EP1516040B1 - Utilisation de copolymeres contenant des groupes d'acide sulfonique comme adjuvants dans les produits detergents - Google Patents

Utilisation de copolymeres contenant des groupes d'acide sulfonique comme adjuvants dans les produits detergents Download PDF

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Publication number
EP1516040B1
EP1516040B1 EP03740180A EP03740180A EP1516040B1 EP 1516040 B1 EP1516040 B1 EP 1516040B1 EP 03740180 A EP03740180 A EP 03740180A EP 03740180 A EP03740180 A EP 03740180A EP 1516040 B1 EP1516040 B1 EP 1516040B1
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copolymers
acid
mol
sulfonic acid
monoethylenically unsaturated
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EP1516040A1 (fr
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Pia Baum
Kathrin Michl
Franz Weingart
Stephan Nied
Gregor Brodt
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BASF SE
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BASF SE
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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

Definitions

  • the invention relates to detergents and cleaners which contain these copolymers as a deposit-inhibiting additive.
  • the so-called "2in1" dishwashing detergents introduced on the market contain, in addition to the cleaner for removing stains on the items to be washed, integral rinse surfactants which ensure a flat flow of water on the items to be washed during the rinse and drying cycle and thus prevent limescale and water stains. Refilling a rinse aid is no longer necessary when using these products.
  • Modern machine dishwashing detergents "3in1" cleaners, are intended to combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, making it unnecessary for the consumer to replenish salt with water hardnesses of 1 to 3.
  • sodium tripolyphosphate is usually added to these cleaners. This in turn, however, results in calcium and magnesium phosphate deposits on the items to be washed.
  • the EP-A-877 002 relates to the use of copolymers of monoethylenically unsaturated acids, unsaturated sulfonic acids and optionally monoethylenically unsaturated dicarboxylic acids and monoethylenically unsaturated comonomers as inhibitors of (poly) phosphate coatings in automatic dishwashing detergents.
  • Nonionic monomers of the formula II are not mentioned.
  • water-soluble copolymers containing sulfonate groups, carboxylate groups and polyalkylene oxide group-containing structural units and having an average molecular weight M w of> 50,000 to 3,000,000 can be used as agents against especially silicate-based scale in water cycles, eg, cooling systems.
  • the sulfonate group-containing structural unit of the individually disclosed copolymers is based on sodium 2-methyl-1,3-butadiene-1-sulfonate.
  • graft copolymers of monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated monomers containing sulfonic acid groups and optionally water-soluble monomers containing alkylene oxide units and other free-radically polymerizable monomers are used on polyhydroxy compounds for inhibiting water hardness in detergents and cleaners.
  • Graft copolymers of acrylic acid, sodium methallylsulfonate and methoxypolyethylene glycol methacrylate on polyvinyl alcohol, triglycerol and starch dextrin are described in detail.
  • the invention was based on the object to remedy the above problems and to provide an additive that can be used advantageously especially in multi-function cleaners and in particular shows a deposit-inhibiting effect.
  • washing and cleaning agents were found which contain the sulfonic acid-containing copolymers as a deposit-inhibiting additive.
  • copolymers comprising sulfonic acid groups comprise as copolymerized component (a) monoethylenically unsaturated carboxylic acids, their esters and / or water-soluble salts, the carboxylic acids themselves or their salts being preferred as component (a).
  • Suitable components (a) are, for example, ⁇ , ⁇ -unsaturated monocarboxylic acids which preferably have 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, 2-ethylpropenoic acid, crotonic acid and vinylacetic acid.
  • unsaturated dicarboxylic acids preferably having 4 to 6 carbon atoms, such as itaconic acid and maleic acid.
  • Suitable esters are in particular the reaction products of these acids with C 1 -C 6 -alcohols, especially methanol, ethanol and butanol, wherein the dicarboxylic acids may be present as mono- or diesters. Examples which may be mentioned are: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, monomethyl maleate and dimethyl maleate.
  • the salts are preferably alkali metal salts, e.g. Sodium or potassium salts, or ammonium salts, with the sodium salts being preferred.
  • Preferred carboxylic acids (a) are acrylic acid, methacrylic acid and maleic acid.
