EP1129172B1 - Agents mouillants pour le lavage en machine de la vaisselle - Google Patents

Agents mouillants pour le lavage en machine de la vaisselle Download PDF

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Publication number
EP1129172B1
EP1129172B1 EP99955925A EP99955925A EP1129172B1 EP 1129172 B1 EP1129172 B1 EP 1129172B1 EP 99955925 A EP99955925 A EP 99955925A EP 99955925 A EP99955925 A EP 99955925A EP 1129172 B1 EP1129172 B1 EP 1129172B1
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Prior art keywords
alkyl
carbon atoms
carboxylic acid
acid esters
formula
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German (de)
English (en)
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EP1129172A1 (fr
EP1129172B8 (fr
Inventor
Rita Köster
Ansgar Behler
Karl-Heinz Schmid
Michael Neuss
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Cognis IP Management GmbH
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Cognis Deutschland GmbH and Co KG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention is a rinse aid for automatic dishwashing containing alkoxylated carboxylic acid esters, in particular those obtained by reaction of Carboxylic acid esters and alkylene oxides in the presence of calcined hydrotalcites have been prepared and the use of the alkoxylated carboxylic esters as surfactants for the preparation such rinse aid.
  • Machine-washed dishes are often subject to higher requirements today than on manually washed dishes. So is also a completely cleaned of leftovers dishes then rated as not flawless, if it still remains after machine dishwashing has whitish spots based on water hardness or other mineral salts, the lack of wetting agents come from dried-up water drops.
  • rinse aid In order to obtain glossy and spotless dishes, you are now successfully using rinse aid one.
  • the addition of rinse aid at the end of the wash program ensures that the water As completely as possible runs off the dishes, so that the different surfaces on End of the washing program are residue-free and flawlessly shiny.
  • rinse aids are mixtures of nonionic surfactants, solubilizers (e.g., cumene sulfonate), organic acids (e.g., citric acid) and solvents (e.g. Ethanol), water and possibly preservatives and fragrances.
  • the task of the surfactants in these means is to influence the interfacial tension of the water so that it runs off in a very thin, coherent film from the dishes can, so that during the subsequent drying process no drops of water, stripes or Films remain behind (so-called net effect).
  • the surfactants also have the Task to dampen the foam caused by food particles in the dishwasher. Since the rinse aid contains mostly acids for an improvement of the clear dry effect, In addition, the surfactants used must be relatively hydrolysis-insensitive to acids be.
  • EP-B1 0 197 434 discloses rinse aids which contain mixed ethers as nonionic surfactants.
  • a variety of different materials glass, metal, silver, plastic, porcelain
  • This variety of materials must be wetted as well as possible in the rinse cycle.
  • Rinse aid formulations which contain exclusively mixed ethers as the surfactant component, do not meet these requirements or only to a small extent, so that the rinsing or drying effect is unsatisfactory, especially in the case of plastic surfaces.
  • German Offenlegungsschrift DE- A1-19611999 and international application WO 94/13618 disclose alkoxylated carboxylic esters which are prepared by homogeneous catalysis in the presence of hydroxides and reducing agents or a cocatalyst . According to the two documents, such compounds can be used in detergents, dishwashing detergents and cleaners.
  • German Offenlegungsschrift DE-A-43 26 112 in turn, describes low-foaming all-purpose cleaners which comprise alkoxylated carboxylic acid esters mixed with alkyl glycosides and optionally other surfactants such as alkyl sulfates, alkyl ether sulfates and fatty alcohol polyglycol ethers.
  • Such general-purpose cleaners are designed for cleaning hard surfaces such as clinker, ceramic tile, enamel, PVC or wooden floors.
  • all-purpose cleaners, in contrast to rinse aids always contain anionic surfactants.
  • all-purpose cleaners, in contrast to rinse aids have a voluminous initial foam.
  • other surfactant concentrations are used in all-purpose cleaners. Thus, different requirements are placed on all-purpose cleaners than on rinse aid.
  • the object of the present invention has been new ecological and toxicological to provide flawless rinse aid, with respect to the application Properties provide at least the same results as marketable rinse aid and the above do not have mentioned disadvantages.
  • An object of the present invention therefore relates to rinse aid for automatic dishwashing comprising mono- and / or polybasic carboxylic acids, solubilizers and alkoxylated carboxylic acid esters of the formula (I), where R 1 is CO for an aliphatic acyl radical having 8 to 18 carbon atoms, OAlk for an O-CH 2 -CH 2 radical, n is a number from 5 to 15 and R 2 is a methyl radical.
