EP0560519B1 - Utilisation de polymères hydrosolubles dans des compositions de nettoyage et polymères hydrosolubles à cet effet - Google Patents

Utilisation de polymères hydrosolubles dans des compositions de nettoyage et polymères hydrosolubles à cet effet Download PDF

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EP0560519B1
EP0560519B1 EP93301511A EP93301511A EP0560519B1 EP 0560519 B1 EP0560519 B1 EP 0560519B1 EP 93301511 A EP93301511 A EP 93301511A EP 93301511 A EP93301511 A EP 93301511A EP 0560519 B1 EP0560519 B1 EP 0560519B1
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Prior art keywords
acid
percent
weight
water
butyl
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English (en)
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EP0560519A3 (en
EP0560519A2 (fr
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David Elliott Adler
Jan Edward Shulman
Thomas Francis Mccallum Iii
Barry Weinstein
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Rohm and Haas Co
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Rohm and Haas Co
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    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the present invention is concerned with the use of polymers comprising, as polymerized units, (a) one or more monomer selected from C 3 -C 6 monoethylenically unsaturated carboxylic acids, and alkali metal and ammonium salts thereof, (b) one or more aminoacryloyl derivative, and (c) optionally, one or more monomer polymerisable with (a) and (b), as additives for cleaning formulations such as hard surface cleaner formulations and particularly automatic machine dishwashing detergent formulations.
  • the polymers improve the spotting and filming characteristics (i.e. reduce spotting and filming) of cleaning formulations such as automatic machine dishwashing detergents.
  • the present invention is also concerned with polymers containing, as polymerized units, (a) one or more monomer selected from C 3 -C 6 monoethylenically unsaturated carboxylic acids, and alkali metal and ammonium salts thereof, (b) one or more aminoacryloyl derivative, and (c) one or more monomer polymerisable with (a) and (b).
  • Polymeric additives are used in automatic machine dishwashing detergent formulations as phosphate substitutes, builders, thickeners, processing aids, film-control agents and spot-control agents. Unlike many other detergent formulations, it is critical that automatic machine dishwashing detergents are low foaming systems. Foam interferes with the mechanical washing action of the water which is sprayed in the machine. This requirement limits the types of polymeric additives and surfactants which can be used in an automatic machine dishwashing detergent formulation.
  • GB-B-2,104,091 discloses amphoteric copolymers containing as polymerized units cationic vinyl monomers and anionic vinyl monomers for use in detergent compositions.
  • the mole ratio of cationic vinyl monomer to anionic vinyl monomer is from 1:99 to 99:1, and is preferably 20:80 to 80:20.
  • the molecular weight of the polymers is from 1,000 to 3,000,000. All of the examples employ copolymers having a 1:1 molar ratio of cationic vinyl monomer to anionic vinyl monomer.
  • the polymers are disclosed to be useful for enhancing the foaming power of surfactant-based liquid detergent compositions.
  • Japanese Patent Application 59-135293A discloses terpolymers comprising at least 10 mole percent of each of (1) an anionic vinyl monomer, (b) a cationic vinyl monomer, and (c) a nonionic vinyl monomer, wherein the molar ratio of anionic vinyl monomer to cationic vinyl monomer is from 1:2 to 2:1. It further discloses that the polymers increase the detergency of detergent compositions, especially when used with surfactants.
  • EP-A-0,132,792 teaches certain cleaning compositions for washing dishes in automatic dishwashers.
  • the compositions contain from 1 to 8 weight percent of a polycarboxylic acid having a molecular weight of 12,000 to 40,000.
  • the detergent contains surfactants and standard additives such as bleaching agents, biocides, perfumes, foaming-inhibitors, and /or solubilizers.
  • the polymer can be poly(acrylic acid), poly(methacrylic acid), or polymers of maleic acid or fumaric acid and ethylene or propylene.
  • the present invention provides a method of enhancing the spotting and filming control of cleaning compositions, e.g. automatic machine dishwashing detergent formulations.
  • the present invention also provides novel water-soluble polymers and a method for their preparation.
  • a method of improving the spotting and filming characteristics of cleaning compositions e.g. automatic machine dishwashing detergents, which comprises adding to a cleaning composition, e.g. an automatic dishwashing detergent formulation, one or more water-soluble polymer comprising, as polymerized units:-
  • the one or more water-soluble polymer comprises, as polymerized units and based on the weight of the polymer, from 95 to 60, preferably from 90 to 70, and most preferably from 90 to 75, percent by weight of the monomer(s) (a), and from 5 to 40, preferably from 10 to 30, and most preferably from 10 to 25, percent by weight of the aminoacryloyl derivative(s) (b).
  • the water-soluble polymer(s) may contain no monoethylenically unsaturated monomer(s) (c).
  • the relative amounts of components (a) and (b) are preferably in the molar ratio of from 4:1 to 150:1. More preferably, the molar ratio of component (a) to component (b) is from 5:1 to 100:1, and most preferably from 10:1 to 50:1.
