EP1542955A1 - Alcoxylats presentant une faible teneur en alcool residuel - Google Patents

Alcoxylats presentant une faible teneur en alcool residuel

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Publication number
EP1542955A1
EP1542955A1 EP03725099A EP03725099A EP1542955A1 EP 1542955 A1 EP1542955 A1 EP 1542955A1 EP 03725099 A EP03725099 A EP 03725099A EP 03725099 A EP03725099 A EP 03725099A EP 1542955 A1 EP1542955 A1 EP 1542955A1
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EP
European Patent Office
Prior art keywords
ppm
less
radical
integer
formulations
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EP03725099A
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German (de)
English (en)
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EP1542955B1 (fr
Inventor
Christian Wulff
Kai-Uwe Baldenius
Martin Scholtissek
Michael Stösser
Norbert Wagner
Edward Bohres
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BASF SE
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BASF SE
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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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to compositions containing at least one alkoxylate of the general formula RO (A) “(B) m H, ner processes for producing such compositions, in particular in the presence of double metal cyanide compounds as a catalyst, and their use as an emulsifier, foam regulator or as a wetting agent for hard surfaces.
  • the present invention also relates to the use of such compositions in detergents and surfactant formulations.
  • Alkoxylates of aliphatic alcohols are widely used as surfactants, emulsifiers or foam suppressants.
  • the wetting and emulsifying properties strongly depend on the type of alcohol and the type and amount of alkoxide adducts.
  • WO 94/11331 relates to the use of alkoxylates of 2-propylheptanol in detergent compositions for degreasing hard surfaces.
  • the alkoxylates have 2 to 16 alkylene oxide groups. Most of the alkylene oxide groups are preferably in the form of ethylene oxide. According to the examples, only ethoxylated alcohols are used. It is also described that the alcohols can be reacted first with ethylene oxide and then with propylene oxide. However, there are no examples or properties of such alkoxylates specified. It is stated that the alkoxylates described have a good detergent and wetting action combined with low foaming. It is also stated that the alkoxylates have a desired thickening effect in formulations.
  • WO 94/11330 relates to alkoxylates of 2-propylheptanol and their use.
  • the alkoxylates contain 2-propylheptanol, first reacted with 1 to 6 mol of propylene oxide and then with 1 to 10 mol of ethylene oxide.
  • a 2-propylheptanol reacted first with 4 mol of propylene oxide and then with 6 mol of ethylene oxide is used.
  • the alkylene oxide adducts show an improved ratio of foaming behavior to detergent action.
  • the alkoxylates show good wetting behavior. They are used in detergent compositions for cleaning textile materials.
  • No. 2,508,036 relates to the use of 2-n-propylheptanol ethoxylates which contain 5 to 15 mol of ethylene oxide as wetting agents in aqueous solutions. It is described that the products can be used as surfactants in detergents.
  • DE-A-102 18 754 and DE-A-102 18 753 relate to the use of cio-alkanol alkoxylate mixtures, in particular alkanol ethoxylate mixtures, such cio-alkanol alkoxylate mixtures and processes for their preparation.
  • DE-A-102 18 752 also describes alkoxylate mixtures and detergents containing them, as well as processes for producing the alkoxylate mixtures and the use of the detergent for washing or cleaning textiles.
  • the alcohol mixtures used according to the invention generally have their own smell, which can be largely suppressed by the complete alkoxylation. Alkoxylates obtained by conventional processes often have their own odor, which is for many applications is disruptive. Furthermore, improved wetting on hard surfaces, improved emulsification behavior and a lower CMC (Critical Micell Concentration) are desirable.
  • R is a linear or branched alkyl radical having 6 to 19 or 18 carbon atoms
  • A is propyleneoxy
  • - B is ethyleneoxy or a mixture of ethyleneoxy and propyleneoxy
  • n is an integer or fractional number with 0 ⁇ n ⁇ 5
  • m is an integer or fractional number with 0 ⁇ m ⁇ 20
  • R is an alkyl radical of the general formula C 5 H ⁇ CH (C 3 H 7 ) CH -, n is an integer or fraction with 0 ⁇ n ⁇ 1,
  • n and m denote an average value which is the average of all molecules. Therefore, n and m can also deviate from integer values.
