EP0996769A1 - Zusammensetzung zur temporären korrosionsschutz von metallischen oberflächen, verfahren zu ihrer herstellung und verwendung, und hergestellte metallteile - Google Patents

Zusammensetzung zur temporären korrosionsschutz von metallischen oberflächen, verfahren zu ihrer herstellung und verwendung, und hergestellte metallteile

Info

Publication number: EP0996769A1
Authority: EP; European Patent Office
Prior art keywords: composition; composition according; emulsion; general formula; compound
Prior art date: 1997-07-01
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

EP98933689A

Other languages

English (en)

French (fr)

Other versions

EP0996769B1 (de

Inventor

Lothaire Scherer

Ronald Kefferstein

Philippe Antoine

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.)

Sollac SA

Original Assignee

Sollac SA

Lorraine de Laminage Continu SA SOLLAC

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.)

1997-07-01

Filing date

1998-06-23

Publication date

2000-05-03

1998-06-23 Application filed by Sollac SA, Lorraine de Laminage Continu SA SOLLAC filed Critical Sollac SA

2000-05-03 Publication of EP0996769A1 publication Critical patent/EP0996769A1/de

2003-03-05 Application granted granted Critical

2003-03-05 Publication of EP0996769B1 publication Critical patent/EP0996769B1/de

2018-06-23 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

238000005260 corrosion Methods 0.000 title claims abstract description 48
230000007797 corrosion Effects 0.000 title claims abstract description 48
229910052751 metal Inorganic materials 0.000 title claims abstract description 35
239000002184 metal Substances 0.000 title claims abstract description 35
238000000034 method Methods 0.000 title claims abstract description 27
238000002360 preparation method Methods 0.000 title description 4
239000000203 mixture Substances 0.000 claims abstract description 116
239000000839 emulsion Substances 0.000 claims abstract description 48
150000001875 compounds Chemical class 0.000 claims abstract description 28
150000003839 salts Chemical class 0.000 claims abstract description 12
239000008346 aqueous phase Substances 0.000 claims abstract description 11
125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
239000007764 o/w emulsion Substances 0.000 claims abstract description 4
229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
239000011737 fluorine Substances 0.000 claims abstract description 3
229910052736 halogen Inorganic materials 0.000 claims abstract description 3
150000002367 halogens Chemical class 0.000 claims abstract description 3
NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract 2
125000004181 carboxyalkyl group Chemical group 0.000 claims abstract 2
239000003112 inhibitor Substances 0.000 claims description 55
239000003921 oil Substances 0.000 claims description 26
HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
239000012071 phase Substances 0.000 claims description 14
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
238000001179 sorption measurement Methods 0.000 claims description 13
238000001035 drying Methods 0.000 claims description 11
239000007864 aqueous solution Substances 0.000 claims description 9
ZPOQJHGXQZVXIO-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)-4-oxo-4-sulfanylbutanoic acid Chemical class C1=CC=C2SC(C(C(O)=S)CC(=O)O)=NC2=C1 ZPOQJHGXQZVXIO-UHFFFAOYSA-N 0.000 claims description 7
239000002480 mineral oil Substances 0.000 claims description 6
-1 fatty acid salt Chemical class 0.000 claims description 5
235000010446 mineral oil Nutrition 0.000 claims description 5
239000004094 surface-active agent Substances 0.000 claims description 5
239000006185 dispersion Substances 0.000 claims description 4
238000004945 emulsification Methods 0.000 claims description 4
229910052788 barium Inorganic materials 0.000 claims description 3
DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
235000014113 dietary fatty acids Nutrition 0.000 claims description 3
239000000194 fatty acid Substances 0.000 claims description 3
229930195729 fatty acid Natural products 0.000 claims description 3
238000010438 heat treatment Methods 0.000 claims description 3