  • the one or more water-soluble polymer comprises, as polymerized units and based on the weight of the polymer, from 92 to 30, preferably from 85 to 40, and most preferably from 80 to 50, percent by weight of the monomer(s) (a), from 5 to 50, preferably from 5 to 40, and most preferably from 10 to 30, percent by weight of the aminoacryloyl derivative(s) (b), and from 3 to 25, preferably from 3 to 20, and most preferably from 5 to 20, percent by weight of the polymerisable monoethylenically unsaturated monomer(s) (c).
  • the relative amounts of components (a) and (b) are preferably in the molar ratio of from 2:1 to 100:1. More preferably, the molar ratio of component (a) to component (b) is from 2.5:1 to 90:1, and most preferably from 3:1 to 50:1.
  • the present invention also provides water-soluble polymers comprising, as polymerized units and based on the weight of the polymer,
  • the relative amounts of components (a) and (b) are preferably in the molar ratio of from 2:1 to 100:1. More preferably, the molar ratio of component (a) to component (b) is from 2.5:1 to 90:1, and most preferably from 3:1 to 50:1.
  • the present invention further provides a method of making a polymer as defined in the preceding two paragraphs, which comprises contacting a mixture of monomers (a), (b) and (c) with an initiator in an amount effective to polymerize said mixture, and maintaining the mixture at an elevated temperature to produce the polymer product.
  • the method may further comprise utilizing one or more solvents, for example, water.
  • one or more of (a), (b) and (c) may be fed to a reactor at an elevated temperature.
  • Component (a) is one or more monomer selected from C 3 -C 6 monoethylenically unsaturated carboxylic acids, and alkali metal and ammonium salts thereof.
  • Suitable carboxylic acids include monoethylenically unsaturated monocarboxylic acids and monoethylenically unsaturated dicarboxylic acids.
  • Suitable monoethylenically unsaturated carboxylic acids include, but are not limited to, acrylic acid (AA), methacrylic acid (MAA), ⁇ -ethacrylic acid, ⁇ , ⁇ -dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid (MALAC), maleic anhydride (MALAN), fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and alkali metal and ammonium salts thereof.
  • the monoethylenically unsaturated carboxylic acid(s) is/ are selected from acrylic acid, methacrylic acid, and alkali metal and ammonium salts thereof. More preferably, the monoethylenically unsaturated carboxylic acid(s) is acrylic acid or methacrylic acid.
  • Component (b) is one or more aminoacryloyl derivative selected from: wherein:
  • Component (c) is one or more monoethylenically unsaturated monomer which is polymerisable with components (a) and (b), with the proviso that, if (c) comprises one or more C 3 -C 6 monoethylenically unsaturated carboxylic acid or alkali metal or ammonium salt thereof, then said monoethylenically unsaturated carboxylic acid or alkali metal or ammonium salt thereof is not the same as (a).
  • (c) is at least partially soluble in water or the reaction solvent, or in the other monomers if no water or solvent is used.
  • Suitable monomers include any of the C 3 -C 6 monoethylenically unsaturated carboxylic acids and their alkali metal and ammonium salts used for component (a), with the proviso that, if (c) comprises one or more C 3 -C 6 monoethylenically unsaturated carboxylic acid or alkali metal or ammonium salt thereof, then said monoethylenically unsaturated carboxylic acid or alkali metal or ammonium salt thereof is not the same as (a); C 1 -C 4 alkyl esters of acrylic acid and methacrylic acid such as methyl acrylate, ethyl acrylate (EA), butyl acrylate (BA), methyl methacrylate (MMA), and butyl methacrylate (BMA); C 1 -C 4 hydroxyalkyl esters of acrylic acid and methacrylic acid such as hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), and hydroxyethy
  • the monomer is acrylamide, C 3 -C 6 monoethylenically unsaturated carboxylic acids or alkali metal or ammonium salts thereof, C 1 -C 4 alkyl esters of acrylic acid or methacrylic acid, or C 1 -C 4 hydroxyalkyl esters of acrylic acid.
  • component (c) is selected from methyl methacrylate, butyl methacrylate, butyl acrylate, ethyl acrylate, t-butyl acrylamide, styrene and 2-acrylamido methylpropane sulfonic acid.
  • the polymers useful in the present invention can be made by methods of polymerization well known to those skilled in the art. They can be prepared by aqueous polymerization, solvent polymerization or bulk polymerization. Preferably, they are prepared by aqueous polymerization. Furthermore, the polymerization can be conducted as a batch, cofeed, heel, semi-continuous or continuous process. Preferably, the polymerization is conducted as a cofeed or continuous process.
  • the initiator and monomers are generally introduced into the reaction mixture as separate streams which are fed linearly (i.e. at constant rates). If desired, the streams can be staggered so that one or more of the streams are completed before the others. If desired, a portion of the monomers or initiators may be added to the reactor before the feeds are begun.
  • the monomers can be fed into the reaction mixture as individual streams or combined into one or more streams. Preferably, the monomer stream containing component (b) is not combined with the monomer stream containing component (a).
