WO2017010571A1 - Agent de traitement à base d'eau, matériau en acier plaqué de zinc ou matériau en acier plaqué d'un alliage de zinc et matériau en acier plaqué de zinc enrobé ou matériau en acier plaqué d'un alliage de zinc enrobé - Google Patents

Agent de traitement à base d'eau, matériau en acier plaqué de zinc ou matériau en acier plaqué d'un alliage de zinc et matériau en acier plaqué de zinc enrobé ou matériau en acier plaqué d'un alliage de zinc enrobé Download PDF

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Publication number
WO2017010571A1
WO2017010571A1 PCT/JP2016/071070 JP2016071070W WO2017010571A1 WO 2017010571 A1 WO2017010571 A1 WO 2017010571A1 JP 2016071070 W JP2016071070 W JP 2016071070W WO 2017010571 A1 WO2017010571 A1 WO 2017010571A1
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Prior art keywords
mass
steel material
plated steel
compound
group
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PCT/JP2016/071070
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English (en)
Japanese (ja)
Inventor
泰平 金藤
智明 細川
植田　浩平
山本　茂樹
英介 工藤
良和 生井
Original Assignee
新日鐵住金株式会社
日本パーカライジング株式会社
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Application filed by 新日鐵住金株式会社, 日本パーカライジング株式会社 filed Critical 新日鐵住金株式会社
Priority to JP2017528740A priority Critical patent/JP6564036B2/ja
Priority to KR1020187000597A priority patent/KR102043572B1/ko
Priority to MYPI2017705131A priority patent/MY183818A/en
Priority to CN201680040716.1A priority patent/CN107849696B/zh
Publication of WO2017010571A1 publication Critical patent/WO2017010571A1/fr

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    • 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
    • C23C22/05—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 aqueous solutions
    • C23C22/06—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 aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—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 aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/42—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 aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
    • 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
    • C23C22/82—After-treatment
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates

Definitions

  • the present invention provides excellent corrosion resistance, chemical resistance (for example, alkali resistance, acid resistance, etc.) and forming processing in a coated steel plate (also referred to as a pre-coated steel plate or a post-coated steel plate) and a post-coated steel material having a zinc and zinc alloy plating layer.
  • Zinc-plated steel materials and zinc alloys having a coating film with excellent corrosion resistance, chemical resistance and coating film adhesion obtained by the aqueous processing agent and imparting coating film adhesion of the part
  • the present invention relates to a plated steel material, a coated galvanized steel material, a coated galvanized steel material, and a method for producing the same.
  • the structure of a typical coated steel plate consists of what coat
  • the treatment for imparting the coating film adhesion includes a chromate treatment, and a paint containing a chromium-based anticorrosive pigment in the primer coating film has been conventionally used.
  • chromate-free coatings and the like due to the environmental load of hexavalent chromium.
  • Chromate-free products are being made indoors that are used in mild conditions such as the home appliance field, but it is difficult to satisfy all end-user requirements for outdoor products that are used in severe outdoor conditions such as the building materials field. However, there is a current situation that chromate-free is not progressing.
  • the coating film adhesion of a coated steel sheet is evaluated by a test by bending.
  • coating film adhesion is required under more severe processing conditions such as a test by drawing.
  • the processing conditions are severe, if the coating film adhesion is insufficient, the coating film swells up and peels off from the side surface, the end surface, and the heel that are subjected to the processing load.
  • a treatment agent mainly composed of a resin is applicable as the chromate-free treatment.
  • conventional treatment agents mainly composed of resins that cannot be prevented from deterioration when exposed to long-term corrosive environments are not necessarily required. The performance is not satisfied.
  • the coating layer composition of the coated steel sheet is zinc-based, the coating layer has ductility when processed, so there is no crack in the coating layer during processing, and a large stress is applied to the coating film formed on the plating layer. It takes. Since the stress causes peeling of the coating film, it is more possible to ensure the adhesion of the coating film after severe processing such as the above-mentioned drawing forming process in the coated steel sheet based on zinc and zinc alloy plated steel sheet. More difficult.
  • a technique relating to a metal surface treatment agent further comprising a water-soluble resin is disclosed. According to these techniques, excellent corrosion resistance and the like can be imparted to the steel material.
  • Patent Document 4 discloses a surface treatment agent containing water, a metal carbonate selected from Mg, Co, Zr, Ni, Zn, and Cu, water-dispersible silica, and a specific organic acid. Yes. According to this surface treatment agent, it is possible to provide a surface-treated steel sheet having excellent coating adhesion and corrosion resistance.
  • the present invention has excellent corrosion resistance, and can form a film having chemical resistance and coating film adhesion of a molded portion, a chromium-free aqueous treatment agent, and a galvanized steel material having the film,
  • An object of the present invention is to provide a zinc alloy-plated steel material, a coated zinc-plated steel material, a painted zinc alloy-plated steel material, and methods for producing the same.
