EP0797692B1 - Inhibiteurs de corrosion non azotes presentant un bon effet de tamponnage - Google Patents

Inhibiteurs de corrosion non azotes presentant un bon effet de tamponnage Download PDF

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Publication number
EP0797692B1
EP0797692B1 EP95941081A EP95941081A EP0797692B1 EP 0797692 B1 EP0797692 B1 EP 0797692B1 EP 95941081 A EP95941081 A EP 95941081A EP 95941081 A EP95941081 A EP 95941081A EP 0797692 B1 EP0797692 B1 EP 0797692B1
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EP
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Prior art keywords
acid
control formulation
corrosion control
carbon atoms
corrosion
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German (de)
English (en)
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EP0797692A1 (fr
Inventor
Karlheinz Hill
Sigrid Igelmund
Bernd Stedry
Jürgen Geke
Andreas Wilde
Harald KÜSTER
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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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • 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
    • C23F11/12—Oxygen-containing compounds

Definitions

  • the invention relates to anti-corrosion agents for temporary corrosion protection metallic, especially ferrous, surfaces that as aqueous emulsion or preferably as an aqueous solution. They are free of nitrogen for wastewater reasons and stand out by a good buffering effect, so that its alkaline pH despite a possible acid input and / or microbiological acid development can be maintained for a longer period of time.
  • Protection of metals at risk of corrosion such as iron, aluminum, Zinc, copper or their alloys against corrosion is a wide range technical task. It arises particularly when the Metal parts due to their processing status or due to their area of application not or not yet with a permanent anti-corrosive Cover such as a varnish are covered. Examples of this are metal parts during technical processing stages such as cutting or non-cutting shaping or cleaning as well as finished metal components such as heat exchangers or piping, which during their function come into contact with corrosive aqueous media. Around corrosion during or between the individual processing steps or to prevent or contain during intended use, you bring the metal surfaces into contact with corrosion inhibitors, which provide temporary protection against corrosion.
  • Inorganic Corrosion inhibitors can, for example, on chromates, nitrites or be constructed from phosphates, which, however, from toxicological and ecological reasons are more or less disadvantageous.
  • Organic corrosion inhibitors are often based on carboxylates, amines, or amides on nitrogen-containing heterocyclic compounds. Against use of secondary amines or of compounds which can split them off, there are serious toxicological problems due to the possibility of nitrosamine formation Concerns. But there are also other nitrogenous compounds not toxicologically harmless or at least because of possible water pollution disadvantageous.
  • Carboxylic acids do not have these disadvantages in practice, however, do not prove to be sufficiently long-term effective, if by an acid entry in the inhibitor baths or by microbiological processes the pH is lowered so far that the carboxylic acids rather than in the less effective acid form in the salt form.
  • EP-B-341 536 describes a water-soluble corrosion inhibitor system, containing alkenyl succinic acid, arylsulfonylanthranilic acid and alkanolamines. This system does not meet the nitrogen-free requirement.
  • GB-B-1 238 205 is a water-soluble corrosion protection combination known, which consists of gluconate and benzoate or salicylate salts. This combination is due to the strong hydrophilicity of the salts used only effective to a limited extent.
  • EP-A-294 649 teaches the use of partially or completely neutralized hydroxyaryl fatty acids as corrosion inhibitors. These have a good anti-corrosion effect but are difficult to access.
  • carboxylic acids as anti-corrosion agents in, for example Cooling lubricants, cleaners and corrosion protection emulsions is common in the prior art.
  • the DE-A-42 29 848 a cooling lubricant emulsion, its corrosion protection system on a combination of long chain fatty acids, short chain fatty acids, Dimer fatty acids and aromatic carboxylic acids such as benzoic acid or salicylic acid.
  • the carboxylic acids with potassium hydroxide neutralized. This system does not contain a buffer component in the The meaning of the present invention.
  • This system also does not contain any buffer components for stabilization of the alkaline pH value when acid is introduced or when acid is formed.
