was determined by two-dimensional liquid chromatography analysis to consist primarily of two distinct homopolymers and a small amount of poly(acrylic acid) / poly(ethylene glycol) copolymer.

[0067] Comparative Examples CF1-CF2 and Example F1: Dishwashing Formulations Dishwashing compositions were prepared in each of Comparative Examples CF1-CF2 and Example F1 having the ingredient formulations specified in Table 2.

[0068] [Table 2]

[0069] Comparative Examples CF3-CF4 and Examples F2-F5: Dishwashing Formulations Dishwashing compositions were prepared in each of Comparative Examples CF3-CF4 and Examples F2-F5 having the ingredient formulations specified in Table 3.

[0070] [Table 3]

[0071] Comparative Examples CF5-CF8 and Examples F6-F7: Dishwashing Formulations Dishwashing compositions were prepared in each of Comparative Examples CF5-CF8 and Examples F6-F7 having the ingredient formulations specified in Table 4.

[0072] [Table 4]

[0073] Procedure for preparing food stains The STIWA food soils described in Table 5 were prepared by the following procedure. a) Boil water. b) Mix instant gravy, benzoic acid, and potato starch in a paper cup and then add the mixture to boiling water. c) Add milk and margarine to the product of (b). d) Cool the product of (c) to about 40°C. e) Add the cooled mixture from (d) to a kitchen mixer (Polytron). f) In a separate paper cup, combine the egg yolks, ketchup, and mustard and mix with a spoon. g) Add the product of (f) to the mixture of (e) in the blender with continuous stirring. h) Blend the product of (g) in a blender for 5 minutes. i) While stirring the product of (h), remove a 50 g aliquot of the product food soil mixture and place it in a wide-mouth vial. j) 50g aliquots are then placed in the freezer. k) A 50g aliquot of the frozen food soil from (j) is placed in the dishwasher at the start of the main wash.

[0074] [Table 5]

[0075] Dishwashing test conditions Machine: Miele SS-ADW, model G1223SC Labor. Wash at 65°C - 30 minute wash cycle, followed by two rinse cycles at 65°C rinse water temperature, and a final 30 minute dry step. After the dry cycle was completed, the dishwasher door was left open for 30 minutes to allow steam to evaporate. Water: The initial water supplied to the dishwasher had a total water hardness of 40°F hardness, Ca 2+ :Mg 2+ = 3:1, and a temporary water hardness of 27°fH. Food soils: 50 g of the composition described in Table 3 was introduced into the wash liquor while frozen in a cup. Each dishwashing composition from Comparative Examples CF1-CF8 and Examples F1-F7 was tested. The food soil was added at the beginning of the wash cycle. The test detergent was also dosed into the dishwasher at the beginning of the wash cycle. Each test detergent was dosed at 17 g (solids basis) per wash. The number of wash cycles used in this experiment to induce filming and spotting was 14.

[0076] Schott® Glass Ratings After 14 wash cycles under the above dishwashing test conditions, the Schott® glasses were allowed to air dry for at least 18 hours. After air drying following the 14th wash, filming and spotting ratings were determined in a light box with controlled lighting from below. The Schott® tumblers were scored for filming and spotting according to ASTM methods, ranging from 1 (no filming / spotting) to 5 (severe filming / spotting). Average scores of 1-5 for filming and spotting were calculated, as reported in Tables 6-8.

[0077] [Table 6]

[0078] [Table 7]

[0079] [Table 8]

[0080] 304 Polished Stainless Steel Coupon Rating After 14 wash cycles under the above dishwashing test conditions, the polished 304 stainless steel coupons were allowed to dry in ambient air for at least 18 hours. After ambient air drying, filming and spotting ratings were determined in a light box with controlled lighting. The polished 304 stainless steel coupons were scored for filming and spotting on a scale of 1 (no filming / spotting) to 5 (severe filming / spotting). The average scores of 1 to 5 for filming and spotting were determined, as reported in Tables 9-11.

[0081] [Table 9]

[0082] [Table 10]

[0083] [Table 11]

[0084] Evaluation of clear plastic beverage containers made from acrylic poly(styrene-acrylic). After 14 wash cycles under the above dishwashing test conditions, the plastic beverage containers were allowed to air dry for at least 18 hours. After air drying, filming and spotting ratings were determined in a light box with controlled lighting. The plastic beverage containers were scored for filming and spotting on a scale ranging from 1 (no filming / spotting) to 5 (severe filming / spotting). The average scores of 1 to 5 for filming and spotting were calculated, as reported in Tables 12-14.