  • the initiators suitable for making the polymers are any of the conventional water-soluble free-radical initiators and redox initiators.
  • Suitable free-radical initiators include, but are not limited to, peroxides, persulfates, peresters, and azo initiators.
  • Suitable redox initiators include but are not limited to peroxides, such as hydrogen peroxide, and persulfates, such as sodium persulfate.
  • mixed initiator systems can be used such as a combination of a free radical initiator and a redox initiator.
  • the level of initiator is generally from 0.1 to 20 percent by weight based on the total amount of polymerisable monomers.
  • the initiator is present at a level of from 1 to 15 percent, and most preferably at a level of from 2 to 10 percent, by weight based on the total amount of polymerisable monomer.
  • Suitable promoters include water-soluble salts of metal ions. Suitable metal ions include iron, copper, cobalt, manganese, vanadium and nickel. Preferably, the one or more promoters are water-soluble salts of iron or copper. When used, the one or more promoters are present at levels of from 1 to 100 ppm based on the total amount of polymerisable monomer. Preferably, the one or more promoters are present at levels of from 3 to 20 ppm based on the total polymerisable monomers.
  • the pH of the polymerizing monomer mixture can be controlled by a buffer system or by the addition of a suitable acid or base and is preferably designed to maintain the pH of the system from between 3 and 8, and most preferably from between 4 and 6.5.
  • a buffer system or by the addition of a suitable acid or base
  • the pH of the system can be adjusted to suit the choice of the redox couple by the addition of an effective amount of a suitable acid or base.
  • the reaction should be conducted up to 70 percent by weight, preferably from 40 to 60 percent by weight of polymerisable monomers based on the total reaction mixture.
  • the reaction should be conducted up to 70 percent by weight, preferably from 40 to 60 percent by weight of polymerisable monomers based on the total reaction mixture.
  • the solvents or water, if used, can be introduced into the reaction vessel as a heel charge, or can be fed into the reactor either as a separate feed stream or as a diluent for one of the other components being fed into the reactor.
  • the temperature of the polymerization reaction will depend on the choice of initiator, solvent and target molecular weight. Generally, the temperature of the polymerization is up to the boiling point of the system although the polymerization can be conducted under pressure if higher temperatures are used. Preferably, the temperature of the polymerization is from 50 to 95 °C and most preferably from 60 to 80 °C.
  • the polymers useful in the present invention are water-soluble. This limits the maximum molecular weight of the polymers. Furthermore, the limit of the molecular weight will vary depending upon the relative amounts, and the hydrophilicity, of the monomer components incorporated into the polymer.
  • chain regulators or chain transfer agents may be employed to assist in controlling the molecular weight of the polymers. Any conventional water-soluble chain regulator or chain transfer agent can be used. Suitable chain regulators include, but are not limited to, mercaptans, hypophosphites, isoascorbic acid, alcohols, aldehydes, hydrosulfites and bisulfites.
  • preferred mercaptans are 2-mercaptoethanol and 3-mercaptopropionic acid; a preferred bisulfite is sodium metabisulfite.
  • M w weight average molecular weight of the polymers is from 500 to 100,000, preferably from 750 to 30,000, and most preferably from 1,000 to 25,000, as measured by aqueous gel permeation chromatography relative to a poly(acrylic acid) standard.
  • the concentration of polymer in a detergent composition is preferably from 0.2 to 10 percent by weight of the composition, and more preferably from 0.5 to 7 percent by weight.
  • the concentration of the polymer in the detergent composition is dependent on the amount of other additives in the detergent composition which have an impact on the desired performance characteristics. For example, if a phosphate containing compound is present in the detergent composition, the effective amount of polymer necessary to achieve the desired performance may be lower than if no phosphate containing compound is present.
  • the detergent composition of this invention can be in the form of either a powder or liquid.
  • liquid also refers to a gel or a slurry.
  • the detergent composition of this invention may include conventional machine dishwashing detergent additives well known to those skilled in the art, in conventional use amounts.
  • the detergent composition of this invention may contain an alkali metal silicate at a concentration of from 0 to 50 percent, more preferably from 1 to 20 percent, by weight of the detergent composition.
  • the alkali metal silicates which may be used in the composition of the current invention generally have an SiO 2 :M 2 O ratio (where M 2 O represents the alkali metal oxide portion of the silicate) of from 1:1 to 3.5:1.
  • the more preferred alkali metal silicates are the sodium silicates.
  • alkali metal silicates are an optional component of the present invention
  • highly alkaline dishwashing detergents containing no silicates may attack aluminum pots and pans and other metal utensils. Therefore, silicates are beneficial when corrosion inhibition of metal parts is desired.
  • the detergent compositions of this invention may optionally include a builder.
  • the level of builder can be from 0 to 90 percent, and more preferably from 20 to 90 percent, by weight of the detergent composition.
  • the builder concentration is dependent on whether the detergent is a liquid or a powder. Generally, a liquid composition will contain less builder than a powder composition.