  • the inventors of the present invention include a specific zirconium compound, an epoxy resin, a specific silanol group-containing compound, a phosphoric acid compound, and a vanadium compound.
  • a water-based treatment agent that satisfies a specific composition ratio for the components, it has excellent corrosion resistance, as well as coated galvanized steel and coated zinc alloy plating that can achieve both high chemical resistance and coating film adhesion at the formed part. It discovered that a steel material was obtained and came to complete this invention.
  • the present invention is as follows. (1) (A) a zirconium compound selected from ammonium zirconium carbonate, potassium zirconium carbonate, basic zirconium carbonate, and zirconium acetate; (B) epoxy resin, (C) a silanol group-containing compound represented by the following formula [I] and / or a condensate thereof, XY (Z) n Si (OH) 3-n (I) (X represents a glycidoxy group or a functional group derived from a glycidoxy group, Y represents an alkyl group having 1 to 10 carbon atoms, Z represents a methoxy group, an ethoxy group, or a methyl group, and n represents an integer of 0 to 2) Represents.) (D) a phosphoric acid compound, (E) a vanadium compound, An aqueous treatment agent containing With respect to the mass of the zirconium compound (A) in terms of Zr, The solid content mass ratio [
  • the epoxy resin is a bisphenol A type epoxy resin containing a carboxyl group, and has a polystyrene equivalent weight average molecular weight of 30,000 to 150,000 by gel permeation chromatography.
  • Water-based treatment agent (3) Zr formed on at least one surface of a galvanized steel sheet or zinc alloy plated steel sheet having a plating layer composition of Zn: 80% by mass or more using the aqueous treatment agent according to (1) or (2).
  • Zinc alloy plated steel (5) Applying the aqueous processing agent according to the above (1) or (2) to at least one surface of a galvanized steel sheet or a zinc alloy plated steel sheet having a plating layer composition of Zn: 80% by mass or more to form a treated film layer, A method for producing a galvanized steel material or a zinc alloy plated steel material, wherein the treated film layer is heated and dried to form a treated film layer having a Zr adhesion amount of 1 to 40 mg / m 2 .
  • aqueous processing agent according to the above (1) or (2) to at least one surface of a galvanized steel sheet or a zinc alloy plated steel sheet having a plating layer composition of Zn: 80% by mass or more to form a treated film layer
  • the treatment film layer is dried by heating to form a treatment film layer having a Zr adhesion amount of 1 to 40 mg / m 2 .
  • at least one layer of paint for a multilayer coating film is applied,
  • the at least one laminated coating film is dried by heating to form a laminated coating film having a total film thickness of 1 to 50 ⁇ m.
  • the water-based treatment agent of the present invention can form a film having excellent corrosion resistance as well as chemical resistance and coating film adhesion at a molded portion, even though it does not contain chromium. For this reason, it becomes possible to remarkably reduce the environmental load of the coated steel sheet used for the outdoors. Therefore, the water-based treatment agent of the present invention has extremely great industrial value.
  • the coated galvanized steel material and coated galvanized steel material of the present invention are not limited to pre-coated steel sheets whose laminated coating is pre-applied by a steel sheet manufacturer, but in any specification of post-coated steel sheets that are applied on the user side after delivery. In addition, the effect of the aqueous treatment agent of the present invention can be expected.
  • the aqueous treating agent of the present invention comprises a zirconium compound (A), an epoxy resin (B), a silanol group-containing compound and / or its condensate (C), a phosphoric acid compound (D), and a vanadium compound (E). Containing.
  • A zirconium compound
  • B epoxy resin
  • C silanol group-containing compound and / or its condensate
  • D a phosphoric acid compound
  • E vanadium compound
  • the zirconium compound (A) is selected from ammonium zirconium carbonate, potassium zirconium carbonate, basic zirconium carbonate, and zirconium acetate.
  • Zirconium compound (A) is a film-forming component capable of forming a three-dimensionally crosslinked zirconium oxide film by hydrolysis and condensation accompanying the elimination of volatile acids such as carbonic acid and acetic acid during film formation (baking). Yes, contributing to the development of processing adhesion, corrosion resistance, and chemical resistance.
  • zirconium activated by acid desorption is firmly bonded to the plating layer surface via oxygen atoms, thereby contributing to the expression of adhesion.
  • zirconium compound (A) cannot be obtained with zircon hydrofluoric acid, fluorozirconate, zirconium nitrate, zirconium sulfate, zirconium oxychloride, etc., but stabilized with carbonic acid and acetic acid, which are volatile acids. It can be obtained only with the obtained zirconium compound.
