EP1682645B1 - Utilisation de copolymeres contenant des unites oxyde d'alkylene comme additifs inhibiteurs de depot dans des compositions de rincage d'un lave-vaisselle - Google Patents

Utilisation de copolymeres contenant des unites oxyde d'alkylene comme additifs inhibiteurs de depot dans des compositions de rincage d'un lave-vaisselle Download PDF

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Publication number
EP1682645B1
EP1682645B1 EP04790785A EP04790785A EP1682645B1 EP 1682645 B1 EP1682645 B1 EP 1682645B1 EP 04790785 A EP04790785 A EP 04790785A EP 04790785 A EP04790785 A EP 04790785A EP 1682645 B1 EP1682645 B1 EP 1682645B1
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mol
copolymers
component
rinse
branched
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German (de)
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EP1682645A1 (fr
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Marcus Guzmann
Heike Becker
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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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets

Definitions

  • the invention relates to rinse aid for machine dishwashers containing these copolymers as a deposit-inhibiting additive, as well as detergent tablets for machine dishwashers, which contain the copolymers formulated as a deposit-inhibiting additive in the rinse aid core.
  • the items to be washed When machine dishwashing, the items to be washed in residue-free cleaned state with flawless glossy surface incurred.
  • the items to be washed should not only be completely cleaned of leftovers but should also have no whitish spots that arise due to the presence of lime or other inorganic and organic salts in the drying of water droplets.
  • rinse aid has been used for some time.
  • the rinse aid is discharged in the rinse after passing through the usually consisting of a pre-rinse cycle and an intermediate rinsing interrupted main wash cycle cleaning program automatically from a dosing tank in the interior of the dishwasher and ensures that the water flows during rinse and drying cycle area and as completely as possible from the dishes and the ware surfaces at the end of the washing program are residue-free and flawlessly shiny.
  • rinse-aid surfactants are already integrated into the detergent formulation, so that the additional metering of a rinse aid can be omitted.
  • Modern machine "3in1" cleaners combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the replenishment of salt at water hardness of 1 to 3 is unnecessary for the consumed.
  • sodium tripolyphosphate is usually added to this cleaner. This in turn, however, results in calcium and magnesium phosphate deposits on the items to be washed.
  • the object of the invention was to provide polymeric additives which are distinguished by their deposit-inhibiting action when used in the rinse cycle of the automatic dishwashing machine.
  • rinse aids for machine dishwashers were found containing these copolymers as a deposit-inhibiting additive.
  • detergent tablets for machine dishwashers were found which contain these copolymers formulated as a deposit-inhibiting additive in the rinse aid core.
  • copolymers to be used according to the invention are not previously published DE-A-102 25 594 ( WO 03/104373 ) described as an additive to detergents and cleaners.
  • the use in rinse aid for machine dishwashers is not described.
  • copolymers containing alkylene oxide units to be used according to the invention comprise 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 methoxypolypropylene glycol (meth) acrylate being preferred and methoxypolyethylene glycol methacrylate being 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, after 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.
  • inorganic peroxo compounds such as
  • 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 for example 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 known to those skilled in the art, e.g. 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 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) 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 by adding base, in particular sodium hydroxide solution or partially neutralized, ie, adjusted to a pH in the range of 4-8, preferably 4.5-7.5.
  • copolymers used according to the invention are distinguished by their outstanding deposit-inhibiting action when used in the rinse cycle of the automatic dishwashing machine.
  • deposits which are caused by the carry-over effect in the rinse cycle abducted components of the cleaner formulation such as deposits of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and coatings consisting of the Dirt components of the rinse, such as fat, protein and starch coverings, called.
  • the copolymers to be used according to the invention improve the cleaning result by their coating-inhibiting effect.
  • 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 copolymer according to the invention was used together with a commercially available 3in1 dishwashing formulation in tablet form (Somat), the copolymer being added only in the final rinse cycle in order to simulate a delayed release of further copolymer.
  • Somat commercially available 3in1 dishwashing formulation in tablet form
  • test was in the following rinsing conditions with the addition of IKW Ballastschmutz (S ⁇ FW Journal, 124th year, 14/98, p 1029) in the main wash cycle and in addition made to the copolymer in the rinse cycle. In addition, neither regenerating salt nor rinse aid formulation were used.
  • Dishwasher Miele G 686 SC rinses: 1 rinse 55 ° C normal (without pre-rinse) ware: Knife (WMF table knife Berlin, monobloc); Glasses (Willy Becher, 0.3 l); black KS plates, black dessert plates; EMSA Superline - Box (cover PE blue, PP box transparent) Dishwashing liquid: Somat 3 in 1 Ballast soil: 50 g in the main rinse cycle; 2 g in the rinse cycle copolymer: 210 mg in the rinse cycle Rinse temperature: 65 ° C Water hardness: 21 ° dH
  • Table 1 Copolymer from Ex. Rating (grade) Knives, glasses, ceramic plates Plastic parts spotting Filming spotting 1 2.2 2.6 1.2 - 1.8 2.0 0.8
  • the copolymer was added directly to the rinse aid formulation. The test was carried out under the conditions given below with addition of IKW ballast dirt in main and final rinse cycles.
  • the copolymer was used in the following rinse aid formulation: 20% by weight Low-foaming nonionic surfactant based on fatty alcohol alkoxylates 10% by weight Sodium cumene sulphonate (40% by weight) 5% by weight isopropanol 4% by weight Copolymer (active substance) 61% by weight water
  • Dishwasher Miele G 686 SC rinses: 1 rinse 55 ° C normal (without pre-rinse) ware: Knife (WMF table knife Berlin, monobloc); Glasses (Willy Becher, 0.3 l); black KS plates, black dessert plates; EMSA Superline - Box (cover PE blue, PP box transparent) Dishwashing liquid: 21 g Ballast soil: 50 g in the main rinse cycle; 2 g in the rinse cycle Rinse temperature: 65 ° C Rinse-aid: 1 g Water hardness: 3 ° dH
  • the door was opened and the dishes were left to dry for 60 minutes with the machine door open.
  • the rating of the dishes followed by visual matching in a black painted light box with halogen spot and pinhole using the grading scale from 0 to 4 described above.