  • builders which may be employed in combination with the polymers useful in the present invention include water soluble inorganic builder salts such as alkali metal polyphosphates, i.e., the tripolyphosphates and pyrophosphates, alkali metal carbonates, borates, bicarbonates, and hydroxides and water soluble organic builders such as polycarboxylates including nitrilotriacetic acid, citrates, tartarates and succinates.
  • zeolite may be added as a builder in amounts from 0 to 40 percent, and more preferably from 5 to 20 percent by weight.
  • Polymeric additives can also be used in the detergent formulations.
  • Conventional polymeric additives include, but are not limited to water-soluble homopolymers of acrylic acid, and copolymers of acrylic acid with a suitable comonomer such as maleic anhydride, and the salts of these polymers.
  • the polymeric additives are present in the detergent formulation at levels of from 0.2 percent to 15 percent, and preferably at a level of from 0.2 to 10 percent, and most preferably from 0.5 percent to 8 percent, by weight of the detergent formulation.
  • the detergent compositions of this invention will generally contain a low-foaming water soluble surfactant.
  • Low-foaming surfactants are preferred for the detergent compositions of the present invention since foam reduces the mechanical efficiency of the wash spray as discussed previously.
  • Certain low-foaming water soluble anionic, nonionic, zwitterionic, amphoteric surfactant or combinations thereof should be employed.
  • the quantity of surfactant used in the detergent formulation will depend on the surfactant chosen and will generally be from 0.1 to 10 percent, and more preferably from 1 to 5 percent, by weight of the detergent composition.
  • Suitable anionic surfactants include soaps such as the salts of fatty acids containing 9 to 20 carbon atoms, e.g. salts of fatty acids derived from coconut oil and tallow; alkylbenzenesulfonates - particularly linear alkylbenzenesulfonates in which the alkyl group contains from 10 to 16 carbon atoms; alcohol sulfates; ethoxylated alcohol sulfates; hydroxyalkylsulfonates; alkenyl and alkyl sulfates and sulfonates; monoglyceride sulfates and acid condensates of fatty acid chlorides with hydroxyalkylsulfonates.
  • soaps such as the salts of fatty acids containing 9 to 20 carbon atoms, e.g. salts of fatty acids derived from coconut oil and tallow; alkylbenzenesulfonates - particularly linear alkylbenzenesulfonates in which the alky
  • the level of anionic surfactant is kept to a minimum and may require the use of a foam suppressant. If used, the level of anionic surfactant is preferably below 5 percent, and most preferably below 3 percent, by weight of the formulation.
  • nonionic surfactants include alkylene oxide (e.g. ethylene oxide) condensates of mono and polyhydroxy alcohols, alkylphenols, fatty acid amides, and fatty amines; amine oxides; sugar derivatives such as sucrose monopalmitate; long chain tertiary phosphine oxides; dialkylsulfoxides; block copolymers of poly(ethylene oxide) and poly(propylene oxide); hydrophobically modified poly(ethylene oxide) surfactants and fatty acid amides, (e.g., mono or diethanolamides of fatty acids containing 10 to 18 carbon atoms).
  • the hydrophobically modified poly(ethylene oxide) surfactants are the preferred nonionic surfactants.
  • Suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium compounds such as 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate.
  • amphoteric surfactants examples include betaines, sulfobetaines and fatty acid imidazole carboxylates and sulfonates.
  • the detergent may also contain up to 20 percent by weight of a bleaching agent, and preferably from 0.5 to 15 percent by weight.
  • Suitable bleaching agents include the halogen, peroxide and peracid bleaches.
  • suitable bleaches include sodium chlorite, potassium chlorite, sodium hypochlorite, potassium hypochlorite, sodium dichloroisocyanurate, sodium perborate, potassium perborate and sodium percarbonate.
  • the detergent may also contain up to 5 percent by weight of conventional adjuvants such as perfumes, colorants, foam suppressants, enzymes and bacterial agents.
  • conventional adjuvants such as perfumes, colorants, foam suppressants, enzymes and bacterial agents.
  • stabilizers or viscosity modifiers such as clays and polymeric thickeners, can be added.
  • Inert diluents may be used in the cleaning compositions, e.g. the detergent compositions, of the present invention.
  • inert diluents such as alkali metal chlorides, sulfates, nitrates and nitrites, may be used in the detergent compositions.
  • examples of such diluents which may be incorporated into the detergent compositions are sodium or potassium chloride, sodium or potassium sulfate and sodium or potassium nitrite.
  • water can be used as a diluent.
  • the amount of diluent used is generally an amount to bring the total amount of the additives in the detergent composition up to 100% by weight.
  • the detergent composition of this invention may be used in machine dishwashers as an aqueous solution at a concentration of 0.2 to 1.5 percent, more preferably from 0.4 to 1 percent, by weight of the aqueous solution.
  • the water temperature during the washing process should be about 37.8°C to 65.6°C (about 100°F to 150°F), and more preferably from about 43.3°C to 57.2°C (about 110°F to 135°F).