239000011734 sodium Substances 0.000 claims description 3
229910052708 sodium Inorganic materials 0.000 claims description 3
229910052717 sulfur Inorganic materials 0.000 claims description 3
125000000217 alkyl group Chemical group 0.000 claims description 2
150000001412 amines Chemical class 0.000 claims description 2
150000003863 ammonium salts Chemical class 0.000 claims description 2
125000001188 haloalkyl group Chemical group 0.000 claims description 2
239000011593 sulfur Substances 0.000 claims description 2
YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
IIQYEFSARPMCIK-UHFFFAOYSA-N [I].[Br].[Cl] Chemical compound [I].[Br].[Cl] IIQYEFSARPMCIK-UHFFFAOYSA-N 0.000 claims 1
125000004429 atom Chemical group 0.000 claims 1
125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
125000000753 cycloalkyl group Chemical group 0.000 claims 1
XUAQLTZKMUSZKS-UHFFFAOYSA-N diazanium;3-(1,3-benzothiazol-2-yl)-4-oxido-4-sulfanylidenebutanoate Chemical compound [NH4+].[NH4+].C1=CC=C2SC(C(C([O-])=S)CC(=O)[O-])=NC2=C1 XUAQLTZKMUSZKS-UHFFFAOYSA-N 0.000 claims 1
WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 2
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 2
GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 2
229910052794 bromium Inorganic materials 0.000 abstract description 2
239000000460 chlorine Substances 0.000 abstract description 2
229910052801 chlorine Inorganic materials 0.000 abstract description 2
229910052740 iodine Inorganic materials 0.000 abstract description 2
125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 abstract 1
ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract 1
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
239000011630 iodine Substances 0.000 abstract 1
239000001301 oxygen Substances 0.000 abstract 1
229910052760 oxygen Inorganic materials 0.000 abstract 1
OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 38
238000012360 testing method Methods 0.000 description 30
230000000694 effects Effects 0.000 description 12
229910000831 Steel Inorganic materials 0.000 description 11
239000010959 steel Substances 0.000 description 11
QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
238000000576 coating method Methods 0.000 description 10
239000000463 material Substances 0.000 description 9
238000012512 characterization method Methods 0.000 description 7
239000002253 acid Substances 0.000 description 6
239000011248 coating agent Substances 0.000 description 6
230000001681 protective effect Effects 0.000 description 6
239000000654 additive Substances 0.000 description 5
230000000996 additive effect Effects 0.000 description 5
229910021529 ammonia Inorganic materials 0.000 description 5
238000002329 infrared spectrum Methods 0.000 description 5
230000008569 process Effects 0.000 description 5
239000000243 solution Substances 0.000 description 5
CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
238000012546 transfer Methods 0.000 description 4
238000010586 diagram Methods 0.000 description 3
238000010348 incorporation Methods 0.000 description 3
230000002035 prolonged effect Effects 0.000 description 3
229920006395 saturated elastomer Polymers 0.000 description 3
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
238000004566 IR spectroscopy Methods 0.000 description 2
FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
239000012298 atmosphere Substances 0.000 description 2
239000002199 base oil Substances 0.000 description 2
238000009472 formulation Methods 0.000 description 2
230000006872 improvement Effects 0.000 description 2
229910052500 inorganic mineral Inorganic materials 0.000 description 2
238000005259 measurement Methods 0.000 description 2
235000010755 mineral Nutrition 0.000 description 2
238000006386 neutralization reaction Methods 0.000 description 2
238000009304 pastoral farming Methods 0.000 description 2
238000001228 spectrum Methods 0.000 description 2
238000003892 spreading Methods 0.000 description 2
230000007480 spreading Effects 0.000 description 2
150000003871 sulfonates Chemical class 0.000 description 2
125000004434 sulfur atom Chemical group 0.000 description 2
238000004381 surface treatment Methods 0.000 description 2
231100000027 toxicology Toxicity 0.000 description 2
