EP0786019B1 - 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 Download PDF

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Publication number
EP0786019B1
EP0786019B1 EP95935435A EP95935435A EP0786019B1 EP 0786019 B1 EP0786019 B1 EP 0786019B1 EP 95935435 A EP95935435 A EP 95935435A EP 95935435 A EP95935435 A EP 95935435A EP 0786019 B1 EP0786019 B1 EP 0786019B1
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EP
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Prior art keywords
oil
fatty acids
acid
guanidinium salts
carbon atoms
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EP95935435A
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German (de)
English (en)
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EP0786019A1 (fr
Inventor
Jürgen Geke
Horst-Dieter Speckmann
Bernd Stedry
Alfred Westfechtel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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 anti-corrosion agents for metallic, especially iron-based surfaces, preferably in the form of oil-in-water emulsions are used.
  • the invention provides alkylamine free Corrosion protection agents are available, which are characterized by good Characterize oil solubility and at the same time the emulsification of the oil phase effect in water.
  • Anti-rust emulsions are used for the temporary protection of metallic materials against atmospheric influences that cause corrosion. She essentially contain 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 as well as water works. T. Forster et al. report in "Surface-Surface", 1989, No. 4, pp. 8-12, on modes of action and investigation methods of anti-rust emulsions.
  • Previously used corrosion protection agents contain components such as for example petroleum sulfonates, salts of alkylsulfonamidocarboxylic acids and Amine or other salts of partial esters of alkyl or alkenyl succinic acid.
  • EP-A-566 956 describes anti-corrosion agents based on an amine-free salt of a half-ester of an alkyl or Alkenyl succinic acid.
  • Sulfur-containing corrosion inhibitors such as alkylarylsulfonic acids, Petroleum sulfonates or salts of alkyl sulfonamido carboxylic acids show the disadvantage that they are easily from microorganisms, such as sulfur-reducing Bacteria can be broken down, causing significant odor nuisance can lead.
  • Corrosion protection agents containing alkylamine, in particular those with secondary amines, because of the risk of formation health-endangering nitrosamines are increasingly viewed critically. Therefore there is a need for sulfur and alkylamine-free anti-corrosion agents.
  • stearic acid derivatives have been described as anti-corrosion agents (DE-C-32 03 491).
  • examples include 9,10-dihydroxystearic acid and their alkali salts and their oligomeric condensates, 9,10-epoxistearic acid, their alkali salts and their oligomeric estolides and finally mixed oligomerizates of 9,10-epoxy and 9,10-dihydroxystearic acid.
  • Anticorrosive in the form of oil-in-water emulsions for use should come as pure oily, i.e. water-free concentrates to be placed on the market by adding water at the location of the Application to be brought into the ready-to-use emulsion form.
  • This Oil concentrates contain the corrosion inhibitors, which are therefore oil-soluble have to be. So that the oil concentrates spontaneously when diluted with water form an emulsion, so it can be self-emulsifying, it was previously required that these concentrates in addition to the corrosion inhibitors Contain emulsifiers. Possible interactions between the surface active Emulsifiers and the polar corrosion inhibitors often act negative on emulsification behavior and on corrosion protection effect from and this complicates the product formulation. This problem could be solved eliminate if oil-soluble anti-corrosion agents with emulsifying Properties could be made available.
  • GB-A-602 617 relates to oil-in-water emulsions which use a guanidine salt as an emulsifier contain a saturated monocarboxylic acid with at least 10 carbon atoms. Such Emulsions are used, for example, as lubricants. Preferably These emulsions contain a combination of a guanidine salt as an emulsifier a saturated fatty acid with at least 10 carbon atoms and an alkylolamine salt a carboxylic acid with at least 10 carbon atoms and also free alkylolamine. It it is mentioned that guanidine salts of unsaturated fatty acids, for example oleates, are unsuitable because of the instability of the resulting emulsions.
  • the object of the present invention is to create new sulfur and to provide alkylamine-free anti-corrosion agents whose Oil solutions are not unacceptably high even at high concentrations of active ingredients Have viscosities, and at the same time an emulsification of the oil phase effect when mixed with water, without additional Emulsifiers are required.
  • “Fatty acids” are understood here to mean carboxylic acids which, if appropriate May be substituted by OH.
  • the unsaturated fatty acids that can be used can be divided into two groups: native fatty acids, like them occur as a component of natural oils and fats and so-called dimer fatty acids, the technically through, usually acid catalyzed, dimerization suitable fatty acids are accessible.
