Automatic dishwasher formulation containing a dispersant copolymer blend

Abstract

1. An automatic dishwashing composition comprising a builder, a nonionic surfactant, and 60 to 98% by weight of a compound of formula I, wherein each R 1 are independently selected from hydrogen and —CH groups), and 2 to 40% by weight of structural units of formula II, 2 independently, -C 1-4 alkyl groups, and each R 3 are independently selected from hydrogen and methyl groups; and a second dispersant polymer comprising 60 to 98 wt. % of structural units of formula I, 1 are independently selected from hydrogen and —CH groups), and 2 to 40% by weight of structural units of formula II, 2 independently, -C 1-4 alkyl groups, and each R 3 and a second dispersant polymer comprising structural units where R is independently selected from hydrogen and a methyl group, wherein the first dispersant polymer and the second dispersant polymer are different.

Description

Technical Field

[0001] The present invention relates to blends of dispersant copolymers for use in automatic dishwashing formulations. In particular, the present invention relates to an automatic dishwashing composition comprising (A) a builder, (B) a nonionic surfactant, and (C) a first dispersant polymer comprising (i) 60 to 98% by weight, based on the solids weight of the first dispersant polymer, of structural units of formula I

[0002]

Chemical Formula

[0003]

Chemical Formula

Background Art

[0004] Automatic dishwashing compositions are generally recognized as a distinct category of detergent compositions from those used for cloth washing or water treatment. Users expect automatic dishwashing compositions to result in a spot-free and film-free appearance on the washed items after the completion of the washing cycle.

[0005] Phosphate-free automatic dishwashing compositions are increasingly desirable. Phosphate-free automatic dishwashing compositions typically rely on non-phosphate builders, such as citrates, carbonates, silicates, disilicates, bicarbonates, aminocarboxylates, and other salts, to capture calcium and magnesium from hard water, leaving insoluble, visible deposits when dried.

[0006] Currently available polymers for use in phosphate-free automatic dishwashing compositions to combat the formation of undesirable deposits on glassware include polyacrylic acid polymers, as well as copolymers of acrylic acid with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and sodium styrene sulfonate (SSS). However, polyacrylic acid polymers cannot prevent certain film deposits on glassware (e.g., magnesium disilicate and calcium phosphonate scales) that appear as a clear blue to blue / white film on glassware and a brownish film on stainless steel. Copolymers of acrylic acid with sulfonated monomers are excellent at preventing silicate and phosphonate scales, but such copolymers are not particularly effective at preventing carbonate scales. In addition, such polymers tend to adversely affect spot formation, requiring the use of strong chelating agents or special surfactants, which leads to an undesirable increase in the overall cost of the dishwashing composition.

[0007] Therefore, there is still a need for new dispersant polymers and dispersant polymer blends for use in automatic dishwashing formulations. Specifically, there is still a need for new dispersant polymer blends for use in automatic dishwashing formulations that provide suitable overall gloss performance, particularly when incorporated into phosphate-free formulations. SUMMARY OF THE INVENTION

[0008] The present invention is an automatic dishwashing composition comprising: (A) a builder; (B) a nonionic surfactant; (C) a first dispersant polymer comprising (i) 60 to 98% by weight, based on the solids weight of the first dispersant polymer, of structural units of formula I

[0009]

Chemical formula

[0010]

Chemical formula

[0011] The present invention relates to an automatic dishwashing composition comprising (A) a builder, (B) a nonionic surfactant, and (C) a first dispersant polymer, wherein (i) based on the solids content weight of the first dispersant polymer, 60 to 80% by weight of formula I (wherein each R 1 (ii) a structural unit (independently selected from hydrogen and -CH3 groups), and based on the solid content weight of the first dispersant polymer, 20 to 40% by weight of Formula II (wherein each R 2 -C 1-4 Selected from alkyl groups, each R 3 (i) a first dispersant polymer comprising structural units (which are independently selected from hydrogen and methyl groups), and (d) a second dispersant polymer comprising (i) >80~98% by weight of formula I (wherein each R 1 (ii) Based on the structural units of the second dispersant polymer (which are independently selected from hydrogen and -CH3 groups), 2 to <20% by weight of Formula II (wherein each R 2 -C 1-4 Selected from alkyl groups, each R 3 The present invention provides an automatic dishwashing composition comprising a second dispersant polymer, which independently contains structural units (selected from hydrogen and methyl groups), wherein the first and second dispersant polymers are different.

[0012] The present invention relates to an automatic dishwashing composition, comprising: (A) 40 to 70% by weight of a builder based on the dry weight of the automatic dishwashing composition, wherein the builder is selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof; (B) 5 to 17.5% by weight of a nonionic surfactant based on the dry weight of the automatic dishwashing composition, wherein the nonionic surfactant comprises a mixture of nonionic alcohol alkoxylates; and (C) 2 to 4% by weight of a first dispersant polymer based on the dry weight of the automatic dishwashing composition, wherein (i) 60 to 80% by weight of formula I (wherein each R) based on the solids content of the first dispersant polymer. 1 (ii) a structural unit (independently selected from hydrogen and -CH3 groups), and based on the solid content weight of the first dispersant polymer, 20 to 40% by weight of Formula II (wherein each R 2 -C 1-4 Selected from alkyl groups, each R 3 (D) a first dispersant polymer comprising structural units (selected independently from hydrogen and methyl groups), and (D) 2 to 4% by weight of a second dispersant polymer based on the dry weight of the automatic dishwashing composition, and (i) >80 to 98% by weight of formula I (wherein each R is selected) based on the solids content of the second dispersant polymer. 1 (ii) Based on the structural units of the second dispersant polymer (which are independently selected from hydrogen and -CH3 groups), 2 to <20% by weight of Formula II (wherein each R 2 -C 1-4 Selected from alkyl groups, each R 3The present invention provides an automatic dishwashing composition comprising: (E) a second dispersant polymer containing structural units (independently selected from hydrogen and methyl groups); (F) 2 to 7.5% by weight of a phosphonate based on the dry weight of the automatic dishwashing composition; (G) 5 to 12% by weight of a bleaching agent based on the dry weight of the automatic dishwashing composition, wherein the bleaching agent is selected from the group consisting of sodium percarbonate and sodium perborate; (H) 3 to 6% by weight of a protease based on the dry weight of the automatic dishwashing composition; and (I) 2.5 to 4.5% by weight of amylase based on the dry weight of the automatic dishwashing composition.

