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WO2015001645A1 - Agent permettant de former un film de revêtement antirouille sur une surface métallique, et procédé permettant de former un film de revêtement antirouille pour un substrat métallique à l'aide de cet agent - Google Patents

Agent permettant de former un film de revêtement antirouille sur une surface métallique, et procédé permettant de former un film de revêtement antirouille pour un substrat métallique à l'aide de cet agent Download PDF

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Publication number
WO2015001645A1
WO2015001645A1 PCT/JP2013/068378 JP2013068378W WO2015001645A1 WO 2015001645 A1 WO2015001645 A1 WO 2015001645A1 JP 2013068378 W JP2013068378 W JP 2013068378W WO 2015001645 A1 WO2015001645 A1 WO 2015001645A1
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Prior art keywords
group
rust
rust preventive
preventive film
metal substrate
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Ceased
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PCT/JP2013/068378
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English (en)
Japanese (ja)
Inventor
岡田和夫
東博通
荒武ひとみ
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OKADA CHELATE CO LTD
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OKADA CHELATE CO LTD
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Priority to PCT/JP2013/068378 priority Critical patent/WO2015001645A1/fr
Publication of WO2015001645A1 publication Critical patent/WO2015001645A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Definitions

  • the present invention further provides anti-corrosion performance directly on the surface of a metal substrate which is easily oxidized, such as a metal substrate plated with zinc or zinc alloy, a metal substrate provided with a zinc layer by molten zinc, or an aluminum substrate, or after pre-coating treatment.
  • a metal surface rust preventive film forming agent for generating a rust preventive film for improving the properties completely free of chromium and a rust preventive film forming method for forming a rust preventive film on a metal substrate using the same.
  • a method of forming a rust prevention film with a treatment solution containing hexavalent chromium has been generally performed.
  • the chromate method has been widely used worldwide as a means for preventing metal rust because of its advantage that the cost is low and the process is very simple.
  • the hexavalent chromium used in the chromate method is feared to affect the human body and the environment, and in Japan, the United States, the EU, China, etc., the ban on the use of hexavalent chromium has been issued.
  • An alternative to the chromate method is a method for producing a rust-preventing film containing trivalent chromium.
  • Examples of surface treatment methods that do not use chromium at all, so-called complete chromium-free treatment methods include, for example, a phosphate film (Patent Document 1), an oxalate film (Patent Document 2), and a film made of metal salt using electrolysis (patent) Document 3), the second rust preventive film of metal ions (Patent Document 4) has been proposed on the organic resin film and tannic acid film, but there are many points that are insufficient in corrosion resistance and the processing temperature is high.
  • there are many problems such as complicated processes and difficulty in use with conventional chromate apparatuses, and many of them have not been put into practical use.
  • Patent Document 5 As a surface treatment method using a silane coupling agent as a rust preventive film forming agent, a technique of an aqueous coating agent containing a thiol compound in an epoxy group-containing silane coupling agent is disclosed (Patent Document 5). However, in the technique of Patent Document 5, even if the amount of the rust preventive film is 0.2 (g / m 2 ), sufficient rust preventive performance is not exhibited.
  • a coating method using a water-soluble resin of a silane coupling agent and a hydrazine derivative and a surface treatment agent containing phosphoric acid and / or hexafluorometal acid is also disclosed (Patent Document 6). Must be heated and dried at °C.
  • the equipment used in the conventional chromate method or the trivalent chromium treatment liquid method is used as it is. It is required to reduce the initial cost for equipment. Specifically, as in the chromate method, the substrate plated with zinc or zinc alloy is immersed in the chromate treatment solution, and then the plated substrate is taken out and the excess chromate solution is shaken off by centrifugal force. It is required that the equipment of the dip and spin method (or “dip spin method”) can be used as it is.
  • Patent Document 7 if an alcohol-based surface treatment agent in which titanium oxide is added to an oligomer of tetraalkoxysilane is used, chromium-free rust-proof coating treatment can be performed by a dip-and-spin method.
