WO2015001645A1 - Agent for forming rust-preventing coating film on metal surface, and method for forming rust-preventing coating film for metal substrate by using same - Google Patents

Agent for forming rust-preventing coating film on metal surface, and method for forming rust-preventing coating film for metal substrate by using same 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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group
rust
rust preventive
preventive film
metal substrate
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PCT/JP2013/068378
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French (fr)
Japanese (ja)
Inventor
岡田和夫
東博通
荒武ひとみ
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株式会社オカダ・キレート
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Priority to PCT/JP2013/068378 priority Critical patent/WO2015001645A1/en
Publication of WO2015001645A1 publication Critical patent/WO2015001645A1/en

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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

Provided are a method for forming a rust-preventing coating film for a metal substrate the surface of which is prone to oxidation when subjected to galvanization or the like, and an agent for forming a rust-preventing coating film which is used in the method. The agent for forming a rust-preventing coating film can impart satisfactory rust prevention properties and decorativeness while being completely free of chromium, and can be treated using the same dip and spin process as conventional chromate treatments. The agent for forming rust-preventing coating film is an alcohol solution containing a trialkoxysilane oliogmer having the chemical structure [R1(OR2)3Si] at a quantity of 0.5-7 wt.% relative to the total quantity of the solution. R1 is a functional group in which the terminal is a vinyl group, epoxy group, styryl group, methacrylic group, acrylic group, amino group, ureido group, mercapto group, sulfide group or isocyanate group. R2 is an alkyl group or alkylene group. Furthermore, it is preferable to incorporate a thermosetting phenolic resin, an organic titanium compound or an organic aluminum compound in the agent.

Description

金属表面防錆皮膜形成剤及びこれを用いた金属基体の防錆皮膜形成方法Metal surface rust preventive film forming agent and metal base rust preventive film forming method using the same
　本発明は亜鉛または亜鉛合金めっきされた金属基体、溶融亜鉛により亜鉛層を設けた金属基体、あるいはアルミニウム基体などの、酸化しやすい金属基体の表面に直接、またはプレ皮膜処理後に、さらに防錆性能を向上させるための防錆皮膜を完全クロムフリーで生成させる金属表面防錆皮膜形成剤、及びこれを用いた金属基体に防錆皮膜を形成させる防錆皮膜形成方法に関する。 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. The present invention relates to 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.
　従来、亜鉛または亜鉛合金めっき金属基体の表面上に防錆性・装飾性を向上させるために、６価クロムを含んだ処理液で防錆皮膜を形成する方法、すなわちクロメート法が一般的に行われてきていた。クロメート法はコストが安価であることのみならず工程が非常にシンプルであるといった利点のために金属防錆の手段として世界的に普及していた。
　しかしながら、クロメート法で使用される６価クロムは人体および環境への影響が危惧され、日本、アメリカ、EU、中国等においては６価クロムについての使用禁止が打ち出された。
　国際的にも環境への配慮について、各国でも議論されている。国内でも家電製品、自動車の部品および建築用部品等においても６価クロムを使用した部品を製品中から排除されてきている。 Conventionally, in order to improve rust prevention and decoration on the surface of a zinc or zinc alloy plated metal substrate, a method of forming a rust prevention film with a treatment solution containing hexavalent chromium, that is, a chromate method has been generally performed. I have been. 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.
However, 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.
Internationally, environmental considerations are also being discussed in various countries. Even in Japan, parts using hexavalent chromium have been excluded from home appliances, automobile parts and building parts.
　クロメート法の代替技術として３価クロムを含んだ防錆皮膜を生成する手法があげられる。しかし原材料３価クロム塩中の不純物として存在する６価クロムの除去が完全にはできにくいこと、および生成された防錆皮膜中の３価クロム化合物が６価クロム化合物へ自然酸化することなどが明らかになった。 An alternative to the chromate method is a method for producing a rust-preventing film containing trivalent chromium. However, it is difficult to completely remove hexavalent chromium present as an impurity in the raw material trivalent chromium salt, and the trivalent chromium compound in the produced anticorrosive film is naturally oxidized to a hexavalent chromium compound. It was revealed.
　そこで３価クロムを含んだ防錆皮膜処理された製品では、溶出試験を行い６価クロムの定量測定した後に比較的６価クロムの溶出量が少ない製品のみを市場に流通させているところが多い。
　しかしながら自然環境への汚染問題を論じるにあたっては、実際の使用のみならず、廃棄処分された後のことまで考慮しなければならない。この点からは、３価クロムを含んだ防錆処理方法は、製品が様々な環境下におかれる可能性を考慮すると、完全な６価クロムフリーを達成することはできないといえる。このため、近い将来３価クロムについても規制の対象となる可能性があることは否めないといった問題がある。 Therefore, in many products treated with a rust-preventive film containing trivalent chromium, only products with relatively little hexavalent chromium elution are distributed in the market after elution testing and quantitative measurement of hexavalent chromium.
However, when discussing the problem of pollution to the natural environment, it is necessary to consider not only actual use but also after disposal. From this point, it can be said that the antirust treatment method containing trivalent chromium cannot achieve complete hexavalent chromium free in consideration of the possibility that the product is placed in various environments. For this reason, there is a problem that it cannot be denied that trivalent chromium may be subject to regulation in the near future.
　また、３価クロムの防錆性能を向上させるためにコバルトイオンを含んだ３価クロムの防錆処理液が一般に販売されている。しかし、最近の研究によりコバルトイオンが３価クロムを６価クロムに酸化させる要因と考えられている。しかも最近のヨーロッパにおけるREACH規制でも、SVHC（要監視物質）としてコバルト塩（硫酸コバルト、硝酸コバルト、炭酸コバルト、酢酸コバルトおよび塩化コバルト）の問題もある。 In addition, in order to improve the anticorrosive performance of trivalent chromium, a trivalent chromium antirust treatment solution containing cobalt ions is generally sold. However, recent research suggests that cobalt ions oxidize trivalent chromium to hexavalent chromium. In addition, recent REACH regulations in Europe also have problems with cobalt salts (cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt acetate, and cobalt chloride) as SVHC (monitoring substances).