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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)
  • Peptides Or Proteins (AREA)

Claims (7)

  1. Utilisation de copolymères contenant des unités oxyde d'alkylène, qui contiennent
    (a) 50 à 93% en mole d'acide acrylique et/ou d'un sel soluble dans l'eau de l'acide acrylique,
    (b) 5 à 30% en mole d'acide méthacrylique et/ou
    d'un sel soluble dans l'eau de l'acide méthacrylique et
    (c) 2 à 20% en mole d'au moins un monomère non ionique de formule I
    Figure imgb0006
     dans laquelle les variables ont la signification suivant :
    R1 hydrogène ou méthyle ;
    R2 une liaison chimique ou un alkylène en C1- C6 non ramifié ou ramifié ;
    R3 des radicaux alkylène en C2-C4 identiques ou différents, non ramifiés ou ramifiés ;
    R4 alkyle en C1-C6 non ramifié ou ramifié ;
    n 3 à 50,
    sous forme copolymérisée de manière statistique ou en blocs, comme additifs inhibant les incrustations dans les agents de rinçage pour lave-vaisselle.
  2. Utilisation selon la revendication 1, caractérisée en ce que les copolymères contiennent 65 à 85% en mole du composant (a), 10 à 25% en mole du composant (b) et 5 à 15% en mole du composant (c) sous forme copolymérisée.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les copolymères contiennent 65 à 75% en mole du composant (a), 15 à 25% en mole du composant (b) et 5 à 10% en mole du composant (c) sous forme copolymérisée.
  4. Utilisation selon les revendications 1 à 3, caractérisée en ce que les copolymères contiennent, en tant que composant (c), un monomère non ionique de formule I dans laquelle R1 signifie méthyle, R2 signifie une liaison chimique, R3 signifie C2-C3-alkylène, R4 signifie C1-C2-alkyle et n vaut 5 à 40, sous forme copolymérisée.
  5. Utilisation selon les revendications 1 à 4, caractérisée en ce que les copolymères contiennent, en tant que composant (c), un monomère non ionique de formule I dans laquelle R1 signifie méthyle, R2 signifie une liaison chimique, R3 signifie éthylène, R4 signifie méthyle et n vaut 10 à 30, sous forme copolymérisée.
  6. Utilisation selon les revendications 1 à 5, caractérisée en ce que les copolymères contiennent, comme groupes terminaux, -SO3 -Na+ et/ou -SO4 -Na+.
  7. Agents de rinçage pour lave-vaisselle, qui contiennent des copolymères selon les revendications 1 à 6 comme additif inhibant les incrustations.
EP04790785A 2003-10-28 2004-10-23 Utilisation de copolymeres contenant des unites oxyde d'alkylene comme additifs inhibiteurs de depot dans des compositions de rincage d'un lave-vaisselle Not-in-force EP1682645B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10350420A DE10350420A1 (de) 2003-10-28 2003-10-28 Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als belagsinhibierende Additive im Klarspülgang des maschinellen Geschirrspülers
PCT/EP2004/011994 WO2005042684A1 (fr) 2003-10-28 2004-10-23 Utilisation de copolymeres contenant des unites oxyde d'alkylene comme additifs inhibiteurs de depot dans le processus de rinçage d'un lave-vaisselle

