EP0786019A1 - Utilisation de sels de guanidine d'acides gras insatures comme principes actifs anticorrosifs - Google Patents

Utilisation de sels de guanidine d'acides gras insatures comme principes actifs anticorrosifs

Info

Publication number
EP0786019A1
EP0786019A1 EP95935435A EP95935435A EP0786019A1 EP 0786019 A1 EP0786019 A1 EP 0786019A1 EP 95935435 A EP95935435 A EP 95935435A EP 95935435 A EP95935435 A EP 95935435A EP 0786019 A1 EP0786019 A1 EP 0786019A1
Authority
EP
European Patent Office
Prior art keywords
oil
fatty acids
acid
use according
guanidinium salts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95935435A
Other languages
German (de)
English (en)
Other versions
EP0786019B1 (fr
Inventor
Jürgen Geke
Horst-Dieter Speckmann
Bernd Stedry
Alfred Westfechtel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0786019A1 publication Critical patent/EP0786019A1/fr
Application granted granted Critical
Publication of EP0786019B1 publication Critical patent/EP0786019B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/146—Nitrogen-containing compounds containing a multiple nitrogen-to-carbon bond

Definitions

  • the invention relates to oil-based corrosion protection agents for metallic, in particular iron-based surfaces, which are preferably used in the form of oil-in-water emulsions.
  • the invention provides alkyla-free anti-corrosion agents which are characterized by good oil solubility and which at the same time cause the oil phase to be emulsified in water.
  • Anti-rust emulsions are used for the temporary protection of metallic materials against atmospheric influences that cause corrosion. They contain essentially non-polar or polar oils, emulsifiers, corrosion inhibitors and water. Their effect is based on the adsorption of inhibitor molecules on the metal surface and the formation of a protective film from emulsion components, which acts as a diffusion barrier for atmospheric oxygen and water. T. Forster et al. report in "Surface-Surface", 1989, No. 4, pp. 8-12, about modes of action and methods of investigation of rust protection emulsions.
  • Corrosion protection agents which have hitherto been used contain constituents such as, for example, petroleum sulfonates, salts of alkylsulfonamidocarboxylic acids and amine or other salts of partial esters of alkyl or alkenylsuccinic acid.
  • EP-A-566 956 describes corrosion protection agents based on an amine-free salt of a half-ester of an alkyl or Alkenyl succinic acid.
  • Sulfur-containing corrosion inhibitors such as, for example, alkylarylsulfonic acids, petroleum sulfonates or salts of alkylsulfonamidocarboxylic acids have the disadvantage that they can easily be broken down by microorganisms such as sulfur-reducing bacteria, which can lead to considerable odor nuisance.
  • stearic acid derivatives have been described as anti-corrosion agents (DE-C-32 03 491).
  • Examples include 9,10-dihydroxystearic acid and its alkali metal salts and their oligomeric condensates, 9,10-epoxy stearic acid, their alkali metal salts and their oligomeric estolides and finally mixed oligomerizates of 9,10-epoxy and 9,10-dihydroxystearic acid .
  • Corrosion protection agents which are to be used in the form of oil-in-water emulsions can be brought onto the market as purely oily, that is to say anhydrous, concentrates in order to be brought into the ready-to-use emulsion form by adding water at the point of use .
  • These oil concentrates contain the corrosion inhibitors, which must therefore be oil-soluble. So that the oil concentrates spontaneously form an emulsion when diluted with water, that is, they can be self-emulsifying, it was previously necessary that these concentrates also contain emulsifiers in addition to the corrosion inhibitors.
  • US Pat. No. 2,978,415 discloses guanidinium salts of unsaturated fatty acids and processes for their preparation. These guanidine soaps of unsaturated fatty acids are used as cleaning-enhancing active substances in the cleaning of textiles with solvents, that is to say in the so-called “chemical cleaning” or “dry cleaning”. For this application, which takes place in the purely organic phase, neither a corrosion protection effect nor an emuIgie ability is important. Accordingly, this US document contains no information on a corresponding effect of the guaniidine soaps of unsaturated fatty acids.
