WO1992006149A1 - Nitritfreie wässrige nassdressiermittel für stahl und verzinkten stahl - Google Patents

Nitritfreie wässrige nassdressiermittel für stahl und verzinkten stahl Download PDF

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Publication number
WO1992006149A1
WO1992006149A1 PCT/EP1991/001868 EP9101868W WO9206149A1 WO 1992006149 A1 WO1992006149 A1 WO 1992006149A1 EP 9101868 W EP9101868 W EP 9101868W WO 9206149 A1 WO9206149 A1 WO 9206149A1
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Prior art keywords
acid
weight
wet dressing
dressing agent
agent according
Prior art date
Application number
PCT/EP1991/001868
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German (de)
English (en)
French (fr)
Inventor
Reinhard Seidel
Karl-Dieter Brands
Armin Friesendorf
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1992006149A1 publication Critical patent/WO1992006149A1/de

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    • 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
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    • C10M2215/08—Amides
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/12—Partial amides of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/12—Partial amides of polycarboxylic acids
    • C10M2215/122—Phtalamic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/20—Containing nitrogen-to-oxygen bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/061—Metal salts

Definitions

  • the invention relates to nitrite-free, aqueous wet dressing agents to avoid roller contamination and corrosion of re-rolled ("trained") steel sheets and galvanized steel sheets which contain benzoylalanines, carboxylic acids and amines, and to a process for re-rolling ("dressing") steel strips using this agent.
  • the obtained, reduced-thickness and hard-rolled sheet is annealed in order to give it a certain softness.
  • This soft sheet the desired processing properties, it has to be re-rolled afterwards.
  • This process step serves to generate a defined roughness on the sheet metal surface, to improve the flatness and to suppress flow figures during storage.
  • the wet dressing agent used is intended to prevent dirt deposits on the rollers, the so-called matting, and for one provide adequate lubrication. Another important requirement is that the aqueous solution wrapped in the strip when it is rolled up does not cause any corrosion or discoloration of the sheet.
  • wet dressing agents used to date mostly contain inorganic nitrite, often in combination with alkanol amines, e.g. Mono-, di- or triethanolamine.
  • WO 81/00579 describes a mixture of inorganic nitrite, the sodium salt of benzoic acid, sodium carbonate and optionally a glycol.
  • the corrosion-inhibiting effect is essentially attributed to sodium nitrite.
  • JP-109 780 describes a wet dressing agent consisting of a substituted benzoic acid, a primary amine and a carboxylic acid.
  • the wet dressing agent which is described in JP 57 151 700 is also nitrite-free.
  • An essential component here is a partial ester or a salt of a dicarboxylic acid with an oxyalkylated amine.
  • nitrite-containing agents are undesirable. Combinations of nitrite and amines are particularly critical due to the risk of nitrosamine formation. Since the wet dressing agents are sprayed onto the sheet metal for use, and are distributed in the air surrounding the roll stand in the form of a fine mist (aerosol formation), they can be inhaled by the operating personnel.
  • the task arises of providing a nitrite-free wet dressing agent which, in terms of its corrosion-inhibiting effect when storing steel strip and galvanized steel strip, is not inferior to the nitrite-containing mixtures.
  • the roller should be kept free of contamination or deposits.
  • the mixtures obtained are also said to be physiologically safe and suitable for use in a process for re-rolling strip steel and galvanized strip steel.
  • the present invention accordingly relates to a nitrite-free, aqueous wet dressing agent to avoid roller contamination and corrosion of re-rolled steel sheets and galvanized steel sheets, containing a carboxylic acid and an amine, characterized in that the nitrite-free, aqueous wet dressing agent
  • R 1 and R 2 are hydrogen or an alkyl radical having 1 to 12 C atoms and R 3 and R 4 may be the same or different and for hydrogen, an unbranched or branched alkyl radical having 1 to 10 C atoms, hydroxyalkylene, Alkoxyalkylene, carboxyalkylene or alkylaminoalkylene radicals which contain 1 to 3 carbon atoms in the alkylene radical and 1 to 3 carbon atoms in the alkyl radical and can be closed to form a saturated heterocyclic 5- or 6-ring,
  • R 1 is an alkyl radical with 1 to 8 carbon atoms, preferably methyl, ethyl,
  • R 2 is hydrogen or a methyl radical
  • R 3 is hydrogen and R 4 is hydrogen, an alkyl radical having 1 to 4 carbon atoms, preferably ethyl or n-butyl, a hydroxyethylene, a carboxymethylene or a dimethylaminopropyl radical
  • R 3 and R 4 each represent a hydroxyethylene radical or R 3 and R 4 together represent an ethoxyethylene or ethyl iminoethylene radical, that is to say are bonded to form a morpholino or piperidino radical, including the binding N atom. Is particularly preferred
  • Mono- and / or dicarboxylic acids with a number of carbon atoms between 6 and 12 are particularly suitable as the carboxylic acid component, it being possible in particular to use mixtures of a mono- and dicarboxylic acid in a ratio of 1:10 to 10: 1.
  • Typical representatives of the monocarboxylic acids are 2-ethylhexanoic acid, lauric acid, isooctanoic acid, benzoic acid, 3-aminobenzoic acid, p-tert-butylbenzoic acid, cinnamic acid and in particular isononanoic acid and 3-nitrobenzoic acid.