  • acrylic acid and methacrylic acid which may advantageously also be present together in the copolymers.
  • the proportion of the carboxylic acids (a) in the copolymers to be used according to the invention is 30 to 95 mol%, preferably 50 to 90 mol% and particularly preferably 60 to 90 mol%.
  • acrylic acid and methacrylic acid are present in the copolymers, their molar ratio is preferably from 15: 1 to 0.05: 1, in particular from 10: 1 to 1: 1, especially from 5: 1 to 1: 1.
  • the monomers I are: vinylsulfonic acid, 2-sulfoethyl (meth) acrylic acid, 2-sulfopropyl (meth) acrylic acid, 3-sulfopropyl (meth) acrylic acid and 4-sulfobutyl (meth) acrylic acid and salts thereof, in particular the sodium salts, vinylsulfonic acid, 2-sulfoethylmethacrylic acid and 2-sulfopropylmethacrylic acid and their sodium salts being preferred, and 2-sulfoethylmethacrylic acid and its sodium salt being particularly preferred.
  • the proportion of the sulfonic acid group-containing monomers (b) in the copolymers to be used according to the invention is 3 to 35 mol%, preferably 5 to 25 mol% and in particular 5 to 20 mol%.
  • the monomers II include: methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypoly ( propylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate, ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, wherein methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate are preferred and methoxypolyethylene glycol methacrylate is particularly preferred.
  • the polyalkylene glycols contain 3 to 50, in particular 10 to 30 alkylene oxide units.
  • the proportion of nonionic monomers (c) in the copolymers to be used according to the invention is 2 to 35 mol%, preferably 5 to 25 mol% and especially 5 to 20 mol%.
  • the copolymers to be used according to the invention generally have an average molecular weight M w of from 3,000 to 40,000, preferably from 10,000 to 30,000 and more preferably from 15,000 to 25,000.
  • the K value of the copolymers is usually from 15 to 35, in particular from 20 to 32, especially from 27 to 30 (measured in 1 wt .-% aqueous solution at 25 ° C, according to H. Fikentscher, cellulose chemistry, Vol. 13, pp. 58-64 and 71-74 (1932)).
  • copolymers to be used according to the invention can be prepared by free-radical polymerization of the monomers. It can be worked by all known radical polymerization. In addition to the bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with the solution polymerization being preferred.
  • the polymerization is preferably carried out in water as a solvent.
  • alcoholic solvents in particular C 1 -C 4 -alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.
  • Suitable polymerization initiators are both thermally and photochemically (photoinitiators) decomposing and thereby radical-forming compounds.
  • thermally activatable polymerization initiators are initiators having a decomposition temperature in the range from 20 to 180 ° C, in particular from 50 to 90 ° C. prefers.
  • suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxy compounds, such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permalate, tert-butyl perisobutyrate, tert.
  • inorganic peroxo compounds such as pe
  • initiators can be used in combination with reducing compounds as starter / regulator systems.
  • reducing compounds include phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.
  • photoinitiators examples include benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and derivatives thereof.
  • thermal initiators are used, with inorganic peroxo compounds, in particular sodium peroxodisulfate (sodium persulfate), being preferred.
  • the peroxo compounds are particularly advantageously used in combination with sulfur-containing reducing agents, in particular sodium hydrogen sulfite, as the redox initiator system.
  • sulfur-containing reducing agents in particular sodium hydrogen sulfite, as the redox initiator system.
  • phosphorus-containing starter / regulator systems may also be used, e.g. Hypophosphites / phosphinates.
  • the amounts of photoinitiator or starter / regulator system are to be matched to the substances used in each case. If, for example, the preferred system peroxodisulfate / hydrogen sulfite is used, usually 2 to 6% by weight, preferably 3 to 5% by weight, of peroxodisulfate and generally 5 to 30% by weight, preferably 5 to 10% by weight. %, Hydrogen sulfite, in each case based on the monomers (a), (b) and (c) used.
  • polymerization regulators can also be used. Suitable compounds are those known in the art, for example sulfur compounds, such as mercaptoethanol, 2-ethylhexyl thioglycolate, Thioglycolic acid and dodecylmercaptan.
  • sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, Thioglycolic acid and dodecylmercaptan.