150000003751 zinc Chemical class 0.000 description 2
PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 1
KYIURDOGVWUTPN-UHFFFAOYSA-N 2,5-diamino-2,5-dimethylhexanedioic acid Chemical compound OC(=O)C(N)(C)CCC(C)(N)C(O)=O KYIURDOGVWUTPN-UHFFFAOYSA-N 0.000 description 1
IXAZNYYEGLSHOS-UHFFFAOYSA-N 2-aminoethanol;phosphoric acid Chemical class NCCO.OP(O)(O)=O IXAZNYYEGLSHOS-UHFFFAOYSA-N 0.000 description 1
QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
229910000997 High-speed steel Inorganic materials 0.000 description 1
DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
238000010521 absorption reaction Methods 0.000 description 1
238000009825 accumulation Methods 0.000 description 1
150000007513 acids Chemical class 0.000 description 1
229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
239000010775 animal oil Substances 0.000 description 1
239000003945 anionic surfactant Substances 0.000 description 1
238000013459 approach Methods 0.000 description 1
AGLSQWBSHDEAHB-UHFFFAOYSA-N azane;boric acid Chemical compound N.OB(O)O AGLSQWBSHDEAHB-UHFFFAOYSA-N 0.000 description 1
IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
229940075397 calomel Drugs 0.000 description 1
150000001735 carboxylic acids Chemical class 0.000 description 1
239000003153 chemical reaction reagent Substances 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
230000003749 cleanliness Effects 0.000 description 1
239000010960 cold rolled steel Substances 0.000 description 1
230000003247 decreasing effect Effects 0.000 description 1
239000008367 deionised water Substances 0.000 description 1
229910021641 deionized water Inorganic materials 0.000 description 1
238000000151 deposition Methods 0.000 description 1
238000011161 development Methods 0.000 description 1
ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
239000000428 dust Substances 0.000 description 1
238000002593 electrical impedance tomography Methods 0.000 description 1
239000003792 electrolyte Substances 0.000 description 1
150000002169 ethanolamines Chemical class 0.000 description 1
238000001704 evaporation Methods 0.000 description 1
230000008020 evaporation Effects 0.000 description 1
150000004665 fatty acids Chemical class 0.000 description 1
239000007789 gas Substances 0.000 description 1
229910001385 heavy metal Inorganic materials 0.000 description 1
PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
238000002955 isolation Methods 0.000 description 1
150000002632 lipids Chemical class 0.000 description 1
238000004519 manufacturing process Methods 0.000 description 1
239000011707 mineral Substances 0.000 description 1
VEHVJXQNSCCNSB-UHFFFAOYSA-N morpholin-4-ium;benzoate Chemical compound C1COCCN1.OC(=O)C1=CC=CC=C1 VEHVJXQNSCCNSB-UHFFFAOYSA-N 0.000 description 1
WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
125000004430 oxygen atom Chemical group O* 0.000 description 1
239000003973 paint Substances 0.000 description 1
229910052697 platinum Inorganic materials 0.000 description 1
BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
229940072033 potash Drugs 0.000 description 1
BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
235000015320 potassium carbonate Nutrition 0.000 description 1
125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
238000012545 processing Methods 0.000 description 1
238000010791 quenching Methods 0.000 description 1
230000000171 quenching effect Effects 0.000 description 1
230000004044 response Effects 0.000 description 1
239000011780 sodium chloride Substances 0.000 description 1
159000000000 sodium salts Chemical class 0.000 description 1
NMTDPTPUELYEPL-UHFFFAOYSA-M sodium;heptanoate Chemical compound [Na+].CCCCCCC([O-])=O NMTDPTPUELYEPL-UHFFFAOYSA-M 0.000 description 1
238000005507 spraying Methods 0.000 description 1
238000003860 storage Methods 0.000 description 1
239000000758 substrate Substances 0.000 description 1
150000003568 thioethers Chemical class 0.000 description 1
238000010200 validation analysis Methods 0.000 description 1
239000008158 vegetable oil Substances 0.000 description 1
235000013311 vegetables Nutrition 0.000 description 1
238000009736 wetting Methods 0.000 description 1