[0013] The present invention provides a method for washing articles in an automatic dishwasher, comprising: preparing at least one article; preparing an automatic dishwashing composition according to the present invention; and applying the automatic dishwashing composition to at least one article. [Modes for carrying out the invention]

[0014] Surprisingly, when the dispersant polymer blend of the present invention is incorporated into an automatic dishwashing composition (particularly a phosphate-free automatic dishwashing composition), as specifically described herein, it has been found that the dispersant polymer blend of the present invention provides, surprisingly, better overall gloss performance (i.e., the sum of film-forming and spot-forming performance on multiple substrates (glass tumblers, wine glasses, PMMA glasses, and stainless steel butter dishes)) compared to conventional dispersant polymers.

[0015] Unless otherwise indicated, ratios, percentages, parts, etc., are expressed by weight. Weight percentages (or weight %) in a composition are based on dry weight, i.e., the percentage excluding all water that may be present in the composition. Percentages of monomer units in a polymer are based on solid weight, i.e., the percentage excluding all water present in the polymer emulsion.

[0016] Where 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 the conventional manner using gel permeation chromatography (GPC) and conventional standards such as polystyrene standards. The GPC technique is discussed in detail in *Modem Size Exclusion Chromatography*, WWYau, JJKirkland, DDBly; Wiley-Interscience, 1979, and in *A Guide to Materials Characterization and Chemical Analysis*, JPSibilia; VCH, 1988, pp. 81–84. Weight-average molecular weight is 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 (preferably ≤0.5% by weight, more preferably ≤0.2% by weight, even more preferably ≤0.01% by weight, still more preferably ≤0.001% by weight, most preferably less than the detection limit) of phosphate (measured as elemental phosphorus).

[0018] As used herein and in the appended claims, the term “structural unit” refers to the remnant of the monomer shown, and therefore the structural units of (meth)acrylic acid are as follows:

[0019] [ka] In the formula, the dotted line represents the bond point to the polymer backbone, R 1 In acrylic acid, the structural unit is hydrogen, and in methacrylic acid, it is a -CH3 group.

[0020] Preferably, the automatic dishwashing composition of the present invention comprises (A) a builder (preferably 1 to 95% by weight (more preferably ≥20% by weight, even more preferably ≥30% by weight, even more preferably ≥40% by weight, most preferably ≥50% by weight, preferably ≤90% by weight, more preferably ≤80% by weight, even more preferably ≤70% by weight, most preferably ≤60% by weight) based on the dry weight of the automatic dishwashing composition) (preferably the builder comprises a mixture of at least one carbonate and at least one citrate) and (B) a nonionic surfactant ( Preferably, 0.2 to 25% by weight (more preferably 2.5 to 20% by weight, most preferably 5 to 17.5% by weight) of a nonionic surfactant (preferably the nonionic surfactant is a nonionic alcohol alkoxylate), and (C) a first dispersant polymer (preferably 0.1 to 12% by weight (more preferably 0.5 to 10% by weight, even more preferably 1 to 6% by weight, most preferably 2 to 4% by weight) based on the dry weight of the first dispersant polymer, and (i) 60 to 98% by weight (preferably 60 to 80% by weight, more preferably 65 to 77.5% by weight, most preferably 70 to 75% by weight) of formula I

[0021] [ka] (In the formula, each R 1 (ii) a structural unit (selected independently from hydrogen and -CH3 groups), and based on the solids content of the first dispersant polymer, 2 to 40% by weight (preferably 20 to 40% by weight, more preferably 22.5 to 35% by weight, most preferably 25 to 30% by weight) of Formula II

[0022] [ka] (In the formula, each R 2 -C 1-4 Selected from alkyl groups, each R 3(i) a first dispersant polymer comprising structural units (independently selected from hydrogen and methyl groups), and (D) a second dispersant polymer (preferably 0.1 to 12% by weight (more preferably 0.5 to 10% by weight, even more preferably 1 to 6% by weight, most preferably 2 to 4% by weight) based on the dry weight of the automatic dishwashing composition, wherein (i) 60 to 98% by weight (preferably >80 to 98% by weight, more preferably 85 to 97.5% by weight, most preferably 88 to 95% by weight) of formula I (wherein each R 1 (ii) a structural unit (selected independently from hydrogen and -CH3 groups), and based on the solid content weight of the second dispersant polymer, 2 to 40% by weight (preferably 2 to <20% by weight, more preferably 2.5 to 15% by weight, most preferably 5 to 12% by weight) of formula II (wherein each R 2 -C 1-4 Selected from alkyl groups, each R 3 The first dispersant polymer and the second dispersant polymer independently contain structural units (selected from hydrogen and methyl groups), and the two dispersant polymers are different.

[0023] Preferably, the automatic dishwashing composition of the present invention includes a builder. Preferably, the automatic dishwashing composition of the present invention includes a builder comprising a mixture of at least one carbonate and at least one citrate. More preferably, the automatic dishwashing composition of the present invention includes a builder comprising at least one carbonate, at least one citrate, and a mixture of at least one citrate. Even more preferably, the automatic dishwashing composition of the present invention includes a builder comprising a mixture of sodium carbonate, sodium percarbonate, and sodium citrate. Most preferably, the automatic dishwashing composition of the present invention includes a builder comprising a mixture of sodium carbonate, sodium percarbonate, sodium silicate, and sodium citrate.

