EP1412539B1 - Agent de degraissage de cuir - Google Patents

Agent de degraissage de cuir Download PDF

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Publication number
EP1412539B1
EP1412539B1 EP02758288A EP02758288A EP1412539B1 EP 1412539 B1 EP1412539 B1 EP 1412539B1 EP 02758288 A EP02758288 A EP 02758288A EP 02758288 A EP02758288 A EP 02758288A EP 1412539 B1 EP1412539 B1 EP 1412539B1
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EP
European Patent Office
Prior art keywords
alcohol
degreasing
degreaser
roh
leather
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EP02758288A
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German (de)
English (en)
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EP1412539A1 (fr
Inventor
Philippe Lamalle
Thomas FÜNGERLINGS
Martin Scholtissek
Jürgen Tropsch
Alfred Ruland
Roland BÖHN
Günter OETTER
Claus Hackmann
Gunther Pabst
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C5/00—Degreasing leather

Definitions

  • the invention relates to degreasing agents for the treatment of hides, skins, pelts and other intermediates in leather and fur production and wool or related proteins based on nonionic surfactants of the Alcohol alkoxylates, a process for degreasing hides, skins, pelts and more Intermediates in leather and fur manufacturing as well as wool or related products Proteins. Furthermore, the invention relates to the use of degreasing agents.
  • the removal of natural fat from animal skins is essential for producing quality high quality leather and fur skins, especially for medium and high quality skins Natural fat.
  • the distribution of performance chemicals in the degreasing The following stages of leather and fur production is made clear by the degreasing improved so that e.g. a uniform tanning and dyeing is possible. Does not happen Removal of natural fat, so the end product in the case of leather is spotty and / or obtained by bacterial degradation of fats and crystallization of high molecular weight Saturated fatty acids during storage fatty spikes, which make the leather look and feel physically negatively affect.
  • Furry skins are uneven dyed velor side, in addition, local hardening with risk of breakage of Fur leather occur.
  • the solvent degreasing is a degreasing with organic solvents. She can either without addition of water (dry degreasing) or in the presence of water (Wet degreasing) done. Due to the use of organic solvents Solvent degreasing leads to significant environmental impact already in today many countries are no longer sustainable.
  • Emulsifier degreasing performed entirely on the use of organic Solvent dispensed.
  • emulsifiers are in this process in particular Nonionic surfactants suitable because they have no binding capacity to the skin or Leather fiber. Thus, they can optimally solubilize the natural fat of the animal skins, without being hindered by interactions with the animal skin.
  • Known Nonionic emulsifiers are addition compounds of ethylene oxide and / or Propylene oxide to alkylphenols, alcohols or fatty acids.
  • the over decades on The most commonly used nonionic surfactants are the alkylphenol ethoxylates. It came in particular having an average of 10 EO (ethylene oxide) units Nonylphenolethoxylat used.
  • Substitutes for the alkylphenol ethoxylates are predominantly alcohol ethoxylates used.
  • DE-A 42 07 806 and DE-A 43 01 553 disclose degreasing compositions based on fatty alcohol alkoxylates which comprise a mixture of predominantly saturated C 12 - to C 18 -fatty alcohol ethoxylates having on average more than 6 EO units in the molecule and a minor amount of shorter chain lead fatty alcohol ethoxylates having not more than 3 EO units in the molecule.
  • the disclosed fatty alcohol ethoxylates are preferably straight chain.
  • EP-A 0 448 948 a process for the production of leathers and furs is disclosed, wherein as surfactants a mixture of a C 10 - to C 18 alkyl / Alkylenpolyglycolether having 3 to 10 EO units in the molecule, a C 8 bis C 18 -alkanol / alkenol and an anionic surfactant or surfactant mixture is used. As a result, a degreasing with no or minimal foaming is achieved.
  • WO 94/11331 and WO 94/11330 relate to the use of 2-propylheptanol with various degrees of alkoxylation in detergent compositions for degreasing hard surfaces or for cleaning textiles.
  • the alkoxides used therein are ethylene oxide (EO) and mixtures of EO with propylene oxide (PO) or butylene oxide (BuO).
  • EO ethylene oxide
  • PO propylene oxide
  • BuO butylene oxide
  • the 2-propylheptanol alkoxylates are characterized in particular by low foaming.
  • the object of the present invention is therefore to provide an alternative to Alkylphenolethoxylaten with the same or even better degreasing properties and a same or cheaper price, which is further optimally biologically compatible.