  • the unsaturated ones that can be used Fatty acids are therefore once characterized in that they are native Represent fatty acids, that is branched or preferably linear, one have up 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 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 suitable from the group of the so-called dimer acids are polybasic, preferably dibasic. Such are in particular dimer acids suitable, which have 36 to 44 carbon atoms.
  • guanidinium salts can be more defined, purer Fatty acids can be used with advantage. Because of economical reasons in practice, however, one becomes guanidinium salts of technical fatty acid mixtures use that in addition to unsaturated fatty acids different C chain lengths also contain certain proportions of saturated fatty acids can. Such technical fatty acid mixtures can, for example can be obtained by splitting suitable natural oils and fats. In terms of the use according to the invention, however, it is necessary that the technical fatty acid mixtures at least 50 wt .-%, preferably at least 80% by weight of unsaturated fatty acids of the above Carbon chain lengths exist.
  • 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 can also be present in addition to unreacted and / or isomerized monomer fatty acids.
  • dimer fatty acids we mean product mixtures that consist of at least 50% by weight, preferably at least 70% by weight, 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 8-9 ) with branched Guerbet alcohols (preferably C 12-20 ) (EP-A-489 809), esters of C 1- 5- nonocarboxylic acids with mono- or polyfunctional alcohols (described for example in DE-A-39 07 391), esters of C 6-11 -nonocarboxylic acids with mono- or polyfunctional alcohols (described for example in DE-A-39 07 392), and Alkoxylation products of triglycerides with 0.5 - 3 mol EO and / or PO, for example glycerol propoxylate trioleate (German patent application DE-A-43 23 771).
  • oil-like solvents These essentially water-insoluble solvents are described below referred to as "oil-like solvents”.
  • Solutions which contain between 1 and 45% by weight are preferably used. contain dissolved in guanidinium salts of unsaturated fatty acids. With less The corrosion protection effect decreases significantly, while at higher levels, the solutions are usually so highly viscous that their Handling and their use for emulsion formation is unnecessarily difficult.
  • hydrocarbons come into consideration at working temperature, So a temperature between about 10 and about 90 ° C liquid are.
  • paraffin oil or mineral oil where in the case of Mineral oil for ecological and toxicological reasons low-aromatic mineral oils are preferred.
  • Suitable oils of this type are commercially available. Examples include pioneer oil 4556 from Hansen & Rosenthal, Enerpar 3036 from Manual BP and Parex Paraffin II from Leuna-Werke.
  • dialkyl ethers are in water dissolve no more than 5% by weight, preferably not more than 0.5% by weight.
  • Suitable examples are dialkyl ethers with 6 to 24, preferably 8 to 18 C atoms per alkyl radical, the alkyl radicals being straight-chain independently of one another or can be branched, saturated or unsaturated and preferably n-octyl, 2-ethylhexyl, stearyl and / or isostearyl radicals represent.
  • dialkyl ethers can still have free hydroxyl groups and are then referred to as hydroxy mixed ethers.
  • the use of such Dialkyl ether in metalworking fluids is for example in German patent application DE-A-42 37 501.
  • Such dialkyl ethers are commercially available, for example from Henkel KGaA at Name Cetiol-OE (dioctyl ether).
  • guanidinium salts As an oil-like solvent for the use according to the invention of the guanidinium salts come acetals based on monovalent aldehydes with 1 to 25, preferably 1 to 10 carbon atoms, and monohydric alcohols with 1 to 25, in particular 2 to 20 carbon atoms.
  • the usage such acetals as a mineral oil substitute, oil component or base oil in lubricating oils and in metalworking fluids is known from EP-A-512 501. There is also a general rule for making such Acetale communicated.
  • the use according to the invention of the guanidinium salts of unsaturated fatty acids happens preferably in such a way that the solution of the guanidinium salts in one of the above-mentioned oil-like solvents or in Mixtures of these are used as the oil phase of an oil-in-water emulsion becomes.
  • the proportion of the oil phase is, including the solution of Guanidinium salts of the unsaturated fatty acids is understood at the Emulsion preferably between 0.5 and 50% by weight, in particular between 5 and 20% by weight.
  • the rule of thumb is that the proportion of the oil phase the lower the concentration, the higher the concentration of the guanidinium salts unsaturated fatty acids in the oil phase.
  • Oil phase a concentration of a guanidinium salt of an unsaturated Fatty acid, for example guanidinium oleate, has between 5 and 20% by weight.
  • the invention encompasses the use of guanidinium salts polyunsaturated fatty acids with 6 to 44 carbon atoms according to one or more of claims 1 to 9, wherein the guanidinium salts are more unsaturated Fatty acids are dissolved in an oil-in-water emulsion and being an oil phase oily solvent or solvent mixture according to one or more of the Claims 6 to 9 is used and the proportion of the oil phase in the Emulsion between 0.5 and 50, preferably 5 to 20 wt .-% and the proportion of Guanidinium salts 1 to 45, preferably 5 to 20 wt .-% based on the oil phase is.