  • EP-A-556 087 reveals the knowledge that monocarboxylic acids with an odd number of carbon atoms, in particular the heptanoic acid, nonanoic acid and undecanoic acid, particularly effective corrosion inhibitors represent.
  • US-A-5 085 793 relates to an antifreezing agent for engine cooling circuits, which contains a corrosion inhibitor.
  • Such formulations consist of a larger amount of a liquid alcohol and a smaller amount of a hydroxyl-substituted aromatic carboxylic acid in which the OH group is adjacent to the carboxyl group.
  • Corrosion inhibitors are, for example, 2-hydroxybenzoic acid, mandelic acid and homophthalic acid.
  • Alkali metal borates, silicates, benzoates, nitrates, nitrites, molybdates and aliphatic C 8-12 dicarboxylic acids can serve as additional corrosion inhibitors.
  • Database WPI (Derwent), Section Ch, Week 7640, Class E14, AN 76-74595X - presentation JP-A-51 093 741 - discloses corrosion inhibitors for metals, preferably for use in open cooling water systems.
  • As a corrosion inhibitor Mixture of dihydroxybenzene and mono- or polycarboxylic acids in concentrations from 2 to 10 ppm.
  • Patent Abstract of Japan, Vol. 005, No. 200 (C-084) - Unit of JP-A-56 120 791 - describes a stabilizer composition with antioxidative properties Prevention of discoloration and corrosion of copper.
  • This composition contains 4,4-thiobis (3-methyl-6-tert-butyl-phenol) and a polyvalent aliphatic Carboxylic acid, for example oxalic acid, tartaric acid or citric acid.
  • the invention is based, nitrogen-free water-soluble or water-dispersible
  • their anti-corrosion agents consists of carboxylic acids and therefore a longer service life and use safety that they are against pH shifts are stabilized.
  • the aromatic hydroxy compound serves as a buffer component, which makes an additional contribution to the corrosion protection effect.
  • the buffered corrosion protection system according to the invention is used in the form of an aqueous emulsion or preferably as an aqueous solution, the particularly effective pH range being from 8.5 to 10.
  • the invention is based on the recognition that the aromatic hydroxy compounds with a pK s value for the hydroxy group in the range of 7.0 to 11 in the mentioned pH range of the ready preparation to develop a particularly good buffering action.
  • aromatic hydroxy compounds with a pK s value for the hydroxy group in the range of 8.5 to 10 are particularly favorable.
  • Salicylic acid which has a pK a value with respect to the hydroxyl group of 13.4 comprising (N.Konopik, O.Leberl “dissociation constants of very weak acids,” Monatshefte 80 (1949), pp 660-662), does not satisfy this condition.
  • the pK S value is known to be the negative decimal logarithm of the acid constant K S , which is generally known as the thermodynamic variable and is a measure of the completeness of the proton transfer reaction from the acid to water and thus of the acid strength. Details on this can be found in general chemistry textbooks. HRChristen is mentioned as an example: "Fundamentals of General and Inorganic Chemistry", Verlag Sauerators, Aarau and Disterweg.Salle, Frankfurt, 4th edition 1973, pp. 353-372.
  • the pK a value for the hydroxy group of the aromatic hydroxy compounds according to the invention refers to the acid-base reaction of the hydroxy group of the aromatic hydroxy compound with water.
  • aromatic hydroxy compounds to be used can be carboxylic acid or sulfonic acid groups whose pK a values are much deeper and have for the inventively exploited buffer effect no meaning, but can improve the corrosion protection effect of the overall system.
  • the anti-corrosion agent according to the invention comes in an aqueous preparation, i.e. as an aqueous emulsion or preferably as an aqueous solution for use.
  • This preparation contains 0.2 to 2% by weight of the component a), 0.1 to 0.6 wt .-% of component b) and the rest water and Agents for adjusting an alkaline pH, preferably alkali metal hydroxides, potassium hydroxide for reasons of solubility in the concentrate is preferred.