  • the alcohol group in the alkoxysilane molecule is dealcoholized to prevent the silane atoms from intermingling with oxygen atoms and extending the bond chain sterically.
  • a rusting film is formed (sol-gel reaction).
  • a rust preventive film using tetraalkoxysilane usually requires a film thickness of at least several ⁇ m in order to be able to exert its effect. Moreover, it is difficult to control the film thickness. For this reason, the diameter of the thread portion of the small-diameter screw is increased, and the pitch diameter is changed to deteriorate the adaptability as a screw. That is, it interferes with the fit between the screw and the nut. Therefore, there is a problem that it is not suitable for small-diameter screws and products that require electrical conductivity. Further, when the film thickness is several ⁇ m or more, there is a problem in that it is difficult to apply to a member that requires electrical conductivity because it impedes electrical conductivity.
  • Patent Document 8 discloses a rust preventive primer for an aluminum member containing a polyolefin resin, addition of a silane coupling agent, an organic solvent such as toluene, an imidazole compound, and the like. In addition, baking at 150 ° C. for about 30 minutes is required.
  • a film forming composition containing a ring agent and an organic boron compound is also disclosed (Patent Document 9).
  • the film-forming composition uses the cellosolve and an aqueous solvent, and the film thickness is as thick as about 30 ⁇ m.
  • JP 2002-12981 A JP 2001-247777 A JP 2000-290782 A JP 2001-98392 A JP2011-157600 JP 2005-206947 A JP 2006-28547 A JP2011-74251 JP-A-10-195381
  • the problem to be solved by the present invention is a metal surface rust preventive film forming agent and a rust preventive film forming method for a metal substrate using the same, which is completely chromium-free but has sufficient rust preventive properties ⁇
  • the process can be processed by the same dip-and-spin method as the conventional chromate treatment, and after that a rust-proof film forming method that does not require a baking process, and the film forming process are enabled.
  • An object of the present invention is to provide a rust preventive film forming agent.
  • the metal surface rust preventive film forming agent of the present invention is a trialkoxysilane having a chemical structure of [R 1 (OR 2 ) 3 Si] (R 1 has a vinyl group, epoxy group, styryl group, methacryl group, An alcohol solution containing 0.5 to 7% by weight of an oligomer of an acrylic group, an amino group, a ureido group, a mercapto group, a sulfide group, a functional group that is an isocyanate group, and R 2 is an alkyl group or an alkylene group) based on the total amount of the solution. Is the most important feature.
  • a metal substrate (or a metal substrate that has been pre-coated) is treated by the dip and spin method using the rust preventive film forming agent,
  • the most important feature is that it has a step of forming a rust preventive film on the surface of the metal substrate by drying at room temperature.
  • the metal surface rust preventive film forming agent and the rust preventive film forming method of the present invention can impart sufficient rust preventive property to the metal substrate while being completely chromium-free rust preventive film forming agent and rust preventive film treatment. . And since the rust preventive film is sufficiently thin, it can be suitably used for small diameter screws and products that require electrical conductivity.
  • the rust preventive film formation method of the present invention is a dip-and-spin method similar to chromate treatment, and the subsequent drying process is also possible at room temperature, so conventional chromate treatment equipment can be used as it is, and transition to a complete chromium-free treatment process It is possible to reduce the initial cost of equipment installation for the purpose.
  • Metal surface rust preventive film forming agent The components contained in the metal surface rust preventive film forming agent of the present invention (hereinafter simply referred to as “rust preventive film forming agent”) will be described below.
  • the antirust film forming agent of the present invention includes a trialkoxysilane oligomer having an oligomer functional group R 1 of trialkoxysilane having a chemical structure of [R 1 (OR 2 ) 3 Si].
  • R 1 in the chemical structural formula is a functional group whose terminal is a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, a ureido group, a mercapto group, a sulfide group, or an isocyanate group. be able to.
  • R 2 in the chemical structural formula is an alkyl group or an alkylene group, and preferably has 1 to 3 carbon atoms.