  • their amount used is usually 0.1 to 15 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.1 to 2.5 wt .-%, based on the monomers (a), (b) and (c).
  • the polymerization temperature is usually at 30 to 200 ° C, preferably at 50 to 150 ° C and particularly preferably at 80 to 120 ° C.
  • the polymerization may be carried out under atmospheric pressure, but is preferably carried out in the closed system under the evolving autogenous pressure.
  • the monomers (a), (b) and (c) can be used as such, but reaction mixtures which are used in the preparation of e.g. the monomers (b) or (c) incurred.
  • reaction mixtures which are used in the preparation of e.g. the monomers (b) or (c) incurred for example, instead of 2-sulfoethyl methacrylate, the monomer mixture obtained in the esterification of 2-hydroxyethanesulfonic acid with an excess of methacrylic acid can be used.
  • methoxypolyethylene glycol methacrylate the monomer mixture obtained in the etherification of methoxypolyethylene glycol with an excess of methacrylic acid can be used.
  • methoxypolyethylene glycol methacrylate the monomer mixture obtained in the etherification of methoxypolyethylene glycol with an excess of methacrylic acid can be used.
  • methoxypolyethylene glycol methacrylate the monomer mixture obtained in the etherification of methoxypolyethylene glyco
  • the aqueous solutions obtained in the preparation of the sulfonic acid group-containing copolymers to be used according to the invention can be neutralized or partially neutralized by adding base, in particular sodium hydroxide solution, i. adjusted to a pH in the range of about 4-8, preferably 4.5-7.5.
  • the sulfonic acid-containing copolymers used in the invention are outstandingly suitable as an additive to detergents and cleaners.
  • the dishwashing detergents can be used in automatic dishwashing detergents. They are characterized mainly by their deposit-inhibiting effect against both inorganic and organic coatings. In particular, there are deposits caused by the remaining components of the cleaner formulation such as linings of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and coatings derived from the constituents of the rinse liquor, such as fat, protein and starch deposits called.
  • the copolymers used according to the invention thereby also increase the detergency of the dishwashing detergent. In addition, they already facilitate the drainage of the water from the dishes at low concentrations, so that the proportion of rinse aid surfactants in the dishwashing detergent can be reduced.
  • copolymers containing sulfonic acid When using the copolymers containing sulfonic acid accordingly particularly clear glasses and high-gloss metal cutlery are obtained, especially when the dishwasher is operated without Regeneriersalz for water softening.
  • the copolymers containing sulfonic acid groups can therefore be used advantageously not only in 2-in-1 cleaners but also in 3-in-1 cleaners.
  • the copolymers used according to the invention can be used directly in the form of the aqueous solutions obtained in the preparation as well as in dried, e.g. by spray drying, fluidized spray drying, drum drying or freeze-drying obtained form are used. Accordingly, the washing and cleaning agents according to the invention may be in solid or liquid form, e.g. as powders, granules, extrudates, tablets, liquids or gels.
  • M w methoxypolyethylene glycol methacrylate
  • Example 2 In the reactor of Example 1, a mixture of 145.9 g of distilled water and 4.44 g of phosphorous acid was heated to 100 ° C internal temperature with nitrogen and stirring. Then, a mixture of 139.8 g of acrylic acid, 100.5 g of 2-acrylamido-2-methylpropanesulfonic acid and 402 g of distilled water was added continuously in 5 hours. In parallel, a mixture of 12.0 g of sodium peroxodisulfate and 108.2 g of distilled water and in 5 h 45.1 g of a 11.3 wt .-% strength sodium bisulfite solution was added continuously in 5.25 h. After stirring for one hour at 100 ° C, the reaction mixture was cooled to room temperature and adjusted by the addition of 50 wt .-% sodium hydroxide solution to a pH of 7.2.
  • Dishwasher Miele G 686 SC rinses: 2 rinses 55 ° C normal (without pre-rinse) ware: Knife (WMF table knife Berlin, Monoblock) and barrel-shaped glass beaker (Matador, Ruhr Kri-stall) Dishwashing liquid: 21 g copolymer: 4.2 g Rinse temperature: 65 ° C Water hardness: 25 ° dH
  • the washware was evaluated 18 hours after cleaning by visual inspection in a black painted light box with halogen spot and pinhole using a grading scale from 10 (very good) to 1 (very bad).
  • the highest grade of 10 corresponds to covering and drip-free surfaces, from grades ⁇ 5, coverings and drops are already visible under normal room lighting, so are perceived as disturbing.
  • test results obtained are summarized in the following table.