  • this aqueous preparation contain other auxiliary substances.
  • the pH of the aqueous preparation is in the range from 7 to 11, preferably in the range from 8.5 to 10, for example at 9.3.
  • Component a) is preferably selected from mono- or polybasic, preferably monobasic, saturated or mono- or polyunsaturated linear or branched carboxylic acids with 6 to 22 carbon atoms and / or unsaturated polybasic, preferably dibasic carboxylic acids with 36 to 44 carbon atoms .
  • carboxylic acids having 6 to 22 carbon atoms are the unbranched saturated carboxylic acids hexanoic acid, octanoic acid and decanoic acid and in particular the monocarboxylic acids with an odd number of carbon atoms to be preferably used according to the teaching of EP-A-556 087, in particular heptanoic acid, nonanoic acid and undecanoic acid .
  • Branched saturated carboxylic acids in particular 2-ethylhexanoic acid, 3,5,5, -trimethylhexanoic acid and 2,2-dimethyloctanoic acid, also offer particular technical advantages.
  • a preferred example of an unsaturated short-chain carboxylic acid is 1,4-hexadienoic acid (sorbic acid).
  • generally saturated or unsaturated fatty acids with 12 to 22 carbon atoms in the molecule or technical mixtures thereof can be used, such as are obtained, for example, when natural fats and oils are cleaved or are also synthetically accessible.
  • Examples include oleic acid and the technical mixture of different fatty acids called tall oil fatty acid, which can be obtained from tall oil and which mainly consists of linoleic and conjugated C 18 fatty acids, oleic acid and 5,9,12-octadecatrienoic acid.
  • Unsaturated polybasic carboxylic acids with 36 to 44 carbon atoms, of which the dibasic representatives are preferably used, are also referred to as "dimer fatty acids". They are technically accessible through - usually acid catalyzed - dimerization of suitable unsaturated fatty acids with 18 to 22 carbon atoms.
  • the reaction products are generally mixtures of acids of different degrees of oligomerization together with unreacted or isomerized starting materials. 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 .
  • the aromatic hydroxy compound b which acts as a buffer, is of particular importance in order to stabilize the anti-corrosion agent against acid entry or acid formation and thus without further maintenance measures for an extended system compared to unbuffered systems Keep period usable.
  • the selected aromatic hydroxy compounds have the advantage over other conceivable buffer systems for the pH range 7 to 11 that they support the anti-corrosion effect of the carboxylic acid components.
  • Mononuclear aromatic hydroxy compounds which can be described by the general formula (II) are preferably used as component b): where X is selected from substituents COOH, SO 3 H or SO 2 -C 6 H 4 -OH and R 1 , R 2 , R 3 and R 4 independently of one another a group X, H, OH or an alkyl, hydroxyalkyl or Hydroxyalkyl ether radical with 1 to 4 carbon atoms.
  • Preferred compounds of the general formula (II) are those which contain only a single substituent X, which is preferably para to the hydroxyl group and in which the substituents R 1 , R 2 , R 3 and R 4 are preferably hydrogen .
  • the substituent X is preferably one of the groups COOH, SO 3 H or SO 2 -C 6 H 4 -OH.
  • Particularly suitable examples of such compounds are 4-hydroxybenzoic acid, 4-phenolsulfonic acid and 4,4'-dihydroxydiphenyl sulfone (bisphenol S).
  • pK S determinations are contained in: B.Jones, JCSpeakman: "Thermodynamic Dissociation Constants of Hydroxy- and Alkoxy-benzoic Acids", J.Chem.Soc. 1944, pp. 19-20. M- and accordingly have to p-hydroxybenzoic acid pK a values of 9.94 or 9.39.
  • the pK a value of 4-phenolsulfonic acid for the phenolic hydroxy group was about 8.9, the one intended to 9.5 of bisphenol S.
