EP2228428A1 - Scale-reducing additive for automatic dishwashing systems - Google Patents

Scale-reducing additive for automatic dishwashing systems Download PDF

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Publication number
EP2228428A1
EP2228428A1 EP10154198A EP10154198A EP2228428A1 EP 2228428 A1 EP2228428 A1 EP 2228428A1 EP 10154198 A EP10154198 A EP 10154198A EP 10154198 A EP10154198 A EP 10154198A EP 2228428 A1 EP2228428 A1 EP 2228428A1
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EP
European Patent Office
Prior art keywords
alternatively
polymer
composition
amps
silicate
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Granted
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EP10154198A
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German (de)
French (fr)
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EP2228428B1 (en
Inventor
Marianne P. Creamer
Jan Edward Schulman
Joseph Manna
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Rohm and Haas Co
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Rohm and Haas Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/12—Carbonates bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—Silicates

Definitions

  • This invention relates generally to a formulation that minimizes mixed inorganic deposits in non-phosphate automatic dishwashing systems.
  • Automatic dishwashing detergents are generally recognized as a class of detergent compositions distinct from those used for fabric washing or water treatment. Automatic dishwashing detergents are required to produce a spotless and film-free appearance on washed items after a complete cleaning cycle.
  • Phosphate-free compositions rely on non-phosphate builders, such as salts of citrate, carbonate, silicate, disilicate, bicarbonate, aminocarboxylates and others to sequester calcium and magnesium from hard water, and upon drying, leave an insoluble visible deposit.
  • Polymers made from acrylic acid, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) are known for use in inhibiting the scale or other insoluble deposits produced from non-phosphate builders.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • U.S. Pat. No. 5,273,675 discloses a polymer made from acrylic acid, maleic acid and AMPS in a composition containing an alkali metal silicate.
  • the problem addressed by this invention is to find a composition capable of reducing formation of mixed inorganic deposits.
  • the present invention is directed to a phosphorus-free automatic dishwashing detergent composition
  • a phosphorus-free automatic dishwashing detergent composition comprising: (a) a polymer comprising polymerized residues of: (i) 65 to 85 wt% acrylic acid, (ii) 5 to 20% maleic acid and (iii) 10 to 30 wt% 2-acrylamido-2-methylpropanesulfonic acid (AMPS); and having M w at least 2,000; and (b) carbonate and silicate in a weight ratio from 2.5:1 to 1:4, respectively, wherein the composition comprises from 10 to 90 wt% total carbonate and silicate.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • Weight average molecular weights, M w are measured by gel permeation chromatography (GPC) using polyacrylic acid standards, as is known in the art. The techniques of GPC are discussed in detail in Modem Size Exclusion Chromatography, W. W. Yau, J. J. Kirkland, D. D. Bly; Wiley-Interscience, 1979 , and in A Guide to Materials Characterization and Chemical Analysis, J. P. Sibilia; VCH, 1988, p. 81-84 . The molecular weights reported herein are in units of daltons.
  • (meth)acrylic refers to acrylic or methacrylic; the term “carbonate” to alkali metal or ammonium salts of carbonate, bicarbonate, percarbonate, sesquicarbonate; the term “silicate” to alkali metal or ammonium salts of silicate, disilicate, metasilicate; and the term “citrate” to alkali metal citrates.
  • the carbonates, silicates or citrates are sodium, potassium or lithium salts; alternatively sodium or potassium; alternatively sodium.
  • phosphorus-free refers to compositions containing less than 0.5 wt% phosphorus (as elemental phosphorus), alternatively less than 0.2 wt%, alternatively less than 0.1 wt%, alternatively no detectable phosphorus.
  • the total weight of carbonate and silicate in the composition is from 10 to 90 wt% of the total weight of the composition. In some embodiments of the invention, total weight of carbonate and silicate is at least 15 wt%, alternatively at least 20 wt%, alternatively at least 25 wt%, alternatively at least 30 wt%, alternatively at least 35 wt%. In some embodiments, the total weight of carbonate and silicate is no more than 85 wt%, alternatively no more than 80 wt%, alternatively no more than 75 wt%, alternatively no more than 70 wt%, alternatively no more than 65 wt%, alternatively no more than 60 wt%.
  • the weight ratio of carbonate to silicate is no more than 3.5:1, alternatively no more than 3:1, alternatively no more than 2.5:1, alternatively no more than 2:1, alternatively no more than 1:1. In some embodiments, the weight ratio of carbonate to silicate is at least 1:3, alternatively at least 1:2.5, alternatively at least 1:2, alternatively at least 1:1.5. In some embodiments of the invention, the composition further comprises an alkali metal citrate and/or aminocarboxylate. In some embodiments, the amount of alkali metal citrate is from 0.01 to 40 wt%, alternatively no more 35 wt%, alternatively no more than 30 wt%, alternatively no more than 25 wt%, alternatively no more than 20 wt%.