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
- C23F11/16—Sulfur-containing compounds
- 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
- C23F11/16—Sulfur-containing compounds
- C23F11/165—Heterocyclic compounds containing sulfur as hetero atom

Definitions

the subject of the present invention is a composition useful for temporarily protecting metal parts from corrosion, a process for preparing said composition and the metal parts coated with a dry film derived therefrom.
the object of the present invention is precisely to propose a new water coating which complies with these requirements.
a first approach consists in incorporating into coatings based on temporary protection oil formulations, one or more corrosion inhibitors.
the corrosion inhibitors present in protective oils are chosen from amino compounds of the alcoholamine type, sulfonate derivatives such as their barium or sodium salts or al ylbenzenes sulfonates and acids of the holeic type.
the present invention relates to a composition useful for imparting temporary protection against corrosion to metal surfaces
a composition useful for imparting temporary protection against corrosion to metal surfaces comprising an oil-in-water emulsion characterized in that said emulsion comprises in its aqueous phase at least one compound of general formula I
a C:, a haloalkyl group, C ⁇ ao with the halogen may be fluorine, chlorine, bromine or iodine, a Ci cvcioalkyle group G, a carboxvhque tonction or carboxvalkyle group G to G, n is an integer varying from 1 to 3 and
X represents a sulfur or oxygen atom, in the form of one of its water-soluble salts
the originality of the claimed composition is also based on the incorporation of a compound of general formula I in the aqueous phase and not in the lipid phase of the emulsion. implementation in the composition claimed Of a non-water-soluble nature, this compound is therefore present in the composition in a neutralized form with a view to giving it a satisfactory hydrosolubihte
This neutralization of the compound or compounds of formula I, used according to the invention can be carried out in a conventional manner by a person skilled in the art. It can, for example, be obtained from ammonia, from morphohne. ethanolamine, ethanol or potash Depending on the reagent used, it may be necessary, if necessary, to adjust the pH of the final composition, to a value compatible with the recommended application, that is to say a a value between 8 2 in and 9> and preferably between 8.5 and 9 This can be easily achieved by adjusting the pH of the final emulsion by an additional addition of neutralizer such as ethanolanine for example
the corrosion inhibitor of general formula I is preferably present in the claimed composition in an amount of 1 to 10 g / 1 and preferably from 1 1 to 3 g 1
the emulsion can be defined as comprising, in dispersion in water, 3 to 13% by volume of an oily phase -s comprising from 75 to 90% by volume of at least one oil and 5 at 10% in olume of at least one surfactant If necessary, an additional corrosion inhibitor may be present at a rate of 5 to 15% by volume, in the oily phase
the emulsion comprises, in dispersion in the aqueous phase, between approximately 3 and 8% and preferably approximately 6% by volume of an) oil
the oil contained in the oily phase of the emulsion may consist of a mineral, vegetable or animal oil
it is a mineral oil and preferably a paraffinic, naphtenic tvpe oil or a mixture of these ⁇
mineral oil preferentially used according to the present invention mention will be made of any especially the soluble oil AQUASAFE 21 ⁇ .e C ⁇ STROL It is preferred to use as surfactant for the oily phase a surfactant of tvpe polvoxvethvlene
a carboxv acid such as a barvum or sodium alkvl-sulfonate or an amine and fatty acid salt is advantageously used as an inhibitor of corrosion of the oily phase.
the claimed composition comprises, as corrosion inhibitor, a water-soluble salt of benzothiazolvlthiosuccinic acid (ABTS) present at a concentration of between 1 and 3 g 1 and preferably of the order of 2.5 g / l in the aqueous phase of an emulsion at 6 ° o in soluble oil which is preferably oil AQUASAFE 213) from C ⁇ STROL
ABTS benzothiazolvlthiosuccinic acid
it is the ammonium salt of benzothiazol lthiosuccinic acid present at a concentration of around 2 5 g / 1
the present invention also relates to a process for the preparation of said composition