  • the dissociation constant of salicylic acid with respect to the OH group is so low that it could not be determined by the method of potentiometric titration selected here using a glass electrode.
  • the buffer capacity is defined as the consumption of 0.1 normal hydrochloric acid, measured in ml, around the pH of 50 g of the anti-corrosion agent to lower 1.3 units, for example by 50 g of Corrosion protection agent from a pH of 9.3 to a pH of 8 to titrate.
  • Such buffer capacities can be achieved when using the components a) achieve that according to the invention with components b) combined.
  • Buffer capacities of a similar size could also be achieved if components a) with other buffers such as suitable amines, Combined borates or phosphates. On the use of amines however, be waived for the reasons mentioned at the beginning. Also on that other ecologically disadvantageous buffer systems such as borates or phosphates can be dispensed with by the present inventive teaching.
  • Suitable anti-corrosion agents refer to the ready-to-use aqueous preparations. In principle, these can Place by dissolving or dispersing the individual components in water in the specified concentration ranges. On the affected technical field, however, it is common to use such combinations of active ingredients to market in the form of concentrates, all components already included in the required proportions and from ready-to-use treatment baths by diluting with water getting produced. Accordingly, the invention also relates to aqueous Active substance concentrates which contain the components a) and b) in the in claim 1 specified proportions included. The drug concentrations in these concentrates are preferably adjusted so that they can be diluted of the concentrate with water by a factor between about 20 and about 200 an aqueous anticorrosive with those described above Contains properties.
  • active ingredient concentrates were made from the inhibitor component a) and the buffer component b) prepared by the individual components in the concentrations given in the table in fully desalinated Water dissolved or dispersed and added so much KOH that one with demineralized water a factor of 50 diluted solution 9.3 had.
  • the buffer capacity was determined using 50 g of the ratio 1:50 diluted concentrate solution with 0.1 normal hydrochloric acid of pH 9.3 titrated to pH 8. The required consumption of hydrochloric acid in ml is called buffer capacity.
  • a plate climate test was carried out to check the corrosion protection effect.
  • steel sheets of the quality ST 1405 with the dimensions 5 cm x 10 cm were brushed with an aqueous surfactant solution, rinsed with water and alcohol and dried.
  • the sheets were then immersed in the concentrate solutions diluted with deionized water by a factor of 50 according to the table, drained and stored in a climatic chamber at 22 ° C. and a relative air humidity of 76%. All examples provided the required corrosion protection (less than 30% corrosion after 40 days of testing).
  • the formulation according to Example 10 was also tested in a larger dilution.
  • the required corrosion protection effect was also achieved by diluting the concentrate by a factor of 75.
  • Active substance concentrates Figures in% by weight in water / KOH No.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (9)

  1. Inhibiteur de corrosion aqueux non azoté renfermant
    a) des anions d'acides carboxyliques comportant 6 à 44 atomes de C et
    b) des composés hydroxylés aromatiques possédant une valeur pKa pour le groupe hydroxyle dans l'intervalle de 7,0 à 111
    dans un rapport pondéral de 1:2 à 20:1, caractérisé en ce qu'il possède dans les préparations aqueuses prêtes à l'emploi des concentrations des composants a) dans l'intervalle de 0,2 à 2 % en poids et des composants b) dans la plage de 0,1 à 0,6 % en poids, ainsi qu'un pouvoir tampon dans l'intervalle de 1 à 8, le pouvoir tampon étant défini comme la consommation d'acide chlorhydrique 0,1 N, déterminée en ml, pour abaisser de 1,3 unité le pH de 50 g de l'inhibiteur de corrosion.
  2. Inhibiteur de corrosion selon la revendication 1, caractérisé en ce qu'il renferme pour le reste dans les préparations aqueuses prêtes à l'emploi, de l'eau, des agents pour l'ajustement d'un pH alcalin, de préférence des hydroxydes de métaux alcalins, en particulier de l'hydroxyde de potassium et, le cas échéant, d'autres adjuvants, et qu'il est sous forme d'émulsion ou de préférence, de solution aqueuse.