  • the polymer comprises polymerized residues which are at least 65 wt% acrylic acid, alternatively at least 67.5 wt%, alternatively at least 70 wt%, alternatively at least 72.5 wt%.
  • the amount of acrylic acid residues in the polymer is no more than 85 wt%, alternatively no more than 82.5 wt%, alternatively no more than 80 wt%, alternatively no more than 77.5 wt%.
  • the maleic acid residues are at least 7.5 wt% of the polymer, alternatively at least 10 wt%, alternatively at least 12.5 wt%.
  • the amount of maleic acid residues is no more than 22.5%, alternatively no more than 20 wt%, alternatively no more than 17.5 wt%, alternatively no more than 15 wt%, alternatively no more than 12.5 wt%.
  • the polymer is made by polymerizing maleic anhydride, which is hydrolyzed to the acid during the polymerization process. All references to maleic acid residues in the polymer include metal salts of maleic acid residues which would be present at pH values near or above the pKa of the carboxylic acid groups.
  • the amount of AMPS residues (including metal or ammonium salts) in the polymer is at least 7.5 wt%, alternatively at least 10 wt%, alternatively at least 12.5 wt%. In some embodiments, the amount of AMPS residues in the polymer is no more than 27.5 wt%, alternatively no more than 25 wt%, alternatively no more than 22.5 wt%, alternatively no more than 20 wt%, alternatively no more than 17.5 wt%.
  • the total amount of maleic acid and AMPS in the polymer is at least 15 wt%, alternatively at least 17 wt%, alternatively at least 19 wt%, alternatively at least 21 wt%, alternatively at least 23 wt%.
  • the polymer contains no more than 5 wt% of esters of acrylic or methacrylic acid, alternatively no more than 2 wt%, alternatively no more than 1 wt%, alternatively no more than 0.5 wt%.
  • the polymer has M w of at least 4,000, alternatively at least 6,000, alternatively at least 8,000, alternatively at least 10,000, alternatively at least 12,000, alternatively at least 14,000. In some embodiments, M w is no more than 300,000, alternatively no more than 200,000, alternatively no more than 100,000.
  • the polymer may be used in combination with other polymers useful for controlling insoluble deposits in automatic dishwashers, including, e.g, polymers comprising combinations of residues of acrylic acid, methacrylic acid, maleic acid or other diacid monomers, esters of acrylic or methacrylic acid including polyethylene glycol esters, styrene monomers, AMPS and other sulfonated monomers, and substituted acrylamides or methacrylamides.
  • the polymer of this invention may be produced by any of the known techniques for polymerization of acrylic monomers.
  • the initiator does not contain phosphorus.
  • the polymer contains less than 1 wt% phosphorus, alternatively less than 0.5 wt%, alternatively less than 0.1 wt%, alternatively the polymer contains no phosphorus.
  • polymerization is initiated with persulfate and the end group on the polymer is a sulfate or sulfonate.
  • the polymer may be in the form of a water-soluble solution polymer, slurry, dried powder, or granules or other solid forms.
  • Other components of the automatic dishwashing detergent composition may include, e.g., surfactants, oxygen and/or chlorine bleaches, bleach activators, enzymes, foam suppressants, colors, fragrances, antibacterial agents and fillers.
  • Typical surfactant levels depend on the particular surfactant used, typically from 0.1 wt% to 10 wt%, alternatively from 0.5 wt% to 5 wt%.
  • Fillers in tablets or powders are inert, water-soluble substances, typically sodium or potassium salts, e.g., sodium or potassium sulfate and/or chloride, and typically are present in amounts ranging from 0 wt% to 75 wt%.
  • Fillers in gel formulations may include those mentioned above and also water. Fragrances, dyes, foam suppressants, enzymes and antibacterial agents usually total no more than 5 wt% of the composition.
  • the composition contains from 0.1 to 2 wt% of a hypochlorite salt, alternatively from 0.5 to 1.5 wt%.
  • the composition has a pH (at 1 wt% in water) of at least 10, alternatively at least 11.5; in some embodiments the pH is no greater than 13.
  • the composition can be formulated in any typical form, e.g., as a tablet, powder, monodose, sachet, paste, liquid or gel.
  • the composition can be used under typical operating conditions for any typical automatic dishwasher.
  • Typical water temperatures during the washing process preferably are from 20°C to 85°C, alternatively from 30°C to 70°C.
  • Typical concentrations for the composition as a percentage of total liquid in the dishwasher preferably are from 0.1 to 1 wt%, alternatively from 0.2 to 0.7 wt%.
  • the composition may be present in the prewash, main wash, penultimate rinse, final rinse, or any combination of these cycles.
  • the composition comprises from 0.5 to 12 wt% of said polymer, alternatively from 1 to 10 wt%, alternatively from 2 to 8 wt%, alternatively from 3 to 7 wt%, alternatively from 3.5 to 6.5 wt%.
  • the weight ratio of polymer to the total amount of carbonate and silicate is no more than 1:2, alternatively no more than 1:3, alternatively no more than 1:4, alternatively no more than 1:5, alternatively no more than 1:6, alternatively no more than 1:7.