this process is characterized in that the compound or compounds of general formula I are incorporated in the form of an aqueous solution at the aqueous phase of the emulsion, prior to its emulsification with the oily phase
the present invention also relates to a process for temporary protection against corrosion of metal parts.
this process is characterized in that it comprises the steps consisting in applying to at least part of said metal part a composition according to the invention, and drying said coated metal part until a
the composition according to the invention is applied to the surface of the metal part so as to saturate its absorption sites with compounds of general formula I and at the end of the heating of said composition, in order to obtain a film there is no compound of general formula I present in the thickness of the applied film
⁇ Processing is carried out in such a way as to saturate its adsorption sites with a compound of general formula I and to prevent the accumulation of this same compound of general formula I at the level of the thickness of the film.
the adjustment of the optimal concentration of inhibitor of general formula I on the surface of the treated metal part can for example be appreciated and performs in the following manner, after having applied and dried on the surface of the 0 part a composition according to the invention of determined concentration in corrosion inhibitor (s) of general formula I
the part is xiviated with 1 acetone, by quenching or by sprinkling Then, the saturation level of the adsorption sites on the surface is measured the metal part treated by performing an infrared spectrum of the hivivated part using the technique of ⁇ infrared spectroscopy to transform Fou ⁇ er (IRFT) under grazing incidence
IRFT Fou ⁇ er
aqueous composition according to the invention can of course be deposited in the form of a film on the surface of the metal parts to be protected by any suitable conventional oven, such as a coating device with a roller or the like or by spraying.
a coating device with a roller or the like or by spraying.
the part thus treated is then subjected drying in order to obtain a dry film according to the invention
the present invention also relates to a metal part coated with a dry film for temporary protection against corrosion obtained from the claimed composition and / or in accordance with the claimed methods.
the surface density of dry film on the surface of the 2o piece varies between 0 3 and 2 g / m " and more preferentially is of the order of 0 5 g / m "
the term "metal parts” means movable thickness plates hot rolled thin sheets hot rolled cold rolled steel sheets as well as various kinds of steel plates and sheets, in particular bare steel.
the metal parts coated with a dry protective film of composition as defined according to the invention prove to be resistant to corrosion and show good aptitude for stamping and sticking.
the dry films obtained according to the claimed process show good adhesion properties with respect to various kinds of substrates on the surface of which they are capable of being applied to their surface
the coatings derived from the claimed compositions have satisfactory and therefore advantageous performance in terms of stamping. This is how their character in terms of friction shows that they have a reduced coefficient of friction compared to conventional coatings.
FIGS. 5 and 6 Characterization of the adsorption power of different inhibitors including ABTS
the ABTS inhibitor is dissolved in an oily emulsion after neutralization with ammonia or with ethanolamine 2 ⁇
an oily emulsion After neutralization and therefore dissolve 1 g of inhibitor in one liter of water , at least
Irgacor L 184 Irgamet 42 from CIBA - Irgacor L 184
inhibitors 1 to 5 are used to additivate an emulsion composed of a soluble mineral oil and water
the mineral oil used is the soluble oil CASTROL AQUASAFE 21 ⁇
the performance of the different compositions tested is assessed by applying them to pickled steel test pieces, polished with G600 paper in proportions such that the final grammage deposited on test pieces is of the order of 500 mg / m " (0 5 ⁇ m )
the test piece is then immersed in an electrolytic mixture of demineralized water, 1% by weight of sodium chloride ( ⁇ aCl)
the steel test piece is kept 30 min in the electrolyte in order to stabilize its electrochemical potential