  • the solution of the problem is based on a degreaser for the treatment of Hides, skins, pelts and other intermediates in leather and fur manufacture and wool or related proteins based on nonionic surfactants of Type of alcohol alkoxylates.
  • the degreasing agent according to the invention is then characterized in that alcohol alkoxylates are used, which are obtained by reacting at least one alcohol ROH with n moles of at least one alkylene oxide per mole of alcohol ROH, wherein R is an alkyl group of 5 to 30 carbon atoms having a main chain of 4 to 29 carbon atoms branched in the middle of the chain with at least one C 1 to C 10 alkyl group; the alkylene oxide has 2 to 6 carbon atoms and where n is an integer between 1 and 100.
  • alcohol alkoxylates are used, which are obtained by reacting at least one alcohol ROH with n moles of at least one alkylene oxide per mole of alcohol ROH, wherein R is an alkyl group of 5 to 30 carbon atoms having a main chain of 4 to 29 carbon atoms branched in the middle of the chain with at least one C 1 to C 10 alkyl group; the alkylene oxide has 2 to 6 carbon atoms and where n is an integer
  • chain center means those carbon atoms of the main chain, ie the longest alkyl chain of the radical R, beginning with the carbon atom C # 2, the numbering starting from the carbon atom (C # 1) which is directly attached to the carbon atom Residual R adjacent oxygen atom is bonded, and ending with the carbon atom ⁇ -2, where ⁇ is the terminal carbon atom of the main chain, wherein C # 2 and the carbon atom ⁇ -2 are included.
  • the carbon atom C # 2 of the main chain of the radical R is preferably substituted by a C 1 - to C 6 -alkyl radical.
  • one or more carbon atoms in the middle of the chain are substituted by two C 1 to C 6 alkyl radicals, ie that one or two carbon atoms in the middle of the chain are quaternary carbon atoms.
  • the degreasing agent according to the invention shows very good emulsifier degreasing Efficiencies. It has a high emulsifying effect, especially in the aqueous medium for natural fats and oils and emulsifies them in such a way that the fat and oils Oil components from the animal skin can be washed out with water.
  • the degreasing agent according to the invention preferably contains a mixture of Alcohol alkoxylates based on 1 to 3 different alcohols ROH, especially preferably to 1 or 2 different alcohols ROH.
  • the number of Carbon atoms of the radical R be different and / or the type of branching.
  • the main chain of the alcohols ROH has 1 to 4 branches, as far as the Chain length more than one junction in the center of the chain allows, especially preferably 1 to 3, very particularly preferably 2 or 3.
  • These branches have in the generally independently of one another 1 to 10 carbon atoms, preferably 1 to 6, more preferably 2 to 4, most preferably 2 or 3 on.
  • Especially preferred Branches are therefore ethyl, n-propyl or iso-propyl groups.
  • the radical R of the alcohol ROH has 5 to 30 carbon atoms. Since the rest of R has at least one branch with at least one carbon atom comprises the main chain has from 4 to 29 carbon atoms.
  • the radical R preferably has 6 to 25 Carbon atoms, more preferably 10 to 20. That is, the main chain has preferably 5 to 24 carbon atoms, more preferably 9 to 19.
  • the backbone has 9 to 15 carbon atoms and the remainder Carbon atoms of the R group are distributed over one or more branches.
  • branched alcohols which are used in the preparation of the invention
  • Alcohol alkoxylates used are required, according to known in the art Methods.
  • a general synthetic possibility for producing branched alcohols is e.g. the reaction of aldehydes or ketones with Grignard reagents (Grignard synthesis).
  • Grignard reagents can also aryl or alkyl-lithium compounds be used, characterized by a higher reactivity distinguished.
  • the branched alcohols can pass through ROH Aldolkondensation be obtained, the reaction conditions to those skilled are known.
  • Alcohol alkoxylates reacted alkylene oxide is preferred selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. It is also possible that a single alcohol ROH with various of the alkylene oxides mentioned, e.g. Ethylene oxide and propylene oxide, is reacted Alcohol alkoxylates can be obtained, each containing blocks of several units an alkylene oxide, e.g. Ethylene oxide, in addition to blocks of several units one further alkylene oxide, e.g. Propylene oxide. Particularly preferably, the Alcohol alkoxylates used according to the invention are ethylene oxide (EO) units, that is the alkylene oxide used is preferably ethylene oxide.
  • EO ethylene oxide
  • Alcohol alkoxylates in which the incorporation of the various alkylene oxides statistically.
  • Such alcohol alkoxylates are referred to below as random mixed alcohol alkoxylates called