  • the weight ratio of polymer to the total amount of carbonate and silicate is at least 1:25, alternatively at least 1:20, alternatively at least 1:15, alternatively at least 1:10.
  • Typical Polymer Preparation To a two liter round bottom flask, equipped with a mechanical stirrer, heating mantle, thermocouple, condenser and inlets for the addition of monomer, initiator and chain regulator was charged 26.0 grams of maleic anhydride and 150 grams of deionized water. The mixture was set to stir and heated to 78°C (+/- 2°C). In the meantime, a monomer solution of 228.8 grams of glacial acrylic acid and 92.4 grams of 50% solution of sodium 2-acrylamido-2-methypropane sulfonic acid in water was added to a graduated cylinder, thoroughly mixed for addition to the flask.
  • An initiator solution of 8.3 grams of sodium persulfate was dissolved in 30 grams of deionized water and added to a syringe for addition to the kettle.
  • a chain regulator (CTA) solution of 18 grams of sodium metabisulfite dissolved in 45.5 grams of deionized water was added to a syringe for addition to the kettle.
  • a chain regulator pre-charge solution was prepared by dissolving 0.73 grams of sodium metabisulfite in 5 grams of deionized water and set aside.
  • a promoter solution of 3.88 grams of a 0.15% iron sulfate heptahydrate solution was added to a vial and set aside.
  • the promoter solution was added, followed by the sodium metabisulfite pre-charge solution. After the reaction temperature recovered to 78°C, the monomer, initiator and CTA solution feeds were begun simultaneously. The monomer feed rate was constant over 120 minutes. The CTA cofeed was added linearly over 105 minutes and the initiator cofeed added linearly over 125 minutes at 78°C.
  • the final polymer had a solids content of 43.68% (as measured in a forced draft oven at 150°C for 60 minutes). pH of the solution was 5.65 and final M w as measured by Gel Permeation Chromatography was 16,872, and Mn was 3329. The residual monomer measured was ⁇ 1 ppm acrylic acid, ⁇ 1 ppm maleic acid, and 839 ppm fumaric acid.
  • Tables 1 and 2 present results obtained using the polymer with a mixture of 4 g sodium carbonate and 6 g sodium disilicate.
  • the polymers used in the present composition (below the double lines) perform better than the comparative polymers, sometimes with the exception of the first comparative entry, which contains phosphorus and thus is not desirable in a "phosphorus-free" formulation.
  • Table 2 polymer M w filming scores 1 cycle 3 cycles 5 cycles none - 1.9 4.1 4.7 85 AA/10 Mal/5 AMPS 18.9K 1.4 2.1 3.4 80 AA/10 Mal/10 AMPS 16.7K 1.6 2.4 2.9 75 AA/10 Mal/15 AMPS 16.9K 1.3 2.0 2.2 70 AA/10 Mal/20 AMPS 19.0K 1.4 2.8 4.2 65 AA/10 Mal/25 AMPS 19.0K 1.5 2.6 3.8
  • Table 3 presents results obtained using the polymer with a mixture of 4 g sodium carbonate, 6 g sodium disilicate and 2 g sodium citrate.
  • Table 3 polymer M w filming scores 1 cycle 3 cycles 5 cycles none - 1.9 3.8 5.0 90 AA/10 Mal (phosphono end group) 1.9K 1.3 1.7 1.9 72 AA/28 AMPS 12K 1.6 3.4 4.6 75 AA/10 Mal/15 AMPS 15.9K 1.4 1.6 2.5 75 AA/10 Mal/15 AMPS 16.9K 1.3 1.6 1.9
  • Table 4 presents results obtained using the polymer with 4 g sodium carbonate alone. This table is comparative because no silicate is present in these tests.
  • Table 4 polymer M w filming scores 1 cycle 3 cycles 5 cycles none - 2.7 5 5+ 100 AA 4.5K 1.4 1.7 1.9 72 AA/28 AMPS 12K 1.6 1.7 1.8 75 AA/10 Mal/15 AMPS 16.9K 1.4 1.7 1.8
  • Table 5 presents results obtained using the polymer with 6 g sodium disilicate alone. This table is comparative because no carbonate is present in these tests.
  • Table 5 polymer M w filming scores 1 cycle 3 cycles 5 cycles none - 2.3 2.1 2.8 100 AA 4.5K 2.1 2.3 3.2 72 AA/28 AMPS 12K 2.0 1.8 1.8 75 AA/10 Mal/15 AMPS 16.9K 2.4 2.1 2.4
  • Table 6 presents results obtained using the polymer with a mixture of 2 g sodium carbonate and 8 g sodium disilicate.
  • Table 6 polymer M w filming scores 1 cycle 3 cycles 5 cycles none - 1.9 2.3 3.6 100 AA 4.5K 1.6 2.1 2.8 72 AA/28 AMPS 12K 1.5 1.8 2.4 75 AA/10 Mal/15 AMPS 16.9K 2.0 2.6 3.1
  • Table 7 presents results obtained using the polymer with a mixture of 8 g sodium carbonate and 2 g sodium disilicate.
  • Table 7 polymer M w filming scores 1 cycle 3 cycles 5 cycles none - 1.7 4.6 5+ 100 AA 4.5K 1.8 3.8 4.7 72 AA/28 AMPS 12K 2.1 5+ 5++ 75 AA/10 Mal/15 AMPS 16.9K 1.7 3.5 5+
  • Table 8 presents results obtained using the polymer with a mixture of 6 g sodium carbonate and 2 g sodium disilicate.
  • Table 8 polymer M w filming scores 1 cycle 3 cycles 5 cycles none - 1.2 4.5 5 100 AA 19.9K 1.2 2.9 4.1 70 AA/30 MAA 19.6K 1.7 5 5+ 40 Mal/60 MAA 19.5K 1.4 2.5 4.3 85 AA/10 Mal/5 AMPS 18.9K 1.3 2.4 4.7 80 AA/10 Mal/10 AMPS 16.7K 1.3 3.1 4.4 75 AA/10 Mal/15 AMPS 16.9K 1.4 4.8 5+ 70 AA/10 Mal/20 AMPS 19.0K 1.3 4.5 5+ 65 AA/10 Mal/25 AMPS 19.0K 1.6 4.4 5+
  • Table 9 presents results obtained using the polymer with a mixture of 1.5 g sodium carbonate and 6 g sodium disilicate.
  • Table 9 polymer M w filming scores 1 cycle 3 cycles 5 cycles none - 1.1 3.7 5.0 100 AA 19.9K 1.5 2.7 4.8 70 AA/30 MAA 19.6K 2.2 3.3 3.8 40 Mal/60 MAA 19.5K 1.6 2.8 3.5 85 AA/10 Mal/5 AMPS 18.9K 1.2 3.1 3.7 80 AA/10 Mal/10 AMPS 16.7K 1.2 3.4 4.0 75 AA/10 Mal/15 AMPS 16.9K 1.1 2.4 3.1 70 AA/10 Mal/20 AMPS 19.0K 1.2 3.1 4.2 65 AA/10 Mal/25 AMPS 19.0K 1.3 2.5 4.4