  • Representatives of dicarboxylic acids are adipic acid, azelaic acid, isosebacic acid, phthalic acid, isophthalic acid, terephthalic acid and in particular sebacic acid.
  • alkanolamines having a carbon number of 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms, can be used.
  • the wet dressing agent according to the invention contains a mixture of diethanolamine and triethanolamine in a ratio of 1: 2 to 1: 8, preferably 1: 4 to 1: 6.
  • the alkanolamine is added to neutralize the carboxylic acids used.
  • the solution alkalized by adding the alkanolamine has a pH of 7 to 10, preferably 8 to 9.
  • aromatic sulfonic acids preferably nitro-substituted aromatic sulfonic acids
  • P-Nitrobenzenesulfonic acid is particularly preferred.
  • sodium or potassium lignin sulfonate can be used to complex the water hardness.
  • other conventional substances for complexing the water hardness can also be used, for example the phosphons known for this acids and / or their water-soluble metal salts, such as 2-hydroxyethane-1,1-diphosphonic acid (HEDP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS) or ethylenediaminetetra (methylenephosphonic acid) (EDTP).
  • HEDP 2-hydroxyethane-1,1-diphosphonic acid
  • PBS 2-phosphonobutane-1,2,4-tricarboxylic acid
  • EDTP ethylenediaminetetra
  • Alkali metal salts are preferably used as water-soluble metal salts. Such compounds are preferably used in an amount of 0.1 to 2% by weight.
  • Boric acid which can be added as a preservative, is preferably used in an amount of 0.5 to 5% by weight.
  • foam-suppressing reagents can also be advantageous to use foam-suppressing reagents.
  • surfactants with a low HLB value such as sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, low molecular weight polyethylene glycol esters of oleic acid, EO adducts of nonylphenol and preferably EO / PO block polymers of polyglycols, in an amount of 0.01 to 2% by weight. -%, preferably 0.05 to 1 wt .-%, are used.
  • N-acylated N-methylglycine such as oleoyl-N-methylglycine (Sarkosyl O R , Ciba Geigy) or lauroyl-N-methylglycine (Sarkosyl L R , Ciba Geigy)
  • oleoyl-N-methylglycine Sarkosyl O R , Ciba Geigy
  • lauroyl-N-methylglycine Sarkosyl L R , Ciba Geigy
  • the salts obtained by neutralization with lithium, sodium or potassium hydroxides, amines or alkanolamines can also be used.
  • a perfume can be added to the wet dressing agent, preferably in an amount of 0.1% by weight.
  • one or more lubricants such as glycols and / or polyethylene glycol compounds, can optionally also be used in an amount of 1 to 30% by weight, preferably 10 to 20% by weight.
  • a preferred composition of the wet dressing agent according to the invention contains
  • a water hardness complexing agent preferably 2-hydroxyethane-1,1-diphosphonic acid and / or alkali metal incin sulfonate, and
  • Another object of the present invention relates to a method for re-rolling strip steel and galvanized strip steel using the wet dressing agent according to the invention, which is applied to the surface before the strip enters the roll gap, characterized in that this agent
  • R 1 and R 2 are hydrogen or an alkyl radical having 1 to 12 C atoms and R 3 and R 4 may be the same or different and for hydrogen, an unbranched or branched alkyl radical having 1 to 10 C atoms, hydroxyalkylene, Are alkoxyalkylene, carboxyalkylene or alkylaminoalkylene radicals which contain 1 to 3 carbon atoms in the alkylene radical and 1 to 3 carbon atoms in the alkyl radical and can be closed to form a saturated heterocyclic 5- or 6-ring,
  • the wet dressing agent according to the invention is used in an application concentration of 2 to 8% by weight, preferably 5% by weight.
  • the solutions were applied by means of spray nozzles in front of the roll gap, the strips were wound up wet and the condition of the surface was observed after several days to several weeks of intermediate storage.
  • the level of contamination of the rollers was assessed during operation.
  • the strip material rolled in the presence of the wet dressing agent according to the invention was in optically perfect condition after the stated time, ie showed no corrosion and no discoloration.
  • the surfaces of the rollers showed no detectable contamination.
  • Wet dressing agent consisting of:
  • Wet dressing agent consisting of:
  • Wet dressing agent consisting of:
  • Wet dressing agent consisting of:
  • Wet dressing agent consisting of:
  • Wet dressing agent consisting of:
  • Wet dressing agent consisting of:
  • Wet dressing agent consisting of:
  • Wet dressing agent consisting of: 5% by weight sebacic acid
  • cold-rolled steel sheets ST 1405 (hereinafter CRS), electrolytically galvanized steel sheets (7.5 ⁇ m on both sides from Hoesch, in the following ZE) and hot-dip galvanized steel sheets (10 ⁇ m on both sides from Thyssen, in the following Z ) degreased with acetone and immersed in a 5 wt .-% treatment solution, which was obtained by diluting the concentrate with tap water. Then the sheets were pressed together, wrapped in commercially available aluminum foil and stored at room temperature. After 4 weeks, the inside of the sheets were checked for corrosion and discoloration. They were rated as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Chemical Treatment Of Metals (AREA)
PCT/EP1991/001868 1990-10-09 1991-09-30 Nitritfreie wässrige nassdressiermittel für stahl und verzinkten stahl WO1992006149A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4032049.9 1990-10-09
DE4032049A DE4032049A1 (de) 1990-10-09 1990-10-09 Nitritfreie waessrige nassdressiermittel fuer stahl und verzinkten stahl