  • propyleneoxy represents -CH 2 -CH (CH 3 ) -O- or - CH (CH 3 ) -CH 2 -O-.
  • Ethyleneoxy stands for -CH 2 -CH 2 -O-.
  • n indicates the number of propylene oxide groups and is a whole or fractional number with 0 ⁇ n
  • R is an alkyl radical of the general formula C 5 HnCH (C 3 H 7 ) CH 2 -, n is an integer or fractional number with 0 ⁇ n ⁇ 1.
  • Ethylene oxide or a mixture of ethylene oxide and propylene oxide is bound to the propylene oxide group, m stands for the number of ethylene oxide or ethylene oxide and propylene oxide groups and is an integer or fractional number with 0 ⁇ m ⁇ 20, preferably 1
  • ⁇ m ⁇ 18 in particular 2 ⁇ m ⁇ 14, for example 2.5 ⁇ m ⁇ 14 or 3 ⁇ m ⁇ 8.
  • the present invention therefore relates to compositions where m is an integer or fraction from 2 to 14.
  • compositions according to the invention have a low residual alcohol content. It is surprising that the residual alcohol content in the compositions according to the invention, which have a defined amount of propylene oxide and then ethylene oxide or ethylene oxide and propylene oxide, is lower than would be expected in theory. From the residual alcohol contents of products which contain only propylene oxide or only ethylene oxide, an expected value can be determined which is higher than the residual alcohol content actually determined for the copolymers according to the invention.
  • the alkoxylates contained in the compositions according to the invention require only a very short length of propylene oxide (PO) block bound directly to the alcohol in order to lower the residual alcohol content. This is particularly advantageous because the biodegradability of the product decreases when the PO block is extended. Such alkoxylates thus allow maximum degrees of freedom in the choice of the length of the PO block, the length decreasing due to the increasing Residual alcohol content and is capped by the deterioration in biodegradability. This is particularly advantageous if the PO block is followed by only a short ethylene oxide block.
  • PO propylene oxide
  • propyleneoxy units can then be present next to the alcohol radical and then ethyleneoxy units. If n and m have a value of more than 1, the corresponding alkoxy radicals are preferably in block form.
  • a distribution of the degree of alkoxylation is generally obtained, which can be adjusted to a certain extent by using different alkoxylation catalysts.
  • the present invention relates to compositions in which B is ethyleneoxy.
  • the alkyl radical R is a linear or single or multiple branched alkyl radical having 6 to 19 or 18 carbon atoms, with the exception of isomer mixtures of an alkyl radical of the general empirical formula C 5 HnCH (C 3 H 7 ) CH 2 -
  • Suitable alcohols which are branched have the hydroxyl group z. B. in 2-, 3-, 4- position, etc.
  • the alkyl radical can be linear or branched again and z.
  • B. wear methyl or ethyl substituents.
  • Examples of suitable alcohols are 2-decanol, 2-dodecanol, 2-tetradecanol, 2-hexadecanol, each accessible by adding water to ⁇ -olefins, (6-ethyl) -2-nonaol, obtainable by reacting 2-ethylhexanol with acetone and subsequent hydrogenation, (7-Ethyl) -3-decanol or (3-methyl-6-ethyl) -2-nonanol, obtainable by reacting 2-ethylhexanol with methyl ethyl ketone and subsequent hydrogenation, 2-hexadecanol or 2-octadecanol, obtainable by reaction of C ⁇ 3 / C 15 - aldehyde with acetone, 3-nonadecanol or (3-methyl) -2-octadecanol, (3-methyl) -2-hexadecanol, 3-heptadecanol, obtainable by reaction of
  • Examples of other suitable alcohols are linear Ci 2 - ⁇ 4 alkanes with a hydroxyl group in a non-terminal position along the chain or mixtures thereof (e.g. Softanol ® alcohols from Nippen Shokubai or Tergitol ® alcohols from Dow.