  • the epoxy resin (B) is a film-forming component, and is intricately intertwined with the zirconium compound (A), the silanol group-containing compound and / or its condensate (C), and imparts toughness and suitable processing followability to the treated film. This contributes to the development of processing adhesion. In addition, the formation of a dense film structure with high hydrolysis resistance contributes to the development of work adhesion, chemical resistance and corrosion resistance. Moreover, the epoxy group and the hydroxyl group in the resin contribute to the adhesion with the upper layer due to the reaction with the organic functional group of the laminated coating film on the upper layer and the hydrogen bonding action. Such an effect of the epoxy resin (B) cannot be obtained with a resin type other than the epoxy resin.
  • acrylic resin has a hard film and is inferior in process followability, so process adhesion cannot be obtained
  • polyurethane resin has inferior durability to moisture, ultraviolet rays, and heat, so long-term corrosion resistance cannot be obtained
  • polyester resin is subject to hydrolysis. It is easy to obtain alkali resistance.
  • Epoxy resin (B) to be contained in the aqueous treatment agent of the present invention can be obtained by a known production method and is not particularly limited.
  • Epoxy resin (B) is an addition reaction and condensation reaction of bisphenol A, bisphenol F, novolak resin, etc., which are usually used in the production of aqueous epoxy resins, and epihalohydrins such as epichlorohydrin or epoxy compounds having two or more glycidyl groups. It can be obtained by dispersing in water an epoxy resin obtained by repeating or repeating the addition reaction.
  • the epoxy resin (B) may be obtained by reacting an epoxy group or a hydroxyl group in the resin with a modifier.
  • a modifier for example, epoxy ester resin reacted with unsaturated fatty acid, acrylic modified epoxy resin reacted with (meth) acrylic acid or its ester, urethane modified epoxy resin reacted with isocyanate compound, silane reacted with silane coupling agent
  • modified epoxy resins phosphoric acid-modified epoxy resins obtained by reacting phosphoric acids or esters thereof.
  • Said epoxy resin (B) may be used independently and may be used in combination of 2 or more type.
  • the epoxy resin (B) is preferably a bisphenol A type epoxy resin containing a carboxyl group.
  • the rigidity and moderate flexibility derived from the bisphenol A type structural unit in the resin contributes to the improvement of the processing adhesion of the coating film.
  • the structure which is hard to hydrolyze contributes to the improvement of chemical resistance and corrosion resistance.
  • the carboxyl group in the epoxy resin is strongly bonded to the plated metal surface due to its polarity, and contributes to the improvement of the adhesion to the plated metal surface.
  • the carboxyl group in the epoxy resin crosslinks with the zirconium compound or the silanol group-containing compound, thereby improving the toughness of the treatment film and contributing to improvement in chemical resistance and corrosion resistance.
  • the carboxyl group in the resin is preferably neutralized with a basic neutralizing agent from the viewpoint of maintaining the mixing stability with the zirconium compound (A) in the treating agent.
  • a basic neutralizing agent it is more preferable to use a volatile amine or ammonia in that it hardly remains in the film forming process.
  • the weight average molecular weight in terms of polystyrene by gel permeation chromatography of the epoxy resin (B) is preferably 30,000 to 150,000. By defining the weight average molecular weight within the above range, it contributes to the development of excellent chemical resistance, and contributes to the development of work adhesion and corrosion resistance.
  • the acid value of the epoxy resin (B) is not particularly limited, but is preferably 10 to 40. By defining the acid value within the above range, it is possible to improve the processing adhesion and liquid stability of the treatment film and improve the chemical resistance.
  • the solid content mass ratio [(B) / Zr] of the mass of the epoxy resin (B) to the mass of the zirconium compound (A) in terms of Zr is 0.7 to 1.5.
  • it is 1.0 to 1.5.
  • it is less than 0.7, sufficient work adhesion and corrosion resistance cannot be obtained.
  • it exceeds 1.5 sufficient work adhesion, chemical resistance and corrosion resistance cannot be obtained.
  • the silanol group-containing compound as component (C) is represented by the following formula [I].
  • X represents a glycidoxy group or a functional group derived from a glycidoxy group
  • Y represents an alkylene group having 1 to 10 carbon atoms
  • Z represents a methoxy group, an ethoxy group, or a methyl group
  • n represents Represents an integer of 0-2.
  • the silanol group-containing compound used in the present invention is a compound obtained by hydrolyzing an organosilicon compound having a glycidoxy group.
  • Hydrolysis of an organosilicon compound is generally performed by adding a hydrolysis aid to water or an alcohol, ketone or cellosolve-based water-soluble organic solvent containing water. Hydrolysis aids are used to bring the pH value of the solvent to a range of 3 to 5, and known ones are not particularly limited.
  • the hydrolysis assistant include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, and carboxylic acids such as acetic acid, lactic acid, tartaric acid and citric acid.
  • acetic acid is particularly preferable in that it volatilizes during the film formation process and hardly remains in the treated film.