　クロムを全く使用しない表面処理方法、いわゆる完全クロムフリー処理方法としては、例えば、リン酸塩皮膜（特許文献１）、しゅう酸塩皮膜（特許文献２）、電解を用いた金属塩による皮膜（特許文献３）、有機樹脂皮膜、タンニン酸皮膜の上に金属イオンの第２防錆皮膜（特許文献４）の提案がなされているが、耐食性に不十分な点が多かったり、処理温度が高かったり、プロセスが複雑で従来のクロメートの装置では利用できにくいといった等の問題点が多く実用化に至っていないのが多い。 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. However, 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.
　このようにめっきされた亜鉛金属上に他の金属酸化物を生成させることで、防錆皮膜を形成させることで、完全クロムフリーで防錆性・装飾性を向上させる方法が種々提案されているが、酸化皮膜だけでは防錆皮膜の厚みを確保することも難しく、防錆皮膜の金属成分が亜鉛よりもイオン化傾向の低い金属では逆に亜鉛を腐食して白錆を生成させやすい。このような理由によって、酸化皮膜単層のみでは十分な耐食性を得ることは難しい。このため、酸化皮膜を付与後、さらに防錆処理を行わなければならないのが実情である。 Various methods for improving rust prevention and decorativeness with complete chromium free by forming other metal oxides on zinc metal plated in this way to form a rust prevention film have been proposed. However, it is difficult to ensure the thickness of the rust preventive film only with the oxide film, and when the metal component of the rust preventive film has a lower ionization tendency than zinc, the zinc is easily corroded to easily generate white rust. For these reasons, it is difficult to obtain sufficient corrosion resistance with only a single oxide film layer. For this reason, after giving an oxide film, it is the actual condition that you have to perform a rust prevention process further.
　他方、防錆皮膜形成剤としてシランカップリング剤を用いる表面処理方法としては、エポキシ基含有シランカップリング剤にチオール化合物を含んだ水系コーティング剤の技術が開示されている（特許文献５）。しかしながら、特許文献５の技術では、防錆皮膜量が0.2（g／ｍ2）であるものでも十分な防錆性能が発揮されていない。 On the other hand, 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.
　シランカップリング剤とヒドラジン誘導体の水溶性樹脂等およびリン酸および／またはヘキサフルオロ金属酸を含有する表面処理剤を用いた塗布法も開示されているが（特許文献６）、この処理法では140℃で加熱・乾燥しなければならない。 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 ℃.
　従来のクロメート法を、新たなクロムフリーの仕上げ工程に、できるだけコストをかけずに移行させるためには、従来のクロメート法、または３価クロム処理液法で使用されてきた設備をそのまま使用し、設備に対するイニシァルコストを抑えることが求められる。具体的には、クロメート法で行われてきたような、クロメート処理液に亜鉛または亜鉛合金めっきした基体を浸漬させ、その後めっきされた基体を取り出して、余分なクロメート液を遠心力で振り落とす、ディップアンドスピン法（或いは「ディップスピン法」）の設備がそのまま使用できることが求められる。 In order to transfer the conventional chromate method to the new chromium-free finishing process with as little cost as possible, 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.
　この点特許文献７では、テトラアルコキシシランのオリゴマーにチタン酸化物を加えたアルコール系表面処理剤を用いれば、ディップアンドスピン法でクロムフリーの防錆皮膜処理が可能とされている。
　特許文献７で用いられているテトラアルコキシシランのアルコール系溶液では、アルコキシシラン分子内のアルコール基を脱アルコールして、シラン原子同士が酸素原子を仲立ちとして結合の鎖を立体的に伸ばすことにより防錆力のある皮膜が形成される（ゾルーゲル反応）。 In this regard, in 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.
In the alcoholic solution of tetraalkoxysilane used in Patent Document 7, 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).
　しかしながら、その反応を短時間で行わせるためには、適切な触媒の存在下においても100℃以上の温度をかけてやる必要があることが一般的である。また、防錆される亜鉛または亜鉛合金めっきされた基体上に有効な密着性の優れた防錆皮膜を形成させるためには亜鉛と珪素原子の結合が必要であり、その仲立ちとしては酸素原子が必要である（Zn－O－Si結合）。酸素原子はテトラアルコキシシラン中に存在し、脱アルコール反応を経て得られるものであり、その脱アルコール反応を促進するためにも加熱することが必須条件となる。
　このため、文献７の表面処理剤によるディップアンドスピン法による防錆皮膜処理においても、該ディップアンドスピン法のみで防錆皮膜形成処理が完了するのではなく、その後150～180℃で10～20分の焼き付けが必要とされ、そのような焼き付け設備の導入が必要になってしまうという問題がある。 However, in order to perform the reaction in a short time, it is generally necessary to apply a temperature of 100 ° C. or higher even in the presence of an appropriate catalyst. In addition, in order to form an effective anti-corrosion film on zinc or zinc alloy-plated substrate to be rust-proof, it is necessary to bond zinc and silicon atoms. Necessary (Zn-O-Si bond). The oxygen atom is present in the tetraalkoxysilane and is obtained through a dealcoholization reaction, and heating is an essential condition for promoting the dealcoholization reaction.
For this reason, even in the rust preventive film treatment by the dip and spin method using the surface treatment agent described in Document 7, the rust preventive film formation process is not completed by the dip and spin method alone, and thereafter 10 to 20 at 150 to 180 ° C. There is a problem that it is necessary to install such a baking equipment.
　加えてテトラアルコキシシランを用いた防錆皮膜は通常その効果が発揮できるようにするためには、少なくとも数μmの膜厚が必要である。しかも、その膜厚をコントロールすることは難しい。このため小径のねじ類のねじ部の径が大きくなり、またそのピッチ径が変化してねじとしての適合性が劣る。すなわち、ねじとナットとの勘合性に支障をきたす。従って、小径のねじ類、導通性を要求される製品には適さないという問題もあった。さらにこの膜厚が数μm以上になる場合には通電性に支障をきたすので、通電性が求められる部材への適用が難しいといった問題もあった。 In addition, a rust preventive film using tetraalkoxysilane usually requires a film thickness of at least several μm 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 μm 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.