a potentiostat, a frequency converter of a reference electrode and a counter electrode a sinusoidal disturbance in potential is imposed on the test (in mV ) for different decreasing frequencies and we measure "response intensity" (in uA'cm " )
test tubes are exposed to the atmosphere of 2 storage halls
Ethanolamine neutralized ABTS inhibitor is introduced at concentrations varying between 0 5 and 20 g / 1 in the aqueous phase in a composition according to 1 invention comprising an aqueous emulsion based on 6% of oil C ASTROL AQU AS FE 2 1
the corrosion resistances of the various corresponding compositions are determined by Humidotherm FKW according to the protocol described in equipment and method The results obtained are represented o on the graph of FIG. 1
composition comprising 2> g 1 of ABTS inhibitor in neutralized form
composition according to the invention comprising an ABTS concentration equal to 2 5 g / l (COMPOSITION 3) and with regard to the control compositions 1 2 and 4 identified more precisely in the chapter 'o Materials and Methods
composition according to the invention that is to say composition 3 comprising a salt of AJBTS in an aqueous emulsion, exhibits a resistance which is significantly prolonged over time. Furthermore, the increase in resistance observed is clearly greater than that resulting from the superposition of the resistances induced respectively by the emulsion and by the ABTS considered isolation.
compositions 1 2, 3 and 4 identified more precisely in the Materials and Methods chapter.
This test consists in stacking test pieces previously coated with the solutions to be tested. The stacks are kept tight in order to simulate the contiguous turns of a steel coil or the stacked sheets of a pack of sheets.
the stacked stack of specimens (“greenhouse pack”) is then introduced into a climatic chamber programmed to carry out alternating cycles of 32 h ("transport cycle”)
composition 3 Only the metal part coated with a composition according to the invention, that is to say composition 3, exhibits a significantly improved corrosion resistance. This increase moreover reflects a difference between the emulsion and the ABTS salt.
compositions 2 and 4 based on an aqueous solution respectively containing ABTS and an Irgacor L 184 / Irgamet 42 mixture, the compositions tested are always composed of Castrol AQUASAFE 21 soluble oil, diluted to 6% in water. demineralized (composition 1) and additive with different inhibitors (compositions 3 and 5 to 9)
ABTS is present in an ammonia-neutralized form.
the drying of emulsions 4 to 6 therefore leads to the evaporation of ammonia.
composition 4 confers an advantageous behavior on the corresponding film compared to a film which has not undergone drying (composition 3). This effect is in fact linked to the implementation of ABTS neutralized with ammonia)
the total resistances are determined by electrochemical impedance. performed according to the protocol described in the Material and Method chapter above.
the single-pass friction tests are carried out in planar friction, with variable transverse pressure from 200 to 2,000 daN with high-speed steel tools, with an area of 1 cm 2 The speed of movement is 2 mm / s
test pieces are cut from hot pickled sheets, grade BS2, in thickness of 2 mm
Composition Has a protective oil used on the sheets as corrosion protection (QUAKER 8021) deposited at a rate of 2 gm "
Composition B AQUASAFE 21 soluble oil at 6% in water deposited at a rate of 500 mg / m "
Composition C Composition B additive of the organic inhibitor ABTS in salt form, (pH of the solution between 7.2 and 8 5) deposited at the rate of 500 mg / m "
composition D identical to composition C, whose pH lo is stabilized between 8.5 and 9 by the addition of ethanolamine, deposited at the rate of
composition A 1 ⁇
measurements of wetting are carried out o of two compositions a composition based on an AQUASAFE 21 emulsion
the test consists in depositing a drop of each of the emulsions on a steel test tube and in following the evolution of the contact angle of the drop (followed by spreading)
the graph represents in figure 4 shows that a drop of emulsion
AQUASAFE 21 additive by ABTS spreads much faster on steel than a drop of classic AQUASAFE 21 emulsion (WITNESS)
WITNESS classic AQUASAFE 21 emulsion
compositions comprise an emulsion having an oily base concentration of AQUASAFE 21 of 5% ! ⁇ T