  • the object of the present invention is to provide new sulfur and alkylamine-free corrosion protection agents, the oil solutions of which do not have unacceptably high viscosities even at high concentrations of the agent, and which at the same time emulsify the oil phase when mixed with water, without additional emulsifiers are required for this.
  • This object is achieved by the use of guanidinium salts of mono- or polyunsaturated fatty acids with 6 to 44 carbon atoms to achieve temporary protection against corrosion on metallic, preferably iron-based surfaces.
  • “Fatty acids” are understood here to mean carboxylic acids, which may be OH-substituted.
  • the unsaturated fatty acids that can be used can be divided into two groups: native fatty acids, as they occur as a component of natural oils and fats, and so-called dimer fatty acids, which are technically accessible through, generally acid-catalyzed, dimerization of suitable fatty acids.
  • the unsaturated fatty acids that can be used are therefore once characterized in that they are native Represent fatty acids, ie are branched or preferably linear, have one to six, preferably one to three double bonds and preferably contain 11 to 28, in particular 18 to 22, carbon atoms.
  • Suitable unsaturated fatty acids of this type are preferably monobasic and, for example, selected from undecylenic acid, myristoleic acid, palmitoleic acid, oleic acid, ricinoleic acid, erucic acid, linoleic acid, linolenic acid, arachidonic acid and mixtures thereof.
  • unsaturated fatty acids from the group of so-called diacids are suitable. These are polybasic, preferably dibasic. Those dimer acids which have 36 to 44 carbon atoms are particularly suitable.
  • Guanidinium salts of defined, pure fatty acids can advantageously be used for the purpose according to the invention.
  • guanidinium salts of technical fatty acid mixtures will be used in practice, which in addition to unsaturated fatty acids of different C chain lengths can also contain certain proportions of saturated fatty acids.
  • Such technical fatty acid mixtures can be obtained, for example, by splitting suitable natural oils and fats.
  • the technical fatty acid mixtures consist of at least 50% by weight, preferably at least 80% by weight, of unsaturated fatty acids of the above-mentioned carbon chain lengths.
  • dimer fatty acids which can likewise be used according to the invention, generally do not represent pure substances either, but can contain fatty acids of different carbon chain lengths and / or different degrees of oligomerization.
  • trimerization or polymerization products may also be present in addition to unreacted and / or isomerized mono-fatty acids. If we are talking about dimer fatty acids here, we mean product mixtures which are at least 50% by weight, preferably at least 70% by weight consist of dimer fatty acid with a C chain length between 36 and 44.
  • Such products are commercially available, for example from Unichema under the product group name Pripol R or from Henkel KGaA under the product group name Empol R.
  • guanidinium salts of the abovementioned fatty acids they are used as solutions in hydrocarbons which are liquid at working temperature, dialkyl ethers and / or acetals which are largely insoluble in water, and mixtures thereof.
  • ester oils such as oleyl oleate, esterification products of aliphatic dicarboxylic acids (preferably C ⁇ -g) with branched Guerbet alcohols (preferably C12-20) (EP-A-489809), esters of Ci-5- Monocarboxylic acids with mono- or polyfunctional alcohols (for example described in DE-A-3907 391), esters of Cß-n-monocarboxylic acids with mono- or polyfunctional alcohols (for example described in DE-A-3907 392), and alkoxylation products of triglycerides with 0.5 - 3 mol E0 and / or PO, for example glycerol propoxylate trioleate (German patent application P 4323771).
  • oil-like solvents These essentially water-insoluble solvents are further referred to as "oil-like solvents".
  • Solutions which contain between 1 and 45% by weight of guanidinium salts of unsaturated fatty acids are preferably used. At lower contents, the corrosion protection effect decreases significantly, while at higher contents, the solutions generally become so highly viscous that their handling and use for the formation of emulsions is unnecessarily difficult. For the purposes of the invention, however, higher concentrations can also be used if the associated difficulties in emulsion formation are accepted, for example prior heating of concentrate and preparation water and the use of technical emulsifying aids such as, for example, fast-running toothed disks or ultrasound.
