EP1513916B1 - Utilisation de copolymeres contenant des unites d'oxyde d'alkylene comme adjuvants dans des compositions pour lave-vaisselle - Google Patents

Utilisation de copolymeres contenant des unites d'oxyde d'alkylene comme adjuvants dans des compositions pour lave-vaisselle Download PDF

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Publication number
EP1513916B1
EP1513916B1 EP03740181A EP03740181A EP1513916B1 EP 1513916 B1 EP1513916 B1 EP 1513916B1 EP 03740181 A EP03740181 A EP 03740181A EP 03740181 A EP03740181 A EP 03740181A EP 1513916 B1 EP1513916 B1 EP 1513916B1
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mol
copolymers
component
oxide units
alkylene
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German (de)
English (en)
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EP1513916A1 (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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the invention relates to automatic dishwashing compositions which contain these copolymers as a deposit-inhibiting additive.
  • the so-called "2inl" dishwashing detergents introduced on the market contain, in addition to the cleaner for removing stains on the items to be washed, integrated rinse aid surfactants which during the rinse and drying cycle ensure a flat flow of water on the items to be washed and thus prevent limescale and water stains. Refilling a rinse aid is no longer necessary when using these products.
  • Modern machine dishwashing detergents "3inl" 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.
  • EP-A-324 568 describes water-soluble copolymers for detergents and cleaners which are obtained by polymerization of acrylic acid, methacrylic acid and alkoxypolyethylene glycol methacrylates which have a long-chain alkoxy radical and / or a long-chain polyethylene glycol block in the presence of isopropanol.
  • the alkoxypolyethylene glycol methacrylate content of these copolymers is ⁇ 1 mol%.
  • copolymers based on at least one monomer from the group of maleic acid, acrylic acid and methacrylic acid and an optionally methoxy- or ethoxylated polyethylene glycol (meth) acrylate as further monomer having an average molecular weight M w of 1,000 up to 10 000, are used for the desizing, cleaning, bleaching and dyeing of natural and synthetic bevels.
  • copolymers of acrylic acid and methoxypolyethylene glycol methacrylate are examples of acrylic acid and methoxypolyethylene glycol methacrylate.
  • JP-A-2000/24691 describes copolymers of unsaturated carboxylic acids and monomers containing polyalkylene oxide units with average molecular weights M w of> 50,000 to 3,000,000 as agents against, in particular, silicates-based scale in water circulations, eg cooling systems.
  • M w average molecular weight of> 50,000 to 3,000,000
  • acrylic acid and methoxypolyethylene glycol methacrylate are disclosed.
  • 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.
  • the copolymers containing alkylene oxide units contain as copolymerized components (a) and (b) acrylic acid or methacrylic acid and / or water-soluble salts of these acids, in particular the alkali metal salts, such as potassium and especially sodium salts, and ammonium salts.
  • the proportion of acrylic acid (a) in the copolymers to be used according to the invention is 50 to 93 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.
  • Methacrylic acid (b) is contained in the copolymers to be used according to the invention to 5 to 30 mol%, preferably to 10 to 25 mol% and especially to 15 to 25 mol%.
  • Particularly suitable examples of the monomers II are: methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol ( meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and Ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, with methoxypolyethylene glycol (meth) acrylate and Methoxypolypropylenglykol (meth) acrylate are preferred and Methoxypolyethylenglykolmethacrylat is particularly preferred.
  • the polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 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 20 mol%, preferably 5 to 15 mol% and especially 5 to 10 mol%.
  • the copolymers to be used according to the invention generally have an average molecular weight M w of from 3,000 to 50,000, 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 40, in particular from 20 to 35, 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 preference is given to initiators having a decomposition temperature in the range from 20 to 180.degree. C., in particular from 50 to 90.degree.
  • 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-butyl perpivalate,
  • 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 dodecyl mercaptan.
  • sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecyl mercaptan.
  • polymerization regulators 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 it is also possible to use reaction mixtures which are obtained in the preparation of the monomers (c).
  • reaction mixtures which are obtained in the preparation of the monomers (c).
  • the monomer mixture obtained in the esterification of polyethylene glycol monomethyl ether with an excess of methacrylic acid can be used instead of methoxypolyethylene glycol methacrylate.
  • the esterification can also be carried out in situ in the polymerization mixture by (1) combining acrylic acid, (2) a mixture of methacrylic acid and polyethylene glycol monomethyl ether and (3) free radical initiator in parallel.
  • a catalyst necessary for the esterification such as methanesulfonic acid or p-toluenesulfonic acid, may additionally be used.
  • copolymers to be used according to the invention may also be obtained by polymer-analogous reaction, e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether.
  • polymer-analogous reaction e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether.
  • preferred is the radical copolymerization of the monomers.
  • the aqueous solutions obtained in the preparation of the carboxylic acid group-containing copolymers to be used according to the invention can be neutralized or partially neutralized by addition of base, in particular of sodium hydroxide solution, i. adjusted to a pH in the range of 4-8, preferably 4.5-7.5.
  • the copolymers used according to the invention are outstandingly suitable as an additive to automatic dishwasher detergents. They are characterized mainly by their deposit-inhibiting effect against both inorganic and organic coatings. In particular, coverings caused by the remaining constituents of the detergent formulation are such as toppings of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and linings derived from the soil 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.
  • the automatic dishwashing agents of the invention may accordingly be in solid or liquid form, e.g. as powders, granules, extrudates, tablets, liquids or gels.
  • reaction mixture was cooled to room temperature and adjusted by addition of 85 g of 50 wt .-% sodium hydroxide solution to a pH of 7.2.
  • 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.
  • table Copolymer from Ex. Rating (grade) knife glasses 1 8.0 7.7 2 6.2 7.5 - 4.0 4.0