  • organosilicon compound having a glycidoxy group examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl. And methyldiethoxysilane. These compounds may be used alone or in combination of two or more.
  • the silanol group-containing compound and / or its condensate (C) used in the present invention is a film-forming component, is intricately entangled with the zirconium compound (A) and the epoxy resin (B), and has a toughness and suitable processing for the treated film. By giving followability, it contributes to the expression of the processing adhesion of the treated film. In addition, the formation of a dense film structure contributes to the development of chemical resistance. In addition, the silanol group (—Si—OH) forms a strong chemical bond of —Si—OM with the plating metal surface via oxygen atoms, which contributes to the improvement of adhesion to the plating metal surface.
  • the glycidoxy group or the functional group derived from the glycidoxy group has a role of maintaining the mixing stability with the zirconium compound (A) and the epoxy resin (B) in the treatment agent.
  • the silanol group-containing compound has a functional group such as highly active amino group, vinyl group or methacryl group at the terminal, the mixing stability with the zirconium compound (A) and the epoxy resin (B) in the treating agent is maintained. These functional groups are not applicable.
  • the solid content mass ratio [SiO 2 / Zr] of the silanol group-containing compound and / or the condensate thereof (C) in terms of SiO 2 with respect to the mass of the zirconium compound (A) in terms of Zr Is 0.15 to 1.5, preferably 0.2 to 1.0.
  • it is less than 0.15 sufficient work adhesion and corrosion resistance cannot be obtained.
  • it exceeds 1.5 sufficient work adhesion, chemical resistance and corrosion resistance cannot be obtained.
  • Phosphoric acid compound (D) and vanadium compound (E) contribute to corrosion resistance as an eluting inhibitor (corrosion inhibiting substance).
  • the anodic dissolution reaction of the plating layer occurs due to sacrificial anticorrosive action.
  • the phosphate compound and vanadium compound contained in the treated coating layer elute, and the plating layer Forms corrosion products with zinc that elutes from the metal and suppresses the progress of corrosion by passivating the plating layer surface.
  • both the phosphoric acid compound (D) and the vanadium compound (E) are contained, a corrosion product having higher electrical insulation is formed and immobilized on the surface of the plating layer, so that the corrosion suppressing effect is remarkably enhanced.
  • the phosphoric acid compound (D) is not particularly limited, and examples thereof include phosphoric acid, an ammonium salt of phosphoric acid, an alkali metal salt of phosphoric acid, and an alkaline earth metal salt of phosphoric acid.
  • the solid content mass ratio [P / Zr] of the P-converted mass of the phosphoric acid compound (D) to the Zr-converted mass of the zirconium compound (A) is 0.025 to 0.1. Preferably, it is 0.03 to 0.07. If it is less than 0.025, the effects on chemical resistance and corrosion resistance do not appear. On the other hand, if it exceeds 0.1, sufficient corrosion resistance cannot be obtained.
  • the solid content mass ratio [V / Zr] in terms of V of the vanadium compound (E) to the mass in terms of Zr of the zirconium compound (A) is 0.02 to 0.05. Preferably, it is 0.02 to 0.03. If it is less than 0.02, the effect on chemical resistance and corrosion resistance does not appear. On the other hand, if it exceeds 0.05, sufficient acid resistance cannot be obtained.
  • the aqueous treatment agent of the present invention preferably does not contain a noble metal component (F) than zinc.
  • a noble metal component (F) include Fe, Co, Ni, Sn, Pb, Bi, Cu, and the like.
  • solid content mass ratio [F / Zr] in the metal element conversion mass of the metal component (F) with respect to the mass in Zr conversion of the zirconium compound (A) is 0.01 or less. This is because the metal component (F) elutes from the treated coating layer in a corrosive environment, and is then deposited on the galvanized layer to promote zinc corrosion in the plated layer, resulting in a decrease in alkali resistance, acid resistance, and corrosion resistance. It is because it tends to do.
  • the aqueous treatment agent of the present invention can be prepared by dissolving or dispersing the above components (A), (B), (C), (D), and (E) in water or an aqueous solvent.
  • Each component is adjusted so as to have a specified composition ratio with a non-volatile content (in the treatment film) excluding the solvent and the volatile component.
  • the solvent is usually water, a small amount (for example, 10% by volume or less of the entire aqueous medium) of alcohol, ketone, cellosolve-based water-soluble organic solvent is used for the purpose of improving the drying property of the obtained treated film layer. You may use together.
  • additives that are commonly used in coating treatment agents such as a surfactant that improves wettability and an antifoaming agent that suppresses foaming, do not impair the effects of the present invention. Can be blended.
  • the pH of the aqueous treatment agent of the present invention is not particularly limited as long as the effects of the present invention can be achieved, but is preferably in the range of 7 to 10. By adjusting the pH to this range, the storage stability can be improved and the corrosion resistance can be improved.