  • the dishwashing tests were performed using a modified version of A.S.T.M. method D 3556-85, Standard Test Method for Deposition on Glassware During Mechanical Dishwashing .
  • This test method covers a procedure for measuring performance of household automatic dishwashing detergents in terms of the buildup of spots and film on glassware. Glass tumblers were given three cycles in a dishwasher, in the presence of food soils, and the levels of spotting and filming allowed by the detergents under test were compared visually.
  • a Kenmore dishwashing machine was used to perform the washing tests.
  • the bottom rack of the dishwasher was randomly loaded with 14-18 dinner plates and the top rack was randomly loaded with several beakers and cups.
  • Four new 113.4 g (10 ounce) tumblers were placed randomly on the top racks as the test glasses.
  • Soil used in the test was a mixture of 80% Parkay Margarine and 20% Carnation Non-fat Dry milk. The amount of soil used for each test was usually 40 grams for the first wash.
  • the polymer syntheses which follow are representative of the cofeed process suitable for preparing polymers of, and polymers useful in, the present invention. Methods of preparing the polymers of, and polymers useful in, the present invention are not limited to this procedure.
  • Three feed solutions were prepared: a monomer solution of 480.0 grams glacial acrylic acid and 200.0 grams of 60 percent APTAC in deionized water; an initiator solution of 2.86 grams of sodium persulfate dissolved in 60.0 grams of deionized water; and a chain regulator solution of 32.25 grams sodium metabisulfite dissolved in 100 grams of deionized water. These solutions were fed into the flask linearly and separately over two hours (except the chain regulator solution which was fed for 105 minutes) while maintaining the mixture at 70 °C. After the feeds were completed, the mixture was maintained at 70°C for ten minutes. The data for this copolymer appear as Examples 16 and 17 in Table 1 below.
  • Table 1 shows the effectiveness of the copolymers for enhancing the spotting and filming properties of automatic machine dishwashing detergents containing them.
  • Table 2 shows the effectiveness of the polymers of the present invention for enhancing the spotting and filming properties of automatic machine dishwashing detergents (Detergent B) containing them.
  • “Acusol”, “Poly-Tergent” and “BRITESIL” are trademarks which may be registered in one or more of the designated countries.

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Claims (23)

  1. Procédé d'amélioration des caractéristiques anti-taches et anti-film de compositions nettoyantes, qui comprend l'addition à une composition nettoyante d'un ou plusieurs polymères hydrosolubles comprenant, sous la forme d'unités polymérisées :
    (a) de 95 à 30 % en poids d'un ou plusieurs monomères choisis parmi les acides carboxyliques en C3 à C6 monoéthyléniquement insaturés et les sels de métal alcalin et d'ammonium de ceux-ci ;
    (b) de 5 à 50 % en poids d'un ou plusieurs dérivés aminoacryloyliques choisis parmi :
    Figure 00320001
    où :
    R1 est choisi parmi l'hydrogène et le groupe méthyle ;
    A est choisi parmi O et NH ;
    R2 et R3 sont chacun indépendamment choisis parmi l'hydrogène, les groupes méthyle, éthyle, propyle, isopropyle, butyle, t-butyle et isobutyle ; ou R2 et R3, avec le carbone auquel ils sont tous les deux attachés, forment un cycle aliphatique en C3 à C7 ;
    M est égal à 0, 1 ou 2, avec la condition que lorsque M est égal à 0, une liaison C-N apparaisse à la place du groupe (CH2)M ; et
    R4 et R5 sont chacun indépendamment choisis parmi l'hydrogène, les groupes méthyle, éthyle, propyle, isopropyle, butyle, t-butyle et isobutyle ; ou R4 et R5, avec le carbone auquel ils sont tous les deux attachés, forment un cycle aliphatique en C3 à C7 ;
    et
    Figure 00320002
    où :
    R1, A, R2, R3, R4, R5 et M sont tels que définis ci-dessus ;
    R6 est choisi parmi l'hydrogène, les groupes méthyle, éthyle, propyle, isopropyle, butyle, t-butyle et isobutyle ;
    et X est tout contre-ion approprié, par exemple un ion halogène, hydroxyde, sulfate, hydrosulfate, phosphate, formate ou acétate ; et
    (c) facultativement, de 3 à 25 % en poids d'un ou plusieurs monomères monoéthyléniquement insaturés polymérisables avec (a) et (b) ; avec la condition que si (c) comprend un ou plusieurs acides carboxyliques en C3 à C6 monoéthyléniquement insaturés ou sels de métal alcalin ou d'ammonium de ceux-ci, alors lesdits un ou plusieurs acides carboxyliques monoéthyléniquement insaturés ou sels de métal alcalin ou d'ammonium de ceux-ci ne soient pas les mêmes que (a) ; en une quantité efficace pour améliorer les caractéristiques anti-taches et anti-film.