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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)
Paints Or Removers (AREA)

EP98933689A 1997-07-01 1998-06-23 Zusammensetzung zum temporären korrosionsschutz von metallischen oberflächen, verfahren zu ihrer herstellung, verwendung und damit hergestellte metallteile Expired - Lifetime EP0996769B1 (de)

Applications Claiming Priority (3)

Application Number	Priority Date	Filing Date	Title
FR9708288		1997-07-01
FR9708288A FR2765595B1 (fr)	1997-07-01	1997-07-01	Composition pour protection temporaire contre la corrosion de pieces metalliques, ses procedes de preparation et d'application et pieces metalliques obtenues a partir de cette composition
PCT/FR1998/001317 WO1999001590A1 (fr)	1997-07-01	1998-06-23	Composition pour protection temporaire contre la corrosion de pieces metalliques, ses procedes de preparation et d'application et pieces metalliques obtenues a partir de cette composition

Publications (2)

Publication Number	Publication Date
EP0996769A1 true EP0996769A1 (de)	2000-05-03
EP0996769B1 EP0996769B1 (de)	2003-03-05

Family

ID=9508700

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP98933689A Expired - Lifetime EP0996769B1 (de)	1997-07-01	1998-06-23	Zusammensetzung zum temporären korrosionsschutz von metallischen oberflächen, verfahren zu ihrer herstellung, verwendung und damit hergestellte metallteile

Country Status (10)

Country	Link
US (1)	US6309697B1 (de)
EP (1)	EP0996769B1 (de)
JP (1)	JP4184595B2 (de)
KR (1)	KR100522925B1 (de)
AT (1)	ATE233834T1 (de)
CA (1)	CA2295864C (de)
DE (1)	DE69811900T2 (de)
ES (1)	ES2193544T3 (de)
FR (1)	FR2765595B1 (de)
WO (1)	WO1999001590A1 (de)

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Publication number	Priority date	Publication date	Assignee	Title
CA2900026C (en) *	2013-02-13	2021-06-01	Basf Se	Antifreeze concentrate with corrosion protection and aqueous coolant composition produced therefrom
IN2013KO01135A (de) *	2013-10-01	2015-04-10	Tata Steel Ltd
CN106609371B (zh) *	2015-10-27	2019-04-16	中国石油化工股份有限公司	一种缓蚀剂及其制备方法和应用
KR102045640B1 (ko) *	2017-12-22	2019-11-15	주식회사 포스코	방청 조성물, 금속 기재의 방청처리 방법 및 방청 코팅층을 포함하는 금속재

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GB1104755A (en) *	1964-06-10	1968-02-28	Ici Ltd	De-watering of metal surfaces
SE401693B (sv) *	1975-09-24	1978-05-22	Berol Kemi Ab	Temporert korrosionsskyddande oljeemulsion
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GB8313322D0 (en) *	1983-05-14	1983-06-22	Ciba Geigy Ag	Heterocyclic-(cyclo)aliphatic carboxylic acids
GB8313321D0 (en) *	1983-05-14	1983-06-22	Ciba Geigy Ag	Preparation of mercaptan substituted carboxylic acids
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IT1185511B (it) *	1985-02-19	1987-11-12	Hoechst Italia	Agenti anticorrosivi acquosi contenenti un sale ammonico dell'acido 2-benzotiazoliltiocarbossilico
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1997
- 1997-07-01 FR FR9708288A patent/FR2765595B1/fr not_active Expired - Fee Related
1998
- 1998-06-23 KR KR10-1999-7012620A patent/KR100522925B1/ko not_active Expired - Fee Related
- 1998-06-23 ES ES98933689T patent/ES2193544T3/es not_active Expired - Lifetime
- 1998-06-23 EP EP98933689A patent/EP0996769B1/de not_active Expired - Lifetime
- 1998-06-23 US US09/446,887 patent/US6309697B1/en not_active Expired - Lifetime
- 1998-06-23 JP JP2000501287A patent/JP4184595B2/ja not_active Expired - Fee Related
- 1998-06-23 DE DE69811900T patent/DE69811900T2/de not_active Expired - Lifetime
- 1998-06-23 AT AT98933689T patent/ATE233834T1/de active
- 1998-06-23 CA CA002295864A patent/CA2295864C/fr not_active Expired - Fee Related
- 1998-06-23 WO PCT/FR1998/001317 patent/WO1999001590A1/fr active IP Right Grant