  3. Inhibiteur de corrosion selon la revendication 1 ou 2, caractérisé en ce qu'il présente un pH dans l'intervalle de 7 à 11.
  4. Inhibiteur de corrosion selon la revendication 3, caractérisé en ce qu'il présente un pH dans l'intervalle de 8,5 à 10.
  5. Inhibiteur de corrosion selon une ou plusieurs des revendications 1 à 4, caractérisé en ce que le composant a) est sélectionné parmi des acides carboxyliques mono- ou polybasiques, saturés ou mono- ou polyinsaturés, linéaires ou ramifiés, comportant 6 à 22 atomes de C et/ou des acides carboxyliques insaturés, polybasiques, comportant 36 à 44 atomes de C.
  6. Inhibiteur de corrosion selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que le composant b) est sélectionné parmi les composés hydroxylés aromatiques mono- bi- ou trinucléaires de la formule générale (I) HO - Arom - X dans laquelle X est sélectionné parmi les substituants COOH, SO3H ou SO2-C6H4-OH et "Arom" représente un système à noyau hexagonal carbocyclique, aromatique, mono- bi- ou trinucléaire du type du benzène, du naphtalène, de l'anthracène ou du phénanthrène, qui peut porter d'autres substituants X, OH et/ou des radicaux alkyle, hydroxyalkyle et/ou hydroxyalkyléther comportant 1 à 4 atomes de C.
  7. Inhibiteur de corrosion selon la revendication 6, caractérisé en ce que le composant b) est sélectionné parmi les composés hydroxylés aromatiques mononucléaires, qui répondent à la formule générale (Il)
    Figure 00200001
    dans laquelle X est sélectionné parmi les substituants COOH, SO3H ou SO2-C6H4-OH, et R1, R2, R3 et R4 représentent indépendamment les uns des autres un groupe X, H, OH ou un radical alkyle, hydroxyalkyle ou hydroxyalkyléther comportant 1 à 4 atomes de C.
  8. Inhibiteur de corrosion selon la revendication 7, caractérisé en ce que le composant b) est sélectionné parmi les composés de la formule générale (II), qui ne renferment qu'un seul substituant X et dans lesquels les substituants R1, R2, R3 et R4 représentent l'hydrogène.
  9. Inhibiteur de corrosion selon une ou plusieurs des revendications 1 à 8, caractérisé en ce qu'il est obtenu par dilution dans de l'eau de concentrés correspondants de substances actives avec un facteur compris entre 20 et 200.
EP95941081A 1994-12-16 1995-12-08 Inhibiteurs de corrosion non azotes presentant un bon effet de tamponnage Expired - Lifetime EP0797692B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4444878 1994-12-16
DE4444878A DE4444878A1 (de) 1994-12-16 1994-12-16 Stickstofffreie Korrosionsinhibitoren mit guter Pufferwirkung
PCT/EP1995/004844 WO1996018757A1 (fr) 1994-12-16 1995-12-08 Inhibiteurs de corrosion non azotes presentant un bon effet de tamponnage

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Publication Number Publication Date
EP0797692A1 EP0797692A1 (fr) 1997-10-01
EP0797692B1 true EP0797692B1 (fr) 1999-10-27

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US (1) US5795372A (fr)
EP (1) EP0797692B1 (fr)
AT (1) ATE186080T1 (fr)
AU (1) AU4260696A (fr)
DE (2) DE4444878A1 (fr)
TR (1) TR199501574A2 (fr)