  • R is an alkyl radical having 8 to 15 carbon atoms, preferably 10 to 15 carbon atoms, such as, for example, propylheptyl.
  • Alkyl radicals R which are suitable according to the invention are derived, for example, from the alcohols octanol, 2-ethylhexanol, nonanol, decanol, undekanol, dodekanol, tridekanol,
  • a preferred embodiment relates to the present compositions, where R is an alkyl radical of the general formula C 5 H ⁇ CH (C 3 H 7 ) CH 2 -.
  • the alcohols used as starter compounds according to the invention can be Guerbet alcohols, in particular ethylhexanol, propylheptanol,
  • the present invention particularly relates to one preferred embodiment, a method in which the starter compound is a Guerbet alcohol.
  • the alcohols used as starter compound can also be mixtures of different isomers.
  • Secondary alcohols or mixtures are also suitable. These can be obtained, for example, by adding ketones to aldehydes with subsequent hydrogenation as described in DE-A-100 35 617. Methyl ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone are preferred. Paraffin oxidation products which are produced, for example, by Bashkirov oxidation are also suitable. Products from Cn to C 6 paraffin mixtures, particularly products from C12-14 paraffin mixtures, are preferred here. Suitable alcohols are also e.g. B. secondary alcohols obtained by adding water to olefins or by radical or other oxidation of olefins.
  • Double metal cyanide compounds for example, can be used as catalysts in the preparation of the compositions according to the invention.
  • the compositions according to the invention thus obtained can have a residual metal content of greater than 0 and less than 50 ppm zinc (ie mg metal per kg of product), in particular greater than 0 and less than 25 ppm zinc or preferably greater than 0 and less than 15 ppm zinc and greater have less than 0 and less than 25 ppm cobalt, in particular greater than 0 and less than 15 ppm cobalt or preferably greater than 0 and less than 7 ppm cobalt.
  • the present invention therefore relates to compositions whose zinc content is greater than 0 and less than or equal to 15 ppm or whose cobalt content is greater than 0 and less than or equal to 7 ppm or whose zinc content is greater than 0 and less or equal to 15 ppm and whose cobalt content is greater than 0 and less than or equal to 7 ppm.
  • the present invention also relates to a process for the preparation of the compositions by reacting at least one alcohol ROH with propylene oxide and ethylene oxide under alkoxylation conditions.
  • the propoxylation which is preferably carried out first according to the invention and only subsequent ethoxylation can reduce the content of residual alcohol in the alkoxylates, since propylene oxide is added more uniformly to the alcohol component.
  • ethylene oxide preferably reacts with ethoxylates, so that when ethylene oxide is initially used for reaction with the alkanols, both a broad homolog distribution and a high content of residual alcohol result. Avoiding large amounts of residual alcohol present in the product is particularly advantageous for reasons of smell.
  • the addition reaction is carried out at temperatures of about 90 to 240 ° C, preferably from 110 to 190 ° C, in a closed vessel.
  • the alkylene oxide or the mixture of different alkylene oxides is fed to the mixture of the alkanol mixture according to the invention and the catalyst under the vapor pressure of the alkylene oxide mixture prevailing at the selected reaction temperature or a higher pressure.
  • the alkylene oxide can be diluted with an inert gas (for example noble gases, nitrogen, CO 2 ) up to 99.9%. This provides additional security against the gas phase decay of this alkylene oxide, in particular in the case of ethylene oxide, and in this embodiment a further alkylene oxide, for example propylene oxide, can also be used as inert gas in the sense of the invention.
  • Suitable alkoxylation conditions are above and in Nikolaus Schönfeldt, interfacial ethylene oxide adducts,ticianliche Verlagsgesellschaft mbH Stuttgart 1984 described.
  • the alkoxylation is carried out in the presence of basic catalysts such as KOH in bulk.
  • the alkoxylation can also be carried out using a solvent.
  • the alcohols are first reacted with a suitable amount of propylene oxide and then with a suitable amount of ethylene oxide. This initiates polymerization of the alkylene oxide, which inevitably leads to a statistical distribution of homologs, the mean value of which is given here as n and m.