[0085] [Table 12]

[0086] [Table 13]

[0087] [Table 14]

[0088] Additional Plastic Test Substrate Evaluation After 14 wash cycles under the above dishwashing test conditions, additional plastic substrates—opaque plastic poly(high density polyethylene) lids (OPL) from food storage containers, blue translucent plastic poly(propylene) lids (Ziploc) from ZIPLOC® food storage containers, and Ny-Hi 登録商標 White translucent plastic poly(propylene) lids (Ny-Hi) from food storage containers were allowed to dry in open air for at least 18 hours. After air drying, filming and spotting ratings were determined in a light box with controlled lighting. Additional plastic beverage containers were scored for filming and spotting on a scale of 1 (no filming / spotting) to 5 (severe filming / spotting). Averages of 1 to 5 for filming and spotting were calculated, as reported in Tables 15-17.

[0089] [Table 15]

[0090] [Table 16]

[0091] [Table 17]

Claims

1. a cleaning surfactant; 1. A dispersant hydrophilic block copolymer comprising: a carboxylic acid polymer segment comprising a monoethylenically unsaturated carboxylic acid monomer unit; and A poly(alkylene oxide) diol polymer segment consisting of poly(alkylene oxide) diol structural units. and a dispersant hydrophilic block copolymer comprising: 90 to 100 weight percent of the poly(alkylene oxide) diol polymer segments are esterified with two monoethylenically unsaturated carboxylic acid monomer structural units present in the carboxylic acid polymer segments per poly(alkylene oxide) diol polymer segment.

2. 40 to 100 weight percent of the dispersant hydrophilic block copolymer is a copolymer of formula (I) 【Chemistry 1】 wherein z １ is 1, and x １ is 0 to 139, and r １ is 0 to 139, and x １ +z １ +r １ = 7 to 140, and z ２ is 1, and x ２ is 0 to 139, and r ２ is 0 to 139, and x ２ +z ２ +r ２ = 7 to 140, and each R １ are independently hydrogen and C １～３ 2. The detergent composition of claim 1, wherein y is selected from the group consisting of alkyl groups, and y is an average of 4 to 84.

3. the molar ratio of poly(alkylene oxide) diol polymer segments to carboxylic acid polymer segments in the dispersant hydrophilic block copolymer is from 0.005 to 0.03; the dispersant hydrophilic block copolymer comprises 0 to 60 weight percent residual carboxylic acid polymer segments that remain unesterified with poly(alkylene oxide) diol polymer segments; 3. The detergent composition of claim 2, wherein the dispersant hydrophilic block copolymer comprises 0 to 1 wt. % residual poly(alkylene oxide) diol polymer segments remaining unesterified with carboxylic acid polymer segments.

4. 4. The detergent composition of claim 3, further comprising a poly(acrylic acid) polymer.

5. 5. The detergent composition of claim 4, selected from laundry detergents and dishwashing detergents.

6. The detergent composition is an automatic dishwashing detergent composition, the cleaning surfactant comprises a nonionic surfactant, and the automatic dishwashing detergent composition comprises: Builder and a phosphonate; an optional additive selected from the group consisting of a carrier, a bleaching agent, a bleach activator, an enzyme, a filler, and mixtures thereof; 6. The detergent composition of claim 5, further comprising:

7. 7. The automatic dishwashing detergent composition of claim 6, containing less than 0.1% by weight of phosphate, measured as elemental phosphorus, based on the weight of the automatic dishwashing detergent composition.

8. 8. The dishwashing detergent formulation of claim 7, containing 0% by weight, based on the weight of the automatic dishwashing detergent composition, of a builder selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycine-N,N-diacetic acid, methylglycine-N,N-diacetic acid, 2-hydroxyethyliminodiacetic acid, glutamic acid-N,N-diacetic acid, 3-hydroxy-2,2'-iminodissuccinate, S,S-ethylenediaminedisuccinic acid aspartic acid-diacetic acid, N,N'-ethylenediaminedisuccinic acid, iminodisuccinic acid, aspartic acid, aspartic acid-N,N-diacetic acid, beta-alaninediacetic acid, polyaspartic acid, salts thereof, and mixtures thereof.

9. 50 to 85 weight percent of the builder selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof, based on the weight of the automatic dishwashing detergent composition; 0.75 to 7 wt. % of said phosphonate, based on the weight of said automatic dishwashing detergent composition; 1.5 to 7.5 wt. % of said nonionic surfactant, based on the weight of said automatic dishwashing detergent composition; 9. The automatic dishwashing detergent composition of claim 8, comprising 4 to 7 wt. % of said dispersant hydrophilic block copolymer, based on the weight of said automatic dishwashing detergent composition.

10. 1. A method of cleaning items in an automatic dishwashing detergent machine, comprising: providing at least one item; Providing an automatic dishwashing detergent composition according to claim 6; applying the automatic dishwashing detergent composition to the at least one item in the automatic dishwashing detergent machine.