  2. Procédé selon la revendication 1, dans lequel (a) est choisi parmi: l'acide acrylique, l'acide méthacrylique, l'acide α-éthacrylique, l'acide β,β-diméthylacrylique, l'acide méthylènemalonique, l'acide vinylacétique, l'acide allylacétique, l'acide éthylidineacétique, l'acide propylidineacétique, l'acide crotonique, l'acide maléique, l'anhydride maléique, l'acide fumarique, l'acide itaconique, l'acide citraconique, l'acide mésaconique, et les sels de métal alcalin et d'ammonium de ceux-ci.
  3. Procédé selon la revendication 1 ou la revendication 2, dans lequel (b) est choisi parmi: l'acrylate de N,N-diméthylaminoéthyle, le méthacrylate de N,N-diméthylaminoéthyle, le N-[3-(diméthylamino)propyl]acrylamide, le N-[3-(diméthylamino)propyl]méthacrylamide, le méthacrylate de tert-butylaminoéthyle, le chlorure de (3-acrylamidopropyl)triméthylammonium, le chlorure de (3-méthacrylamidopropyl)triméthylammonium et le N-[3-(diméthylamino)-2,2-diméthylpropyl]acrylamide.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel le poids moléculaire moyen en poids du polymère est de 500 à 100 000.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel le ou les polymères hydrosolubles comprennent, sous la forme d'unités polymérisées, de 95 à 60 % en poids de (a) et de 5 à 40 % en poids de (b).
  6. Procédé selon la revendication 5, dans lequel (a) est présent à une proportion de 70 à 90 % en poids.
  7. Procédé selon la revendication 5, dans lequel (b) est présent à une proportion de 10 à 30 % en poids.
  8. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel le ou les polymères hydrosolubles comprennent, sous la forme d'unités polymérisées, de 92 à 30 % en poids de (a), de 5 à 50 % en poids de (b) et de 3 à 25 % en poids de (c).
  9. Procédé selon la revendication 8, dans lequel (a) est présent à une proportion de 40 à 85 % en poids.
  10. Procédé selon la revendication 8 ou la revendication 9, dans lequel (b) est présent à une proportion de 5 à 40 % en poids.
  11. Procédé selon l'une quelconque des revendications 8 à 10, dans lequel (c) est choisi parmi les acides carboxyliques en C3 à C6 mono-éthyléniquement insaturés et les sels de métal alcalin et d'ammonium de ceux-ci, les esters d'alkyle en C1 à C4 de l'acide acrylique et de l'acide méthacrylique, les esters d'hydroxyalkyle en C1 à C4 de l'acide acrylique et de l'acide méthacIylique, l'acrylamide, les acrylamides alkyl-substitués, les acrylamides N,N-dialyl-substitués, le styrène, le styrène sulfoné, les alkylacrylamides sulfonés, les sulfonates de vinyle, l'acide vinylsulfonique, l'acide allylsulfonique, l'acide méthallylsulfonique, l'acide vinylphosphonique, l'acétate de vinyle, les alcools allyliques, les alcools allyliques sulfonés, l'acrylonitrile, la N-vinylpyrrolidone, le N-vinyl-formamide, le N-vinylimidazole, la N-vinylpyridine et la N-vinyl-2-méthylimidazoline ; avec la condition que si (c) comprend un ou plusieurs acides carboxyliques en C3 à C6 monoéthyliquement insaturés ou sels de métal alcalin ou d'ammonium de ceux-ci, alors lesdits un ou plusieurs acides carboxyliques monoéthyléniquement insaturés ou sels de métal alcalin ou d'ammonium de ceux-ci ne soient pas les mêmes que (a).
  12. Procédé selon l'une quelconque des revendications 8 à 10, dans lequel (c) est choisi parmi l'acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de butyle, le méthacrylate de méthyle, le méthacrylate de butyle, l'acrylate d'hydroxéthyle, l'acrylate d'hydroxypropyle, le méthacrylate d'hydroxyéthyle, l'acrylamide, le N-t-butylacrylamide, le N-t-octylacrylamide, le N,N-diméthylacrylamide, le pipéridineacrylamide, le styrène, le styrène sulfoné, l'acide vinylsulfonique, l'acide allylsulfonique, l'acide méthallylsulfonique, l'acide vinylphosphonique, l'acétate de vinyle, l'acrylonitrile, la N-vinylpyrrolidone, le N-vinylformamide, le N-vinylimidazole, la N-vinylpyridine, la N-vinyl-2-méthylimidazoline et l'acide 2-acrylamidométhylpropanesulfonique.
  13. Procédé selon l'une quelconque des revendications 8 à 12, dans lequel (c) est présent à une proportion de 3 à 20 % en poids.
  14. Procédé selon l'une quelconque des revendications précédentes, dans lequel le polymère est présent dans la composition à une proportion de 0,2 à 10 % en poids.
  15. Procédé selon l'une quelconque des revendications précédentes, dans lequel la composition nettoyante est une composition détergente pour machine à laver la vaisselle automatique.
  16. Composition nettoyante, qui comprend un polymère hydrosoluble tel que défini dans l'une quelconque des revendications 1 à 13.