  • the viscosity of the solutions of the guanidinium salts can be increased by adding glycols unsaturated fatty acids in the oil-like solvents on application technology favorable values can be set without the ability to form emulsions Water is affected by this.
  • glycols are butyl diglycol, Hexylene glycol or dipropylene glycol suitable in the guanidinium salt solution Amounts from 1 to 10% by weight can be added.
  • the glycols can either be the solution of the guanidinium salts Unsaturated fatty acids added in oil-like solvents or the oily solvent before the reaction described below of guanidinium salts of volatile acids with unsaturated fatty acids be added. Because of the favorable effect on corrosion protection the use of hexylene glycol is preferred.
  • the procedure is preferably such that a solution of the guanidinium salts in the oil-like solvent Mixed water. Since the guanidinium salts in both the oil-like solvents are soluble in water, they will be between water and distribute oil phase. The distribution balance depends on the individual case the chosen oily solvent and the type of unsaturated Fatty acid. As described in Example 11, an emulsion can also do this are obtained by having an aqueous solution of the guanidinium salts emulsified with oil. Here too it is to be expected that there will be a distribution equilibrium which sets guanidinium salts.
  • 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 C 12/14 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 C 12/14 fatty alcohol mixture
  • anionic emulsifiers such as, for example, alkylbenzenesulfonates
  • the emulsion can be in the form of a conventional, milky opaque Emulsion present. It can also be advantageous for special purposes be the emulsion in the form of an almost transparent so-called microemulsion with an oil content of up to 50% by weight, as is caused by phase inversion is available from a water-in-oil emulsion.
  • Example 11 One possible implementation is in Example 11 below specified.
  • the invention relates to oil-in-water emulsions that are considered by Phase inversion microemulsions are available, the oil phase of which oily solvent or solvent mixture selected from at Working temperature liquid hydrocarbons, largely water-insoluble Dialkyl ethers, alcohols, ester oils and / or acetals and mixtures thereof, represents and guanidinium salts of mono- or polyunsaturated fatty acids with 6 to 44 carbon atoms in concentrations of 1 to 45% by weight, preferably 5 to 20 Wt .-%, dissolved in relation to the oil phase and the proportion of Oil phase on the emulsion between 0.5 and 50 wt .-%, preferably 5 to 20 % By weight.
  • oily solvent or solvent mixture selected from at Working temperature liquid hydrocarbons, largely water-insoluble Dialkyl ethers, alcohols, ester oils and / or acetals and mixtures thereof, represents and guanidinium salts of mono- or polyunsaturated fatty acids with 6 to
  • 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, the product remaining 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
  • Examples 1 to 5 describe processes according to the invention for the preparation of solutions and emulsions used.
  • reaction mixture is heated to 100 ° C. and stirred until the acid number is less than 20 (about 2 hours). A slight gassing can be observed during the reaction time and the solution changes color from light yellow to beige brown. During the reaction, the elimination of 1 mol of carbonic acid corresponding to 1 mol of H 2 O and 1 mol of CO 2 , 62 g, is theoretically to be expected. A viscous, beige-brown, transparent oil solution is obtained as the reaction product.
  • Solvent dioctyl ether Cetiol-0E, Henkel KGaA.
  • reaction time A slight gassing can be observed during the reaction time and the solution changes color from light yellow to beige brown.
  • water jet vacuum is applied (15 min) at 100 ° C to remove CO 2 and water.
  • the reaction mixture is diluted with 6620 g of mineral oil.
  • a beige-brown, transparent oil solution is obtained as a reaction product, from which emulsions can be produced by adding 90% by weight of water.
  • Example 10 The corrosion protection effect of an emulsion was analogous to Example 10 tested by adding the product from Example 5 with water in the Weight ratio 1: 9 was obtained: after 7 days there was no corrosion, severe corrosion observed after 20 days.
  • the product from example was used for a corrosion test analogous to example 10 5 mixed with 5 wt .-% hexylene glycol. By adding water An emulsion was obtained in a weight ratio of 1: 9 and for testing the corrosion protection effect used. Result: After 8 days none, severe corrosion after 13 days.
  • a microemulsion by the phase inversion method To prepare 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 (pioneer oil 4556) and 6.1 parts by weight of emulsifier (adduct of 4 mol of ethylene oxide with a C 12/14 fatty alcohol mixture) at a temperature above the phase inversion temperature of 35 ° determined by preliminary tests C mixed by stirring and cooled below the phase inversion temperature. A transparent microemulsion was obtained which can be diluted by adding water.
  • mineral oil pioneer oil 4556
  • emulsifier adduct of 4 mol of ethylene oxide with a C 12/14 fatty alcohol mixture