  • suitable oil-like solvents for the guanidinium salts of unsaturated fatty acids are hydrocarbons which are liquid at working temperature, that is to say a temperature between about 10 and about 90 ° C.
  • hydrocarbons which are liquid at working temperature, that is to say a temperature between about 10 and about 90 ° C.
  • paraffin oil or mineral oil in the case of mineral oil low-aromatic mineral oils are preferred for ecological and toxicological reasons.
  • Suitable oils of this type are commercially available. Examples include pioneering oil 4556 from Hansen & Rosenthal, Enerpar 3036 from Irish BP and Parex Paraffin II from Leu-na-Werke.
  • liquid, largely water-insoluble dialkyl ethers are liquid, largely water-insoluble dialkyl ethers.
  • “Largely water-insoluble” is understood to mean those dialkyl ethers which do not dissolve in water by more than 5% by weight, preferably not more than 0.5% by weight.
  • Suitable examples are dialkyl ethers having 6 to 24, preferably 8 to 18, carbon atoms per alkyl radical, where the alkyl radicals can, independently of one another, be straight-chain or branched-chain, saturated or unsaturated and preferably n-octyl, 2-ethylhexyl, stearyl and / or represent isostearyl radicals.
  • dialkyl ethers can still have free hydroxyl groups and are then referred to as hydroxy ischether.
  • the use of such dialkyl ethers in metalworking fluids is described, for example, in German patent application P 4237501.
  • Such dialkyl ethers are commercially available, for example from Henkel KGaA under the name Cetiol-OE (dioctyl ether).
  • Other suitable oil-like solvents for the use of the guani dinium salts according to the invention are acetals based on monovalent aldehydes having 1 to 25, preferably 1 to 10, carbon atoms and monohydric alcohols having 1 to 25, in particular 2 to 20, carbon atoms.
  • the use of such acetals as mineral oil substitute, oil component or base oil in lubricating oils and in metalworking fluids is known from EP-A-512 501. A general regulation for the production of such acetals is also given there.
  • the guanidinium salts of unsaturated fatty acids are preferably used in such a way that the solution of the guanidinium salts in one of the above-mentioned oil-like solvents or in mixtures thereof is used as the oil phase of an oil-in-water emulsion.
  • the proportion of oil in the emulsion which means the solution of the guanidinium salts of the unsaturated fatty acids, in the emulsion is preferably between 0.5 and 50% by weight, in particular between 5 and 20% by weight.
  • the rule of thumb here is that the proportion of the oil phase can be chosen to be lower the higher the concentration of the guaniidinium salts of unsaturated fatty acids in the oil phase.
  • Suitable glycols are, for example, butyl diglycol, hexylene glycol or dipropylene glycol, which contain 1 to 10% by weight of the guanidinium salt solution.
  • the glycols can either be added to the solution of the guaniidinium salts of unsaturated fatty acids in oil-like solvents or added to the oil-like solvent before the reaction of guanidinium salts of volatile acids with unsaturated fatty acids described below. Because of the beneficial effect on corrosion protection, the use of hexylene glycol is preferred.
  • the invention further relates to the oil-in-water emulsions suitable for the use according to the invention of guanidinium salts of unsaturated fatty acids.
  • guanidinium salts of unsaturated fatty acids can be used as cooling lubricant emulsions in metal cutting, the emulsions being able to contain further active ingredients known for this area of application, for example lubrication-enhancing additives or biocides.
  • the invention comprises oil-in-water emulsions, the oil phase of which is an oil-like solvent or solvent mixture according to one or more of claims 6 to 9 and the guanidinium salts of unsaturated fatty acids according to one or more of claims 1 to 5 in concentrations of Contains 1 to 45 wt .-%, preferably 5 to 20 wt .-% dissolved with respect to the oil phase, the proportion of the oil phase in the emulsion between 0.5 and 50 preferably 5 to 20 wt .-%.