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Abstract

A phosphorus-free automatic dishwashing detergent composition containing a polymer of acrylic acid, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS); a carbonate; and a silicate. The composition contains carbonate and silicate in a weight ratio from 2.5:1 to 1:4, respectively; from 10 to 90 wt% total carbonate and silicate.

Description

    Background
  • This invention relates generally to a formulation that minimizes mixed inorganic deposits in non-phosphate automatic dishwashing systems.
  • Automatic dishwashing detergents are generally recognized as a class of detergent compositions distinct from those used for fabric washing or water treatment. Automatic dishwashing detergents are required to produce a spotless and film-free appearance on washed items after a complete cleaning cycle. Phosphate-free compositions rely on non-phosphate builders, such as salts of citrate, carbonate, silicate, disilicate, bicarbonate, aminocarboxylates and others to sequester calcium and magnesium from hard water, and upon drying, leave an insoluble visible deposit. Polymers made from acrylic acid, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) are known for use in inhibiting the scale or other insoluble deposits produced from non-phosphate builders. For example, U.S. Pat. No. 5,273,675 discloses a polymer made from acrylic acid, maleic acid and AMPS in a composition containing an alkali metal silicate. However, this reference does not disclose a composition or method for inhibiting formation of mixed inorganic deposits.
  • The problem addressed by this invention is to find a composition capable of reducing formation of mixed inorganic deposits.
    • Statement of Invention
  • The present invention is directed to a phosphorus-free automatic dishwashing detergent composition comprising: (a) a polymer comprising polymerized residues of: (i) 65 to 85 wt% acrylic acid, (ii) 5 to 20% maleic acid and (iii) 10 to 30 wt% 2-acrylamido-2-methylpropanesulfonic acid (AMPS); and having Mw at least 2,000; and (b) carbonate and silicate in a weight ratio from 2.5:1 to 1:4, respectively, wherein the composition comprises from 10 to 90 wt% total carbonate and silicate.
    • Detailed Description
  • All percentages are weight percentages (wt%), and all temperatures are in °C, unless otherwise indicated. Weight average molecular weights, Mw, are measured by gel permeation chromatography (GPC) using polyacrylic acid standards, as is known in the art. The techniques of GPC are discussed in detail in Modem Size Exclusion Chromatography, W. W. Yau, J. J. Kirkland, D. D. Bly; Wiley-Interscience, 1979, and in A Guide to Materials Characterization and Chemical Analysis, J. P. Sibilia; VCH, 1988, p. 81-84. The molecular weights reported herein are in units of daltons. As used herein the term "(meth)acrylic" refers to acrylic or methacrylic; the term "carbonate" to alkali metal or ammonium salts of carbonate, bicarbonate, percarbonate, sesquicarbonate; the term "silicate" to alkali metal or ammonium salts of silicate, disilicate, metasilicate; and the term "citrate" to alkali metal citrates. In some embodiments of the invention, the carbonates, silicates or citrates are sodium, potassium or lithium salts; alternatively sodium or potassium; alternatively sodium. The term "phosphorus-free" refers to compositions containing less than 0.5 wt% phosphorus (as elemental phosphorus), alternatively less than 0.2 wt%, alternatively less than 0.1 wt%, alternatively no detectable phosphorus.
  • The total weight of carbonate and silicate in the composition is from 10 to 90 wt% of the total weight of the composition. In some embodiments of the invention, total weight of carbonate and silicate is at least 15 wt%, alternatively at least 20 wt%, alternatively at least 25 wt%, alternatively at least 30 wt%, alternatively at least 35 wt%. In some embodiments, the total weight of carbonate and silicate is no more than 85 wt%, alternatively no more than 80 wt%, alternatively no more than 75 wt%, alternatively no more than 70 wt%, alternatively no more than 65 wt%, alternatively no more than 60 wt%. In some embodiments of the invention, the weight ratio of carbonate to silicate is no more than 3.5:1, alternatively no more than 3:1, alternatively no more than 2.5:1, alternatively no more than 2:1, alternatively no more than 1:1. In some embodiments, the weight ratio of carbonate to silicate is at least 1:3, alternatively at least 1:2.5, alternatively at least 1:2, alternatively at least 1:1.5. In some embodiments of the invention, the composition further comprises an alkali metal citrate and/or aminocarboxylate. In some embodiments, the amount of alkali metal citrate is from 0.01 to 40 wt%, alternatively no more 35 wt%, alternatively no more than 30 wt%, alternatively no more than 25 wt%, alternatively no more than 20 wt%.
  • In some embodiments of the invention, the polymer comprises polymerized residues which are at least 65 wt% acrylic acid, alternatively at least 67.5 wt%, alternatively at least 70 wt%, alternatively at least 72.5 wt%. In some embodiments, the amount of acrylic acid residues in the polymer is no more than 85 wt%, alternatively no more than 82.5 wt%, alternatively no more than 80 wt%, alternatively no more than 77.5 wt%. In some embodiments of the invention, the maleic acid residues are at least 7.5 wt% of the polymer, alternatively at least 10 wt%, alternatively at least 12.5 wt%. In some embodiments, the amount of maleic acid residues is no more than 22.5%, alternatively no more than 20 wt%, alternatively no more than 17.5 wt%, alternatively no more than 15 wt%, alternatively no more than 12.5 wt%. Typically, the polymer is made by polymerizing maleic anhydride, which is hydrolyzed to the acid during the polymerization process. All references to maleic acid residues in the polymer include metal salts of maleic acid residues which would be present at pH values near or above the pKa of the carboxylic acid groups. In some embodiments of the invention, the amount of AMPS residues (including metal or ammonium salts) in the polymer is at least 7.5 wt%, alternatively at least 10 wt%, alternatively at least 12.5 wt%. In some embodiments, the amount of AMPS residues in the polymer is no more than 27.5 wt%, alternatively no more than 25 wt%, alternatively no more than 22.5 wt%, alternatively no more than 20 wt%, alternatively no more than 17.5 wt%. In some embodiments of the invention, the total amount of maleic acid and AMPS in the polymer is at least 15 wt%, alternatively at least 17 wt%, alternatively at least 19 wt%, alternatively at least 21 wt%, alternatively at least 23 wt%.