  • the length of the polyether chains (n + m) varies statistically within the reaction product around an average value, which essentially results from the amount added and the stoichiometric values.
  • different molecular weight distributions are obtained. For example, products with a narrow molecular weight distribution often have good solubility.
  • the alkoxylation is catalyzed by strong bases, which are expediently added in the form of an alkali metal alcoholate, alkali metal hydroxide, alkaline earth metal oxide or alkaline earth metal hydroxide, generally in an amount of 0.01 to 1% by weight, based on the amount of the alkanol R 2 --OH (see G. Gee et al., J. Chem. Soc. (1961), p. 1345; B. Wojtech, Makromol. Chem. 66, (1966), p. 180).
  • Acid catalysis of the addition reaction is also possible.
  • Lewis acids such as A1C1 3 or BF 3 dietherate, BF 3 , BF 3 x H 3 PO 4 , SbCl 4 x 2 H 2 O, hydrotalcite (see PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press) are also suitable , New York (1963)).
  • Double metal cyanide (DMC) compounds are also suitable as catalysts.
  • the present invention relates to a process carried out in the presence of a double metal cyanide compound as a catalyst. Therefore, in a preferred embodiment, the present invention relates to a method for Preparation of compositions, the alkoxylation taking place in the presence of a double metal cyanide compound (DMC compound) as a catalyst.
  • DMC compound double metal cyanide compound
  • DMC compounds suitable as catalysts are described, for example, in WO 99/16775 and DE-A-101 17 273.
  • double metal cyanide compounds of the general formula I are suitable as catalysts for the alkoxylation:
  • Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , V 4+ , V 5+ , Cr 2 *, Cr 3+ , Rh 3+ , Ru 2+ , Ir 3 + is
  • a and X independently of one another are an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, hydrogen sulfate,
  • L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters,
  • Polyesters polycarbonate, ureas, amides, primary, secondary and tertiary amines, ligands with pyridine nitrogen, nitriles, sulfides, phosphides, phosphites, phosphines, phosphonates and phosphates,
  • k is a fractional or whole number greater than or equal to zero
  • e the number of ligand molecules is a fractional or an integer greater than 0 or 0,
  • f and h are independently a fractional or whole number greater than 0 or 0.
  • organic additives P are mentioned: polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyakylene glycol glycidyl ethers, polyacrylamide,
  • catalysts can be crystalline or amorphous. In the event that k is zero, crystalline double metal cyanide compounds are preferred. In the event that k is greater than zero, both crystalline, partially crystalline and substantially amorphous catalysts are preferred. There are various preferred embodiments of the modified catalysts. A preferred embodiment are catalysts of the formula (I) in which k is greater than zero. The preferred catalyst then contains at least one double metal cyanide compound, at least one organic ligand and at least one organic additive P.
  • k is zero, optionally e is also zero and X is exclusively a carboxylate, preferably formate, acetate and propionate.
  • Such catalysts are described in WO 99/16775.
  • crystalline double metal cyanide catalysts are preferred.
  • Double metal cyanide catalysts, as described in WO 00/74845, which are crystalline and platelet-shaped, are furthermore preferred.
  • the modified catalysts are produced by combining a metal salt solution with a cyanometalate solution, which can optionally contain both an organic ligand L and an organic additive P.
  • the organic ligand and optionally the organic additive are then added.
  • an inactive double metal cyanide phase is first produced and this is subsequently converted into an active double metal cyanide phase by recrystallization, as described in PCT / EP01 / 01893.
  • f, e and k are not equal to zero.
  • double metal cyanide catalysts which contain a water-miscible organic ligand (generally in amounts of 0.5 to 30% by weight) and an organic additive (generally in amounts of 5 to 80% by weight) such as described in WO 98/06312.
  • the catalysts can be prepared either with vigorous stirring (24,000 rpm with Turrax) or with stirring as described in US Pat. No. 5,158,922.
  • Double metal cyanide compounds which contain zinc, cobalt or iron or two thereof are particularly suitable as catalysts for the alkoxylation. Berlin blue, for example, is particularly suitable.
  • Crystalline DMC compounds are preferably used.