  • volatile alkali components such as ammonia
  • volatile acid components such as an acetic acid and a formic acid
  • the solid content concentration of the aqueous treatment agent of the present invention is not particularly limited as long as the effect of the present invention can be achieved, but is preferably in the range of 1 to 20% by mass. When the solid content concentration of the aqueous treatment agent is within this range, a film can be efficiently formed, and the storage stability of the aqueous treatment composition can be improved.
  • the aqueous treatment agent of the present invention contains a specific zirconium compound, an epoxy resin, a specific silanol group-containing compound and / or a condensate thereof as main components.
  • a volatile acid-stabilized zirconium compound (A) is applied, and three-dimensionally cross-linked by hydrolysis and condensation accompanying detachment of volatile acid in the process film formation (baking) process.
  • a zirconium oxide film is formed.
  • Such a coating made of zirconium oxide has extremely high chemical resistance, and hardly dissolves even in a concentrated acid or alkaline environment.
  • the epoxy resin (B) is optimal as a component for imparting toughness to the film.
  • the epoxy resin has both rigidity and flexibility in structure, and has high hydrolyzability. Moreover, it contributes to adhesiveness expression with a laminated coating film by reaction with the organic functional group of the top coat film of the epoxy group or the hydroxyl group in the epoxy resin, or a hydrogen bonding action. Moreover, it crosslinks with the zirconium compound to form a dense structure. For this reason, it is presumed that toughness could be imparted to the coating without deteriorating the high chemical resistance of the zirconium oxide coating by blending the epoxy resin in an appropriate ratio with respect to the zirconium compound.
  • silanol group-containing compound a compound called a silane coupling agent is generally known, and the silanol group (—Si—OH) at the molecular end is oriented in the vicinity of the material, and the plating metal surface and oxygen atoms are interposed— In order to form a strong chemical bond of Si-OM, it adheres firmly.
  • the organic functional group at the reverse end contributes to adhesion with the laminated coating film.
  • the inventors of the present invention are the silanol group-containing compound containing a glycidoxy group or an organic functional group derived from a glycidoxy group and / or a condensate thereof that most effectively acts to impart admixture stability and adhesion. It was found that (C). Glycidoxy groups have poor reactivity and can maintain their mixing stability. Also, adhesion with laminated coatings via hydrogen bonds, moderate flexibility derived from organic groups, and plating metal surfaces derived from silanol groups. Adhesion could also be imparted.
  • the blending ratio of the zirconium compound and the silanol group-containing compound is also important. Silanol group-containing compounds themselves are easy to elute under concentrated acid and alkaline environments, and excessive compounding amount of silanol group-containing compounds will reduce chemical resistance. It is presumed that the silanol group and zirconium are three-dimensionally cross-linked by blending at a proper ratio, and elution of the silanol group-containing compound is suppressed. As described above, by blending a specific zirconium compound, an epoxy resin, a specific silanol group-containing compound and / or a condensate thereof in a specific ratio, the chemical resistance and the coating film adhesion of the molded portion are excellent. It is estimated that the treatment film layer could be formed.
  • the aqueous treatment agent of the present invention can be applied to a galvanized steel sheet or a zinc alloy plated steel sheet having a plating layer composition of Zn: 80% by mass or more.
  • a galvanized steel material and the zinc alloy plated steel material known galvanized steel sheets and galvanized steel sheets can be used. Examples thereof include a hot dip galvanized steel sheet, an alloyed hot dip galvanized steel sheet, an electrogalvanized steel sheet, a hot dip Zn—Al plated steel sheet, a hot dip Zn—Al—Mg plated steel sheet, and an electric Zn—Ni plated steel sheet.
  • washing with a degreasing agent hot water washing, acid Washing, alkali washing, solvent washing and the like can be performed in appropriate combination.
  • a degreasing agent hot water washing, acid Washing, alkali washing, solvent washing and the like
  • the treatment coating layer of the galvanized steel material or the zinc alloy plated steel material of the present invention is formed on the surface by bringing the aqueous treatment agent of the present invention into contact with the plated steel sheet, followed by heating and drying without washing.
  • the contact method of the aqueous treatment agent of the present invention is not particularly limited, and examples thereof include known methods such as a roll coater method, a dipping method, and a spray method.
  • the heating and drying method is not particularly limited, but heating and drying with a hot air furnace, an induction heating furnace, an electric furnace or the like is preferable. Further, the ultimate steel plate temperature at the time of drying is not particularly limited, but 50 to 150 ° C. is preferable.