  • In some embodiments of the invention, the polymer contains no more than 5 wt% of esters of acrylic or methacrylic acid, alternatively no more than 2 wt%, alternatively no more than 1 wt%, alternatively no more than 0.5 wt%.
  • In some embodiments of the invention, the polymer has Mw of at least 4,000, alternatively at least 6,000, alternatively at least 8,000, alternatively at least 10,000, alternatively at least 12,000, alternatively at least 14,000. In some embodiments, Mw is no more than 300,000, alternatively no more than 200,000, alternatively no more than 100,000.
  • The polymer may be used in combination with other polymers useful for controlling insoluble deposits in automatic dishwashers, including, e.g, polymers comprising combinations of residues of acrylic acid, methacrylic acid, maleic acid or other diacid monomers, esters of acrylic or methacrylic acid including polyethylene glycol esters, styrene monomers, AMPS and other sulfonated monomers, and substituted acrylamides or methacrylamides.
  • The polymer of this invention may be produced by any of the known techniques for polymerization of acrylic monomers. In some embodiments of the invention, the initiator does not contain phosphorus. In some embodiments of the invention, the polymer contains less than 1 wt% phosphorus, alternatively less than 0.5 wt%, alternatively less than 0.1 wt%, alternatively the polymer contains no phosphorus. In some embodiments of the invention, polymerization is initiated with persulfate and the end group on the polymer is a sulfate or sulfonate. The polymer may be in the form of a water-soluble solution polymer, slurry, dried powder, or granules or other solid forms.
  • Other components of the automatic dishwashing detergent composition may include, e.g., surfactants, oxygen and/or chlorine bleaches, bleach activators, enzymes, foam suppressants, colors, fragrances, antibacterial agents and fillers. Typical surfactant levels depend on the particular surfactant used, typically from 0.1 wt% to 10 wt%, alternatively from 0.5 wt% to 5 wt%. Fillers in tablets or powders are inert, water-soluble substances, typically sodium or potassium salts, e.g., sodium or potassium sulfate and/or chloride, and typically are present in amounts ranging from 0 wt% to 75 wt%. Fillers in gel formulations may include those mentioned above and also water. Fragrances, dyes, foam suppressants, enzymes and antibacterial agents usually total no more than 5 wt% of the composition.
  • In some embodiments of the invention, the composition contains from 0.1 to 2 wt% of a hypochlorite salt, alternatively from 0.5 to 1.5 wt%. In some embodiments of the invention, the composition has a pH (at 1 wt% in water) of at least 10, alternatively at least 11.5; in some embodiments the pH is no greater than 13.
  • The composition can be formulated in any typical form, e.g., as a tablet, powder, monodose, sachet, paste, liquid or gel. The composition can be used under typical operating conditions for any typical automatic dishwasher. Typical water temperatures during the washing process preferably are from 20°C to 85°C, alternatively from 30°C to 70°C. Typical concentrations for the composition as a percentage of total liquid in the dishwasher preferably are from 0.1 to 1 wt%, alternatively from 0.2 to 0.7 wt%. With selection of an appropriate product form and addition time, the composition may be present in the prewash, main wash, penultimate rinse, final rinse, or any combination of these cycles.
  • In some embodiments of the invention, the composition comprises from 0.5 to 12 wt% of said polymer, alternatively from 1 to 10 wt%, alternatively from 2 to 8 wt%, alternatively from 3 to 7 wt%, alternatively from 3.5 to 6.5 wt%. In some embodiments of the invention, the weight ratio of polymer to the total amount of carbonate and silicate is no more than 1:2, alternatively no more than 1:3, alternatively no more than 1:4, alternatively no more than 1:5, alternatively no more than 1:6, alternatively no more than 1:7. In some embodiments of the invention, the weight ratio of polymer to the total amount of carbonate and silicate is at least 1:25, alternatively at least 1:20, alternatively at least 1:15, alternatively at least 1:10.
    • Examples
  • Typical Polymer Preparation - To a two liter round bottom flask, equipped with a mechanical stirrer, heating mantle, thermocouple, condenser and inlets for the addition of monomer, initiator and chain regulator was charged 26.0 grams of maleic anhydride and 150 grams of deionized water. The mixture was set to stir and heated to 78°C (+/- 2°C). In the meantime, a monomer solution of 228.8 grams of glacial acrylic acid and 92.4 grams of 50% solution of sodium 2-acrylamido-2-methypropane sulfonic acid in water was added to a graduated cylinder, thoroughly mixed for addition to the flask. An initiator solution of 8.3 grams of sodium persulfate was dissolved in 30 grams of deionized water and added to a syringe for addition to the kettle. A chain regulator (CTA) solution of 18 grams of sodium metabisulfite dissolved in 45.5 grams of deionized water was added to a syringe for addition to the kettle. A chain regulator pre-charge solution was prepared by dissolving 0.73 grams of sodium metabisulfite in 5 grams of deionized water and set aside. A promoter solution of 3.88 grams of a 0.15% iron sulfate heptahydrate solution was added to a vial and set aside.