  • a crystalline DMC compound of the Zn-Co type is used as the catalyst, which contains zinc acetate as a further metal salt component.
  • Such compounds crystallize in a monoclinic structure and have a platelet-shaped habit.
  • Such connections are described for example in WO 00/74845 or PCT / EP01 / 01893.
  • DMC compounds suitable as catalysts can in principle be produced in all ways known to the person skilled in the art.
  • the DMC compounds can be produced by direct precipitation, the “incipient wetness” method, by preparation of a precursor phase and subsequent recrystallization.
  • the DMC compounds can be used as a powder, paste or suspension or deformed into a shaped body, introduced into shaped bodies, foams or the like, or applied to shaped bodies, foams or the like.
  • the catalyst concentration used for the alkoxylation, based on the final quantity structure is typically less than 2000 ppm (ie mg catalyst per kg of product), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, particularly preferably less than 25 ppm.
  • compositions according to the invention show good wetting on hard surfaces.
  • the advantageous wetting behavior of the mixtures according to the invention can be determined, for example, by measuring the contact angle on glass, polyethylene oxide or steel.
  • the present invention therefore also relates to the use of a composition according to the invention or a composition prepared by a process according to the invention as an emulsifier, foam regulator and as a wetting agent for hard surfaces, in particular the use in detergents, surfactant formulations for cleaning hard surfaces, humectants, cosmetic, pharmaceutical and crop protection formulations, Paints, coating materials, adhesives,
  • leather degreasing agents formulations for the textile industry, fiber processing, metal processing, food industry, water treatment, paper industry, fermentation or mineral processing and in emulsion polymerizations.
  • compositions according to the invention results in better performance, in particular in fast cleaning processes. This is surprising in that the chain and lengthening of the starting alcohol usually reduces the dynamic and wetting properties. With the compositions according to the invention, the wetting rate of aqueous formulations can thus be increased.
  • the compositions according to the invention can thus also be used as solubilizers, which in particular do not negatively, but rather positively influence the wetting ability of wetting aids, even in dilute systems. They can be used to increase the solubility of wetting aids in aqueous formulations that contain non-ionic surfactants. They are used in particular to increase the wetting rate in aqueous wetting agents.
  • compositions according to the invention also serve to reduce the interfacial tension, for example in aqueous surfactant formulations.
  • the reduced interfacial tension can be determined, for example, using the pendant drop method. This also results in a better effect of the compositions according to the invention as an emulsifier or co-emulsifier.
  • the compositions according to the invention can also be used to reduce the interfacial tension in short times of usually less than one second or to accelerate the setting of the interfacial tension in aqueous surfactant formulations. Preferred areas of use of the compositions according to the invention are described in more detail below.
  • compositions according to the invention are preferably used in the following areas:
  • Surfactant formulations for cleaning hard surfaces Suitable surfactant formulations which can be added with the alkoxylates according to the invention are, for example, in Formulating Detergents and Personal Care
  • soap such as LAS or paraffin sulfonates or FAS or FAES
  • acids such as phosphoric acid, amidosulfonic acid, citric acid, lactic acid, acetic acid, other organic and inorganic acids
  • solvents such as ethylene glycol, isopropanol
  • complexing agents such as EDTA, NTA, MGDA , Phosphonates
  • polymers such as polyacrylates, copolymers maleic acid-acrylic acid, alkali donors such as hydroxides, silicates, carbonates, perfumes, oxidizing agents such as perborates, peracids or trichloroisocyanuric acid, Na- or K-dichloroisocyanurates, enzymes; see also
  • Metal degreasing industrial applications such as detergents for the food industry, bottle washing, etc. It can also be printing roller and plate cleaning agents in the printing industry. Suitable further ingredients are known to the person skilled in the art.
  • Humectants especially for the printing industry.
  • Cosmetic, pharmaceutical and crop protection formulations are described, for example, in EP-A-0 050 228. There may be other common ingredients for pesticides.
  • Paints, coatings, paints, pigment preparations and adhesives in the paint and film industry Paints, coatings, paints, pigment preparations and adhesives in the paint and film industry.