  • rinse aid containing alkoxylated Carbonklam and especially in admixture with mixed ethers, hydroxy mixed ethers and / or fatty alcohol polypropylene / polyethylene glycol ethers not only have a high ecotoxicological value Compatibility, but the requirements for a branded product in the Fully comply with the performance characteristics. In particular, show Such rinse agents have an excellent wetting agent effect and excellent foam damping.
  • Alkoxylated carboxylic acid esters which are compulsorily contained in the rinse aids according to the invention are known from the prior art.
  • such alkoxylated carboxylic acid esters are accessible by esterification of alkoxylated carboxylic acids with methanol.
  • the compounds are prepared by reacting carboxylic acid esters with alkylene oxides using catalysts, in particular using calcined hydrotalcite according to German Offenlegungsschrift DE-A-39 14 131, which provide compounds having a restricted homolog distribution.
  • Preferred acyl radicals are derived from carboxylic acids having 8 to 18 carbon atoms more naturally or of synthetic origin, in particular of straight-chain saturated and / or unsaturated fatty acids, including technical mixtures thereof, as defined by Fat cleavage from animal and / or vegetable fats and oils are available, for example from coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rapeseed oil, cottonseed oil, Fish oil, beef tallow and lard.
  • carboxylic acids examples include Capric acid, lauric acid, isotridecanoic acid, myristic acid, Palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, Petroselinic, linoleic, linolenic, elaeostearic.
  • R 2 is a methyl radical
  • alkoxylated carboxylic acid esters of the formula (I) with on average 5, 7, 9 or 11 moles of ethylene oxide.
  • alkoxylated carboxylic esters derived from short chain carboxylic acids in particular those with 8 to 10 carbon atoms, derived.
  • High cleaning performances are included alkoxylated carboxylic acid esters obtained from longer-chain carboxylic acids, in particular those with 12 to 18 carbon atoms, derived.
  • the alkoxylated carboxylic esters can be used as the sole nonionic surfactant in the rinse aids be contained, preferably in amounts of from 0.5 to 40 wt.%, In particular in amounts from 5 to 35% by weight.
  • the alkoxylated carboxylic acid esters are preferably in a mixture with further nonionic surfactants in the rinse aids.
  • nonionic surfactants which may be considered are mixed ethers, hydroxy mixed ethers, Fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid amide polyglycol ethers, Fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yloligoglycosides, Fatty acid N-alkyl glucamides, protein hydrolysates (especially vegetable products Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates.
  • these can be a conventional, but preferably have a narrow homolog distribution.
  • Preferred are as other nonionic surfactants fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl-glucamides, Hydroxy mixed ethers and / or mixed ethers.
  • the nonionic surfactants used are alkyl and alkenyl oligoglycosides which follow the formula (II) , R 3 O- [G] p (II) in which R 3 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the index number p in the general formula (II) indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10.
  • the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 3 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis.
  • the alkyl or alkenyl radical R 3 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above.
  • Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
  • fatty acid N-alkylpolyhydroxyalkylamides which follow the formula (III) where R 5 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 4 is an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.
  • the fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • a reducing sugar with an alkylamine or an alkanolamine
  • acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984 An overview of this topic by H.Kelkenberg can be found in Tens.Surf.Deterg. 25 , 8 (1988).
  • the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose.
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (IV) :
  • the fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IV) in which R 4 is an alkyl group and R 5 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures.
  • R 4 is an alkyl group
  • R 5 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, l
  • fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative.
  • the polyhydroxyalkylamides can also be derived from maltose and palatinose.
  • Fatty alcohol polyethylene glycol / polypropylene or polybutylene glycol ethers of the formula (V) can be prepared, for example, in accordance with European Patent Application EP- A2-161,537 or German Offenlegungsschriften DE-A1 39 28 602 and DE-A1-39 28 600 .
  • R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms
  • o is a number from 1 to 5
  • m is 0.
  • monofunctional alcohols are the so-called fatty alcohols such as caproic, caprylic, lauryl, myristyl and stearyl alcohol and their technical mixtures, as obtained in the high pressure hydrogenation of technical methyl esters based on fats and oils suitable.
  • Examples of monofunctional, branched alcohols are so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are prepared by the oxo process and so-called Guerbet alcohols which are branched in the 2-position with an alkyl group.
  • Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
  • R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms
  • o is a number from 2 to 7
  • m is a number from 3 to 7 stands.
  • Further particularly preferred further nonionic surfactants are the so-called mixed ethers.
  • the mixed ethers are adducts of ethylene oxide and / or propylene oxide with fatty alcohols, which are end-capped by subsequent reaction with an alkyl chloride in the presence of bases.
  • Particularly suitable mixed ethers are those which have been prepared by end-capping with an alkyl halide having 1 to 8 carbon atoms, in particular having 1 to 4 carbon atoms of the fatty alcohol polyglycol ethers of formula (V) and / or (VI) .
  • Typical examples are mixed ethers based on a technical C 12/18 or C 12/14 cocoalcohol residue, to which 5 to 10 moles of ethylene oxide have been attached and which have been end-capped with a methyl group or with a butyl group, for example Dehypon (R) LS-54, LS-104, LT-54, LS-104, LS -531, Henkel KGaA, Dusseldorf / FRG).
  • R Dehypon
  • the alcohols are used in the form of their alkoxylates, which are prepared by reaction of the alcohols with ethylene oxide, propylene oxide and / or butylene oxide in a known manner.
  • Very particularly suitable hydroxy mixed ethers of the formula (VII) are those in which R 8 is a saturated straight-chain alkyl radical having 8 to 14 C atoms, R 9 is hydrogen, R 10 is a saturated straight-chain alkyl radical having 8 to 12 C atoms, x stands for 0 or for numbers from 1 to 3 and y for numbers from 10 to 25 and z for the number 1.
  • R 8 is a saturated straight-chain alkyl radical having 8 to 14 C atoms
  • R 9 is hydrogen
  • R 10 is a saturated straight-chain alkyl radical having 8 to 12 C atoms
  • x stands for 0 or for numbers from 1 to 3
  • y for numbers from 10 to 25 and z for the number 1.
  • the rinse aids according to the invention may comprise the alkoxylated carboxylic acid esters and the others nonionic surfactants, in particular the mixed ethers, hydroxy mixed ethers and fatty alcohol polyglycol ethers in a weight ratio of 10:90 to 80:20, especially of 30: 70 to 40: 60 included.
  • the weight ratio of the other nonionic surfactants among each other is less critical.
  • the rinse aid formulations according to the invention contain, in addition to those already described Surfactants as the most important additives mono- and / or polyvalent carboxylic acids, preferably Hydroxy carboxylic acids.
  • Typical examples are malic acid (monohydroxy succinic acid), Tartaric acid (dihydroxysuccinic acid), saturated aliphatic dicarboxylic acids such as oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, gluconic acid (hexane-pentahydroxy-1-carboxylic acid), preferably, however, anhydrous citric acid.
  • additives include, in particular, dyes, fragrances and preservatives in question, preferably in amounts of from 0 up to 1% by weight.
  • solubilizers are included in the rinse aids. When Solubilizer recommends cumene sulfonate in amounts of 0 to 25, in particular of 0.2 to 15% by weight - calculated as the active substance content.
  • hydrotropes may additionally be present in the rinse aid. Hydrotropes are ethanol and / or isopropanol in amounts of from 0 to 25% by weight. The ad 100% by weight missing balance is water.
  • the rinse aids according to the invention contain ecotoxicologically particularly compatible ingredients, show an excellent wetting capability over a wide variety of materials as well as excellent foam damping behavior.
  • Another object of the invention relates to the use of alkoxylated carboxylic acid esters as a surfactant for the preparation of rinse aids for automatic dishwashing.
  • the alkoxylated carboxylic acid esters used show an excellent solubility in water, without going through a gel phase.
  • the rinse aid can both in the household area as well as in the institutional field.
  • rinse aid ingredients default Ex.1 Ex. 2
  • Example 3 Example 4 C 8/18 CO (EO) 10 CH 3 - 15 2.0 5.0 5.0 hydroxy mixed - - 5.0 10.0 - C 12/14 -FA + 5EO + 4PO 15.0 - 8.0 - 10.0 cumene 8.0 5.0 3.0 2.0 5.0 citric acid 5.0 5.0 5.0 5.0 ad 100% by weight of water rinse effect + better than better than better than better than default default default default default default default default default default default default default default default default default default default default default default default default default default default default