  • Once the kettle contents reached reaction temperature of 78°C, the promoter solution was added, followed by the sodium metabisulfite pre-charge solution. After the reaction temperature recovered to 78°C, the monomer, initiator and CTA solution feeds were begun simultaneously. The monomer feed rate was constant over 120 minutes. The CTA cofeed was added linearly over 105 minutes and the initiator cofeed added linearly over 125 minutes at 78°C.
  • At the completion of the feeds, 5 grams of deionized water was added to the monomer feed vessel, as rinse. The reaction was held for 15 minutes at 78°C. In the meantime, the chaser solution of 0.90 grams of sodium persulfate and 15 grams of deionized water was mixed and set aside.
  • At the completion of the hold, the above chaser solution was added linearly over 10 minutes and held for 15 minutes at 78°C.
  • At the completion of the final hold, cooling was begun with the addition of 100 grams of deionized water. At 50°C or below a solution of 168.9 grams of 50% sodium hydroxide was added to an addition funnel and slowly added to the kettle, controlling the exotherm to keep the temperature below 70°C. Finally, 1.9 grams of a scavenger solution of 35% hydrogen peroxide was added to the kettle. The reaction was then cooled and packaged.
  • The final polymer had a solids content of 43.68% (as measured in a forced draft oven at 150°C for 60 minutes). pH of the solution was 5.65 and final Mw as measured by Gel Permeation Chromatography was 16,872, and Mn was 3329. The residual monomer measured was <1 ppm acrylic acid, < 1 ppm maleic acid, and 839 ppm fumaric acid.
  • Polymer Testing - All polymers were tested for scale reduction by incorporating them at 1 g with sodium carbonate and/or sodium disilicate (BRITESIL H 20, PQ Corp.), and in some cases citrate, as indicated and washing glasses for 5 cycles in a Kenmore dishwasher (solids added to pre-wash and main wash cycles) using water with 400 ppm hardness (2:1 Ca+2:Mg+2) at 130 °F (54.4 °C) with no food soil. Glasses were evaluated after 1, 3 and 5 cycles using the scale from ASTM method 3556-85 (1=clean, 5=heavy film).
  • Tables 1 and 2 present results obtained using the polymer with a mixture of 4 g sodium carbonate and 6 g sodium disilicate. Table 1
    polymer Mw filming scores
    1 cycle 3 cycles 5 cycles
    none - 1.6 4.1 4.9
    90 AA/10 Mal (phosphono end group, 1.7 wt% P) 1.9K 1.7 2.1 2.7
    100 AA 4.5K 1.9 2.8 3.6
    75 AA/10 Mal/15 AMPS 15.9K 1.8 2.0 2.1
    65 AA/20 Mal/15 AMPS 12K 2.1 2.6 3.0
    75 AA/10 Mal/15 AMPS 16.9K 1.3 2.1 3.1
    Note: AA=acrylic acid; Mal=maleic acid; AMPS=2-acrylamido-2-methylpropanesulfonic acid, sodium salt; numbers associated with these abbreviations indicate wt% in the polymer. In Mw, K=1000, i.e., 1.9K=1,900
  • The polymers used in the present composition (below the double lines) perform better than the comparative polymers, sometimes with the exception of the first comparative entry, which contains phosphorus and thus is not desirable in a "phosphorus-free" formulation. Table 2
    polymer Mw filming scores
    1 cycle 3 cycles 5 cycles
    none - 1.9 4.1 4.7
    85 AA/10 Mal/5 AMPS 18.9K 1.4 2.1 3.4
    80 AA/10 Mal/10 AMPS 16.7K 1.6 2.4 2.9
    75 AA/10 Mal/15 AMPS 16.9K 1.3 2.0 2.2
    70 AA/10 Mal/20 AMPS 19.0K 1.4 2.8 4.2
    65 AA/10 Mal/25 AMPS 19.0K 1.5 2.6 3.8
  • Table 3 presents results obtained using the polymer with a mixture of 4 g sodium carbonate, 6 g sodium disilicate and 2 g sodium citrate. Table 3
    polymer Mw filming scores
    1 cycle 3 cycles 5 cycles
    none - 1.9 3.8 5.0
    90 AA/10 Mal (phosphono end group) 1.9K 1.3 1.7 1.9
    72 AA/28 AMPS 12K 1.6 3.4 4.6
    75 AA/10 Mal/15 AMPS 15.9K 1.4 1.6 2.5
    75 AA/10 Mal/15 AMPS 16.9K 1.3 1.6 1.9
  • Table 4 presents results obtained using the polymer with 4 g sodium carbonate alone. This table is comparative because no silicate is present in these tests. Table 4
    polymer Mw filming scores
    1 cycle 3 cycles 5 cycles
    none - 2.7 5 5+
    100 AA 4.5K 1.4 1.7 1.9
    72 AA/28 AMPS 12K 1.6 1.7 1.8
    75 AA/10 Mal/15 AMPS 16.9K 1.4 1.7 1.8
  • Table 5 presents results obtained using the polymer with 6 g sodium disilicate alone. This table is comparative because no carbonate is present in these tests. Table 5
    polymer Mw filming scores
    1 cycle 3 cycles 5 cycles
    none - 2.3 2.1 2.8
    100 AA 4.5K 2.1 2.3 3.2
    72 AA/28 AMPS 12K 2.0 1.8 1.8
    75 AA/10 Mal/15 AMPS 16.9K 2.4 2.1 2.4
  • Table 6 presents results obtained using the polymer with a mixture of 2 g sodium carbonate and 8 g sodium disilicate. Table 6
    polymer Mw filming scores
    1 cycle 3 cycles 5 cycles
    none - 1.9 2.3 3.6
    100 AA 4.5K 1.6 2.1 2.8
    72 AA/28 AMPS 12K 1.5 1.8 2.4
    75 AA/10 Mal/15 AMPS 16.9K 2.0 2.6 3.1
  • Table 7 presents results obtained using the polymer with a mixture of 8 g sodium carbonate and 2 g sodium disilicate. Table 7
    polymer Mw filming scores
    1 cycle 3 cycles 5 cycles
    none - 1.7 4.6 5+
    100 AA 4.5K 1.8 3.8 4.7
    72 AA/28 AMPS 12K 2.1 5+ 5++
    75 AA/10 Mal/15 AMPS 16.9K 1.7 3.5 5+
  • Table 8 presents results obtained using the polymer with a mixture of 6 g sodium carbonate and 2 g sodium disilicate. Table 8
    polymer Mw filming scores
    1 cycle 3 cycles 5 cycles
    none - 1.2 4.5 5
    100 AA 19.9K 1.2 2.9 4.1
    70 AA/30 MAA 19.6K 1.7 5 5+
    40 Mal/60 MAA 19.5K 1.4 2.5 4.3
    85 AA/10 Mal/5 AMPS 18.9K 1.3 2.4 4.7
    80 AA/10 Mal/10 AMPS 16.7K 1.3 3.1 4.4
    75 AA/10 Mal/15 AMPS 16.9K 1.4 4.8 5+
    70 AA/10 Mal/20 AMPS 19.0K 1.3 4.5 5+
    65 AA/10 Mal/25 AMPS 19.0K 1.6 4.4 5+
  • Table 9 presents results obtained using the polymer with a mixture of 1.5 g sodium carbonate and 6 g sodium disilicate. Table 9
    polymer Mw filming scores
    1 cycle 3 cycles 5 cycles
    none - 1.1 3.7 5.0
    100 AA 19.9K 1.5 2.7 4.8
    70 AA/30 MAA 19.6K 2.2 3.3 3.8
    40 Mal/60 MAA 19.5K 1.6 2.8 3.5
    85 AA/10 Mal/5 AMPS 18.9K 1.2 3.1 3.7
    80 AA/10 Mal/10 AMPS 16.7K 1.2 3.4 4.0
    75 AA/10 Mal/15 AMPS 16.9K 1.1 2.4 3.1
    70 AA/10 Mal/20 AMPS 19.0K 1.2 3.1 4.2
    65 AA/10 Mal/25 AMPS 19.0K 1.3 2.5 4.4