  • the preparation of such emulsions is preferably carried out by mixing a solution of the guanidinium salts in the oil-like solvent with water. Since the guanidinium salts are soluble both in the oil-like solvents and in water, they will be distributed between the water and oil phases. In individual cases, the distribution equilibrium depends on the chosen oily solvent and the type of unsaturated fatty acid. As described in Example 11, an emulsion can also be be obtained by emulsifying an aqueous solution of the guanidinium salts with oil. Here too it is to be expected that a distribution equilibrium of the guanidinium salts will be established.
  • the proportion of the oil phase, which contains the guanidinium salts of unsaturated fatty acids at least partially dissolved, in the oil-in-water emulsion is from about 0.5 to about 50% by weight and is preferably in the range from about 5 to about 20% by weight .-%.
  • Such an emulsion is usually stable for the periods of several hours required in terms of application technology without further co-emulsifiers. In special circumstances, for example if the emulsion contains further active ingredients such as builder salts or use-related impurities, it may be necessary to stabilize the emulsion by using additional co-emulsifiers.
  • Nonionic surfactants in particular ethoxylation products of fatty alcohols, such as, for example, an adduct of 6 moles of ethylene oxide with 1 mole of a C12 / 14-fatty alcohol mixture, or anionic emulsifiers such as, for example, alkylbenzenesulfonates, are suitable for this.
  • fatty alcohols such as, for example, an adduct of 6 moles of ethylene oxide with 1 mole of a C12 / 14-fatty alcohol mixture
  • anionic emulsifiers such as, for example, alkylbenzenesulfonates
  • the emulsion can be in the form of a conventional, milky opaque emulsion.
  • the emulsion can also be advantageous to use the emulsion in the form of an almost transparent so-called micro-emulsion with an oil content of up to 50% by weight, as can be obtained by phase inversion from a water-in-oil emulsion .
  • PIT phase inversion temperature
  • guanidinium salts of unsaturated fatty acids is described in the above-mentioned US Pat. No. 2,978,415.
  • a mixture of unsaturated fatty acids can be dissolved in an organic solvent such as methyl isobutyl ketone and guanidinium carbonate can be added.
  • an organic solvent such as methyl isobutyl ketone
  • guanidinium carbonate can be added.
  • the solvent and the water of reaction can be removed, leaving the product in the form of a brown, waxy paste.
  • oil-like solvents as the solvent for the reaction of the unsaturated fatty acids with guanidinium salts of volatile acids, for example guanidinium carbonate, as the oil phase to be used for later emulsion preparation.
  • guanidinium salts of volatile acids for example guanidinium carbonate
  • Rosion inhibitors are known, are unsuitable for the use according to the invention, since their oil solutions in the concentration ranges according to the invention are not mobile liquids, but wax-like pastes.
  • Solvent dioctyl ether Cetiol-OE, Henkel KGaA.
  • Example 8 Product from up to 16 days no corrosion Example 3 after 25 days termination with traces of corrosion
  • Example 10 Analogously to Example 10, the corrosion protection effect of an emulsion was tested, which was obtained by adding water to the product from Example 5 in a weight ratio of 1: 9: no corrosion was observed after 7 days and severe corrosion after 20 days.
  • glycols for example butyl diglycol, hexylene glycol, dipropylene glycol
  • Example 10 For a corrosion test analogous to Example 10, the product from Example 5 was mixed with 5% by weight of hexylene glycol. By adding water in a weight ratio of 1: 9, an emulsion was obtained and used for testing the corrosion protection effect. Result: No corrosion after 8 days and severe corrosion after 13 days.
  • a microemulsion by the phase inversion method 2.6 parts by weight of this guanidinium oleate and 0.26 part by weight of sodium citrate were dissolved in 51.04 parts by weight of water.
  • the solution was mixed with 40 parts by weight of mineral oil (pioneering oil 4556) and 6.1 parts by weight of emulsifier (adduct of 4 moles of ethylene oxide with a C12 / 14- " alcohol mixture) at a temperature above that obtained by preliminary tests
  • the phase inversion temperature of 35 ° C. was mixed by stirring and cooled below the phase inversion temperature, and a transparent microemulsion was obtained which could be diluted by adding water.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Colloid Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Paints Or Removers (AREA)
  • Load-Engaging Elements For Cranes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Connection Of Plates (AREA)