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Claims (11)

  1. Produits de rinçage aqueux pour lave-vaisselle, contenant des acides carboxyliques mono-et/ou polyvalents, des agents solubilisants et des esters d'acides carboxyliques alcoxylés de formule (I)
    Figure 00210001
    dans laquelle R1CO représente un radical acyle aliphatique portant 8 à 18 atomes de carbone, OAlk représente un radical O-CH2CH2, n représente des nombres de 5 à 15, et R2 représente un radical méthyle.
  2. Produits de rinçage selon la revendication 1,
    caractérisés en ce qu'
    ils contiennent des esters d'acides carboxyliques alcoxylés de formule (I) qui ont été obtenus par réaction d'acides carboxyliques avec des oxydes d'alkylène en présence d'hydrotalcite calcinée.
  3. Produits de rinçage selon l'une quelconque des revendications 1 à 2,
    caractérisés en ce qu'
    ils contiennent les esters d'acides carboxyliques alcoxylés en quantités de 0,5 à 40 % en poids.
  4. Produits de rinçage selon l'une quelconque des revendications 1 à 3,
    caractérisés en ce qu'
    ils contiennent les esters d'acides carboxyliques alcoxylés en mélange avec d'autres tensioactifs non ioniques, choisis en particulier dans le groupe des éthers polyglycoliques d'alcools gras, des oligoglucosides d'alkyle, des N-alkyl-glucamides d'acides gras, des hydroxy éthers mixtes et/ou des éthers mixtes.
  5. Produits de rinçage selon la revendication 4,
    caractérisés en ce qu'
    ils contiennent des esters d'acides carboxyliques alcoxylés en mélange avec des polyglycosides d'alkyle de formule (II), R3O-[G]p dans laquelle R3 représente un radical alkyle et/ou alcényle portant 4 à 22 atomes de carbone, G un radical sucre portant 5 ou 6 atomes de carbone, et p des nombres de 1 à 10.
  6. Produits de rinçage selon la revendication 4,
    caractérisés en ce qu'
    ils contiennent des esters d'acides carboxyliques alcoxylés en mélange avec des N-alkyl-polyhydroxyalkylamides d'acides gras de formule (III)
    Figure 00220001
    dans laquelle R5CO représente un radical acyle aliphatique portant 6 à 22 atomes de carbone, R4 un radical alkyle ou hydroxyalkyle portant 1 à 4 atomes de carbone et [Z] un radical polyhydroxyalkyle linéaire ou ramifié portant 3 à 12 atomes de carbone et 3 à 10 groupes hydroxyle.
  7. Produits de rinçage selon la revendication 4,
    caractérisés en ce qu'
    ils contiennent des esters d'acides carboxyliques alcoxylés en mélange avec des polyéthylène glycol-/ polypropylène glycol- ou polybutylène glycol éthers d'alcools gras de formule (V) R6O(CH2CH2O)p[MO]mH dans laquelle R6 représente un radical alkyle et/ou alkylène portant 8 à 22 atomes de C, MO représente un radical oxyde de propylène et/ou oxyde de butylénie, p représente un nombre de 1 à 15, et m représente 0 ou un nombre de 1 à 10.
  8. Produits de rinçage selon la revendication 4,
    caractérisés en ce qu'
    ils contiennent des esters d'acides carboxyliques alcoxylés en mélange avec des polypropylène glycol-/polyéthylène glycol éthers d'alcools gras de formule (VI) R7O[CH2(CH3)CHO]r(CH2CH2O)qH dans laquelle R7 représente un radical alkyle et/ou alkylène portant 8 à 22 atomes de C, r représente un nombre de 1 à 10, et q représente un nombre de 0 à 15.
  9. Produits de rinçage selon la revendication 4,
    caractérisés en ce qu'
    ils contiennent des esters d'acides carboxyliques alcoxylés en mélange avec des hydroxy éthers mixtes de formule (VII), R8O[CH2CH(CH3)O]x(CH2CHR9O)y[CH2CH(OH)R10]z dans laquelle R8 représente un radical alkyle et/ou alkylène portant 4 à 18 atomes de C, R9 représente un atome d'hydrogène ou un radical méthyle ou éthyle, R10 représente un radical alkyle portant 2 à 22 atomes de C, x représente 0 ou un nombre de 1 à 10, y un nombre de 1 à 30, et z = 1.
  10. Produits de rinçage selon l'une quelconque des revendications 4 à 9,
    caractérisés en ce qu'
    ils contiennent les esters d'acides carboxyliques alcoxylés et les autres tensioactifs non ioniques dans un rapport pondéral de 10/90 à 80/20.
  11. Produits de rinçage selon l'une quelconque des revendications 1 à 10,
    caractérisés en ce qu'
    ils contiennent des acides carboxyliques mono-et/ou polyvalents, de préférence de l'acide citrique, dans des quantités de 1 à 50 % en poids.
EP99955925A 1998-11-09 1999-10-30 Agents mouillants pour le lavage en machine de la vaisselle Expired - Lifetime EP1129172B8 (fr)

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DE19851453 1998-11-09
DE19851453A DE19851453A1 (de) 1998-11-09 1998-11-09 Klarspüler für das maschinelle Geschirrspülen
PCT/EP1999/008289 WO2000027987A1 (fr) 1998-11-09 1999-10-30 Agents mouillants pour le lavage en machine de la vaisselle

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EP1129172A1 EP1129172A1 (fr) 2001-09-05
EP1129172B1 true EP1129172B1 (fr) 2005-05-11
EP1129172B8 EP1129172B8 (fr) 2005-07-06

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US (1) US7871971B1 (fr)
EP (1) EP1129172B8 (fr)
DE (2) DE19851453A1 (fr)
ES (1) ES2243083T3 (fr)
WO (1) WO2000027987A1 (fr)

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US7871971B1 (en) 2011-01-18
EP1129172A1 (fr) 2001-09-05
ES2243083T3 (es) 2005-11-16
DE59912051D1 (de) 2005-06-16
WO2000027987A1 (fr) 2000-05-18
EP1129172B8 (fr) 2005-07-06
DE19851453A1 (de) 2000-05-11

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