Claims (10)

  1. A phosphorus-free automatic dishwashing detergent composition comprising:
    (a) a polymer comprising polymerized residues of: (i) 65 to 85 wt% acrylic acid, (ii) 5 to 20% maleic acid and (iii) 10 to 30 wt% 2-acrylamido-2-methylpropanesulfonic acid; and having Mw at least 2,000; and
    (b) carbonate and silicate in a weight ratio from 2.5:1 to 1:4, respectively, wherein the composition comprises from 10 to 90 wt% total carbonate and silicate.
  2. The composition of claim 1 in which said polymer comprises polymerized residues of:
    (i) 62.5 to 80 wt% acrylic acid, (ii) 7.5 to 15% maleic acid and (iii) 10 to 20 wt% 2-acrylamido-2-methylpropanesulfonic acid.
  3. The composition of claim 1 in which the composition comprises from 15 to 50 wt% total carbonate and silicate.
  4. The composition of claim 1 in which the composition comprises carbonate and silicate in a weight ratio from 1.5:1 to 1:4.
  5. The composition of claim 1 in which said polymer contains less than 0.5 wt% phosphorus.
  6. The composition of claim 1 in which said polymer comprises polymerized residues of:
    (i) 65 to 80 wt% acrylic acid, (ii) 7.5 to 15% maleic acid and (iii) 10 to 20 wt% 2-acrylamido-2-methylpropanesulfonic acid; the composition comprises from 15 to 50 wt% total carbonate and silicate; and carbonate and silicate in a weight ratio from 1.5:1 to 1:4.
  7. The composition of claim 6 in which said polymer has Mw at least 8,000.
  8. The composition of claim 7 in which said polymer comprises polymerized residues of:
    (i) 70 to 80 wt% acrylic acid, (ii) 7.5 to 12.5 wt% maleic acid and (iii) 12.5 to 17.5 wt% 2-acrylamido-2-methylpropanesulfonic acid.
  9. The composition of claim 8 in which said polymer contains less than 0.5 wt% phosphorus.
  10. The composition of claim 9 further comprising at least 0.1 wt% of a hypochlorite salt and having a pH of at least 11.5.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016153581A1 (en) * 2015-03-24 2016-09-29 Rohm And Haas Company Control of scale in warewash applications
CN107075425A (en) * 2014-10-09 2017-08-18 罗门哈斯公司 Additive for reducing spot in automatic tableware washing system
WO2019083718A1 (en) * 2017-10-23 2019-05-02 Dow Global Technologies Llc Gradient copolymers for use in automatic dishwashing systems
WO2022189536A1 (en) * 2021-03-12 2022-09-15 Reckitt Benckiser Finish B.V. Automatic dishwashing composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6294124B2 (en) * 2014-03-31 2018-03-14 株式会社日本触媒 Copolymer and process for producing the same
CN107075418B (en) * 2014-10-09 2020-11-13 罗门哈斯公司 Additive for reducing stains in automatic dishwashing systems
JP6637075B2 (en) * 2015-03-20 2020-01-29 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ Automatic dishwashing detergent
CN111936609A (en) * 2018-03-13 2020-11-13 埃科莱布美国股份有限公司 Warewashing alkaline detergent composition comprising terpolymer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3743739A1 (en) * 1987-12-23 1989-07-06 Basf Ag Dishwashing compositions containing water-soluble polymers
US5273675A (en) 1990-02-16 1993-12-28 Rohm And Haas Company Phosphate-free liquid cleaning compositions containing polymer
EP0770673A2 (en) * 1995-10-27 1997-05-02 Rohm And Haas Company Polycarboxylates for automatic dishwashing detergents
WO2001072941A1 (en) * 2000-03-29 2001-10-04 National Starch And Chemical Investment Holding Corporation Polymers that inhibit calcium phosphate and calcium carbonate scale in autodish applications
WO2003042347A1 (en) * 2001-11-14 2003-05-22 The Procter & Gamble Company Automatic dishwashing composition in unit dose form comprising an anti-scaling polymer
EP2130898A1 (en) * 2008-06-04 2009-12-09 Rohm and Haas Company Polymers and Their Use for Inhibition of Scale Build-Up in Automatic Dishwashing Applications