　金属アルミニウムの表面に防錆処理をすることがある。例えば特許文献８では、ポリオレフィン樹脂、シランカップリング剤などの添加、トルエンなどの有機系溶剤、イミダゾール化合物などを含有するアルミニウム部材用防錆プライマーが開示されているが、かかる防錆プライマーでも、乾燥に１５０℃で３０分程度の焼付け処理を必要がある。 ¡Anti-rust treatment may be applied to the surface of metallic aluminum. For example, 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.
　また金属製品、セラミック製品、ガラス製品、プラスチック成形品、木材製品等の材料の表面保護と美粧性を目的として、オルガノアルコキシシラン、特定のシリル基含有樹脂、特定のシランカップリング剤、該シランカップリング剤、有機ホウ素化合物を含有する被膜形成用組成物も開示されている（特許文献９）。しかし、被膜形成用組成物は該セロソルブと水系の溶媒を用いており、また膜厚も３０μｍ前後と厚い。 In addition, for the purpose of surface protection and cosmetics for materials such as metal products, ceramic products, glass products, plastic molded products, and wood products, organoalkoxysilanes, specific silyl group-containing resins, specific silane coupling agents, and silane cups A film forming composition containing a ring agent and an organic boron compound is also disclosed (Patent Document 9). However, the film-forming composition uses the cellosolve and an aqueous solvent, and the film thickness is as thick as about 30 μm.
特開２００２－１２９８１JP 2002-12981 A 特開２００１－２４７９７７JP 2001-247777 A 特開２０００－２９０７８２JP 2000-290782 A 特開２００１－９８３９２JP 2001-98392 A 特開２０１１－１５７６００JP2011-157600 特開２００５－２０６９４７JP 2005-206947 A 特開２００６－２８５４７JP 2006-28547 A 特開２０１１－７４２５１JP2011-74251 特開平１０－１９５３８１JP-A-10-195381
　上記現状を鑑みて、本発明が解決しようとする課題は、金属表面防錆皮膜形成剤及びこれを用いた金属基体に対する防錆皮膜形成方法あって、完全クロムフリーでありながら十分な防錆性・装飾性を付与でき、その工程が従来のクロメート処理と同じディップアンドスピン法で処理可能で、しかもその後に焼き付け工程等も不要な防錆皮膜形成方法と、かかる皮膜形成工程を可能にするための防錆皮膜形成剤を提供することを目的とする。 In view of the above-mentioned present situation, 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・ To provide decorativeness, 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.
　本発明の金属表面防錆皮膜形成剤は、〔Ｒ１（ＯＲ２）３Ｓｉ〕の化学構造を持つトリアルコキシシラン（R１は、その末端がビニル基、エポキシ基、スチリル基、メタクリル基、アクリル基、アミノ基、ウレイド基、メルカプト基、スルフィド基、イソシアネート基である官能基、R２はアルキル基またはアルキレン基）のオリゴマーを溶液全量に対して0.5～７重量％含むアルコール溶液であることを最も主要な特徴とする。 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.
　また本発明の防錆皮膜形成方法は、金属基体（或いはプレ皮膜処理された金属基体）に対して、前記防錆皮膜形成剤を用いてディップアンドスピン法にて処理した後、該金属基体を常温にて乾燥させることにより、該金属基体表面に防錆皮膜を生成させる工程を有することを最も主要な特徴とする。 In the rust preventive film forming method of the present invention, 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.
　本発明の金属表面防錆皮膜形成剤及び防錆皮膜形成方法は、完全クロムフリーの防錆皮膜形成剤及び防錆皮膜処理でありながら、金属基体に十分な防錆性を付与することができる。そしてその防錆皮膜は十分に薄いので小径のねじ類や導通性を要求される製品に対しても好適に使用できる。 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.
　本発明の防錆皮膜形成方法は、クロメート処理同様のディップアンドスピン方法で、かつその後の乾燥工程も常温で可能であるので、従来のクロメート処理設備がそのまま使用でき、完全クロムフリー処理工程へ移行するための設備導入のイニシャルコストを抑えることが可能である。 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.
　化学反応を伴う酸化皮膜形成処理においては、温度管理・液濃度管理・浸漬時間管理およびpＨ管理等の専門的な工程管理および複雑な設備を要する。しかし本発明の防錆皮膜形成方法においては、ほとんど工程管理をする必要もなく、装置もディップ槽が１つあればよいのでこの点からもコストも低減できる。したがって経済性に非常に優れた完全クロムフリーの工程が可能である。
　さらに、排水処理の必要がないので、この点においても経済性が優れている。 In an oxide film forming process accompanied by a chemical reaction, specialized process management and complicated equipment such as temperature management, liquid concentration management, immersion time management and pH management are required. However, in the method of forming a rust preventive film of the present invention, there is almost no need for process control, and the apparatus and the dip tank need only be one, so that the cost can be reduced from this point. Therefore, a completely chromium-free process that is very economical is possible.
Furthermore, since there is no need for wastewater treatment, this point is also economical.
〔金属表面防錆皮膜形成剤〕
　本発明の金属表面防錆皮膜形成剤（以下、単に「防錆皮膜形成剤」と称する。）に含まれる成分について、以下説明する。 [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.
（トリアルコキシシランオリゴマー）
　本発明の防錆皮膜形成剤には〔Ｒ１（ＯＲ２）３Ｓｉ〕の化学構造を持つトリアルコキシシランのオリゴマー官能基R１を有するトリアルコキシシランオリゴマーが含まれる。
　ここで前記化学構造式中のR１は、その末端がビニル基、エポキシ基、スチリル基、メタクリル基、アクリル基、アミノ基、ウレイド基、メルカプト基、スルフィド基、イソシアネート基である官能基を挙げることができる。なかでもその末端がメタクリル基、アクリル基、アミノ基、ウレイド基、メルカプト基である官能基がより好ましく、その末端がメルカプト基である官能基が最も好ましい。前記化学構造式中のR２はアルキル基またはアルキレン基であり、その炭素数は１～３が好ましい。 (Trialkoxysilane oligomer)
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].