  • Formulations for the textile industry such as leveling agents or formulations for yarn cleaning.
  • Metal processing such as metal finishing and electroplating.
  • Emulsion polymerization and preparation of dispersions Emulsion polymerization and preparation of dispersions.
  • Such formulations usually contain ingredients such as surfactants, builders, fragrances and dyes, complexing agents, polymers and other ingredients. Typical formulations are described, for example, in WO 01/32820. Further ingredients suitable for different applications are in EP-A-0 620 270, WO 95/27034, EP-A-0 681 865, EP-A-0 616 026, EP-A-0 616 028, DE-A-42 37 178 and US 5,340,495 and in Schönfeldt, as described by way of example.
  • compositions according to the invention can be used in all areas in which the action of surface-active substances is necessary.
  • the present invention therefore also relates to detergents, cleaning agents, wetting agents, coatings, adhesives, leather degreasing agents, moisturizers or textile treatment agents or cosmetic, pharmaceutical or crop protection formulations comprising a composition according to the invention or a composition produced by a method according to the invention.
  • the agents preferably contain 0.1 to 20% by weight of the compositions.
  • compositions according to the invention are characterized in particular by a low residual alcohol content, so that they are advantageously suitable for a large number of fields of application.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention se rapporte à des compositions comprenant au moins un alcoxylat de formule générale RO(A)n(B)mH, à un procédé de production de ces compositions, en particulier en présence de composés de type cyanure métallique double qui servent de catalyseurs, ainsi qu'à leur utilisation en tant qu'émulsifiants, régulateurs de mousse ou agents mouillants pour surfaces dures. La présente invention concerne en outre l'utilisation desdites compositions dans des détergents et formulations de tensioactifs.
EP03725099A 2002-09-18 2003-04-25 Alcoxylats presentant une faible teneur en alcool residuel Revoked EP1542955B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10243365A DE10243365A1 (de) 2002-09-18 2002-09-18 Alkoxylate mit niedrigem Restalkohol-Gehalt
DE10243365 2002-09-18
PCT/EP2003/004330 WO2004033405A1 (fr) 2002-09-18 2003-04-25 Alcoxylats presentant une faible teneur en alcool residuel

Publications (2)

Publication Number Publication Date
EP1542955A1 true EP1542955A1 (fr) 2005-06-22
EP1542955B1 EP1542955B1 (fr) 2010-10-06

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Application Number Title Priority Date Filing Date
EP03725099A Revoked EP1542955B1 (fr) 2002-09-18 2003-04-25 Alcoxylats presentant une faible teneur en alcool residuel

Country Status (12)

Country Link
US (1) US7332465B2 (fr)
EP (1) EP1542955B1 (fr)
JP (1) JP5134762B2 (fr)
CN (1) CN1296337C (fr)
AT (1) ATE483675T1 (fr)
AU (1) AU2003227678A1 (fr)
BR (1) BR0314399A (fr)
CA (1) CA2499351A1 (fr)
DE (2) DE10243365A1 (fr)
ES (1) ES2353745T3 (fr)
MX (1) MXPA05002906A (fr)
WO (1) WO2004033405A1 (fr)

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EP2809754A1 (fr) 2012-02-01 2014-12-10 Basf Se Liquides réfrigérants et/ou lubrifiants pour la production de tranches de semi-conducteurs
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BR0314399A (pt) 2005-07-19
US20050272626A1 (en) 2005-12-08
US7332465B2 (en) 2008-02-19
AU2003227678A1 (en) 2004-05-04
DE50313163D1 (de) 2010-11-18
CA2499351A1 (fr) 2004-04-22
ATE483675T1 (de) 2010-10-15
JP5134762B2 (ja) 2013-01-30
CN1688529A (zh) 2005-10-26
EP1542955B1 (fr) 2010-10-06
DE10243365A1 (de) 2004-04-01
ES2353745T3 (es) 2011-03-04
WO2004033405A1 (fr) 2004-04-22
JP2005539133A (ja) 2005-12-22
MXPA05002906A (es) 2005-05-27
CN1296337C (zh) 2007-01-24

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