  • the amounts of alkylene oxide used are from 1 to 100 moles of alkylene oxide per mole of alcohol, preferably 1 to 25 mol, more preferably 3 to 15 mol and most preferably 5 to 12 mol.
  • the degree of alkoxylation achieved is in the inventively used Alcohol alkoxylates widely distributed, and depending on the amount of alkylene oxide used between 1 and 100 moles of alkylene oxide per mole of alcohol. It was found that by reacting the alcohols used in the invention with alkylene oxides achieved molecular weight distribution (due to the degree of alkoxylation of Alcohols) does not correspond to a Gaussian distribution.
  • Such a Gaussian distribution results in an alkoxylation of oxo alcohols (technical alcohols, which are about 60 Wt .-% linear alcohols and about 40 wt .-% branched with methyl groups Alcohols) to alcohol alkoxylates, as in the art in leather degreasing agents are used, as well as in an alkoxylation of alkylphenols whose Alkoxylation products have so far show the best results in leather degreasing.
  • oxo alcohols consisting of oxo alcohols (technical alcohols, which are about 60 Wt .-% linear alcohols and about 40 wt .-% branched with methyl groups Alcohols)
  • alcohol alkoxylates as in the art in leather degreasing agents are used, as well as in an alkoxylation of alkylphenols whose Alkoxylation products have so far show the best results in leather degreasing.
  • the molecular weight distribution is at a Alkoxylation
  • FIG. 1 this is based on the distribution of the degrees of ethoxylation on Example of a C10-oxo-alcohol, an alkylphenol (nonylphenol) (each Comparative Examples) and a branched C10-alcohol according to the invention, each ethoxylated with 8 moles of ethylene oxide per mole of alcohol (8EO).
  • the left column represents the degrees of ethoxylation of Ethoxylation of the inventively used C10-alcohol; the middle column the Ethoxylation degrees of ethoxylation of the C10-oxo-alcohol and the right column the Degree of ethoxylation of the ethoxylation of the alkylphenol.
  • the number n given in the present application thus relates to the used amount of alkylene oxide.
  • a preferred embodiment of the present invention contains degreasing agents used according to the invention in addition to the alcohol alkoxylates> 1 to 25, preferably> 1 to 10% by weight, based on the amount of the alcohol alkoxylates used, unreacted alcohol ROH.
  • the degreaser of the invention comprises a mixture of Alcohol alkoxylates containing either based on different alcohols are and / or with a different amount or different alkylene oxides have been implemented, they can be present in any proportions.
  • Degreasing agent e.g. two different alcohol alkoxylates, these may be in Ratios of 20: 1 to 1: 1, preferably 9: 1 to 1: 1.
  • Degreasing agent e.g. two different alcohol alkoxylates, these may be in Ratios of 20: 1 to 1: 1, preferably 9: 1 to 1: 1.
  • the components present in excess over the other two components It is too possible that 2 components form the majority of the alcohol alkoxylates and of the third component contains only minor amounts. Furthermore, it is possible that all three components are contained approximately equally in the degreasing agent.
  • Alcohol alkoxylates are generally 8 to 16, preferably 9 to 14.
  • the alcohol alkoxylates are prepared from the branched alcohols by reaction with alkylene oxides.
  • the reaction conditions are known to the person skilled in the art. In general, the reaction is carried out on an alkali metal catalyst. Usually NaOH or KOH are used. It is also possible to use Ca (OH) 2 , Ba (OH) 2 , Sr (OH) 2 or hydrotalcite as catalysts.
  • the reaction is preferably carried out in the absence of water.
  • the reaction temperature is generally 70 to 180 ° C.
  • the alcohol first with ethylene oxide and then with propylene oxide or first with propylene oxide and then with ethylene oxide, which is preferred.
  • the simultaneous addition takes place of various alkylene oxides, again a mixture of ethylene oxide and Propylene oxide is preferably used.
  • the degreasing agent according to the invention can be used in different process stages, in which the use of a degreaser is useful or necessary, in the leather and Fur production can be used. So the use is e.g. when shedding, limping, Deliming, staining, pimpling and / or tanning and after a stripping, in the Treatment of wet blue or wet white, in the wet dressing process and in the Processing of Borkeledern possible. These individual process stages are the Specialist known.
  • Suitable components are e.g. other formulation agents such as wetting agents, Raw components with surfactant action, e.g. Ether sulfates or dispersants; Defoamers such as paraffins and siloxanes; Carrier oils such as higher alkanes, rich in aromatics vegetable or synthetic oils, white oil or mineral oil; other nonionic, anionic, cationic and / or amphoteric surfactants.