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE902759A1 (en) * 1990-02-16 1991-08-28 Rohm & Haas Liquid cleaning compositions containing water-soluble¹polymer
DK166548B1 (en) * 1991-03-15 1993-06-07 Cleantabs As PHOSPHATE-FREE MACHINE DISHWASH
US5759978A (en) * 1995-12-06 1998-06-02 Basf Corporation Non-phosphate machine dishwashing compositions containing polycarboxylate polymers and polyalkylene oxide homopolymers

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3743739A1 (en) * 1987-12-23 1989-07-06 Basf Ag Dishwashing compositions containing water-soluble polymers
US5273675A (en) 1990-02-16 1993-12-28 Rohm And Haas Company Phosphate-free liquid cleaning compositions containing polymer
EP0770673A2 (en) * 1995-10-27 1997-05-02 Rohm And Haas Company Polycarboxylates for automatic dishwashing detergents
WO2001072941A1 (en) * 2000-03-29 2001-10-04 National Starch And Chemical Investment Holding Corporation Polymers that inhibit calcium phosphate and calcium carbonate scale in autodish applications
WO2003042347A1 (en) * 2001-11-14 2003-05-22 The Procter & Gamble Company Automatic dishwashing composition in unit dose form comprising an anti-scaling polymer
EP2130898A1 (en) * 2008-06-04 2009-12-09 Rohm and Haas Company Polymers and Their Use for Inhibition of Scale Build-Up in Automatic Dishwashing Applications

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J. P. SIBILIA: "A Guide to Materials Characterization and Chemical Analysis", 1988, VCH, pages: 81 - 84
W. W. YAU; J. J. KIRKLAND; D. D. BLY: "Modem Size Exclusion Chromatography", 1979, WILEY-INTERSCIENCE

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107075425A (en) * 2014-10-09 2017-08-18 罗门哈斯公司 Additive for reducing spot in automatic tableware washing system
CN107075425B (en) * 2014-10-09 2020-09-04 罗门哈斯公司 Additive for reducing stains in automatic dishwashing systems
WO2016153581A1 (en) * 2015-03-24 2016-09-29 Rohm And Haas Company Control of scale in warewash applications
CN107429198A (en) * 2015-03-24 2017-12-01 罗门哈斯公司 Incrustation scale control in dish washing application
WO2019083718A1 (en) * 2017-10-23 2019-05-02 Dow Global Technologies Llc Gradient copolymers for use in automatic dishwashing systems
CN111201254A (en) * 2017-10-23 2020-05-26 陶氏环球技术有限责任公司 Gradient copolymers for use in automatic dishwashing systems
CN111201254B (en) * 2017-10-23 2022-06-17 陶氏环球技术有限责任公司 Gradient copolymers for use in automatic dishwashing systems
WO2022189536A1 (en) * 2021-03-12 2022-09-15 Reckitt Benckiser Finish B.V. Automatic dishwashing composition

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