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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)

Claims (8)

  1. Utilisation de copolymères contenant des unités d'oxyde d'alkylène qui contiennent :
    (a) de 50 à 93 % en mole d'acide acrylique et/ou d'un sel hydrosoluble de l'acide acrylique,
    (b) de 5 à 30 % en mole d'acide méthacrylique et/ou d'un sel hydrosoluble de l'acide méthacrylique,
    et
    (c) de 2 à 20 % en mole minimum d'un monomère non ionique selon la formule I
    Figure imgb0006
     dans laquelle les variables ont la signification suivante :
    R1 : hydrogène ou méthyle ;
    R2 : une liaison chimique, ou bien un alkylène linéaire ou ramifié en C1-C6 ;
    R3 : des radicaux alkylènes linéaires ou ramifiés en C2-C4, identiques ou différents ;
    R4 : des alkyles linéaires ou ramifiés en C1-C6 ;
    n : de 3 à 50,
    intégrés par polymérisation statique ou bloc par bloc, en tant qu'adjuvant pour des compositions pour lave-vaisselle.
  2. Utilisation selon la revendication 1, caractérisée en ce que les copolymères contiennent, intégrés par polymérisation, de 65 à 85 % en mole du composant (a), de 10 à 25 % en mole du composant (b), et de 5 à 15 % en mole du composant (c).
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les copolymères contiennent, intégrés par polymérisation, de 65 à 75 % en mole du composant (a), de 15 à 25 % en mole du composant (b), et de 5 à 10 % en mole du composant (c).
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que les copolymères contiennent, intégré par polymérisation, en tant que composant (c) un monomère non ionique selon la formule I, dans laquelle R1 désigne du méthyle, R2 une liaison chimique, R3 des alkylènes en C2-C3, R4 des alkyles en C1-C2, et n de 5 à 40.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que les copolymères contiennent, intégré par polymérisation, en tant que composant (c) un monomère non ionique selon la formule I, dans laquelle R1 désigne du méthyle, R2 une liaison chimique, R3 de l'éthylène, R4 du méthyle, et n de 10 à 30.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que les copolymères contiennent en tant que terminaisons -SO3 - Na+ et/ou -SO4 - Na+.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que les copolymères sont utilisés en tant qu'adjuvant inhibiteur de dépôt dans des compositions pour lave-vaisselle.
  8. Compositions pour lave-vaisselle contenant des copolymères selon les revendications 1 à 7, en tant qu'adjuvant inhibiteur de dépôt.
EP03740181A 2002-06-07 2003-06-04 Utilisation de copolymeres contenant des unites d'oxyde d'alkylene comme adjuvants dans des compositions pour lave-vaisselle Expired - Lifetime EP1513916B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10225594 2002-06-07
DE10225594A DE10225594A1 (de) 2002-06-07 2002-06-07 Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als Zusatz in Wasch- und Reinigungsmitteln
PCT/EP2003/005823 WO2003104373A1 (fr) 2002-06-07 2003-06-04 Utilisation de copolymeres contenant des unites d'oxyde d'alkylene comme adjuvants dans des produits detergents