  • Another object of the present invention is a method for degreasing Hides, skins, pelts and other intermediates in leather and fur manufacture and wool or related proteins, in which an inventive Degreasing agent is used.
  • the degreasing process according to the invention can be carried out in the fleet or without liquor be performed. If the process is carried out without a liquor, an addition takes place the degreasing agent of the invention to be degreased hides, skins, pelts or other intermediates and then walking.
  • the alcohol alkoxylates contained in the degreasing agent according to the invention are generally in an amount of 0.5 to 5 wt .-%, preferably 1 to 3 wt .-%, based on the weight of hides, skins, pelts or other intermediates in the leather and fur production.
  • This information refers to the total content of Alcohol alkoxylates contained in the degreasing agent according to the invention.
  • Use of several alcohol alkoxylates results from the above Ratios of the proportion of the individual alcohol alkoxylates.
  • the degree of degreasing increases with the amount used up to the specified upper limit in general, the Degreasing depends inter alia on the natural fat content of animal skins.
  • the process according to the invention is generally carried out at a pH of from 2 to 10 carried out.
  • the pH varies from acid to basic.
  • the salinity levels present during the degreasing process correspond to the usually used in the various stages of the process salt contents.
  • the salinity the liquor is generally 0 to 100 g NaCl / l.
  • the temperature of the process according to the invention is generally from 15 to 45.degree. preferably 28 to 34 ° C.
  • the temperature is also in the different process stages differently. For example, higher temperatures can be applied after tanning the leather be as before, as too high temperatures before tanning, if necessary, the quality affect the leather or fur to be produced. An increase in temperature leads in general, to an increase in the degree of degreasing.
  • the duration of the process depends on the process level in which the Inventive degreasing agent is used. In general, the duration of the Degreasing 0.5 hours to 10 hours, preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours. The degree of degreasing generally increases with increasing Duration until a maximum is reached.
  • the fleet length should be at least as long that a micelle formation is present so that the degreaser can unfold its effect. For good Efficiencies are preferably several shortest possible fleets with changing Baths used.
  • degreasing agents according to the invention can in the leather degreasing Efficiencies ((difference in fat content before degreasing and after degreasing) x 100 / (fat content before degreasing)) of ⁇ 50%, preferably ⁇ 55%.
  • the degreased material is generally watered rinsed.
  • emulsifier degreasing thereby reduces the Wastewater pollution on the substances natural fat and surfactant.
  • a Separation of these substances from the aqueous phase thereby possible, that the heated aqueous mixture.
  • At elevated temperature penalize the invention used nonionic surfactants in solubility.
  • Loss of emulsifier effect is an emulsion separation.
  • Another object of the present invention is the use of the Degreasing agent used according to the invention for degreasing hides, skins, pelts and other intermediates in the leather and fur production and of Wool or related proteins.
  • the blister samples taken before degreasing and degreasing then became dried and treated in the laboratory with dichloromethane. From the starting fat content and The fat content after degreasing was then the efficiency of the degreasing be determined.
  • Table 1 shows comparisons of the efficiencies achieved in the leather degreasing with oxo alcohol ethoxylates and alkylphenol ethoxylates against ethoxylates of branched alcohols ROH used in the invention. attempt Surfactant (s) Efficiency [%] 1V Nonylphenol ethoxylate with 3EO / 9EO approx.
  • The% data in the following examples are wt .-%, based on the Pelt weight.
  • a sheepskin hide (New Zealand) was tossed in 150% water with 10% common salt and 1.5% soda for 1 hour and then fleshed. A sample of the pelvic fat was cut off for fat analysis. Subsequently, the nakedness in the barrel with 1.5% Alkylphenolethoxylat (9 EO) was rolled, after 60 minutes 100% water of 30 ° C was added and drumming for a further 30 minutes. The liquor was drained, 1% alkylphenol ethoxylate (9 EO) added and tumbled for 60 minutes. At the end of this time, 100% water at 30 ° C. was added again and the mixture was tumbled for a further 30 minutes.
  • the fat content was 25.3% before degreasing and 11.1% after degreasing.
  • the fat content before degreasing was 22.7% and after degreasing 8.7%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Cosmetics (AREA)