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Also Published As

Publication number	Publication date
KR100522925B1 (ko)	2005-10-19
EP0996769B1 (de)	2003-03-05
ES2193544T3 (es)	2003-11-01
CA2295864C (fr)	2008-04-08
FR2765595B1 (fr)	1999-10-01
US6309697B1 (en)	2001-10-30
WO1999001590A1 (fr)	1999-01-14
ATE233834T1 (de)	2003-03-15
KR20010020606A (ko)	2001-03-15
DE69811900T2 (de)	2004-02-12
FR2765595A1 (fr)	1999-01-08
JP4184595B2 (ja)	2008-11-19
CA2295864A1 (fr)	1999-01-14
JP2001509542A (ja)	2001-07-24
DE69811900D1 (de)	2003-04-10

Publication	Publication Date	Title
Georges et al.	2008	Synergistic effect of tolutriazol and sodium carboxylates on zinc corrosion in atmospheric conditions
WO2008107529A1 (fr)	2008-09-12	Inhibiteur de corrosion
EP0996769B1 (de)	2003-03-05	Zusammensetzung zum temporären korrosionsschutz von metallischen oberflächen, verfahren zu ihrer herstellung, verwendung und damit hergestellte metallteile
EP0754779B1 (de)	1998-09-09	Verfahren zur Oberflächenbehandlung von mit Zink oder Zinklegierung teilplattiertem Stahlblech
EP0763575A1 (de)	1997-03-19	Überzugszusammensetzung zum Korrosionsschutz von Metallen
FR2767140A1 (fr)	1999-02-12	Procede de traitement de surface de pieces metalliques
Eldougdoug et al.	2018	Corrosion inhibition of Tri-cationic surfactant on carbon steel in hydrochloric acid solution
EP1963545B1 (de)	2010-11-17	Behandlungsverfahren der metallischen oberflächen durch carboxilierung, benutzung dieses verfahrens für den zeitweiligen korrosionsschutz und verfahren zur herstellung eines geformten carboxylierten bleches
WO2008017739A1 (fr)	2008-02-14	Compositions a base d'acides carboxyliques pour protection temporaire de surfaces metalliques et films secs obtenus a partir desdites compositions
LU82255A1 (fr)	1980-06-06	Compositions de protection de surafaces d'acier et procede pour leur preparation
WO2007054536A1 (fr)	2007-05-18	Inhibition de la corrosion
EP0313447A1 (de)	1989-04-26	Zusammensetzung zum oberflächlichen Schutz von Zink gegen "Weissrost" und entsprechende Verfahren
FR2822852A1 (fr)	2002-10-04	Procede de traitement par carboxylatation de surfaces metalliques
EP0038364B1 (de)	1984-02-01	Verfahren, um stahlmaterialien widerstandsfähig gegen rost zu machen
EP1082392B1 (de)	2004-03-10	Wasserlösliche zusammensetzung als beschichtung für metalloberflächen in form von trockenen filmen, die abdichtend gegenüber atmosphärischer korrosion sind
TW200401769A (en)	2004-02-01	Novel imidazolyl alcohol compound method for making the same, and surface treatment agent using such imidazolyl alcohol compound
Kuznetsov et al.	2006	Adsorption of organic anions on iron in aqueous solutions: An ellipsometric study
WO2001051682A1 (fr)	2001-07-19	Procede d'oxalatation de la surface zinguee d'une tole
WO1997021793A1 (fr)	1997-06-19	Procede de traitement de la surface metallique d'une tole
WO2019043339A1 (fr)	2019-03-07	Procede de preparation d'acide sulfonique
EP0897969B1 (de)	2001-03-14	Verfahren zur Behandlung von Metallblech-Oberflächen zur Verbesserung der Verklebung, der Tiefziehverarbeitung und der Entfettung
WO2012140488A1 (fr)	2012-10-18	Procédé de traitement de protection des métaux à base de composition hydrosoluble d'huile(s) végétale(s) saponifiée(s), et produits et compositions obtenus
FR2787355A1 (fr)	2000-06-23	Procede de traitement de surfaces metalliques, notamment de toles d'acier, destine en particulier a ameliorer leurs performances tribologiques
McEwan et al.	2006	The optimisation of hexadecanethiol coatings to improve the tarnish resistance of sterling silver
IT8147576A1 (it)	1982-07-15	Procedimento di trattamento antiruggine di materiale di partenza per acciaio.

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