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EP1682645A1 EP1682645A1 (fr) 2006-07-26
EP1682645B1 true EP1682645B1 (fr) 2009-02-11

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US (1) US7530360B2 (fr)
EP (1) EP1682645B1 (fr)
JP (1) JP2007510021A (fr)
AT (1) ATE422533T1 (fr)
CA (1) CA2543543A1 (fr)
DE (2) DE10350420A1 (fr)
ES (1) ES2318349T3 (fr)
WO (1) WO2005042684A1 (fr)

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WO2008119833A1 (fr) 2007-04-03 2008-10-09 Henkel Ag & Co. Kgaa Agents de traitement de surfaces dures
EP2487230B1 (fr) 2007-04-03 2014-12-03 Henkel AG & Co. KGaA Moyen de lavage et de nettoyage protégeant les couleurs
KR20090128438A (ko) 2007-04-03 2009-12-15 헨켈 아게 운트 코. 카게아아 제 １ 세척력을 개선하는 활성 성분을 가지는 세제
BRPI0818439B1 (pt) 2007-10-12 2017-07-04 Basf Se A phosphate-free cleaning formulation for machine dishwash, and use of a mixture of hydrofobically modified polycarboxilates and hydrofilically modified polycarboxilates
US8685911B2 (en) * 2009-11-30 2014-04-01 The Procter & Gamble Company Rinse aid compositions
US20110126858A1 (en) * 2009-11-30 2011-06-02 Xinbei Song Method for rinsing cleaned dishware
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CN103492436B (zh) 2010-11-23 2016-01-20 巴斯夫欧洲公司 作为洗涤和清洁产品的水垢抑制添加剂的包含羧酸基团、磺基和聚氧化烯基团的共聚物
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US9670435B2 (en) 2010-11-23 2017-06-06 Basf Se Copolymers comprising carboxylic acid groups, sulfo groups and polyalkylene oxide groups as a scale-inhibiting additive to washing and cleaning products
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9127236B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid terpolymer for hard water scale control

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US7530360B2 (en) 2009-05-12
WO2005042684A1 (fr) 2005-05-12
US20070082831A1 (en) 2007-04-12
JP2007510021A (ja) 2007-04-19
DE10350420A1 (de) 2005-06-02
ATE422533T1 (de) 2009-02-15
DE502004008984D1 (de) 2009-03-26
CA2543543A1 (fr) 2005-05-12
ES2318349T3 (es) 2009-05-01
EP1682645A1 (fr) 2006-07-26

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