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  • Chemical & Material Sciences (AREA)
  • 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)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Claims (9)

  1. Utilisation de copolymères renfermant des groupes acide sulfonique, qui comprennent
    (a) de 30 à 95 % en mole d'au moins un acide carboxylique monoéthyléniquement insaturé, un ester d'acide carboxylique monoéthyléniquement insaturé ou un sel hydrosoluble d'un acide carboxylique monoéthyléniquement insaturé,
    (b) de 3 à 35 % en mole d'au moins un monomère renfermant des groupes acide sulfonique de formule I
    Figure imgb0011
     dans laquelle les variables ont la signification suivante :
    R : hydrogène ou méthyle ;
    X : une liaison chimique ou un -COO-R1- ;
    R1 : un alkylène non ramifié ou ramifié en C1-C4 ;
    M : hydrogène, métal alcalin ou ammonium,
    et
    (c) de 2 à 35 % en mole minimum d'un monomère non ionique selon la formule II
    Figure imgb0012
    dans laquelle les variables ont la signification suivante :
    R2 hydrogène ou méthyle ;
    R3 : une liaison chimique, ou bien un alkylène non ramifié ou ramifié en C1-C6 ;
    R4 des radicaux alkylènes non ramifiés ou ramifiés en C2-C4, identiques ou différents ;
    R5 : des alkyles non ramifiés ou ramifiés en C1-C6 ;
    n : de 3 à 50,
    intégrés par polymérisation statistique ou bloc par bloc, en tant qu'adjuvant pour des compositions de lavage et de nettoyage.
  2. Utilisation selon la revendication 1, caractérisée en ce que les copolymères contiennent, intégrés par polymérisation, de 50 à 90 % en mole du composant (a), de 5 à 25 % en mole du composant (b), et de 5 à 25 % en mole du composant (c).
  3. Utilisation selon la revendication 1 ou 2,
    caractérisée en ce que l'acide carboxylique monoéthyléniquement insaturé (a) est l'acide acrylique, l'acide méthacrylique et/ou l'acide maléique.
  4. Utilisation selon les revendications 1 à 3,
    caractérisée en ce que l'acide carboxylique monoéthyléniquement insaturé (a) est l'acide acrylique ou un mélange d'acide acrylique et d'acide méthacrylique.
  5. Utilisation selon les revendications 1 à 4,
    caractérisée en ce que les copolymères contiennent, intégré par polymérisation, en tant que composant (b), un monomère renfermant des groupes acide sulfonique de formule I, dans laquelle R désigne du méthyle, X du -COO-C2H4- et M du sodium ou de l'hydrogène.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que les copolymères contiennent, intégré par polymérisation, en tant que composant (c) un monomère non ionique selon la formule II, dans laquelle R2 désigne du méthyle, R3 une liaison chimique, R4 de l'éthylène, R5 du méthyle, et n de 10 à 30.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que les copolymères contiennent en tant que terminaisons -SO3 - Na+ et/ou -SO4 - Na+.
  8. Utilisation selon l'une quelconque des revendications 1 à 7, caractérisée en ce que les copolymères sont utilisés en tant qu'adjuvant inhibiteur de dépôt dans des compositions pour lave-vaisselle.
  9. Compositions de lavage et de nettoyage contenant des copolymères selon les revendications 1 à 7, en tant qu'adjuvant inhibiteur de dépôt.
EP03740180A 2002-06-10 2003-06-04 Utilisation de copolymeres contenant des groupes d'acide sulfonique comme adjuvants dans les produits detergents Expired - Lifetime EP1516040B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10225794A DE10225794A1 (de) 2002-06-10 2002-06-10 Verwendung von sulfonsäuregruppenhaltigen Copolymeren als Zusatz in Wasch- und Reinigungsmitteln
DE10225794 2002-06-10
PCT/EP2003/005821 WO2003104372A1 (fr) 2002-06-10 2003-06-04 Utilisation de copolymeres contenant des groupes d'acide sulfonique comme adjuvants dans les produits detergents

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EP1516040B1 true EP1516040B1 (fr) 2009-08-12

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US (2) US20050202994A1 (fr)
EP (1) EP1516040B1 (fr)
JP (1) JP2005533137A (fr)
CN (1) CN1297647C (fr)
AT (1) ATE439419T1 (fr)
AU (1) AU2003274111A1 (fr)
CA (1) CA2488329C (fr)
DE (2) DE10225794A1 (fr)
ES (1) ES2328683T3 (fr)
MX (1) MXPA04011362A (fr)
WO (1) WO2003104372A1 (fr)

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MXPA04011362A (es) 2005-02-14
ATE439419T1 (de) 2009-08-15
CA2488329C (fr) 2010-11-23
CA2488329A1 (fr) 2003-12-18
WO2003104372A1 (fr) 2003-12-18
US20050202994A1 (en) 2005-09-15
DE10225794A1 (de) 2003-12-18
US7645345B2 (en) 2010-01-12
CN1659265A (zh) 2005-08-24
US20080281053A1 (en) 2008-11-13
EP1516040A1 (fr) 2005-03-23
CN1297647C (zh) 2007-01-31
JP2005533137A (ja) 2005-11-04
AU2003274111A1 (en) 2003-12-22
DE50311809D1 (de) 2009-09-24

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