Here, 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. Of these, a functional group whose terminal is a methacryl group, an acrylic group, an amino group, a ureido group or a mercapto group is more preferable, and a functional group whose terminal is a mercapto group is most preferable. R 2 in the chemical structural formula is an alkyl group or an alkylene group, and preferably has 1 to 3 carbon atoms.
　かかるトリアルコキシシランオリゴマーの具体例を挙げると、
官能基R１末端がビニル基のものとして、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルプロピオキシシラン、
官能基R１末端がエポキシ基のものとして、2-（3,4エポキシシクロヘキシル）エチルトリメトキシシラン、2-（3,4エポキシシクロヘキシル）エチルトリエトキシシラン、2-（3,4エポキシシクロヘキシル）プロポキシシラン、３－グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルトリプロポキシシラン、
官能基R１末端がスチリル基のものとして、ｐ-スチリルトリメトキシシラン、ｐ-スチリルトリエトキシシラン、ｐ-スチリルトリプロポキシシラン、
官能基R１末端がメタクリル基のものとして、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロプロピルトリエトキシシラン、3-メタクリロキシプロピルトリプロピオキシシラン、
官能基R１末端がアクリル基のものとして、3-アクリロトリメトキシシラン、3-アクリロトリエトキシシラン、3-アクリロトリプロピオキシシラン、
官能基R１末端がアミノ基のものとして、Ｎ-2-（アミノエチル）-3-アミノプロピルトリメトキシシラン、Ｎ-2-（アミノエチル）-3-アミノプロピルトリエトキシシラン、Ｎ-2-（アミノエチル）-3-アミノプロピルトリプロピオキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリプロピオキシシラン、
官能基R１末端がウレイド基のものとして、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリメトキシシラン、
官能基R１末端がメルカプト基のものとして、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、
官能基R１末端がスルフィド基のものとして、ビス（トリメトキシシリルプロピル）テトラスルフィド、ビス（トリエトキシシリルプロピル）テトラスルフィド、
官能基R１末端がイソシアネート基のものとして、3-イソシアネートトリメトキシシラン、3-イソシアネートトリエトキシシラン、3-イソシアネートトリプロピオキシシランを挙げることができるが、これらに限られるものではない。 Specific examples of such trialkoxysilane oligomers are as follows:
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, 3-methacryloxypropyltrimethoxysilane, 3-methacrylopropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane,
Functional group R As one end of which is an acrylic group, 3-acrylotrimethoxysilane, 3-acrylotriethoxysilane, 3-acrylotripropoxysilane,
Functional group R 1- terminal amino group is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (Aminoethyl) -3-aminopropyltripropoxyoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane,
Functional group R As one having a ureido group at one end, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane,
Functional group R As one having a mercapto group at one end, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane,
Functional group R As one having a sulfide group at one end, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide,
Examples of the functional group R 1 terminal having an isocyanate group include, but are not limited to, 3-isocyanate trimethoxysilane, 3-isocyanate triethoxysilane, and 3-isocyanate tripropoxyoxysilane.
　前記化学構造を持つアルコキシシランのオリゴマーによる防錆皮膜は薄膜で十分な防錆性能を発揮する。このためその濃度は、アルコール溶液全量に対して0.5～７重量％とすることができる。0.5重量％以下の濃度では防錆効果がなく、7重量％以上では経済性が悪く膜厚も厚くなる。 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.
（有機チタンまたは有機アルミニウム）
　本発明の防錆皮膜形成剤には、さらに二次アルコキシシランオリゴマー化触媒を含有させることが好ましい。二次アルコキシシランオリゴマー化触媒は、防錆しようとする金属基体に形成される一次アルコキシシランオリゴマー防錆皮膜を、常温乾燥下で更なるアルコキシシランオリゴマー分子間の脱アルコール反応を経て、より防錆性能が上昇する高分子化を促進させる。二次アルコキシシランオリゴマー化触媒としては、有機シチタンまたは有機アルミニウムが好ましい。二次アルコキシシランオリゴマー化触媒の添加量としては、含有しているアルコキシシランオリゴマーの重量に対して0.2～5重量％の範囲で添加することが好ましい。二次アルコキシシランオリゴマー化触の金属中に化合している有機物はアルコキシであり、メトキシまたはエトキシが好ましい。具体的には、テトラメトキシチタン、テトラエトキシチタン、トリメトキシアルミニウムおよびトリエトキシアルミニウム等を挙げることができる。 (Organic titanium or organoaluminum)
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. As the secondary alkoxysilane oligomerization catalyst, 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.
（熱硬化性フェノール系樹脂）
　本発明における完全クロムフリー防錆皮膜形成剤の粘度を調節し、金属基体への密着性を向上させ、金属製品の摩擦抵抗を調節するための有機樹脂成分としてはアルコールに可溶のワックス成分を含有している立体構造を持つアルキド樹脂やフェノール樹脂を用いることができる。とくに本発明では熱硬化性フェノール系樹脂を用いることが好適であることが分かった。なかでもタンニン酸の重合度を変えた樹脂（以下「変性タンニン」と称す。）が好ましい。 (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.
　変性タンニンとしてはハイタンニンまたは特製タンニン（大日本住友製薬製）にエチルグリコールと反応させタンニン成分を縮合させたもの（（株）オカダ・キレート社　NCR-Wの主成分）を用いる。樹脂の好ましい濃度としては、防錆皮膜処理後の望まれる表面状態によって変動するが、アルコール溶液全量に対して、２～１５重量％が好ましく、さらには１～１０重量％がより好ましい。 As the 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.
（アルコール溶媒）
　本発明の防錆皮膜形成剤には、溶媒としてアルコールが用いられる。アルコール溶媒としては低沸点のエチルアルコール、イソプロピルアルコールまたはノルマルプロピルアルコールが好ましい。 (Alcohol solvent)
In the rust preventive film forming agent of the present invention, alcohol is used as a solvent. As the alcohol solvent, low boiling point ethyl alcohol, isopropyl alcohol or normal propyl alcohol is preferred.