  • the coating amount of the treatment coating layer formed on the galvanized steel material or the zinc alloy plated steel material by the contact with the aqueous treatment agent of the present invention is 1 to 40 mg / m 2 as the Zr adhesion amount, preferably 5 to 30 mg / m 2. m 2 . If the amount of Zr adhesion is less than 1 mg / m 2 , the effect of the treatment film layer cannot be obtained, and if it exceeds 40 mg / m 2 , the formed film tends to cause cohesive failure, and the work adhesion decreases.
  • the coated galvanized steel material or the coated zinc alloy plated steel material of the present invention has a laminated coating film composed of at least one layer on the treated coating layer of the galvanized steel material or the zinc alloy plated steel material, and is generally a precoated steel sheet. And a coated steel sheet called a post-coated steel sheet.
  • the total film thickness of the laminated coating film of the coated galvanized steel material or the coated zinc alloy plated steel material of the present invention is 1 to 50 ⁇ m. By adjusting the film thickness within this range, chemical resistance, corrosion resistance, and work adhesion can be improved.
  • the structure of the laminated coating film is not particularly limited, but for outdoor use under harsh conditions, an intermediate coating film layer containing an anticorrosive pigment for the purpose of improving corrosion resistance is provided on the treated coating layer.
  • a structure in which a top coat film layer in which a color pigment is blended for the purpose of imparting designability is further laminated can be applied.
  • a top coat film layer for the purpose of imparting design properties is formed on the treated film layer without an intermediate coat film layer containing a rust preventive pigment.
  • a structure having a coating structure in which a functional pigment such as a conductive pigment or a functional pigment is blended is also applicable.
  • the rust preventive pigment known chromate-free pigments can be used.
  • phosphate phosphate rust preventive pigments such as zinc phosphate, iron phosphate, aluminum phosphate, and magnesium phosphate, calcium molybdate, and molybdate.
  • molybdate anticorrosion pigments such as aluminum and barium molybdate
  • vanadium anticorrosion pigments such as vanadium oxide and calcium vanadate
  • fine silica anticorrosion pigments such as water-dispersible silica and fumed silica.
  • the coloring pigment known inorganic and organic coloring pigments can be used.
  • the inorganic coloring pigment titanium oxide (TiO 2 ), zinc oxide (ZnO), zirconium oxide (ZrO 2 ), calcium carbonate (CaCO 3 ). ), Barium sulfate (BaSO 4 ), alumina (Al 2 O 3 ), kaolin clay, carbon black, iron oxide (Fe 2 O 3 , Fe 3 O 4 ), etc., and organic color pigments such as Hansa Yellow, pyrazolone orange, azo And pigments.
  • the method of forming the laminated coating film there are no particular restrictions on the method of forming the laminated coating film.
  • a forming method in which a coating process is contacted by a known method such as a roll coater method, a dipping method, or a spray method, and then a step of performing heat drying by a known method such as a hot air furnace, an induction heating furnace, or an electric furnace is repeated.
  • the ultimate steel plate temperature during drying is not particularly limited, but is preferably 80 to 250 ° C.
  • Preparation of aqueous treatment agent 1 Preparation of aqueous treatment agent 1 (Nos. 1-31 and 35-39)
  • the components (A) to (F) selected from the following are sequentially added to deionized water in the combinations and mixing ratios of the raw materials shown in Table 1, and water treatment agents for examples (Nos. 1 to 14, 35) are added.
  • To 38) and comparative aqueous treatment agents (No. 15 to 31, 39) were obtained.
  • Deionized water was added to adjust the nonvolatile content to 7% by mass.
  • ⁇ Zirconium compound (A)> A1: Zirconium ammonium carbonate
  • a reaction vessel was charged with 200 parts by mass of bisphenol A-type liquid epoxy resin, 30 parts by mass of polyethylene glycol diglycidyl ether, and 80 parts by mass of butyl cellosolve, and heated to 100 ° C. under nitrogen reflux and stirring. After dissolution, 5 parts by mass of triethylamine was added and reacted at 120 ° C. for 5 hours. Next, 100 parts by mass of bisphenol A type liquid epoxy resin and 80 parts by mass of methyl isobutyl diketimine were added and heating, nitrogen reflux and stirring were continued for 4 hours.
  • carboxyl group-free bisphenol type epoxy resin (B2) had a weight average molecular weight of 18,000 and an acid value of 25 mgKOH / g.
  • a reaction vessel was charged with 200 parts by weight of a bisphenol A-type liquid epoxy resin, 30 parts by weight of polyethylene glycol diglycidyl ether and 80 parts by weight of butyl cellosolve, and heated to 100 ° C. under nitrogen reflux and stirring. After dissolution, 5 parts by mass of triethylamine was added and reacted at 120 ° C. for 5 hours. Next, a mixed liquid of 30 parts by mass of butyl acrylate, 20 parts by mass of acrylic acid, 10 parts by mass of methyl methacrylate, 25 parts by mass of styrene, and 30 parts by mass of butyl cellosolve was dropped over 2 hours using a dropping funnel.