  • Functional group R 1 terminal is vinyl group, vinyltrimethoxysilane, vinyltriethoxysilane, vinylpropoxysilane
  • Functional group R As the one terminal is an epoxy group, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4epoxycyclohexyl) propoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, Functional group R As the one terminal is a styryl group, p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltripropoxysilane, Functional group R As one end of methacryl group,
  • the anticorrosive film made of an alkoxysilane oligomer having the above chemical structure is a thin film and exhibits sufficient antirust performance. Therefore, the concentration can be 0.5 to 7% by weight with respect to the total amount of the alcohol solution. If the concentration is 0.5% by weight or less, there is no rust prevention effect, and if it is 7% by weight or more, the economical efficiency is poor and the film thickness is also thick.
  • the rust preventive film forming agent of the present invention preferably further contains a secondary alkoxysilane oligomerization catalyst.
  • the secondary alkoxysilane oligomerization catalyst is a rustproofer by further subjecting the primary alkoxysilane oligomer rust-preventing film formed on the metal substrate to be rustproofed to a further dealcoholization reaction between alkoxysilane oligomer molecules under normal temperature drying. Promotes polymerization with increased performance.
  • organic titanium or organic aluminum is preferable.
  • the addition amount of the secondary alkoxysilane oligomerization catalyst is preferably in the range of 0.2 to 5% by weight based on the weight of the contained alkoxysilane oligomer.
  • the organic compound combined in the metal of the secondary alkoxysilane oligomerization catalyst is alkoxy, preferably methoxy or ethoxy. Specific examples include tetramethoxy titanium, tetraethoxy titanium, trimethoxy aluminum, and triethoxy aluminum.
  • thermosetting phenolic resin As an organic resin component for adjusting the viscosity of the completely chromium-free rust preventive film forming agent in the present invention, improving the adhesion to the metal substrate, and adjusting the frictional resistance of the metal product, a wax component soluble in alcohol is used. An alkyd resin or a phenol resin having a three-dimensional structure can be used. In particular, it has been found that it is preferable to use a thermosetting phenolic resin in the present invention. Among them, a resin having a different degree of polymerization of tannic acid (hereinafter referred to as “modified tannin”) is preferable.
  • modified tannin a resin having a different degree of polymerization of tannic acid
  • modified tannin high tannin or special tannin (manufactured by Dainippon Sumitomo Pharma Co., Ltd.) reacted with ethyl glycol and condensed with a tannin component (Okada Chelate Co., Ltd. NCR-W main component) is used.
  • the preferred concentration of the resin varies depending on the desired surface condition after the antirust coating treatment, but is preferably 2 to 15% by weight, more preferably 1 to 10% by weight, based on the total amount of the alcohol solution.
  • Alcohol solvent In the rust preventive film forming agent of the present invention, alcohol is used as a solvent.
  • alcohol solvent low boiling point ethyl alcohol, isopropyl alcohol or normal propyl alcohol is preferred.
  • Alkoxysilane oligomer is a compound with a certain degree of viscosity.
  • a heat source is required to dry the rust preventive film containing a viscous compound in a short time. Therefore, by reducing the concentration of the alkoxysilane oligomer in the low-boiling alcohol, the rust preventive film on the surface of the metal substrate can be cured in a short time even in natural drying.
  • a silane coupling agent such as an alkoxysilane oligomer in the present invention has an affinity for both an organic solvent and an aqueous solvent, it is often used as a useful rust preventive agent for both oil-based paints and water-based paints.
  • a silane coupling agent such as an alkoxysilane oligomer in the present invention
  • water-based paints that have little impact on the environment has been active.
  • water itself has a strong hydrogen bond between water molecules, which naturally causes surface tension and is suitable for the coating method, but the dip and spin method has various problems such as liquid pooling.
  • n-butylcellosolve 2-n-butoxyethanol
  • tert -Butyl cellosolve 2-n-butoxyethanol
  • concentration with respect to the total amount of the alcohol solution is preferably 5 to 15% by weight.