Claims (13)

  1. Agent de dégraissage pour le traitement de peaux, de fourrures, de peaux planées et d'autres produits intermédiaires dans la fabrication des cuirs et des fourrures, ainsi que de laine ou de protides apparentés, à base d'agents tensioactifs non ioniques du type des alcoxylates d'alcool, caractérisé en ce qu'on met en oeuvre des alcoxylates d'alcool qui sont obtenus par réaction d'au moins un alcool ROH avec n moles d'au moins un oxyde d'alkylène par mole d'alcool ROH,
    dans lequel
    R est un radical alkyle comportant 5 à 30 atomes de carbone, qui présente, avec 4 à 29 atomes de carbone, une chaíne principale, qui est la chaíne alkylique la plus longue du radical R et qui est ramifiée avec au moins un radical alkyle en C1-C10 au milieu de la chaíne, en commençant avec l'atome de carbone C#2, où la numérotation part de à l'atome de carbone (C#1), qui est lié directement à l'atome d'oxygène voisin du radical R, en se terminant avec l'atome de carbone ω-2, où ω est l'atome de carbone terminal de la chaíne principale, C#2 et l'atome de carbone ω-2 étant inclus,
    l'oxyde d'alkylène présente 2 à 6 atomes de carbone,
    et
    n a une valeur de nombre entier entre 1 et 100.
  2. Agent de dégraissage suivant la revendication 1, caractérisé en ce que l'agent de dégraissage contient un mélange d'alcoxylates d'alcool, à base de 1 à 3 alcools ROH différents.
  3. Agent de dégraissage suivant la revendication 1 ou 2, caractérisé en ce que la chaíne principale est ramifiée au milieu de la chaíne avec au moins un radical alkyle en C2-C4.
  4. Agent de dégraissage suivant l'une des revendications 1 à 3, caractérisé en ce que le radical R présente 10 à 20 atomes de carbone, dont 9 à 19 atomes de carbone forment la chaíne principale.
  5. Agent de dégraissage suivant l'une des revendications 1 à 4, caractérisé en ce que l'oxyde d'alkylène est de l'oxyde d'éthylène.
  6. Agent de dégraissage suivant l'une des revendications 1 à 5, caractérisé en ce que n a une valeur de nombre entier de 3 à 15.
  7. Agent de dégraissage suivant l'une des revendications 1 à 6, caractérisé en ce que l'agent de dégraissage est un mélange d'alcoxylates d'alcool à base d'au moins un alcoxylate d'alcool, qui a été obtenu par réaction d'un alcool ROH avec n > 6 moles d'au moins un oxyde d'alkylène par mole d'alcool ROH, et d'au moins un autre alcoxylate d'alcool, qui a été obtenu par réaction d'un alcool ROH avec n = 1 à 6 moles d'au moins un oxyde d'alkylène par mole d'alcool ROH, l'alcool ROH et l'oxyde d'alkylène dans les au moins deux alcoxylates d'alcool pouvant être identiques ou différents.
  8. Agent de dégraissage suivant l'une des revendications 1 à 7, caractérisé en ce que l'agent de dégraissage contient, outre les alcoxylates d'alcool, > 1 à 25 % en poids, par rapport à la quantité des alcoxylates d'alcool mis en oeuvre, d'alcool ROH n'ayant pas réagi.
  9. Procédé de dégraissage de peaux, de fourrures, de peaux planées et d'autres produits intermédiaires dans la fabrication des cuirs et des fourrures, ainsi que de laine ou de protides apparentés, caractérisé en ce qu'on met en oeuvre un agent de dégraissage suivant l'une des revendications 1 à 8.
  10. Procédé suivant la revendication 9, caractérisé en ce qu'on met en oeuvre les alcoxylates d'alcool en une quantité de 0,5 à 5 % en poids, par rapport au poids des peaux, fourrures, peaux planées ou autres produits intermédiaires dans la fabrication des cuirs et des fourrures ou respectivement de la laine ou des protides apparentés.
  11. Procédé suivant la revendication 9 ou 10, caractérisé en ce qu'on ajuste une température de 15 à 45°C.
  12. Utilisation de l'agent de dégraissage suivant l'une des revendications 1 à 8, pour le dégraissage de peaux, de fourrures, de peaux planées et d'autres produits intermédiaires dans le cadre de la fabrication des cuirs et des fourrures ainsi que de laine ou de protides apparentés.
  13. Agent de dégraissage suivant l'une des revendications 1 à 4, 6 ou 7, caractérisé en ce que l'alcoxylate d'alcool est obtenu par réaction d'un alcool avec de l'oxyde d'éthylène et de l'oxyde de propylène.
EP02758288A 2001-07-20 2002-07-01 Agent de degraissage de cuir Revoked EP1412539B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10134441A DE10134441A1 (de) 2001-07-20 2001-07-20 Lederentfettungsmittel
DE10134441 2001-07-20
PCT/EP2002/007245 WO2003010340A1 (fr) 2001-07-20 2002-07-01 Agent de degraissage de cuir