　アルコキシシランオリゴマーはある程度の粘性をもつ化合物である。粘性を有する化合物を含む防錆皮膜を短時間にて乾燥させるためには熱源が必要となる。そこで、低沸点アルコール中のアルコキシシランオリゴマーの濃度を低減させることで、自然乾燥においても金属基体表面の防錆皮膜が短時間で硬化させることが可能となる。 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.
　本発明におけるアルコキシシランオリゴマーのようなシランカップリング剤は有機系溶媒および水溶媒の両者に親和性があるため、油性塗料にも水性塗料にも、有益な防錆剤として用いられることが多い。近年においては環境への影響が少ない水系塗料の開発が盛んである。しかし、水自身はその水分子間での水素結合が強いことが、自ずと表面張力を生じ、塗布工法には適するが、ディップアンドスピン工法には液溜りなどの種々の問題が生じる。 Since 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. In recent years, the development of water-based paints that have little impact on the environment has been active. However, 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.
　水系の防錆皮膜形成剤においては、表面張力が強く働くため金属基体表面に防錆皮膜を形成させるために、塗布工法には適するが、従来行われてきているクロメート法で用いられているディップアンドスピン工法においては液溜りを効率的に除去することが難しく、アルコール溶媒を用いたアルコール系防錆皮膜形成剤が最適である。アルコキシシランオリゴマーの濃度を低減させることと、アルコール溶媒の使用によりこの工程は自然乾燥での適応可能となり、工程の簡素化が図れるとともに経済性にも優れた完全クロムフリーのシステムが構築できる。 In water-based anticorrosive film forming agents, the surface tension works strongly, so it is suitable for the coating method to form an antirust film on the metal substrate surface, but it is a dip used in the conventional chromate method. In the Andspin method, it is difficult to remove the liquid pool efficiently, and an alcohol-based rust preventive film forming agent using an alcohol solvent is optimal. By reducing the concentration of the alkoxysilane oligomer and using an alcohol solvent, this process can be adapted to natural drying, and the process can be simplified and a complete chromium-free system excellent in economy can be constructed.
（粘度調整剤）
　本発明の完全クロムフリー防錆皮膜形成剤の白化防止成分および粘度調整成分としては、一般の塗料に用いられている２-n-ブトキシエタノール（n-ブチルセロソルブ）または２-tert-ブトキシエタノール（tert-ブチルセロソルブ）が好ましい。アルコール溶液全量に対する濃度としては５～１５重量％が好ましい。 (Viscosity modifier)
As the whitening prevention component and viscosity adjusting component of the complete chromium-free rust preventive film forming agent of the present invention, 2-n-butoxyethanol (n-butylcellosolve) or 2-tert-butoxyethanol (tert -Butyl cellosolve) is preferred. The concentration with respect to the total amount of the alcohol solution is preferably 5 to 15% by weight.
〔金属基体の防錆皮膜形成方法〕
　以上、本発明の防錆皮膜処理剤について説明したが、以下では該処理剤を用いた金属基体の防錆皮膜形成方法（以下、単に「防錆皮膜形成方法」と称する。）について説明する。 [Method of forming a rust preventive film on a metal substrate]
The rust preventive film treatment agent of the present invention has been described above. Hereinafter, a method for forming a rust preventive film on a metal substrate using the treatment agent (hereinafter simply referred to as “rust preventive film formation method”) will be described.
（金属基体）
　本発明の防錆皮膜形成方法で処理を受ける金属基体は、その表面が金属成分である基体であれば足り、特段制限されない。ただし本発明の防錆皮膜形成方法は、新たな設備導入のイニシァルコストを抑えつつクロメート処理法からの速やかに移行できる処理方法を目指して開発されたものである。したがって、本発明の処理方法で主に処理されるのは、その表面に亜鉛めっきまたは亜鉛合金めっきされた金属基体である。さらには亜鉛めっきまたは亜鉛合金めっきされた金属基体に予備的な防錆処理（プレ皮膜処理）された金属基体に対しても、高い防錆効果を発揮する防錆皮膜を形成する。
　加えて、本発明の防錆皮膜形成方法は、その表面に溶融亜鉛により亜鉛層を設けた基体に対しても高い防錆効果を発揮する防錆皮膜を形成する。さらにはアルミニウム基体などの表面が酸化しやすい金属から形成される金属基体に対しても高い防錆効果を発揮する防錆皮膜を形成する。 (Metal base)
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. However, 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. Furthermore, 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.
In addition, 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.
（工程フローチャート）
　防錆皮膜形成方法における簡単な工程フローチャートを示すと以下のようになる。
Ａ．金属基体に直接防錆皮膜形成剤で処理する場合
Figure JPOXMLDOC01-appb-T000001
 Ｂ．金属基体にプレ皮膜処理し、その後防錆皮膜形成剤で処理する場合
Figure JPOXMLDOC01-appb-T000002
 (Process flowchart)
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
Figure JPOXMLDOC01-appb-T000001
 B. When pre-coating on a metal substrate and then treating with a rust preventive film former
Figure JPOXMLDOC01-appb-T000002
（プレ皮膜処理）
　本発明の防錆皮膜処理方法では、Ａの工程のように金属基体に、直接本発明の防錆皮膜形成剤で防錆皮膜形成させることもできるが、Ｂの工程のように、一旦プレ皮膜処理を行った後に本発明の防錆皮膜形成剤で防錆皮膜形成させることもできる。プレ皮膜処理としては、主に白色プレ皮膜形成処理と黒色プレ皮膜形成処理を挙げることができる。なおこれらのプレ皮膜処理工程も完全クロムフリー工程である。 (Pre-film treatment)
In the rust preventive film treatment method of the present invention, 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. Examples of 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.