[0024] More preferably, the automatic dishwashing composition of the present invention contains 1 to 95% by weight of builder, based on the dry weight of the automatic dishwashing composition. Preferably, the automatic dishwashing composition of the present invention contains ≥1% by weight (preferably ≥20% by weight, more preferably ≥30% by weight, even more preferably ≥40% by weight, most preferably ≥50% by weight) of builder, based on the dry weight of the automatic dishwashing composition. Preferably, the automatic dishwashing composition of the present invention contains ≤90% by weight (preferably ≤80% by weight, more preferably ≤70% by weight, most preferably ≤60% by weight) of builder, based on the dry weight of the automatic dishwashing composition. The weight percentages of carbonate, citrate, and silicate builders are based on the actual weight of the salts containing metal ions.

[0025] As used herein and in the appended claims, the term “carbonate” refers to alkali metal or ammonium salts of carbonates, bicarbonates, percarbonates, and / or sesquicarbonates. Preferably, the carbonate used in the automatic dishwashing composition (if any) is selected from the group consisting of sodium, potassium, and lithium carbonates (more preferably sodium or potassium salts, most preferably sodium salts). The percarbonate used in the automatic dishwashing composition (if any) is selected from the group consisting of sodium, potassium, lithium, and ammonium salts (more preferably sodium or potassium salts, most preferably sodium salts). More preferably, the carbonate used in the automatic dishwashing composition (if any) comprises at least one of sodium carbonate, sodium bicarbonate, and sodium percarbonate. Preferably, if the builder used in the automatic dishwashing composition of the present invention contains carbonates, the automatic dishwashing composition preferably contains 0 to 97% by weight (preferably 10 to 75% by weight, more preferably 20 to 60% by weight, most preferably 25 to 50% by weight) of carbonates based on the dry weight of the automatic dishwashing composition.

[0026] As used herein and in the appended claims, the term “citrate” refers to an alkali metal salt of citrate. Preferably, the citrate used in the automatic dishwashing composition (if any) is selected from the group consisting of sodium, potassium, and lithium citrates (more preferably sodium or potassium salts, most preferably sodium salts). More preferably, the citrate used in the automatic dishwashing composition (if any) is sodium citrate. Preferably, if the builder used in the automatic dishwashing composition of the present invention contains a citrate, the automatic dishwashing composition preferably contains 0 to 97% by weight (preferably 5 to 75% by weight, more preferably 10 to 50% by weight, most preferably 15 to 30% by weight) of citrate based on the dry weight of the automatic dishwashing composition.

[0027] As used herein and in the appended claims, the term “silicate” refers to alkali metal silicates. Preferably, the silicate used in the automatic dishwashing composition (if any) is selected from the group consisting of sodium, potassium, and lithium silicates (more preferably sodium or potassium salts, most preferably sodium salts). More preferably, the silicate used in the automatic dishwashing composition (if any) is sodium disilicate. Preferably, silicates are used as builders in the automatic dishwashing composition of the present invention. Preferably, if the builder used in the automatic dishwashing composition of the present invention contains silicates, the automatic dishwashing composition preferably contains 0 to 97% by weight (preferably 0.1 to 10% by weight, more preferably 0.5 to 7.5% by weight, most preferably 0.75 to 4% by weight) of silicate based on the dry weight of the automatic dishwashing composition.

[0028] Preferably, the automatic dishwashing composition of the present invention contains 0.2 to 25% by weight (preferably 2.5 to 20% by weight, more preferably 5 to 17.5% by weight) of a nonionic surfactant based on the dry weight of the automatic dishwashing composition. More preferably, the automatic dishwashing composition of the present invention contains 0.2 to 25% by weight (preferably 2.5 to 20% by weight, more preferably 5 to 17.5% by weight) of a nonionic surfactant based on the dry weight of the automatic dishwashing composition, and the surfactant contains at least one of alcohol alkoxylates. Most preferably, the automatic dishwashing composition of the present invention contains 0.2 to 25% by weight (preferably 2.5 to 20% by weight, more preferably 5 to 17.5% by weight) of a nonionic surfactant based on the dry weight of the automatic dishwashing composition, and the nonionic surfactant is a blend of alcohol alkoxylate surfactants (preferably a blend of at least two different nonionic alcohol alkoxylate surfactants, more preferably a blend of two to three different nonionic alcohol alkoxylate surfactants).

[0029] Preferably, the automatic dishwashing composition of the present invention contains 0.2 to 25% by weight (preferably 2.5 to 20% by weight, more preferably 5 to 17.5% by weight) of a nonionic surfactant based on the dry weight of the automatic dishwashing composition, wherein the nonionic surfactant is of formula III

[0030] [ka] (In the formula, w is an average of 5 to 45 (preferably 7 to 40), R 4 It consists of hydrogen and linear or branched C 1-20 Alkyl alkyl groups (preferably hydrogen and linear or branched C) 1-15 Alkyl alkyl groups, more preferably hydrogen and linear C 1-15 Selected from groups consisting of alkyl groups, (wherein R 5 C is linear or branched 1-20 Alkyl alkyl groups (preferably linear C) 1-20 (Alkyl alkyl group), and each R 6These are hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-butyl group, and 2-methyl-2-butyl group (preferably hydrogen, methyl group, and ethyl group), however, R 4 and R 5 The total number of carbon atoms is 5 to 21 (preferably 6 to 20 carbon atoms, more preferably 7 to 18) (preferably the nonionic surfactant is a blend of at least two different nonionic surfactants according to formula III, and more preferably the nonionic surfactant is a blend of two to three different nonionic surfactants according to formula III). More preferably, the automatic dishwashing composition of the present invention comprises a concentrated hard surface cleaning composition, the concentrated hard surface cleaning composition comprising 0.2 to 25% by weight (preferably 2.5 to 20% by weight, more preferably 5 to 17.5% by weight) of a nonionic surfactant based on the weight of the concentrated hard surface cleaning composition, the nonionic surfactant being formula III (wherein w is on average 7 to 40, R 4 It consists of hydrogen and linear C 1-15 Selected from the group consisting of alkyl groups, R 5 C is linear or branched 1-20 It is an alkyl group, however, R 4 and R 5 It contains a nonionic surfactant of formula III (where the total number of carbon atoms is 6 to 20). Most preferably it contains 0.2 to 25% by weight (preferably 2.5 to 20% by weight, more preferably 5 to 17.5% by weight) of a nonionic surfactant, wherein the nonionic surfactant is of formula III (wherein w is on average 7 to 40, and R 4 It consists of hydrogen and linear C 1-15 Selected from the group consisting of alkyl groups, R 5 is linear C 1-20 It is an alkyl group, however, R 4 and R 5 It contains a nonionic surfactant (the total number of carbon atoms is between 7 and 18).