  • rust preventive film formation method a method for forming a rust preventive film on a metal substrate using the treatment agent.
  • the metal substrate subjected to the treatment by the rust preventive film forming method of the present invention is not particularly limited as long as its surface is a substrate having a metal component.
  • the rust preventive film forming method of the present invention has been developed with the aim of a treatment method that can quickly shift from the chromate treatment method while suppressing the initial cost of introducing new equipment. Therefore, what is mainly processed by the processing method of the present invention is a metal substrate whose surface is galvanized or zinc alloy plated.
  • a rust preventive film exhibiting a high rust preventive effect is also formed on a metal substrate that has been subjected to preliminary rust prevention treatment (pre-coating treatment) on a zinc-plated or zinc alloy-plated metal substrate.
  • the rust preventive film forming method of the present invention forms a rust preventive film exhibiting a high rust preventive effect even on a substrate having a zinc layer formed on the surface thereof by molten zinc. Furthermore, a rust preventive film that exhibits a high rust preventive effect is also formed on a metal substrate formed of a metal whose surface is easily oxidized, such as an aluminum substrate.
  • a simple process flow chart in the method of forming a rust preventive film is as follows. A. When treating a metal substrate directly with a rust preventive film former B. When pre-coating on a metal substrate and then treating with a rust preventive film former
  • the rust preventive film can be directly formed on the metal substrate with the rust preventive film forming agent of the present invention as in the process A, but once in the pre-film as in the process of B. After the treatment, the rust preventive film can be formed with the rust preventive film forming agent of the present invention.
  • the pre-film treatment include a white pre-film formation process and a black pre-film formation process. These pre-coating processes are also completely chrome-free processes.
  • a white pre-film formation treatment As the white pre-film forming treatment, it is preferable to form a pre-film with a thermosetting resin such as polyphenol.
  • a modified tannin as a polyphenol a white pre-film-forming treatment can be performed using a treatment liquid obtained by reacting with ethyl glycol and condensing a tannin component.
  • the modified tannin include high tannin and special tannin (manufactured by Dainippon Sumitomo Pharma Co., Ltd.).
  • NCR-W manufactured by Okada Chelate is commercially available.
  • the black pre-coating forming treatment is preferably a step obtained by drying a pre-coating of about 1 ⁇ m formed in a black reaction aqueous solution for zinc plating containing an antimony compound and a manganese compound.
  • NCR-B manufactured by Okada Chelate Co., Ltd. is commercially available as a pre-film treatment liquid for performing such black pre-film formation treatment.
  • Example 1 2.375% by weight of 3-glycoxypropyltriethoxysilane oligomer (average molecular weight 2,000 to 5,000), modified tannic acid (non-chromium reagent NCR-W manufactured by Okada Chelate Co., Ltd.) as an organic resin Rust prevention film forming agent (complete chromium free rust prevention film forming agent) by dissolving 6.0% by weight, 10.0% by weight of 2-n-butoxyethanol and 0.125% by weight of tetraethoxytitanium in isopropyl alcohol was prepared.
  • modified tannic acid non-chromium reagent NCR-W manufactured by Okada Chelate Co., Ltd.
  • Rust prevention film forming agent complete chromium free rust prevention film forming agent
  • a test piece is a wrenched pan head machine screw (M6X2mm) made of SWRCH (carbon steel wire for cold heading) and galvanized with a plating film thickness of 6-14 ⁇ m. It was immersed in a forming agent (25 ° C.) for 5 seconds, and then left in a room (20 ° C., relative humidity 60%) for 2 minutes to obtain a rust-proof test piece.
  • M6X2mm wrenched pan head machine screw
  • the complete chrome-free rust-proof test piece obtained by the rust-proof coating treatment was tested for rust-proofing power using a salt spray tester (STP-90, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS-2371. It was. As an evaluation method, the corrosion resistance was judged by examining the time until white rust and red rust exceeded 5% on the test piece.