（白色プレ皮膜形成処理）
　白色プレ皮膜形成処理としてはポリフェノールのような熱硬化性樹脂でプレ皮膜を形成させることが好ましい。具体的にはポリフェノールとして変性タンニンを用いて、エチルグリコールと反応させタンニン成分を縮合させたものを処理液として白色プレ皮膜形成処理することができる。変性タンニンとしてはハイタンニンまたは特製タンニン（大日本住友製薬製）を挙げることができる。またかかる白色プレ皮膜形成処理を行うプレ皮膜処理液としては（株）オカダ・キレート社のNCR-Wが市販されている。 (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. Specifically, using 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. Examples of the modified tannin include high tannin and special tannin (manufactured by Dainippon Sumitomo Pharma Co., Ltd.). As a pre-film treatment solution for performing such a white pre-film formation treatment, NCR-W manufactured by Okada Chelate is commercially available.
（黒色プレ皮膜形成処理）
　黒色プレ皮膜形成処理としては、アンチモン化合物及びマンガン化合物を含んだ亜鉛めっき用黒色反応水溶液中で生成される1μm前後のプレ皮膜を乾燥して得る工程であることが好ましい。かかる黒色プレ皮膜形成処理を行うプレ皮膜処理液としては（株）オカダ・キレート社製のNCR-Bが市販されている。 (Black pre-film formation treatment)
The black pre-coating forming treatment is preferably a step obtained by drying a pre-coating of about 1 μm 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.
　以下、実施例および比較例により本発明についてさらに詳しく説明するが、本発明はこれら実施例の様態に限られるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the modes of these Examples.
　〔実施例１〕
　３－グリコキシプロピルトリエトキシシランオリゴマー（平均分子量２，０００～５，０００）の２．３７５重量％、有機樹脂として変性タンニン酸（（株）オカダ・キレート社製　ノンクロム反応剤　NCR-W）の６．０重量％、２－n－ブトキシエタノールの１０．０重量％およびテトラエトキシチタンの０．１２５重量％をイソプロピルアルコールに溶解させて防錆皮膜形成剤（完全クロムフリー防錆皮膜形成剤）を調製した。
ＳＷＲＣＨ（冷間圧造用炭素鋼線材）材質の十字穴付きなべ頭小ねじ（Ｍ６Ｘ２mm）に、めっき膜厚６～１４μmの亜鉛めっきを施したものを試験片とし、この試験片を前記防錆皮膜形成剤（２５℃）に５秒間浸漬し、その後室内（２０℃、相対湿度６０％）で２分放置して、防錆した試験片を得た。 [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.
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 6-14μm. 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.
　前記防錆皮膜処理で得られた完全クロムフリーの防錆処理した試験片の防錆力をＪＩＳ－２３７１に準拠した塩水噴霧試験機（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 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.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　〔実施例２～４〕
　実施例１と同様の試験片に実施例２，３においては表３に示した濃度にて３－メルカプトプロピルトリエトキシシランオリゴマーのそれぞれ防錆皮膜形成剤を作製し、実施例１と同様の防錆法にて、防錆した試験片を得た。
実施例４においても同様の試験片に表１に示した濃度にて３－アミノプロピルトリエトキシシランオリゴマーの防錆皮膜形成剤を作製し、実施例１と同様の防錆法にて、防錆した試験片を得た。
それぞれの試験片についてＪＩＳ－２３７１に準拠した塩水噴霧試験機（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 [Examples 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.
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.
　〔実施例５～７〕
　亜鉛めっきを施した試験片に対して、防錆皮膜処理を行う前にプレ皮膜形成処理を行った。プレ皮膜形成処理としては、商品名「NCR-W」（（株）オカダ・キレート社製）の変性タンニン酸を固体タンニン濃度として１．８ｇ／Lの水溶液になるように調整した白色処理剤を用いた白色プレ皮膜形成処理を行った。
実施例１と同様の試験片を用い、希硝酸（pＨ１．７）液に１０秒浸漬したのち、水洗し、前記白色処理剤（pＨ５．５、液温２５℃）に６０秒浸漬した後、水洗し、乾燥させて白色プレ皮膜が形成された試験片を得た。
実施例５においては上記試験片に実施例１で示した３－グリコキシプロピルトリエトキシシランオリゴマーの防錆皮膜形成剤にて同様の処理を行い、試験片を得た。
実施例６においては実施例２で示した３－メルカプトプロピルトリエトキシシランオリゴマーと同じ防錆皮膜形成剤にて同様の処理を行い、試験片を得た。
実施例７においては実施例２で用いた３－メルカプトプロピルトリエトキシシランオリゴマーの2分の１の濃度の防錆皮膜形剤を作製して実施例２と同様の処理を行い、試験片を得た。
それぞれの試験片についてＪＩＳ－２３７１に準拠した塩水噴霧試験機（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 [Examples 5 to 7]
A pre-film formation treatment was performed on the galvanized test piece before the rust-proof film treatment. As the pre-film forming 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.
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.
In Example 5, 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.
In 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.
In 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.
　〔実施例８～１１〕
　亜鉛めっきを施した試験片に対して、防錆皮膜処理を行う前にプレ皮膜処理を行った。プレ皮膜処理としては、商品名「NCR-B」（（株）オカダ・キレート社製）を濃度として１５倍希釈水溶液になるように調整した黒色処理剤を用いた黒色プレ皮膜形成処理を行った。
実施例１と同様の試験片を用い、希硝酸（pＨ１．７）液に１０秒浸漬したのち、水洗し、前記黒色処理剤（pＨ４．０、液温２５℃）に４０秒浸漬した後、水洗し、乾燥させて黒色プレ皮膜が形成された試験片を得た。
実施例８においては上記試験片に実施例１で示した３－グリコキシプロピルトリエトキシシランオリゴマーの防錆皮膜形成剤にて同様の処理を行い、試験片を得た。
実施例９においては実施例２で用いた３－メルカプトプロピルトリエトキシシランオリゴマーの防錆皮膜形成剤にて同様の処理を行い、試験片を得た。
実施例１０においては実施例２で用いた３－メルカプトプロピルトリエトキシシランオリゴマーの2分の１の濃度の防錆皮膜形剤を作製して実施例２と同様の処理を行い、試験片を得た。
実施例１１においては実施例２で用いた３－メルカプトプロピルトリエトキシシランオリゴマーの2．５分の１の濃度の防錆皮膜形剤を作製して実施例２と同様の処理を行い、試験片を得た。
それぞれの試験片についてＪＩＳ－２３７１に準拠した塩水噴霧試験機（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 [Examples 8 to 11]
A pre-coating treatment was performed on the galvanized test piece before the anti-rust coating treatment. As the pre-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.). .