  17. Composition nettoyante selon la revendication 16, qui est sous la forme d'une composition détergente pour machine à laver la vaisselle automatique.
  18. Composition nettoyante selon la revendication 17, dans laquelle le polymère est présent à une proportion de 0,2 à 10 % en poids.
  19. Polymère hydrosoluble selon l'une quelconque des revendications 8 à 13.
  20. Procédé de préparation d'un polymère tel que défini dans l'une quelconque des revendications 8 à 13, qui comprend les étapes consistant à mettre en contact un mélange des monomères (a), (b) et (c) avec un amorceur en une quantité efficace pour polymériser ledit mélange, et à maintenir le mélange à une température élevée pour fournir le produit polymère.
  21. Procédé selon la revendication 20, qui comprend en outre l'utilisation d'un solvant, par exemple de l'eau.
  22. Procédé selon la revendication 20 ou la revendication 21, dans lequel un ou plusieurs de (a), (b) et (c) sont introduits dans un réacteur à une température élevée.
  23. Utilisation, dans une composition nettoyante, par exemple une composition pour machine à laver la vaisselle automatique, d'un ou plusieurs polymères hydrosolubles tels que définis dans l'une quelconque des revendications 1 à 13, pour améliorer les caractéristiques anti-taches et anti-film de la composition.
EP93301511A 1992-03-10 1993-02-26 Utilisation de polymères hydrosolubles dans des compositions de nettoyage et polymères hydrosolubles à cet effet Expired - Lifetime EP0560519B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US84890892A 1992-03-10 1992-03-10
US848802 1992-03-10
US07/848,802 US5308532A (en) 1992-03-10 1992-03-10 Aminoacryloyl-containing terpolymers
US848908 1992-03-10

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EP0560519A2 EP0560519A2 (fr) 1993-09-15
EP0560519A3 EP0560519A3 (en) 1996-12-04
EP0560519B1 true EP0560519B1 (fr) 1998-08-05

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AT (1) ATE169331T1 (fr)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6090773A (en) 1996-01-29 2000-07-18 Johnson & Johnson Consumer Products, Inc. Personal cleansing
US6489286B1 (en) 1996-01-29 2002-12-03 Johnson & Johnson Consumer Companies, Inc. Personal cleansing compositions
US7915212B2 (en) 1999-05-26 2011-03-29 Rhodia Inc. Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US7939601B1 (en) 1999-05-26 2011-05-10 Rhodia Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses, and coagulants

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4323638A1 (de) * 1993-07-15 1995-01-19 Henkel Kgaa Verhinderung von Wasserflecken bei der technischen Reinigung
US5906972A (en) * 1994-10-14 1999-05-25 Rhodia Inc. Liquid detergent composition
DE19532542B4 (de) * 1995-09-04 2008-12-18 Henkel Ag & Co. Kgaa Klarspülmittel mit kationischen Polymeren
BR9811023A (pt) * 1997-07-23 2000-09-19 Unilever Nv Composição detergente que evita a corrosão das louças em máquinas automáticas para lavar louças, processo para evitar o desbotamento ou corrosão de louças durante o processo de lavagem em uma máquina para lavar louças automática, e, uso de um polìmero solúvel em água catiÈnico ou anfótero em uma composição para adição a uma máquina de lavar louças automática
BR9812789A (pt) * 1997-11-21 2000-10-17 Procter & Gamble Composições detergentes compreendendo realçadores de água de sabão poliméricos e seu uso
BR9812788A (pt) 1997-11-21 2000-10-17 Procter & Gamble Composições lìquidas detergentes compreendendo intensificadores poliméricos de espuma
DE19914367A1 (de) 1998-04-17 1999-10-21 Henkel Kgaa Wasserbeständige hydraulisch abbindende Zusammensetzungen
WO1999058633A1 (fr) * 1998-05-11 1999-11-18 Unilever Plc Compositions detergentes pour lave-vaisselle et compositions adjuvantes de rinçage
CA2333610A1 (fr) 1998-06-02 1999-12-09 Joanna Margaret Clarke Compositions detergentes pour la vaisselle contenant des diamines organiques
AU2004200189B2 (en) * 1999-05-26 2006-11-02 Rhodia Inc. Polymers, Compositions and Methods of use for Foams, Laundry Detergents, Shower Rinses, and Coagulants
EP1180130A1 (fr) * 1999-05-26 2002-02-20 The Procter & Gamble Company Compositions de detergent liquide contenant des activateurs polymeres bloc de mousse
US7241729B2 (en) 1999-05-26 2007-07-10 Rhodia Inc. Compositions and methods for using polymeric suds enhancers