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EP1513916A1 EP1513916A1 (fr) 2005-03-16
EP1513916B1 true EP1513916B1 (fr) 2006-10-11

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US (1) US20050245427A1 (fr)
EP (1) EP1513916B1 (fr)
JP (1) JP2005531653A (fr)
CN (1) CN1273577C (fr)
AT (1) ATE342332T1 (fr)
AU (1) AU2003274115A1 (fr)
BR (1) BR0311490B1 (fr)
CA (1) CA2488032C (fr)
DE (2) DE10225594A1 (fr)
MX (1) MXPA04011456A (fr)
WO (1) WO2003104373A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10350420A1 (de) * 2003-10-28 2005-06-02 Basf Ag Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als belagsinhibierende Additive im Klarspülgang des maschinellen Geschirrspülers
DE102005028460A1 (de) * 2005-06-17 2006-12-28 Basf Ag Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als Zusatz zu wäßrigen Systemen
DE102005041349A1 (de) 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
DE102005041347A1 (de) 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
DE102008028229A1 (de) * 2008-06-16 2009-12-17 Fit Gmbh Zusammensetzung zur Herstellung von Reinigungsmitteln, Tablettiermischung, Polymerkombination, Reinigunsmittel-Formkörper und Verfahren zur deren Herstellung
US8685911B2 (en) * 2009-11-30 2014-04-01 The Procter & Gamble Company Rinse aid compositions
JP5668936B2 (ja) * 2011-09-06 2015-02-12 三浦工業株式会社 全窒素の定量方法
WO2020027310A1 (fr) * 2018-08-03 2020-02-06 株式会社日本触媒 Copolymère d'acide polycarboxylique

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US3719647A (en) * 1971-01-25 1973-03-06 Procter & Gamble New polymers and detergent compositions containing them
JP2901294B2 (ja) * 1989-12-12 1999-06-07 日華化学株式会社 繊維製品用洗浄性向上剤
JP2000024691A (ja) * 1998-07-09 2000-01-25 Jsr Corp 水溶性共重合体（塩）およびスケール防止剤
US6998453B2 (en) * 2001-10-03 2006-02-14 Nippon Shokubai Co., Ltd. (Meth)acrylic acid type polymer and unsaturated polyalkylene glycol type copolymer, and methods for production thereof

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MXPA04011456A (es) 2005-02-14
DE50305365D1 (de) 2006-11-23
CN1659264A (zh) 2005-08-24
CN1273577C (zh) 2006-09-06
AU2003274115A1 (en) 2003-12-22
JP2005531653A (ja) 2005-10-20
BR0311490B1 (pt) 2013-04-09
DE10225594A1 (de) 2003-12-18
ATE342332T1 (de) 2006-11-15
US20050245427A1 (en) 2005-11-03
WO2003104373A1 (fr) 2003-12-18
CA2488032C (fr) 2010-09-14
EP1513916A1 (fr) 2005-03-16
CA2488032A1 (fr) 2003-12-18
BR0311490A (pt) 2005-03-15

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