[0031] Preferably, the automatic dishwashing composition of the present invention contains a first dispersant polymer. More preferably, the automatic dishwashing composition of the present invention contains 0.1 to 12% by weight of the first dispersant polymer based on the dry weight of the automatic dishwashing composition. Even more preferably, the automatic dishwashing composition of the present invention contains 0.5 to 10% by weight of the first dispersant polymer based on the dry weight of the automatic dishwashing composition. Even more preferably, the automatic dishwashing composition of the present invention contains 1 to 6% by weight of the first dispersant polymer based on the dry weight of the automatic dishwashing composition. Most preferably, the automatic dishwashing composition of the present invention contains 2 to 4% by weight of the first dispersant polymer based on the dry weight of the automatic dishwashing composition.

[0032] Preferably, the first dispersant polymer used in the automatic dishwashing composition of the present invention is 60 to 98% by weight (preferably 60 to 80% by weight, more preferably 65 to 77.5% by weight, most preferably 70 to 75% by weight) of formula (I) (wherein each R) based on the solids content weight of the first dispersant polymer. 1 The first dispersant polymer used in the automatic dishwashing composition of the present invention contains 60 to 98% by weight (preferably 60 to 80% by weight, more preferably 65 to 77.5% by weight, most preferably 70 to 75% by weight) of formula I (wherein R) based on the solids weight of the first dispersant polymer. 1 It contains structural units that are hydrogen in an amount of 75-100 mol% (preferably 90-100 mol%, more preferably 98-100 mol%, even more preferably ≥99 mol%, most preferably 100 mol%).

[0033] Preferably, the first dispersant polymer used in the automatic dishwashing composition of the present invention is a compound of formula II (wherein each R) of which 2 to 40% by weight (preferably 20 to 40% by weight, more preferably 22.5 to 35% by weight, most preferably 25 to 30% by weight) based on the solids content weight of the first dispersant polymer. 2 -C 1-4Selected from alkyl groups (preferably methyl, ethyl, and butyl groups, more preferably ethyl and butyl groups, more preferably ethyl group), each R 3 The first dispersant polymer used in the automatic dishwashing composition of the present invention comprises 2 to 40% by weight (preferably 20 to 40% by weight, more preferably 22.5 to 35% by weight, most preferably 25 to 30% by weight) of formula II (wherein each R is selected independently). 2 The groups are independently selected from ethyl and butyl groups, and each R 3 R comprises structural units (which are independently selected from hydrogen and methyl groups). Most preferably, the first dispersant polymer used in the automatic dishwashing composition of the present invention comprises 2 to 40% by weight (preferably 20 to 40% by weight, more preferably 22.5 to 35% by weight, most preferably 25 to 30% by weight) of structural units of formula II, based on the solids weight of the first dispersant polymer, 2 R is an ethyl group in 75-100 mol% (preferably 90-100 mol%, more preferably 98-100 mol%, most preferably 100 mol%) of the structural units of formula II in the first dispersant polymer, 3 This is hydrogen in the first dispersant polymer at a concentration of 75-100 mol% (preferably 90-100 mol%, more preferably 98-100 mol%, and most preferably 100 mol%) of the structural units of formula II.

[0034] Preferably, the first dispersant polymer used in the automatic dishwashing composition of the present invention has a weight-average molecular weight of 4,000 to 50,000 Daltons. More preferably, the first dispersant polymer used in the automatic dishwashing composition of the present invention has a weight-average molecular weight of 4,200 to 25,000 Daltons. Even more preferably, the first dispersant polymer used in the automatic dishwashing composition of the present invention has a weight-average molecular weight of 4,500 to 15,000 Daltons. Most preferably, the first dispersant polymer used in the automatic dishwashing composition of the present invention has a weight-average molecular weight of 4,750 to 10,000 Daltons.

[0035] Preferably, the automatic dishwashing composition of the present invention contains a second dispersant polymer. More preferably, the automatic dishwashing composition of the present invention contains 0.1 to 12% by weight of the second dispersant polymer based on the dry weight of the automatic dishwashing composition. Even more preferably, the automatic dishwashing composition of the present invention contains 0.5 to 10% by weight of the second dispersant polymer based on the dry weight of the automatic dishwashing composition. Even more preferably, the automatic dishwashing composition of the present invention contains 1 to 6% by weight of the second dispersant polymer based on the dry weight of the automatic dishwashing composition. Most preferably, the automatic dishwashing composition of the present invention contains 2 to 4% by weight of the second dispersant polymer based on the dry weight of the automatic dishwashing composition.

[0036] Preferably, the second dispersant polymer used in the automatic dishwashing composition of the present invention is 60 to 98% by weight (preferably >80 to 98% by weight, more preferably 85 to 97.5% by weight, most preferably 88 to 95% by weight) of formula (I) (wherein each R) based on the solids content weight of the second dispersant polymer. 1 The first dispersant polymer contains structural units (selected independently from hydrogen and -CH3 groups). More preferably, the second dispersant polymer used in the automatic dishwashing composition of the present invention contains 60 to 98% by weight (preferably >80 to 98% by weight, more preferably 85 to 97.5% by weight, most preferably 88 to 95% by weight) of formula I (wherein R) based on the solids weight of the second dispersant polymer. 1 It contains structural units that are hydrogen in an amount of 75-100 mol% (preferably 90-100 mol%, more preferably 98-100 mol%, even more preferably ≥99 mol%, most preferably 100 mol%).