  • Example 2 to 4 A rust preventive film-forming agent of 3-mercaptopropyltriethoxysilane oligomer was prepared on the same test piece as in Example 1 at the concentrations shown in Table 3 in Examples 2 and 3, and the same anti-corrosion agent as in Example 1 was prepared. A rust-proof specimen was obtained by the rust method. Also in Example 4, a 3-aminopropyltriethoxysilane oligomer rust preventive film-forming agent was prepared on the same test piece at the concentration shown in Table 1, and the same rust preventive method as in Example 1 was used to prevent rust. A test piece was obtained.
  • test piece was tested with a salt spray tester (STP-90 manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS-2371.
  • STP-90 manufactured by Suga Test Instruments Co., Ltd.
  • JIS-2371 JIS-2371
  • Examples 5 to 7 A pre-film formation treatment was performed on the galvanized test piece before the rust-proof film treatment.
  • a white treating agent prepared by adjusting a modified tannic acid of a trade name “NCR-W” (manufactured by Okada Chelate Co., Ltd.) as a solid tannin concentration to an aqueous solution of 1.8 g / L.
  • the white pre-film formation process used was performed.
  • Example 5 Using the same test piece as in Example 1, after immersing in dilute nitric acid (pH 1.7) for 10 seconds, washing with water and immersing in the white treatment agent (pH 5.5, liquid temperature 25 ° C.) for 60 seconds, The specimen was washed with water and dried to obtain a white pre-coating.
  • the test piece was treated in the same manner with the 3-glycoxypropyltriethoxysilane oligomer rust preventive film forming agent shown in Example 1 to obtain a test piece.
  • Example 6 the same treatment was performed with the same rust preventive film forming agent as the 3-mercaptopropyltriethoxysilane oligomer shown in Example 2 to obtain a test piece.
  • Example 7 a rust preventive film form having a concentration half that of the 3-mercaptopropyltriethoxysilane oligomer used in Example 2 was prepared and treated in the same manner as in Example 2 to obtain a test piece. It was. Each test piece was tested with a salt spray tester (STP-90 manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS-2371. As an evaluation method, the corrosion resistance was judged by examining the time until white rust and red rust exceeded 5% on the test piece.
  • STP-90 manufactured by Suga Test Instruments Co., Ltd.
  • Example 8 to 11 A pre-coating treatment was performed on the galvanized test piece before the anti-rust coating treatment.
  • a black pre-coating forming treatment was performed using a black treating agent adjusted to be a 15-fold diluted aqueous solution with a trade name “NCR-B” (manufactured by Okada Chelate Co., Ltd.).
  • NCR-B trade name “NCR-B” (manufactured by Okada Chelate Co., Ltd.).
  • Example 8 the test piece was subjected to the same treatment with the 3-glycoxypropyltriethoxysilane oligomer rust preventive film forming agent shown in Example 1 to obtain a test piece.
  • Example 9 the same treatment was performed with the rust preventive film forming agent of 3-mercaptopropyltriethoxysilane oligomer used in Example 2 to obtain a test piece.
  • Example 10 a rust preventive film form having a concentration half that of the 3-mercaptopropyltriethoxysilane oligomer used in Example 2 was prepared and treated in the same manner as in Example 2 to obtain a test piece. It was.
  • Example 11 a rust preventive film form having a concentration of 1/2 of the 3-mercaptopropyltriethoxysilane oligomer used in Example 2 was prepared, and the same treatment as in Example 2 was performed. Got. Each test piece was tested with a salt spray tester (STP-90 manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS-2371. As an evaluation method, the corrosion resistance was judged by examining the time until white rust and red rust exceeded 5% on the test piece.
  • STP-90 manufactured by Suga Test Instruments Co., Ltd.
  • Example 12 The test piece coated with molten zinc on the iron material was subjected to the same rust-proof coating treatment as in Example 6 to obtain a test piece.
  • the test piece of Example 12 was tested in accordance with JIS-2371 (STP-90 manufactured by Suga Test Instruments Co., Ltd.). As an evaluation method, the corrosion resistance was judged by examining the time until white rust and red rust exceeded 5% on the test piece.