Publications (2)

Publication Number Publication Date
EP1412539A1 EP1412539A1 (fr) 2004-04-28
EP1412539B1 true EP1412539B1 (fr) 2005-10-05

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US (1) US20060143833A1 (fr)
EP (1) EP1412539B1 (fr)
JP (1) JP3884010B2 (fr)
KR (1) KR100866854B1 (fr)
AR (1) AR034672A1 (fr)
AT (1) ATE305981T1 (fr)
BR (1) BR0211297B1 (fr)
DE (2) DE10134441A1 (fr)
ES (1) ES2249614T3 (fr)
WO (1) WO2003010340A1 (fr)

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JP5250382B2 (ja) * 2008-10-24 2013-07-31 省二 奥海 皮なめしの前処理方法及び皮なめし方法
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KR970007329B1 (ko) * 1993-09-17 1997-05-07 마쯔시다덴기산교 가부시기가이샤 납땜플럭스제거용 세정제조성물
US5501816A (en) * 1994-07-12 1996-03-26 Basf Corporation Aqueous based solvent free degreaser composition
US6133218A (en) * 1997-07-29 2000-10-17 Basf Corporation Aqueous based solvent free cleaner compositions containing two nonionic surfactants
JP2001519376A (ja) * 1997-10-14 2001-10-23 ザ、プロクター、エンド、ギャンブル、カンパニー 中間鎖分岐界面活性剤を含んでなるパーソナルクレンジング組成物
DE10035617A1 (de) * 2000-07-21 2002-01-31 Basf Ag Sekundäre C¶1¶¶0¶-C¶1¶¶8¶-Tensidalkohole

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DE50204483D1 (de) 2006-02-16
AR034672A1 (es) 2004-03-03
DE10134441A1 (de) 2003-02-06
JP2004536206A (ja) 2004-12-02
ATE305981T1 (de) 2005-10-15
US20060143833A1 (en) 2006-07-06
ES2249614T3 (es) 2006-04-01
BR0211297B1 (pt) 2012-01-10
KR20040023810A (ko) 2004-03-19
EP1412539A1 (fr) 2004-04-28
KR100866854B1 (ko) 2008-11-04
JP3884010B2 (ja) 2007-02-21
BR0211297A (pt) 2004-09-14
WO2003010340A1 (fr) 2003-02-06

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