[0037] Preferably, the second dispersant polymer used in the automatic dishwashing composition of the present invention contains 2 to 40% by weight (preferably 2 to <20% by weight, more preferably 2.5 to 15% by weight, most preferably 5 to 12% by weight) of formula II (wherein each R) based on the solids content weight of the second dispersant polymer.2 -C 1-4 Selected from alkyl groups (preferably methyl, ethyl, and butyl groups, more preferably ethyl and butyl groups, more preferably ethyl group), each R 3 The first dispersant polymer comprises structural units (which are independently selected from hydrogen and methyl groups). More preferably, the second dispersant polymer used in the automatic dishwashing composition of the present invention is 2 to 40% by weight (preferably 2 to <20% by weight, more preferably 2.5 to 15% by weight, most preferably 5 to 12% by weight) of formula II (wherein each R is selected), based on the solids weight of the second dispersant polymer. 2 The groups are independently selected from ethyl and butyl groups, and each R 3 The second dispersant polymer used in the automatic dishwashing composition of the present invention contains 2 to 40% by weight (preferably 2 to <20% by weight, more preferably 2.5 to 15% by weight, most preferably 5 to 12% by weight) of formula II (wherein R, R) based on the solids content weight of the second dispersant polymer. 2 It is 75-100 mol% (preferably 90-100 mol%, more preferably 98-100 mol%, most preferably 100 mol%), and is an ethyl group, R 3 It contains structural units (which are hydrogen) in an amount of 75-100 mol% (preferably 90-100 mol%, more preferably 98-100 mol%, and most preferably 100 mol%).

[0038] Preferably, the second dispersant polymer used in the automatic dishwashing composition of the present invention has a weight-average molecular weight of 1,000 to <4,000 Daltons. More preferably, the second dispersant polymer used in the automatic dishwashing composition of the present invention has a weight-average molecular weight of 1,200 to 3,750 Daltons. Even more preferably, the second dispersant polymer used in the automatic dishwashing composition of the present invention has a weight-average molecular weight of 1,500 to 3,500 Daltons. Most preferably, the second dispersant polymer used in the automatic dishwashing composition of the present invention has a weight-average molecular weight of 1,750 to 3,250 Daltons.

[0039] Preferably, both the first and second dispersant polymers used in the automatic dishwashing composition of the present invention contain ≤0.3% by weight (more preferably ≤0.1% by weight, even more preferably ≤0.05% by weight, still more preferably ≤0.03% by weight, and most preferably ≤0.01% by weight) structural units of polyethylenically unsaturated crosslinked monomers.

[0040] Preferably, both the first and second dispersant polymers used in the automatic dishwashing composition of the present invention contain ≤1% by weight (preferably ≤0.5% by weight, more preferably ≤0.001% by weight, even more preferably ≤0.0001% by weight, most preferably <detection limit) of sulfonated monomer structural units. More preferably, both the first and second dispersant polymers used in the automatic dishwashing composition of the present invention contain ≤1% by weight (preferably ≤0.5% by weight, more preferably ≤0.001% by weight, even more preferably ≤0.0001% by weight, most preferably < the detection limit) of structural units of sulfonated monomers selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamide-2-methylpropanesulfonic acid, 4-styrenesulfonic acid, vinylsulfonic acid, 3-allyloxysulfonic acid, 2-hydroxy-1-propanesulfonic acid (HAPS), 2-sulfoethyl(meth)acrylic acid, 2-sulfopropyl(meth)acrylic acid, 3-sulfopropyl(meth)acrylic acid, 4-sulfobutyl(meth)acrylic acid, and salts thereof. Most preferably, both the first and second dispersant polymers used in the automatic dishwashing composition of the present invention contain ≤1% by weight (preferably ≤0.5% by weight, more preferably ≤0.001% by weight, even more preferably ≤0.0001% by weight, most preferably < the detection limit) of structural units of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) monomer.

[0041] The automatic dishwashing composition of the present invention optionally further comprises additives. Preferably, the automatic dishwashing composition of the present invention further comprises additives selected from the group consisting of phosphonates (e.g., HEDP), alkali sources, bleaching agents (e.g., sodium percarbonate, sodium perborate), bleaching activators (e.g., tetraacetylethylenediamine (TAED)), bleaching catalysts (e.g., manganese(II) acetate, cobalt(II) chloride, bis(TACN)), magnesium trioxide diacetate), enzymes (e.g., protease, amylase, lipase, or cellulase), foam inhibitors, colorants, fragrances, additional builders, antimicrobial agents, fillers, deposit-controlling polymers, and mixtures thereof. More preferably, the automatic dishwashing composition of the present invention further comprises additives selected from the group consisting of phosphonates, bleaching agents, bleaching activators, enzymes, fillers, and mixtures thereof. More preferably, the automatic dishwashing composition of the present invention further comprises an additive, the additive comprising a phosphonate (e.g., HEDP), a bleaching agent (e.g., sodium percarbonate, sodium perborate), a bleaching activator (e.g., tetraacetylethylenediamine (TAED)), and an enzyme (e.g., protease, amylase, lipase, or cellulase). Most preferably, the automatic dishwashing composition of the present invention further comprises an additive, the additive comprising a phosphonate, the phosphonate being selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and its salts, a bleaching agent comprising sodium percarbonate, a bleaching activator comprising tetraacetylethylenediamine (TAED), and an enzyme comprising protease and amylase.