  • Example 13 The test piece in which the zinc layer was provided with molten zinc on the surface of the iron piece was subjected to the same rust-proof coating treatment as in Example 9 to obtain a test piece.
  • the test piece of Example 13 was tested in accordance with JIS-2371 (STP-90 manufactured by Suga Test Instruments Co., Ltd.). As an evaluation method, the corrosion resistance was judged by examining the time until white rust and red rust exceeded 5% on the test piece.
  • Example 14 A 3-mercaptopropyltriethoxysilane oligomer anticorrosive film-form treatment agent having the concentration shown in Example 2 was prepared on an aluminum (A2014) test piece, and the same antirust film-form treatment method as in Example 1 was used. A rust-proof specimen was obtained. The test piece of Example 14 was tested in accordance with JIS-2371 (STP-90 manufactured by Suga Test Instruments Co., Ltd.). As an evaluation method, the corrosion resistance was judged by examining the time until the white rust exceeded 5% on the test piece.
  • JIS-2371 STP-90 manufactured by Suga Test Instruments Co., Ltd.
  • Example 15 A rust preventive film-forming agent containing no organic resin as compared with Example 1 was prepared directly on the same test piece shown in Example 1, and the same treatment as in Example 1 was performed. Got. Each test piece was tested with a salt spray tester (STP-90 manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS-2371. As an evaluation method, the corrosion resistance was judged by examining the time until white rust and red rust exceeded 5% on the test piece.
  • STP-90 manufactured by Suga Test Instruments Co., Ltd.
  • Example 16 Directly on the same test piece shown in Example 1, a rust preventive film forming agent that does not contain only an organometallic catalyst as compared with Example 1 was prepared, and the same treatment as in Example 1 was performed. A specimen was obtained. Each test piece was tested with a salt spray tester (STP-90 manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS-2371. As an evaluation method, the corrosion resistance was judged by examining the time until white rust and red rust exceeded 5% on the test piece.
  • a salt spray tester STP-90 manufactured by Suga Test Instruments Co., Ltd.
  • Example 1 A rust preventive film-forming agent containing no alkoxysilane oligomer and its oligomerization catalyst was prepared directly on the same test piece shown in Example 1 as compared with Example 1, and the same as in Example 1. Processing was performed to obtain a test piece. Each test piece was tested with a salt spray tester (STP-90 manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS-2371. As an evaluation method, the corrosion resistance was judged by examining the time until white rust and red rust exceeded 5% on the test piece.
  • STP-90 manufactured by Suga Test Instruments Co., Ltd.
  • a test piece of aluminum (A2014) was subjected to a test in accordance with JIS-2371 (STP-90, manufactured by Suga Test Instruments Co., Ltd.) without performing a rust prevention treatment.
  • JIS-2371 STP-90, manufactured by Suga Test Instruments Co., Ltd.
  • the corrosion resistance was judged by examining the time until white rust and red rust exceeded 5% on the test piece.
  • test piece treated with the rust preventive film forming agent of the present invention was directly applied to the surface of the galvanized test piece, although the corrosion resistance of the test piece treated with the rust preventive film was excellent after the pre-film treatment was added. Even one piece can clear the generally required corrosion resistance (for example, SST white rust time of 72 hours or more). Moreover, as a pre-rust prevention film, the improvement of the anti-rust performance was observed in the order of NCR-B (black pre-film formation treatment)> NCR-W (white pre-film formation treatment). (4) Regarding the change in the concentration of the alkoxysilane oligomer in the rust-preventing film forming agent, the higher the oligomer concentration, the higher the rust-preventing performance.
  • the metal surface rust preventive film forming treatment of the present invention is effective not only for galvanized metal bases but also for rust prevention of metals having a zinc layer formed by molten zinc and aluminum metal bases. all right.