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WO1992006149A1 true WO1992006149A1 (de) 1992-04-16

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Country Link
CN (1) CN1060491A (es)
AU (1) AU8656191A (es)
DE (1) DE4032049A1 (es)
MX (1) MX9101490A (es)
TR (1) TR25379A (es)
WO (1) WO1992006149A1 (es)
ZA (1) ZA918045B (es)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997008279A1 (de) * 1995-08-31 1997-03-06 Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. Verwendung von phosphonsäurederivaten in wasserhaltigen schmier- und kühlschmierstoffen
FR2742447A1 (fr) * 1995-12-14 1997-06-20 Bp Chemicals Snc Composition d'antigel et fluide aqueux comprenant la composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9418743D0 (en) * 1994-09-16 1994-11-02 Dupont Uk Limited Fount solutions for printing processes
DE19621837C1 (de) * 1996-05-31 1997-09-11 Thyssen Stahl Ag Verfahren und Vorrichtung zum Behandeln von insbesondere feuerbeschichtetem Feinblech unter Einsatz von gegen das Feinblech gedrückter Rollen, insbesondere Walzen
EP2261418A1 (en) * 2009-05-25 2010-12-15 Vistaprint Technologies Limited Pre-treatment liquid for liquid absorbing printing substrates

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379072A (en) * 1981-10-08 1983-04-05 Nalco Chemical Company Water-based rust inhibitor
US4419253A (en) * 1981-11-06 1983-12-06 Nalco Chemical Company Synthetic post-pickle fluid
EP0163107A1 (de) * 1984-04-30 1985-12-04 Henkel Kommanditgesellschaft auf Aktien Verwendung von Benzoylalaninen als Korrosionsinhibitoren für wässrige Systeme
DE3734090A1 (de) * 1986-10-13 1988-04-14 Nippon Kokan Kk Wasserloesliches walzoel fuer das dressierwalzen und verfahren zum dressierwalzen unter verwendung eines solchen walzoels
WO1991001363A1 (de) * 1989-07-14 1991-02-07 Henkel Kommanditgesellschaft Auf Aktien Nitritfreie wässrige nassdressiermittel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379072A (en) * 1981-10-08 1983-04-05 Nalco Chemical Company Water-based rust inhibitor
US4419253A (en) * 1981-11-06 1983-12-06 Nalco Chemical Company Synthetic post-pickle fluid
EP0163107A1 (de) * 1984-04-30 1985-12-04 Henkel Kommanditgesellschaft auf Aktien Verwendung von Benzoylalaninen als Korrosionsinhibitoren für wässrige Systeme
DE3734090A1 (de) * 1986-10-13 1988-04-14 Nippon Kokan Kk Wasserloesliches walzoel fuer das dressierwalzen und verfahren zum dressierwalzen unter verwendung eines solchen walzoels
WO1991001363A1 (de) * 1989-07-14 1991-02-07 Henkel Kommanditgesellschaft Auf Aktien Nitritfreie wässrige nassdressiermittel

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997008279A1 (de) * 1995-08-31 1997-03-06 Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. Verwendung von phosphonsäurederivaten in wasserhaltigen schmier- und kühlschmierstoffen
FR2742447A1 (fr) * 1995-12-14 1997-06-20 Bp Chemicals Snc Composition d'antigel et fluide aqueux comprenant la composition

Also Published As

Publication number Publication date
DE4032049A1 (de) 1992-04-16
MX9101490A (es) 1992-06-05
TR25379A (tr) 1993-03-01
ZA918045B (en) 1992-06-24
AU8656191A (en) 1992-04-28
CN1060491A (zh) 1992-04-22

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