[0042] Preferably, the automatic dishwashing composition of the present invention optionally further comprises 0 to 15% by weight (more preferably 0.1 to 12.5% ​​by weight, even more preferably 0.5 to 10% by weight, most preferably 2 to 7.5% by weight) of phosphonate based on the dry weight of the automatic dishwashing composition. More preferably, the automatic dishwashing composition of the present invention optionally further comprises 0 to 15% by weight (more preferably 0.1 to 12.5% ​​by weight, even more preferably 0.5 to 10% by weight, most preferably 2 to 7.5% by weight) of phosphonate based on the dry weight of the automatic dishwashing composition, wherein the phosphonate has a weight-average molecular weight of ≤1,000 Daltons. More preferably, the automatic dishwashing composition of the present invention further optionally comprises 0 to 15% by weight (more preferably 0.1 to 12.5% ​​by weight, even more preferably 0.5 to 10% by weight, most preferably 2 to 7.5% by weight) of a phosphonate based on the dry weight of the automatic dishwashing composition, wherein the phosphonate comprises 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 composition of the present invention further optionally comprises 0 to 15% by weight (more preferably 0.1 to 12.5% ​​by weight, even more preferably 0.5 to 10% by weight, most preferably 2 to 7.5% by weight) of a phosphonate based on the dry weight of the automatic dishwashing composition, wherein the phosphonate is selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and its salts.

[0043] The fillers contained in tablets or powders are inert, water-soluble substances, typically sodium or potassium salts (e.g., sodium sulfate, potassium sulfate, sodium chloride, potassium chloride). In tablets and powders, the fillers are typically present in amounts ranging from 0% to 75% by weight. Fillers contained in gel formulations typically include those mentioned for use in tablets and powders, and even in water. Fragrances, dyes, foam inhibitors, enzymes, and antimicrobial agents are usually present in a total amount of 10% or less by weight, or 5% or less by weight, of the automatic dishwashing composition.

[0044] The automatic dishwashing composition of the present invention optionally further comprises an alkali source. Suitable alkali sources include, but are not limited to, alkali metal carbonates and alkali metal hydroxides, such as sodium carbonate or potassium carbonate, bicarbonates, sesquicarbonates, sodium hydroxide, lithium hydroxide or potassium hydroxide, or mixtures thereof. Sodium hydroxide is preferred. The amount of alkali source in the automatic dishwashing composition of the present invention (if present) is at least 1% by weight (preferably at least 20% by weight) and up to 80% by weight (preferably up to 60% by weight), based on the dry weight of the automatic dishwashing composition.

[0045] The automatic dishwashing composition of the present invention optionally further comprises a bleaching agent (e.g., sodium percarbonate). The amount of bleaching agent in the automatic dishwashing composition of the present invention (if present) is preferably 1 to 25% by weight (preferably 2.5 to 20% by weight, more preferably 5 to 12% by weight) based on the dry weight of the automatic dishwashing composition.

[0046] The automatic dishwashing composition of the present invention optionally further comprises a bleaching activator (e.g., tetraacetylethylenediamine (TAED)). The amount of the bleaching activator in the automatic dishwashing composition of the present invention (if present) is preferably 1 to 10% by weight (preferably 2.5 to 7.5% by weight) based on the dry weight of the automatic dishwashing composition.

[0047] Preferably, the automatic dishwashing composition of the present invention optionally further comprises enzymes (e.g., proteases and amylases). More preferably, the automatic dishwashing composition of the present invention optionally further comprises 0 to 20% by weight (preferably 2 to 15% by weight, more preferably 4 to 12% by weight) of enzymes based on the dry weight of the automatic dishwashing composition. Most preferably, the automatic dishwashing composition of the present invention further comprises 1 to 10% by weight (preferably 2 to 7.5% by weight, more preferably 3 to 6% by weight) of proteases and 1 to 10% by weight (preferably 2 to 7.5% by weight, most preferably 2.5 to 4.5% by weight) of amylase based on the dry weight of the automatic dishwashing composition.

[0048] Preferably, the automatic dishwashing composition of the present invention contains ≤1% by weight (preferably ≤0.5% by weight, more preferably ≤0.2% by weight, even more preferably ≤0.1% by weight, even more preferably ≤0.01% by weight, most preferably < the detection limit) of phosphate (measured as elemental phosphorus) based on the dry weight of the automatic dishwashing composition. Preferably, the automatic dishwashing composition of the present invention is phosphate-free.

[0049] Preferably, the automatic dishwashing composition of the present invention is 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'-iminodisuccinate, S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid, N,N'-ethylenediaminedisuccinate, iminodisuccinate, aspartic acid, aspartic acid-N,N-diacetic acid, beta-alaninediacetic acid, polyaspartic acid, salts thereof, and mixtures thereof, based on the dry weight of the automatic dishwashing composition, in an amount of ≤1% by weight (preferably ≤0.5% by weight, more preferably ≤0.2% by weight, even more preferably ≤0.1% by weight, even more preferably ≤0.01% by weight, most preferably < the detection limit). Most preferably, the automatic dishwashing composition of the present invention contains 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'-iminodisuccinate, S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid, N,N'-ethylenediaminedisuccinate, iminodisuccinate, aspartic acid, aspartic acid-N,N-diacetic acid, beta-alaninediacetic acid, polyaspartic acid, salts thereof, and mixtures thereof.

[0050] Preferably, the automatic dishwashing composition of the present invention has a pH value of at least 7 (preferably ≥9, more preferably ≥9.5) in 1% by weight of water. Preferably, the automatic dishwashing composition of the present invention has a pH value of 13 or less in 1% by weight of water.

[0051] Preferably, the automatic dishwashing composition of the present invention can be formulated in any typical form, such as tablets, powders, lumps, single doses, pouches, pastes, liquids, or gels. The automatic dishwashing composition of the present invention is useful for washing dishes and cookware, plates, and other items in an automatic dishwasher.

[0052] Preferably, the automatic dishwashing composition of the present invention is suitable for use under typical operating conditions. For example, when used in an automatic dishwasher, 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 composition is preferably 0.1 to 1% by weight, preferably 0.2 to 0.7% by weight, as a percentage of the total liquid in the dishwasher. By selecting an appropriate product form and addition time, the automatic dishwashing composition of the present invention may be present in the pre-wash, main wash, second-to-last rinse, final rinse, or any combination of these cycles.