WO (1) WO1996018757A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19539854A1 (de) * 1995-10-26 1997-04-30 Henkel Kgaa Öllösliche stickstofffreie Korrosionsinhibitoren mit guter Pufferwirkung
US6033495A (en) 1997-01-31 2000-03-07 Elisha Technologies Co Llc Aqueous gel compositions and use thereof
DE19830819A1 (de) * 1998-07-09 2000-01-13 Basf Ag Gefrierschutzmittelkonzentrate und diese enthaltende Kühlmittelzusammensetzungen für Kühlkreisläufe in Verbrennungsmotoren
US6500360B2 (en) * 1999-06-18 2002-12-31 Bernard Bendiner Sorbic acid and/or its derivatives, such as potassium sorbate, as a preventative for rust, corrosion and scale on metal surfaces
JP2003253478A (ja) * 2002-03-01 2003-09-10 Japan Organo Co Ltd 水系用の有機系防食剤及び水系の防食方法
DE102010002349A1 (de) 2010-02-25 2011-08-25 Behr GmbH & Co. KG, 70469 Zusätze für Heiz- und Kühlmittel
DE102011004765A1 (de) 2010-02-25 2011-08-25 Behr GmbH & Co. KG, 70469 Zusätze für silikathaltige Heiz- und Kühlmittel
US20120309830A1 (en) * 2010-11-30 2012-12-06 Ecolab Usa Inc. Mixed fatty acid soap/fatty acid based insecticidal, cleaning, and antimicrobial compositions
DE102012204683A1 (de) 2012-03-23 2013-09-26 Henkel Ag & Co. Kgaa Korrosionsschutzsystem für die Behandlung von Metalloberflächen

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3589859A (en) * 1967-10-09 1971-06-29 Exxon Research Engineering Co Gluconate salt inhibitors
GB1501868A (en) * 1974-05-30 1978-02-22 Cooper Ltd Ethyl Corrosion inhibitors
JPS5193741A (ja) * 1975-02-14 1976-08-17 Kinzokuboshokuzai
JPS56120791A (en) * 1980-02-27 1981-09-22 Sumitomo Chem Co Ltd Stabilizer composition without discoloring copper
JPS58133382A (ja) * 1982-02-03 1983-08-09 Katayama Chem Works Co Ltd 塩化カルシウムブライン用防食剤
JPS63310981A (ja) * 1987-06-12 1988-12-19 Nippon Oil & Fats Co Ltd 水性錆止め剤
DE3815884A1 (de) * 1988-05-10 1989-11-23 Basf Ag Mischungen aus alkanolaminsalzen von alkenylbernsteinsaeuren und arylsulfonylanthranilsaeuren zur verwendung als korrosionsschutzmittel fuer waessrige systeme
US4935205A (en) * 1988-06-10 1990-06-19 W. R. Grace & Co.-Conn. Corrosion inhibition
DE3933137A1 (de) * 1989-10-04 1991-04-18 Henkel Kgaa Verfahren zur herstellung stabiler, niedrig-viskoser o/w-rostschutzemulsionen
US5085793A (en) * 1990-11-19 1992-02-04 Texaco Chemical Company Corrosion-inhibited antifreeze/coolant composition
DE69325828D1 (de) * 1992-02-14 1999-09-09 Atochem Elf Sa Verwendung zur inhibierung der Kupferkorrosion einer Zusammensetzung bestehend aus Heptansoiuce oder dessen Derivate und Natriumtetraborat.
DE4229848A1 (de) * 1992-09-07 1994-03-10 Henkel Kgaa Aminfreie Kühlschmierstoffe
DE4323909A1 (de) * 1993-07-16 1995-01-19 Henkel Kgaa Mittel zum Reinigen und Passivieren von Metalloberflächen
US5556451A (en) * 1995-07-20 1996-09-17 Betz Laboratories, Inc. Oxygen induced corrosion inhibitor compositions

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EP0797692A1 (fr) 1997-10-01
WO1996018757A1 (fr) 1996-06-20
ATE186080T1 (de) 1999-11-15
AU4260696A (en) 1996-07-03
US5795372A (en) 1998-08-18
TR199501574A2 (tr) 1996-07-21
DE59507145D1 (de) 1999-12-02
DE4444878A1 (de) 1996-06-20

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