Using the same test piece as in Example 1, after being immersed in dilute nitric acid (pH 1.7) for 10 seconds, washed with water and immersed in the black treatment agent (pH 4.0, liquid temperature 25 ° C.) for 40 seconds, The sample was washed with water and dried to obtain a black pre-coated film.
In 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.
In 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.
In 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.
In 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.
　〔実施例１２〕
　鉄素材上に溶融亜鉛にて被服された試験片に実施例６と同様の防錆皮膜形処理を行い、試験片を得た。
実施例１２の試験片についてＪＩＳ－２３７１に準拠した（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 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.
　〔実施例１３〕
　鉄片表面に溶融亜鉛にて亜鉛層を設けた試験片に、実施例９と同様の防錆皮膜形処理を行い、試験片を得た。
実施例１３の試験片についてＪＩＳ－２３７１に準拠した（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 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.
〔実施例１４〕
　アルミニウム（Ａ２０１４）の試験片に、実施例２で示した濃度の３－メルカプトプロピルトリエトキシシランオリゴマーの防錆皮膜形処理剤を作製し、実施例１と同様の防錆皮膜形処理方法にて、防錆した試験片を得た。
実施例１４の試験片についてＪＩＳ－２３７１に準拠した（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 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.
　〔実施例１５〕
　実施例１で示した、同じ試験片の上に直接、実施例１と比較して有機樹脂が含まれていない防錆皮膜形成剤を作製して実施例１と同様の処理を行い、試験片を得た。
それぞれの試験片についてＪＩＳ－２３７１に準拠した塩水噴霧試験機（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 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.
　〔実施例１６〕
　実施例１で示した、同じ試験片の上に直接、実施例１と比較して有機金属触媒のみが含まれていない防錆皮膜形成剤を作製して実施例１と同様の処理を行い、試験片を得た。
それぞれの試験片についてＪＩＳ－２３７１に準拠した塩水噴霧試験機（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 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.
　〔比較例１〕
　実施例１で示した、同じ試験片の上に直接、実施例１と比較してアルコキシシランオリゴマーおよびそのオリゴマー化触媒が含まれていない防錆皮膜形成剤を作製して実施例１と同様の処理を行い、試験片を得た。
それぞれの試験片についてＪＩＳ－２３７１に準拠した塩水噴霧試験機（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 [Comparative 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.
　〔比較例２〕
　鉄片表面に溶融亜鉛にて亜鉛層を設けた試験片に、防錆処理を行わずＪＩＳ－２３７１に準拠した（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 [Comparative Example 2]
A test piece in which a zinc layer was provided with molten zinc on the surface of the iron piece was not subjected to rust prevention treatment and 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.
　〔比較例３〕
　アルミニウム（Ａ２０１４）の試験片に、防錆処理を行わずＪＩＳ－２３７１に準拠した（スガ試験機株式会社製　ＳＴＰ－９０）にて試験を行った。評価の方法としては、試験片に白錆および赤錆が５％を超えるまでの時間を調べることによって、耐食性を判断した。 [Comparative Example 3]
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. 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.
　実施例１～１６および比較例１～３の試験から次のようなことがいえる。
（１）本発明の防錆皮膜形成剤には〔Ｒ１（ＯＲ２）３Ｓｉ〕で表わされるトリアルコキシシランのオリゴマーの存在が必須であり、触媒および／または有機樹脂も防錆性能を維持するためにはそれぞれ含有させたほうが好ましいことがわかった。
（２）トリアルコキシシランオリゴマーに付加されている種々の有機官能基の比較試験により、亜鉛めっきされた表面に直接防錆皮膜処理された試験片については
　　　メルカプト基＞エポキシ基＞アミノ基の順で、その耐食性に違いが見られた。
（３）プレ皮膜処理を付加した後、防錆皮膜処理された試験片の耐食性が優れていたが、亜鉛めっきされた試験片表面に直接、本発明の防錆皮膜形成剤で処理された試験片でも、一般的に求められる耐食性（例えば；SST白錆時間７２時間以上）はクリアーできる。また、プレ防錆皮膜としてはNCR-B（黒色プレ皮膜形成処理）＞NCR-W（白色プレ皮膜形成処理）の順序にて防錆性能の向上が見られた。
（４）アルコキシシランオリゴマーの防錆皮膜形成剤中の濃度変化についてはオリゴマー濃度が高いほど、高い防錆性能が示された。１．００％～１．２５％の濃度でも十分な防錆性能があることもわかった。
（５）本発明の金属表面防錆皮膜形成処理は、亜鉛めっきされた金属基体だけでなく、溶融亜鉛によって亜鉛層が形成された金属やおよびアルミニウム金属基体の防錆にも効果があることがわかった。

  From the tests of Examples 1 to 16 and Comparative Examples 1 to 3, the following can be said.
(1) The presence of a trialkoxysilane oligomer represented by [R 1 (OR 2 ) 3 Si] is essential for the rust preventive film forming agent of the present invention, and the catalyst and / or organic resin also maintains the rust preventive performance. In order to achieve this, it has been found that each of them is preferably contained.
(2) According to the comparison test of various organic functional groups added to the trialkoxysilane oligomer, the test pieces treated with a rust preventive film directly on the galvanized surface are in the order of mercapto group> epoxy group> amino group. There was a difference in their corrosion resistance.
(3) The 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. It was also found that there was sufficient rust prevention performance even at a concentration of 1.00% to 1.25%.
(5) 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.