[0053] Preferably, the method of washing articles in an automatic dishwasher according to the present invention comprises preparing at least one article (e.g., cookware, heat-resistant ceramics, tableware, table utensils, plates, and / or glassware), preparing the automatic dishwashing composition of the present invention, and applying the automatic dishwashing composition to at least one article (preferably inside the automatic dishwasher).

[0054] Herein, several embodiments of the present invention will be described in detail by the following examples.

[0055] Weight average molecular weight, M W ;Number average molecular weight, M NPolydispersibility (PDI) values ​​were measured by gel permeation chromatography (GPC) on an Agilent 1100 series LC system equipped with an Agilent 1100 series refractive index. The sample was dissolved in HPCL-grade THF / FA mixture (100:5 volume / volt ratio) at a concentration of approximately 9 mg / mL, filtered through a 0.45 μm syringe filter, and then injected into 4.6 × 10 mm Shodex KF Guard columns, 8.0 × 300 mm Shodex KF 803 columns, 8.0 × 300 mm Shodex KF 802 columns, and 8.0 × 100 mm Shodex KF-D columns. A flow rate of 1 mL / min and a temperature of 40°C were maintained. Columns were calibrated using a narrow molecular weight PS standard (EasiCal PS-2, Polymer Laboratories, Inc.).

[0056] Dispersant polymers DP1-DP2: Dispersant polymer composition The dispersant polymer compositions used herein had the compositions and weight-average molecular weights listed in Table 1.

[0057] [Table 1]

[0058] Comparative Examples C1-C3 and Examples 1-2: Dishwashing Performance Dishwashing compositions were prepared using Comparative Examples C1-C3 and Examples 1-2, each having the component formulations specified in Table 2. The protease used in each component formulation was Savinase® 12T protease, available from Novozymes. The amylase used in each component formulation was Stainzyme® 12T amylase, available from Novozymes.

[0059] [Table 2]

[0060] Procedure for preparing food stains The IKW food contamination loads listed in Table 3 were prepared using the following procedure. a) Combine the vegetable oil and whole eggs and mix thoroughly by hand until the mixture is homogeneous. b) Add ketchup and mustard and stir vigorously. c) Melt the fat, cool it to about 40°C, then add it to mixture b) and blend thoroughly. d) Stir the cream and milk from c). e) Add the powdered solid components from d) and mix everything together to make a smooth paste.

[0061] Finally, place 50g of the stain mixture into a 100mL glass pot. Quickly freeze them and store in the freezer until needed.

[0062] [Table 3]

[0063] Conditions for the dishwashing test Machine: Miele SS-ADW, Model G1222SC Labor 2 (GSL2). Wash at 50°C for 8 minutes / rinse at 65°C. Water: Total hardness 600 ppm, Ca:Mg = 3:1. Ratio of deionized water to 300 ppm sodium bicarbonate (TH = 37°FH, TAC = 23°FH). Food stains: 50 g of the composition described in Table 3 was introduced into the washing solution while frozen in a cup. Each dishwashing composition from Comparative Examples C1-C2 and Example 1 was tested, with 17 g added per wash.

[0064] Evaluation of film formation and spot formation After 5 and 15 washing cycles under the above dishwashing test conditions, glass tumblers, wine glasses, PMMA glasses, and stainless steel butter dishes were air-dried. Following air-drying after the 5th and 15th washing cycles, film formation and spotting were assessed by trained evaluators by observation in a light-emitting box with controlled lighting from below. Film formation and spotting were evaluated for glass tumblers, wine glasses, PMMA glasses, and stainless steel butter dishes according to the ASTM method, on a scale of 1 (no film / spotting) to 5 (severe film formation / spotting). For the 5th and 15th cycle scores, the mean values ​​of film formation and spotting were determined from 1 to 5, as reported in Tables 4 and 5.

[0065] [Table 4]

[0066] [Table 5]

[0067] Conditions for the dishwashing test Machine: Miele SS-ADW, Model G1222SC Labor 2 (GSL2). Wash at 65°C for 8 minutes / Rinse at 65°C. Water: Total hardness 600 ppm, Ca:Mg = 3:1. Ratio of deionized water to 300 ppm sodium bicarbonate (TH = 37°FH, TAC = 23°FH). Food stains: 50 g of the composition described in Table 3 was introduced into the washing solution while frozen in a cup. Each dishwashing composition from Comparative Examples C1-C2 and Example 1 was tested, with 17 g added per wash.

[0068] Evaluation of film formation and spot formation After five washing cycles under the above dishwashing test conditions, glass tumblers, wine glasses, PMMA glasses, and stainless steel butter dishes were air-dried. Following the fifth washing and subsequent air-drying, film formation and spotting were assessed by trained evaluators by observation in a light-emitting box with controlled lighting from below. Film formation and spotting were evaluated for the glass tumblers, wine glasses, PMMA glasses, and stainless steel butter dishes according to the ASTM method, on a scale of 1 (no film / spotting) to 5 (severe film formation / spotting). The mean values ​​for film formation and spotting were determined from 1 to 5, as reported in Table 6.

[0069] [Table 6]

[0070] Conditions for the dishwashing test Machine: Miele SS-ADW, Model G1222SC Labor 2 (GSL2). Wash at 50°C for 8 minutes / rinse at 65°C. Water: Total hardness 600 ppm, Ca:Mg=3:1 ratio of deionized water to 300 ppm sodium bicarbonate (TH=37°FH, TAC=23°FH). Food stains: 50 g of the compositions described above in Table 3 were introduced into the washing solution while frozen in cups. Each dishwashing composition from Comparative Example C3 and Example 2 was tested, and 16.15 g was added per wash.

[0071] Evaluation of film formation and spot formation After 15 washing cycles under the above dishwashing test conditions, glass tumblers, wine glasses, PMMA glasses, and stainless steel butter dishes were air-dried. Following the 15th washing cycle and subsequent air-drying, film formation and spotting were assessed by trained evaluators by observation in a light-emitting box with controlled lighting from below. Film formation and spotting were evaluated for the glass tumblers, wine glasses, PMMA glasses, and stainless steel butter dishes according to the ASTM method, on a scale of 1 (no film / spotting) to 5 (severe film formation / spotting). The mean values ​​for film formation and spotting were determined from 1 to 5, as reported in Table 7.