Abstract

On utilise des sels de guanidine d'acides gras mono-insaturés ou polyinsaturés ayant 6 à 44 atomes de C pour réaliser une protection temporaire de surfaces métalliques contre la corrosion. Les sels de guanidine sont de préférence dissous dans une émulsion huile dans eau. L'invention concerne également des émulsions huile dans eau dont la phase huile peut être constituée de différents solvants huileux contenant les sels de guanidine d'acides gras insaturés.
EP95935435A 1994-10-14 1995-10-05 Utilisation de sels de guanidine d'acides gras insatures comme principes actifs anticorrosifs Expired - Lifetime EP0786019B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4436764A DE4436764A1 (de) 1994-10-14 1994-10-14 Verwendung von Guanidiniumsalzen ungesättigter Fettsäuren als Korrosionsschutzwirkstoff
DE4436764 1994-10-14
PCT/EP1995/003931 WO1996012054A1 (fr) 1994-10-14 1995-10-05 Utilisation de sels de guanidine d'acides gras insatures comme principes actifs anticorrosifs

Publications (2)

Publication Number Publication Date
EP0786019A1 true EP0786019A1 (fr) 1997-07-30
EP0786019B1 EP0786019B1 (fr) 1999-05-12

Family

ID=6530785

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95935435A Expired - Lifetime EP0786019B1 (fr) 1994-10-14 1995-10-05 Utilisation de sels de guanidine d'acides gras insatures comme principes actifs anticorrosifs

Country Status (9)

Country Link
US (1) US5749947A (fr)
EP (1) EP0786019B1 (fr)
JP (1) JPH10507231A (fr)
AT (1) ATE180022T1 (fr)
CA (1) CA2202678A1 (fr)
DE (2) DE4436764A1 (fr)
ES (1) ES2132722T3 (fr)
FR (1) FR2725599B3 (fr)
WO (1) WO1996012054A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19747895A1 (de) * 1997-10-30 1999-05-06 Henkel Kgaa Metallbehandlungsflüssigkeit für den neutralen pH-Bereich
FR2795432B1 (fr) * 1999-06-28 2001-08-24 Atofina Compositions inhibitrices de la corrosion pour fluides de transfert de chaleur
DE102007027372A1 (de) * 2007-06-11 2008-12-18 Cognis Oleochemicals Gmbh Verfahren zur Hydrierung von Glycerin
US8766024B2 (en) * 2009-11-20 2014-07-01 Phillips 66 Company Process to mitigate the corrosion of oils/fats
WO2016068336A1 (fr) * 2014-10-30 2016-05-06 旭化成ケミカルズ株式会社 Agent et agent auxiliaire de promotion d'absorption transdermique
EP3842486A4 (fr) * 2018-08-24 2021-07-21 Mitsubishi Gas Chemical Company, Inc. Composition de caoutchouc et pneu

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2978415A (en) * 1957-04-17 1961-04-04 American Cyanamid Co Guanidine soaps as dry cleaning detergents
DE3203491A1 (de) * 1982-02-03 1983-08-11 Henkel KGaA, 4000 Düsseldorf Verwendung von stearinsaeurederivaten als korrosionsschutzmittel
DE3907392A1 (de) * 1989-03-08 1990-09-13 Henkel Kgaa Ester von carbonsaeuren mittlerer kettenlaenge als bestnadteil der oelphase in invert-bohrspuelschlaemmen
DE3907391A1 (de) * 1989-03-08 1990-09-13 Henkel Kgaa Verwendung ausgewaehlter esteroele niederer carbonsaeuren in bohrspuelungen
US5318954A (en) * 1989-03-08 1994-06-07 Henkel Kommanditgesellschaft Auf Aktien Use of selected ester oils of low carboxylic acids in drilling fluids
DE3929069A1 (de) * 1989-09-01 1991-03-07 Henkel Kgaa Neues basisoel fuer die schmierstoffindustrie
DZ1577A1 (fr) * 1991-05-08 2002-02-17 Hoechst Ag Emploi d'acetals.
EP0566956B1 (fr) * 1992-04-22 1996-07-31 Hoechst Aktiengesellschaft Inhibiteur de corrosion
DE4237501A1 (de) * 1992-11-06 1994-05-11 Henkel Kgaa Dialkylether in Metalloberflächen-Behandlungsmitteln
DE4323771A1 (de) * 1993-07-15 1995-01-19 Henkel Kgaa Grundöl auf Triglyceridbasis für Hydrauliköle
DE4323908A1 (de) * 1993-07-16 1995-01-19 Henkel Kgaa Verfahren zur Herstellung von O/W-Emulsionen zum Reinigen und Passivieren von Metalloberflächen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9612054A1 *

Also Published As

Publication number Publication date
WO1996012054A1 (fr) 1996-04-25
US5749947A (en) 1998-05-12
ES2132722T3 (es) 1999-08-16
JPH10507231A (ja) 1998-07-14
DE59505930D1 (de) 1999-06-17
DE4436764A1 (de) 1996-04-18
EP0786019B1 (fr) 1999-05-12
FR2725599B3 (fr) 1999-08-06
ATE180022T1 (de) 1999-05-15
CA2202678A1 (fr) 1996-04-25
FR2725599A1 (fr) 1996-04-19

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