WO2000071660A1 (fr) * 1999-05-26 2000-11-30 The Procter & Gamble Company Compositions de detergent liquide contenant des activateurs polymeres bloc de mousse
US6602836B2 (en) 2000-05-11 2003-08-05 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Machine dishwashing compositions containing cationic bleaching agents and water-soluble polymers incorporating cationic groups
US6703358B1 (en) * 2000-07-13 2004-03-09 Rhodia Chimie Cleaning composition for hard surfaces
US6376631B1 (en) 2000-09-27 2002-04-23 Rhodia, Inc. Processes to control the residual monomer level of copolymers of tertiary amino monomer with a vinyl-functional monomer
DE10141006A1 (de) * 2001-08-21 2003-03-06 Basf Ag Verwendung von amphoteren Polymeren als schmutzablösungsfördernder Zusatz von Mitteln für die Behandlung von Oberflächen
DE50208257D1 (de) * 2002-06-25 2006-11-09 Cognis Ip Man Gmbh Waschmittel mit Polymeren
JP4145865B2 (ja) * 2004-11-18 2008-09-03 花王株式会社 硬質表面用洗浄剤
EP1698688B1 (fr) 2005-03-04 2010-04-07 Rohm and Haas Company Compositions de lessive et utilisation
US7807766B2 (en) 2005-09-21 2010-10-05 Cognis Ip Management Gmbh Polymers for use in cleaning compositions
DE102005060431A1 (de) * 2005-12-15 2007-06-21 Henkel Kgaa Maschinelles Geschirrspülmittel
BRPI0715378A2 (pt) 2006-08-10 2013-06-18 Basf Se formulaÇço de limpeza para mÁquina de lavar louÇa, uso de uma combinaÇço de copolÍmeros e de agentes complexantes, e, processo para limpeza de louÇa em mÁquina
DE102009029636A1 (de) * 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Maschine Geschirrspülmittel
EP3153571A1 (fr) * 2015-10-09 2017-04-12 Backer, Scott Additif de réduction de taches dans des systèmes de lavage automatique de vaisselle
EP3228687B1 (fr) 2016-04-08 2019-05-22 The Procter and Gamble Company Composition de lavage de vaisselle
EP3257928B1 (fr) 2016-06-17 2019-12-11 The Procter and Gamble Company Composition de détergent de lave-vaisselle automatique
EP3290503A3 (fr) * 2016-09-01 2018-05-30 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
EP3814465A1 (fr) * 2018-06-27 2021-05-05 Rohm and Haas Company Procédé de nettoyage de plastique mettant en oeuvre un copolymère dispersant
US11732219B2 (en) * 2019-06-14 2023-08-22 Dow Global Technologies Llc Cleaning booster polymer
CN110655604A (zh) * 2019-10-31 2020-01-07 深圳大学 物理水凝胶及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115339A (en) * 1971-11-18 1978-09-19 Hercules Incorporated High molecular-weight, water-soluble vinyl polymers
JPS5813700A (ja) * 1981-07-17 1983-01-26 花王株式会社 食器用洗浄剤組成物
JPS59135293A (ja) * 1983-01-21 1984-08-03 花王株式会社 洗浄剤組成物
EP0132792A1 (fr) * 1983-07-20 1985-02-13 DISPO-Kommerz AG Agent de nettoyage sous forme de poudre soluble dans l'eau pour surfaces dures
CA1334389C (fr) * 1986-03-26 1995-02-14 Ernest H. Brumbaugh Composition anti-taches pour lave-vaisselle
DE3614336A1 (de) * 1986-04-28 1987-10-29 Henkel Kgaa Fluessige waessrige reinigungsmittel fuer harte oberflaechen
DE3624813A1 (de) * 1986-07-23 1988-03-10 Stockhausen Chem Fab Gmbh Amphotere wasserloesliche polymere, verfahren zu ihrer herstellung und ihre verwendung als dispergierhilfsmittel
FR2613378A1 (fr) * 1987-04-03 1988-10-07 Sandoz Sa Compositions detergentes pour lave-vaisselle
JPH04236208A (ja) * 1991-01-21 1992-08-25 Nippon Shokubai Co Ltd 両性高分子電解質の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6090773A (en) 1996-01-29 2000-07-18 Johnson & Johnson Consumer Products, Inc. Personal cleansing
US6489286B1 (en) 1996-01-29 2002-12-03 Johnson & Johnson Consumer Companies, Inc. Personal cleansing compositions
US7915212B2 (en) 1999-05-26 2011-03-29 Rhodia Inc. Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US7939601B1 (en) 1999-05-26 2011-05-10 Rhodia Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses, and coagulants
US8492481B2 (en) 1999-05-26 2013-07-23 Rhodia Inc. Block polymers, compositions and methods for use for foams, laundry detergents, and shower rinses and coagulants
US9044413B2 (en) 1999-05-26 2015-06-02 Solvay Usa Inc. Block polymers, compositions and methods for use for foams, laundry detergents, and shower rinses and coagulants

Also Published As

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AU3388293A (en) 1993-09-16
ATE169331T1 (de) 1998-08-15
DE69320082T2 (de) 1999-05-06
DE69320082D1 (de) 1998-09-10
EP0560519A3 (en) 1996-12-04
EP0560519A2 (fr) 1993-09-15

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