EP2228428B1 - Additif de réduction de tartre pour systèmes de lavage automatique de la vaisselle - Google Patents

Additif de réduction de tartre pour systèmes de lavage automatique de la vaisselle Download PDF

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Publication number
EP2228428B1
EP2228428B1 EP20100154198 EP10154198A EP2228428B1 EP 2228428 B1 EP2228428 B1 EP 2228428B1 EP 20100154198 EP20100154198 EP 20100154198 EP 10154198 A EP10154198 A EP 10154198A EP 2228428 B1 EP2228428 B1 EP 2228428B1
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Prior art keywords
alternatively
polymer
composition
amps
carbonate
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EP20100154198
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German (de)
English (en)
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EP2228428A1 (fr
Inventor
Marianne P. Creamer
Jan Edward Shulman
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.
  • DE 3 743 739 discloses a dishwashing composition
  • a dishwashing composition comprising carbonate or sulfate, sodium silicate and a copolymer made of (meth)acrylic acid, (meth)acrylamide and a sulfonated monomer (e.g. AMPS).
  • 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) 62.5 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 1:3, 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 2:1, alternatively no more than 1:1. In some embodiments, the weight ratio of carbonate to silicate is 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 12.5 wt%.
  • 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.
  • Table 1 presents 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 presents results obtained using the polymer with a mixture of 4 g sodium carbonate, 6 g sodium disilicate and 2 g sodium citrate.
  • Table 2 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) (comparative) 1.9K 1.3 1.7 1.9 72 AA/28 AMPS (comparative) 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 3 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 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 presents results obtained using the polymer with a mixture of 2 g sodium carbonate and 8 g sodium disilicate.
  • Table 6 presents results obtained using the polymer with a mixture of 8 g sodium carbonate and 2 g sodium disilicate.
  • Table 7 presents results obtained using the polymer with a mixture of 6 g sodium carbonate and 2 g sodium disilicate.
  • Table 7 (comparative) 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 8 presents results obtained using the polymer with a mixture of 1.5 g sodium carbonate and 6 g sodium disilicate.
  • Table 8 (comparative) 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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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (10)

  1. Une composition de détergent pour lave-vaisselle automatique contenant moins de 0,5 % en poids de phosphore comprenant:
    (a) un polymère comprenant des résidus polymérisés de : (i) entre 62,5 et 85 % en poids d'acide acrylique, (ii) entre 5 et 20 % d'acide maléique et (iii) entre 10 et 30 % en poids d'acide 2-acrylamido-2-méthylpropanesulfonique ; et présentant une Mr d'au moins 2 000 ; et
    (b) du carbonate et du silicate dans un rapport en poids compris entre 2,5/1 et 1/3, respectivement, la composition comprenant entre 10 et 90 % en poids de carbonate et de silicate au total.
  2. La composition de la revendication 1 dans laquelle ledit polymère comprend des résidus polymérisés de :
    (i) entre 62,5 et 80 % en poids d'acide acrylique, (ii) entre 7,5 et 15 % d'acide maléique et (iii) entre 10 et 20 % en poids d'acide 2-acrylamido-2-méthylpropanesulfonique.
  3. La composition de la revendication 1, la composition comprenant entre 15 et 50 % en poids de carbonate et de silicate au total.
  4. La composition de la revendication 1, la composition comprenant du carbonate et du silicate dans un rapport en poids compris entre 1,5/1 et 1/3.
  5. La composition de la revendication 1 dans laquelle ledit polymère contient moins de 0,5 % en poids de phosphore.
  6. La composition de la revendication 1 dans laquelle ledit polymère comprend des résidus polymérisés de :
    (i) entre 65 et 80 % en poids d'acide acrylique,
    (ii) entre 7,5 et 15 % d'acide maléique et
    (iii) entre 10 et 20 % en poids d'acide 2-acrylamido-2-méthylpropanesulfonique ; la composition comprenant entre 15 et 50 % en poids de carbonate et de silicate au total ; et du carbonate et du silicate dans un rapport en poids compris entre 1,5/1 et 1/3.
  7. La composition de la revendication 6 dans laquelle ledit polymère présente une Mr d'au moins 8 000.
  8. La composition de la revendication 7 dans laquelle ledit polymère comprend des résidus polymérisés de :
    (i) entre 70 et 80 % en poids d'acide acrylique, (ii) entre 7,5 et 12,5 % en poids d'acide maléique et (iii) entre 12,5 et 17,5 % en poids d'acide 2-acrylamido-2-méthylpropanesulfonique.
  9. La composition de la revendication 8 dans laquelle ledit polymère contient moins de 0,5 % en poids de phosphore.
  10. La composition de la revendication 9 comprenant de plus au moins 0,1 % en poids d'un sel hypochlorite et présentant un pH d'au moins 11,5.
EP20100154198 2009-03-13 2010-02-22 Additif de réduction de tartre pour systèmes de lavage automatique de la vaisselle Active EP2228428B1 (fr)

Applications Claiming Priority (2)

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US21002509P 2009-03-13 2009-03-13
US33730010P 2010-02-02 2010-02-02

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EP2228428A1 EP2228428A1 (fr) 2010-09-15
EP2228428B1 true EP2228428B1 (fr) 2013-01-16

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107075418A (zh) * 2014-10-09 2017-08-18 罗门哈斯公司 用于在自动餐具洗涤体系中减少污渍的添加剂
US11292992B2 (en) 2017-10-23 2022-04-05 Dow Global Technologies Llc Gradient copolymers for use in automatic dishwashing systems

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JP6294124B2 (ja) * 2014-03-31 2018-03-14 株式会社日本触媒 共重合体およびその製造方法
AU2015328204B2 (en) * 2014-10-09 2019-04-04 Rohm And Haas Company Additive for reducing spotting in automatic dishwashing systems
WO2016153668A1 (fr) * 2015-03-20 2016-09-29 Rohm And Haas Company Détergent pour lavage automatique de vaisselle
BR112017020157A2 (pt) * 2015-03-24 2018-06-05 Rohm & Haas controle de incrustação em aplicações para lavagem de louças
CN111936609A (zh) 2018-03-13 2020-11-13 埃科莱布美国股份有限公司 包括三元共聚物的器皿清洗碱性洗涤剂组合物
GB202103439D0 (en) * 2021-03-12 2021-04-28 Reckitt Benckiser Finish Bv Composition

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Publication number Priority date Publication date Assignee Title
CN107075418A (zh) * 2014-10-09 2017-08-18 罗门哈斯公司 用于在自动餐具洗涤体系中减少污渍的添加剂
CN107075418B (zh) * 2014-10-09 2020-11-13 罗门哈斯公司 用于在自动餐具洗涤体系中减少污渍的添加剂
US11292992B2 (en) 2017-10-23 2022-04-05 Dow Global Technologies Llc Gradient copolymers for use in automatic dishwashing systems

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CA2696155A1 (fr) 2010-09-13
JP5544192B2 (ja) 2014-07-09
JP2014028870A (ja) 2014-02-13
EP2228428A1 (fr) 2010-09-15
CA2696155C (fr) 2013-04-23

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