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Abstract

La présente invention se rapporte à un procédé permettant de former un film de revêtement antirouille pour un substrat métallique dont la surface est sujette à l'oxydation lorsqu'il est soumis à une galvanisation ou analogue, et à un agent permettant de former un film de revêtement antirouille qui est utilisé dans le procédé. L'agent permettant de former un film de revêtement antirouille peut donner des propriétés antirouille satisfaisantes et un caractère décoratif satisfaisant tout en étant complètement dépourvu de chrome, et peut être traité à l'aide du même procédé par immersion et rotation que les traitements de chromatation classiques. L'agent permettant de former un film de revêtement antirouille est une solution alcoolique qui contient un oligomère de trialcoxysilane qui comporte la structure chimique [R1(OR2)3Si] en une quantité comprise entre 0,5 et 7 % en poids par rapport à la quantité totale de la solution. R1 est un groupe fonctionnel dans lequel l'extrémité est un groupe vinyle, un groupe époxy, un groupe styryle, un groupe méthacrylique, un groupe acrylique, un groupe amino, un groupe uréido, un groupe mercapto, un groupe sulfure ou un groupe isocyanate. R2 est un groupe alkyle ou un groupe alkylène. En outre, il est préférable d'incorporer dans l'agent une résine phénolique thermodurcissable, un composé de titane organique ou un composé d'aluminium organique.
PCT/JP2013/068378 2013-07-04 2013-07-04 Agent permettant de former un film de revêtement antirouille sur une surface métallique, et procédé permettant de former un film de revêtement antirouille pour un substrat métallique à l'aide de cet agent Ceased WO2015001645A1 (fr)

Priority Applications (1)

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PCT/JP2013/068378 WO2015001645A1 (fr) 2013-07-04 2013-07-04 Agent permettant de former un film de revêtement antirouille sur une surface métallique, et procédé permettant de former un film de revêtement antirouille pour un substrat métallique à l'aide de cet agent

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PCT/JP2013/068378 WO2015001645A1 (fr) 2013-07-04 2013-07-04 Agent permettant de former un film de revêtement antirouille sur une surface métallique, et procédé permettant de former un film de revêtement antirouille pour un substrat métallique à l'aide de cet agent

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108728746A (zh) * 2018-08-07 2018-11-02 重庆维富金属制品有限公司 一种新型镀锌钢板及其加工方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1095933A (ja) * 1996-09-26 1998-04-14 Japan Energy Corp コーティング組成物及びそれを塗布した金属材料
JPH11124544A (ja) * 1997-10-24 1999-05-11 Nippon Shokubai Co Ltd 金属表面処理用組成物および表面処理金属板
JP3414348B2 (ja) * 2000-01-07 2003-06-09 住友金属工業株式会社 耐黒変性に優れたクロムフリー処理亜鉛系めっき鋼板
JP2006192716A (ja) * 2005-01-13 2006-07-27 Nippon Steel Corp 表面処理金属，その製造方法および表面処理液
JP2008214744A (ja) * 2007-03-07 2008-09-18 Okada Chelate:Kk 亜鉛または亜鉛合金めっきされた金属表面上の黒色防錆処理液および黒色防錆皮膜処理方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1095933A (ja) * 1996-09-26 1998-04-14 Japan Energy Corp コーティング組成物及びそれを塗布した金属材料
JPH11124544A (ja) * 1997-10-24 1999-05-11 Nippon Shokubai Co Ltd 金属表面処理用組成物および表面処理金属板
JP3414348B2 (ja) * 2000-01-07 2003-06-09 住友金属工業株式会社 耐黒変性に優れたクロムフリー処理亜鉛系めっき鋼板
JP2006192716A (ja) * 2005-01-13 2006-07-27 Nippon Steel Corp 表面処理金属，その製造方法および表面処理液
JP2008214744A (ja) * 2007-03-07 2008-09-18 Okada Chelate:Kk 亜鉛または亜鉛合金めっきされた金属表面上の黒色防錆処理液および黒色防錆皮膜処理方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108728746A (zh) * 2018-08-07 2018-11-02 重庆维富金属制品有限公司 一种新型镀锌钢板及其加工方法

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