  • the resulting carboxyl group-containing bisphenol A type epoxy resin (B3) had a weight average molecular weight of 84,000 and an acid value of 41 mgKOH / g.
  • a reaction vessel was charged with 200 parts by weight of a bisphenol A-type liquid epoxy resin, 30 parts by weight of polyethylene glycol diglycidyl ether, and 80 parts by weight of butyl cellosolve, and heated to 100 ° C. under nitrogen reflux and stirring. After dissolution, 0.5 part by mass of triethylamine was added and reacted at 120 ° C. for 5 hours.
  • Carboxyl group-containing novolak type epoxy resin 200 parts by mass of novolac type liquid epoxy resin, 30 parts by mass of polyethylene glycol diglycidyl ether, and 80 parts by mass of butyl cellosolve are charged in a reaction vessel, heated to 100 ° C. under nitrogen reflux and stirring, and dissolved. Then, 3 parts by mass of triethylamine was added and reacted at 120 ° C. for 5 hours.
  • b2 Acrylic resin
  • a reaction vessel 100 parts by mass of deionized water, 3 parts by mass of a reactive surfactant (Aqualon KH-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), heated to 50 ° C. under nitrogen reflux and stirring.
  • a mixed monomer solution 20 parts by mass of butyl acrylate, 2 parts by mass of acrylic acid, 15 parts by mass of methyl methacrylate, and 13 parts by mass of styrene, 0.2 part by mass of ammonium persulfate, and 4 parts by mass of ion-exchanged water
  • the solution was added dropwise using a dropping funnel over 2 hours. After completion of the dropwise addition, heating, nitrogen reflux and stirring were continued for 3 hours. After cooling to 30 ° C., stirring was continued for 5 hours to obtain an acrylic resin emulsion (b2).
  • b3 Polyester resin In a reaction vessel, 1 mol of total acid component consisting of terephthalic acid (41 mol%), isophthalic acid (40 mol%), dimethyl-5-sulfonate sodium isophthalate (2 mol%) and trimellitic anhydride (17 mol%) 2 mol of all alcohol components consisting of ethylene glycol (90 mol%) and trimethylolpropane (10 mol%), and 0.25 g of calcium acetate and 0.1 g of N-butyl titanate as a catalyst, Stir and heat to 180 ° C. to melt the contents. Then, after heating to 200 degreeC, stirring was continued for about 2 hours and esterification or transesterification was performed.
  • 1 mol of total acid component consisting of terephthalic acid (41 mol%), isophthalic acid (40 mol%), dimethyl-5-sulfonate sodium isophthalate (2 mol%) and trimellitic anhydride (17 mol%) 2 mol of all alcohol components consisting of ethylene glycol
  • the mixture was heated to 260 ° C., and after about 15 minutes, the pressure in the system was reduced to 0.5 mmHg and subjected to a polycondensation reaction for about 3 hours. After completion of the reaction, the mixture was allowed to cool under nitrogen introduction, and the contents were taken out. Add appropriate amounts of ammonia water and deionized water to a final pH of 6-7 to the taken out contents, stir in an autoclave at 100 ° C for 2 hours, and finally add 30% solids with deionized water. A polyester resin (b3) of an aqueous emulsion adjusted to 1 was obtained.
  • C2 Silanol group-containing compound by adding 0.02 part by weight of acetic acid, 20 parts by weight of ethanol and 25 parts by weight of 3-glycidoxypropyltriethoxysilane to 60 parts by weight of deionized water and stirring at 60 ° C. for 2 hours (C2) was obtained.
  • c1 30 parts by mass of N-2- (aminoethyl) -3-aminopropyltriethoxysilane was added to 70 parts by mass of deionized water and stirred at 25 ° C. for 2 hours to obtain a silanol group-containing compound (c1). It was.
  • aqueous treatment agent 2 (No. 32)
  • the aqueous treatment composition described in the example of Patent Document 1 was prepared for a comparative example.
  • 1.5 parts by mass of ⁇ -aminopropyltriethoxysilane, 0.5 parts by mass of water-dispersible silica (Snowtex N; manufactured by Nissan Chemical Industries, Ltd.), and zirconium ammonium carbonate in terms of zirconium ions 0.02 mass part was mixed and the aqueous processing agent (No. 32) was obtained.
  • aqueous treatment agent 3 (No. 33)
  • the aqueous treatment composition described in the Examples of Patent Document 4 was prepared as a comparative example. 100 parts by mass of deionized water, 25 parts by mass of ammonium zirconium carbonate, 25 parts by mass of water-dispersible silica (Snowtex N; manufactured by Nissan Chemical Industries, Ltd.) and 5 parts by mass of tartaric acid are mixed, and an aqueous treatment agent (No. 33) is added. Obtained.