Claims (7)

  1. 　〔Ｒ１（ＯＲ２）３Ｓｉ〕の化学構造を持つトリアルコキシシラン（R１は、その末端がビニル基、エポキシ基、スチリル基、メタクリル基、アクリル基、アミノ基、ウレイド基、メルカプト基、スルフィド基、イソシアネート基である官能基、R２はアルキル基またはアルキレン基）のオリゴマーを溶液全量に対して0.5～７重量％含むアルコール溶液であることを特徴とする金属表面防錆皮膜形成剤。 Trialkoxysilane having a chemical structure of [R 1 (OR 2 ) 3 Si] (R 1 has 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 metal surface rust preventive film-forming agent, which is an alcohol solution containing 0.5 to 7% by weight of an oligomer of 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.
  2. 　前記アルコール溶液に、さらに熱硬化性フェノール系樹脂を溶液全量に対して２～１５重量％含む請求項１に記載の防錆皮膜形成剤。 The rust preventive film-forming agent according to claim 1, wherein the alcohol solution further contains 2 to 15% by weight of a thermosetting phenol resin with respect to the total amount of the solution.
  3. 　前記Ｒ１が、その末端がエポキシ基、メルカプト基またはアミノ基である官能基である請求項１または２に記載の防錆皮膜形成剤。 The rust preventive film-forming agent according to claim 1 or 2, wherein R 1 is a functional group whose terminal is an epoxy group, a mercapto group, or an amino group.
  4. 　前記アルコール溶液中に、さらに有機チタンまたは有機アルミニウムを前記オリゴマー重量に対して０．２～５重量％含む請求項１～３のいずれかの項に記載の防錆皮膜形成剤。 The rust preventive film forming agent according to any one of claims 1 to 3, wherein the alcohol solution further contains 0.2 to 5% by weight of organic titanium or organic aluminum based on the weight of the oligomer.
  5. 　金属基体に、請求項１～４のいずれかの項に記載の防錆皮膜形成剤を用いてディップアンドスピン法にて処理し、該金属基体を常温にて乾燥させることにより、該金属基体表面に防錆皮膜を生成させる金属基体の防錆皮膜形成方法。 The surface of the metal substrate is treated by a dip-and-spin method using the anticorrosive film forming agent according to any one of claims 1 to 4 and dried at room temperature. A method for forming a rust preventive film on a metal substrate that forms a rust preventive film on a substrate.
  6. 　金属基体に、熱硬化性樹脂によるプレ防錆皮膜を形成するプレ防錆工程を行った後、
    　該プレ防錆皮膜が形成された金属基体に、請求項１～４のいずれかの項に記載の防錆皮膜形成剤を用いてディップアンドスピン法にて処理し、該金属基体を常温にて乾燥させることにより、該金属基体表面に防錆皮膜を生成させる金属基体の防錆皮膜形成方法。     After performing a pre-rust prevention process to form a pre-rust prevention film with a thermosetting resin on a metal substrate,
    The metal substrate on which the pre-rust preventive film is formed is treated by a dip and spin method using the rust preventive film forming agent according to any one of claims 1 to 4, and the metal substrate is treated at room temperature. A method for forming a rust preventive film on a metal substrate, wherein a rust preventive film is formed on the surface of the metal substrate by drying.
  7. 　金属基体に、アンチモン化合物及びマンガン化合物との黒色酸化反応で生成する酸化プレ防錆皮膜を形成するプレ防錆工程を行った後、
    　該酸化プレ防錆皮膜が形成された金属基体に、請求項１～４のいずれかの項に記載の防錆皮膜形成剤を用いてディップアンドスピン法にて処理し、該金属基体を常温にて乾燥させることにより、該金属基体表面に防錆皮膜を生成させる金属基体の防錆皮膜形成方法。     After performing a pre-rust prevention step to form an oxidized pre-rust prevention film generated by a black oxidation reaction with an antimony compound and a manganese compound on a metal substrate,
    The metal base on which the oxidized pre-rust preventive film is formed is treated by a dip and spin method using the rust preventive film forming agent according to any one of claims 1 to 4, and the metal base is brought to room temperature. A method for forming a rust preventive film on a metal substrate, wherein a rust preventive film is formed on the surface of the metal substrate by drying the substrate.
PCT/JP2013/068378 2013-07-04 2013-07-04 Agent for forming rust-preventing coating film on metal surface, and method for forming rust-preventing coating film for metal substrate by using same WO2015001645A1 (en)

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CN108728746A (en) * 2018-08-07 2018-11-02 重庆维富金属制品有限公司 A kind of novel galvanizing steel plate and its processing method

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JPH1095933A (en) * 1996-09-26 1998-04-14 Japan Energy Corp Coating composition and metal material coated with the same
JPH11124544A (en) * 1997-10-24 1999-05-11 Nippon Shokubai Co Ltd Metal surface treatment composition and surface-treated metal plate
JP3414348B2 (en) * 2000-01-07 2003-06-09 住友金属工業株式会社 Chrome-free treated galvanized steel sheet with excellent blackening resistance
JP2006192716A (en) * 2005-01-13 2006-07-27 Nippon Steel Corp Surface-treated metal, its manufacturing method and surface treatment liquid
JP2008214744A (en) * 2007-03-07 2008-09-18 Okada Chelate:Kk Black rust prevention treatment liquid on galvanized or galvannealed metal surface, and black rust prevention film treatment method

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JPH1095933A (en) * 1996-09-26 1998-04-14 Japan Energy Corp Coating composition and metal material coated with the same
JPH11124544A (en) * 1997-10-24 1999-05-11 Nippon Shokubai Co Ltd Metal surface treatment composition and surface-treated metal plate
JP3414348B2 (en) * 2000-01-07 2003-06-09 住友金属工業株式会社 Chrome-free treated galvanized steel sheet with excellent blackening resistance
JP2006192716A (en) * 2005-01-13 2006-07-27 Nippon Steel Corp Surface-treated metal, its manufacturing method and surface treatment liquid
JP2008214744A (en) * 2007-03-07 2008-09-18 Okada Chelate:Kk Black rust prevention treatment liquid on galvanized or galvannealed metal surface, and black rust prevention film treatment method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108728746A (en) * 2018-08-07 2018-11-02 重庆维富金属制品有限公司 A kind of novel galvanizing steel plate and its processing method

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