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  • Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Colloid Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Paints Or Removers (AREA)
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Claims (11)

  1. Utilisation de sels de guanidinium d'acides gras une fois ou plusieurs fois non saturés, ayant de 6 à 44 atomes de carbone, en vue de l'obtention d'une protection temporaire contre la corrosion des surfaces métalliques.
  2. Utilisation conformément à la revendication 1,
    caractérisée en ce que
    les acides gras une fois ou plusieurs fois non saturés sont choisis parmi les acides gras natifs et/ou les acides gras dimères.
  3. Utilisation conformément à la revendication 2,
    caractérisée en ce que
    les acides gras natifs sont ramifiés ou linéaires possèdent de une à six double liaisons et renferment de 11 à 28 atomes de carbone.
  4. Utilisation conformément à la revendication 3,
    caractérisée en ce que
    les acides gras natifs sont monobasiques et sont choisis parmi l'acide undecylénique, l'acide myristoléique, l'acide palmitoléique, l'acide oléique, l'acide ricinoléique, l'acide érucique, l'acide linoléique, l'acide linolénique, l'acide arachidonique et leurs mélanges.
  5. Utilisation conformément à la revendication 2,
    caractérisée en ce que
    les acides gras dimères sont polybasiques et renferment de 36 à 44 atomes de carbone.
  6. Utilisation conformément à l'une ou plusieurs des revendications 1 à 5,
    caractérisée en ce que
    les sels de guanidinium sont mis en oeuvre sous forme de solutions dans des solvants du type huileux choisis parmi les hydrocarbures liquides à la température de travail, les dialkyléthers largement insolubles dans l'eau, les alcools, les huiles estérifiées, et/ou les acétals ainsi que des mélanges de ceux-ci, à des concentrations comprises entre 1 à 45 % en poids.
  7. Utilisation conformément à la revendication 6,
    caractérisée en ce que
    comme solvant pour les sels de guanidinium on utilise des dialkyléthers ayant de 6 à 24 atomes de carbone par radical alkyle, pour lesquels les radicaux alkyle indépendamment l'un de l'autre, sont à chaíne droite ou ramifiée, saturés ou non saturés.
  8. Utilisation conformément à la revendication 6,
    caractérisée en ce que
    comme solvant pour les sels de guanidinium on utilise un ou plusieurs acétals à base d'aldéhydes monovalents ayant de 1 à 25 atomes de carbone, et d'alcools monovalents ayant de 1 à 25 atomes de carbone.
  9. Utilisation conformément à la revendication 6,
    caractérisée en ce que
    comme solvant pour les sels de guanidinium on utilise des hydrocarbures sous forme d'huile de paraffine ou d'huile minérale.
  10. Utilisation conformément à une ou plusieurs des revendications 1 à 9,
    caractérisée en ce que
    les sels de guanidinium d'acide gras non saturés sont dissous dans une émulsion huile dans l'eau dans laquelle comme phase huileuse on utilise un solvant du type huileux ou un mélange de solvants, conformément à une ou plusieurs des revendications 6 à 9, et en ce que la proportion en quantité de la phase huileuse dans l'émulsion s'élève à entre 0,5 et 50 % en poids et la proportion de sels de guanidinium à 1 à 45 % en poids en ce qui concerne la phase huileuse.
  11. Emulsion huile dans l'eau qui se présente sous forme de microémulsion que l'on peut obtenir par inversion de phase, dans laquelle leur phase huileuse représente un solvant du type huileux ou un mélange de solvants, choisi parmi les hydrocarbures liquides à température de travail, les dialkyléthers largement insolubles dans l'eau, les alcools, les huiles estérifiées, et/ou les acétals ainsi que des mélanges de ceux-ci et renferme dissous les sels de guanidinium d'acides gras une fois ou plusieurs fois non saturés ayant de 6 à 44 atomes de carbone, à des concentrations allant de 1 à 45 % en poids en ce qui concerne la phase huileuse, et dans laquelle le pourcentage en quantité de phase huileuse dans l'émulsion s'élève à entre 0,5 et 50 % en poids.
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

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

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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)

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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

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US5749947A (en) 1998-05-12
WO1996012054A1 (fr) 1996-04-25
FR2725599B3 (fr) 1999-08-06
ES2132722T3 (es) 1999-08-16
CA2202678A1 (fr) 1996-04-25
EP0786019A1 (fr) 1997-07-30
DE4436764A1 (de) 1996-04-18
DE59505930D1 (de) 1999-06-17
ATE180022T1 (de) 1999-05-15
JPH10507231A (ja) 1998-07-14
FR2725599A1 (fr) 1996-04-19

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