[0072] [Table 7]

[0073] Conditions for the dishwashing test Machine: Miele SS-ADW, Model G1222SC Labor 2 (GSL2). Wash at 65°C for 8 minutes / Rinse at 65°C. Water: Total hardness 600 ppm, Ca:Mg=3:1 ratio of deionized water to 300 ppm sodium bicarbonate (TH=37°FH, TAC=23°FH). Food stains: 50 g of the compositions described above in Table 3 were introduced into the washing solution while frozen in cups. Each dishwashing composition from Comparative Example C3 and Example 2 was tested, and 16.15 g was added per wash.

[0074] Evaluation of film formation and spot formation After 15 washing cycles under the above dishwashing test conditions, glass tumblers, wine glasses, PMMA glasses, and stainless steel butter dishes were air-dried. Following the 15th washing cycle and subsequent air-drying, film formation and spotting were assessed by trained evaluators by observation in a light-emitting box with controlled lighting from below. Film formation and spotting were evaluated for the glass tumblers, wine glasses, PMMA glasses, and stainless steel butter dishes according to the ASTM method, on a scale of 1 (no film / spotting) to 5 (severe film formation / spotting). The mean values ​​for film formation and spotting were determined from 1 to 5, as reported in Table 8.

[0075] [Table 8]

Claims

1. A composition for automatic dishwashing, (a) Builders and (b) Nonionic surfactants, (c) A first dispersant polymer having a weight-average molecular weight of 4,200 to 25,000 Daltons, (i) Based on the solid content weight of the first dispersant polymer, 65 to 77.5% by weight of Formula I 【Chemistry 1】 (In the formula, each R １ These are independently hydrogen and -CH ３ Structural units (selected from the base), and (ii) Based on the solid content weight of the first dispersant polymer, 22.5 to 35% by weight of Formula II 【Chemistry 2】 (In the formula, each R ２ It is independently, -C １－４ Selected from alkyl groups, each R ３ A first dispersant polymer comprising a structural unit (selected from hydrogen and methyl groups), (d) A second dispersant polymer having a weight-average molecular weight of 1,200 to 3,750 Daltons, (i) Based on the solid content weight of the second dispersant polymer, 85 to 97.5% by weight of formula I (wherein each R １ These are independently hydrogen and -CH ３ Structural units (selected from the base), and (ii) Based on the solid content weight of the second dispersant polymer, 2.5 to 15% by weight of Formula II (where each R ２ is independently selected from -C １－４ alkyl group, and each R ３ is independently selected from hydrogen and methyl group) of the second dispersant polymer, and (e) phosphonates Includes, A composition for automatic dishwashing, wherein the first dispersant polymer and the second dispersant polymer are different.

2. The automatic dishwashing composition according to claim 1, wherein the builder comprises a mixture of at least one carbonate and at least one citrate.

3. The automatic dishwashing composition according to claim 2, wherein the automatic dishwashing composition contains less than 0.1% by weight of phosphate, measured as elemental phosphorus based on the dry weight of the automatic dishwashing composition.

4. The automatic dishwashing composition according to claim 3, wherein the automatic dishwashing composition contains 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'-iminodisuccinate, S,S-ethylenediaminedisuccinate aspartic acid-diacetic acid, N,N'-ethylenediaminedisuccinate, iminodisuccinate, aspartic acid, aspartic acid-N,N-diacetic acid, beta-alaninediacetic acid, polyaspartic acid, salts thereof, and mixtures thereof, based on the dry weight of the automatic dishwashing composition.

5. The automatic dishwashing composition according to claim 4, further comprising an additive selected from the group consisting of bleaching agents, bleaching activators, enzymes, fillers, and mixtures thereof.

6. Based on the dry weight of the automatic dishwashing composition, 40 to 70% by weight of the builder, the builder is The builder is selected from the group consisting of carbonates, bicarbonates, citrates, silicates, and mixtures thereof. Based on the dry weight of the automatic dishwashing composition, 5 to 17.5% by weight of the nonionic surfactant, wherein the nonionic surfactant comprises a mixture of nonionic alcohol alkoxylate surfactants, Based on the dry weight of the automatic dishwashing composition, 2 to 4% by weight of the first dispersant polymer, wherein at least 98 mol% of the structural units of formula I, R １ is hydrogen, and in at least 98 mol% of the structural unit of formula II, R ２ is an ethyl group, and in at least 98 mol% of the structural unit of formula II, R ３ The first dispersant polymer, wherein hydrogen is present, Based on the dry weight of the automatic dishwashing composition, 2 to 4% by weight of the second dispersant polymer, wherein at least 98 mol% of the structural units of formula I, R １ is hydrogen, and in at least 98 mol% of the structural unit of formula II, R ２ is an ethyl group, and in at least 98 mol% of the structural unit of formula II, R ３ The second dispersant polymer, wherein hydrogen is present, Based on the dry weight of the aforementioned automatic dishwashing composition, 2 to 7.5% by weight of the phosphonate and Based on the dry weight of the aforementioned automatic dishwashing composition, 5 to 12% by weight of a bleaching agent, selected from the group consisting of sodium percarbonate and sodium perborate, Based on the dry weight of the aforementioned automatic dishwashing composition, a bleach activator in an amount of 2.5 to 7.5% by weight, wherein the bleach activator is tetraacetylethylenediamine, Based on the dry weight of the aforementioned automatic dishwashing composition, 3 to 6% by weight of protease and Based on the dry weight of the aforementioned automatic dishwashing composition, 2.5 to 4.5% by weight of amylase The automatic dishwashing composition according to claim 5, comprising:

7. A method for washing items in an automatic dishwasher, Prepare at least one item, To prepare the automatic dishwashing composition described in claim 1, Apply the automatic dishwashing composition to the at least one article. Methods that include...

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