  • aqueous treatment agent 4 No. 34
  • ZM-1300AN manufactured by Nippon Parkerizing Co., Ltd.
  • This example is an example of a prior art chromate treatment composition.
  • T1 60 parts by mass of a polyester resin, 15 parts by mass of a butylated melamine resin, 10 parts by mass of titanium oxide, and 15 parts by mass of carbon black were mixed to obtain a top coat paint.
  • FC-E6406 manufactured by Nihon Parkerizing Co., Ltd.
  • FC-E6406 manufactured by Nihon Parkerizing Co., Ltd.
  • FC-E6406 was sprayed at a concentration of 20 g / L and a temperature of 60 ° C. for 10 seconds to degrease.
  • each water system was applied to the surface of various steel plates after pretreatment using a bar coater so that the Zr adhesion amount (Cr: represents the Cr adhesion amount) becomes a predetermined amount.
  • a treating agent was applied.
  • the substrate was heated and dried in a hot air drying furnace so that the ultimate plate temperature was 80 ° C.
  • the intermediate coating composition was applied using a bar coater so as to have a dry film thickness of 5 ⁇ m. Subsequently, it was heated and dried in a hot air drying furnace so that the ultimate plate temperature was 210 ° C.
  • top coat layer After forming the intermediate coat layer, the top coat was applied using a bar coater to a dry film thickness of 15 ⁇ m. Subsequently, it was heated and dried in a hot air drying furnace so that the ultimate plate temperature was 220 ° C.
  • the generation density of blisters is evaluated according to ASTM D 714, and the symbols used have the following meanings.
  • Acid resistance Sulfuric acid resistance test Each test plate was immersed in a 5% by weight sulfuric acid aqueous solution at room temperature for 24 hours, then the size and density of the generated blisters were observed with the naked eye, and evaluated according to the same criteria as alkali resistance. Went.
  • Examples 1 to 24 which are coated zinc and zinc alloy-plated steel sheets having a treated coating layer of the present invention, have a work adhesion (bending work adhesion, drawing work adhesion, etc.) and chemical resistance. Excellent results were obtained in all the performances (alkali resistance, acid resistance, etc.) and corrosion resistance, and the same performance as that of Comparative Example 21 which is a chromate type was shown. Further, all of the aqueous treatment agents used in Examples 1 to 24 were excellent in storage stability.
  • Comparative Example 1 containing no zirconium compound (A) is remarkably inferior in all of processing adhesion, corrosion resistance, and chemical resistance. Further, Comparative Example 2 containing a zirconium compound outside the scope of the present invention instead of the zirconium compound (A) was remarkably inferior in work adhesion and corrosion resistance.
  • Comparative Example 3 not including the epoxy resin (B) has insufficient performance.
  • Comparative Examples 4 and 5 including a resin outside the scope of the present invention had insufficient work adhesion, corrosion resistance, chemical resistance, and the like.
  • Comparative Example 6 not containing the silanol group-containing compound (C) is remarkably inferior in processing adhesion. Moreover, the comparative example 7 which contains the silanol group containing compound outside the range of this invention instead was insufficient in process adhesiveness and corrosion resistance.
  • Comparative Example 8 containing no phosphoric acid compound (D) and Comparative Example 9 containing no vanadium compound (E) were insufficient in corrosion resistance.
  • Comparative Examples 12 and 13 in which the blending ratio of the silanol group-containing compound (C) was outside the scope of the present invention were insufficient in work adhesion and corrosion resistance.
  • Comparative Examples 14 and 15 in which the blending ratio of the phosphoric acid compound (D) was outside the scope of the present invention were remarkably inferior in corrosion resistance.
  • Comparative Examples 16 and 17 in which the compounding ratio of the vanadium compound (E) was outside the scope of the present invention were remarkably inferior in corrosion resistance.
  • Comparative Example 18 in which the Zr adhesion amount was outside the range of the present invention was remarkably inferior in work adhesion and corrosion resistance.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
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Abstract

La présente invention concerne un agent de traitement à base d'eau qui, même dépourvu de chrome, confère une résistance à la corrosion, une résistance aux alcalins, une résistance aux acides et une adhésivité de film d'enrobage à une section de formage et de traitement. La présente invention concerne plus précisément un agent de traitement à base d'eau contenant (A) un composé de zirconium, (B) une résine époxy, (C) un composé contenant un groupe silanol représenté par la formule (I) et/ou un condensat de celui-ci : XY(Z)nSi(OH)3-n ... (I), (D) un composé de phosphate et (E) un composé de vanadium quadrivalent. Par rapport à la masse en termes de Zr du composé de zirconium (A), le rapport massique [(B)/Zr] de la masse de la résine époxy (B) est compris entre 0,7 et 1,5, le rapport massique [SiO2/Zr] de la masse en termes de SiO2 du composé contenant un groupe silanol et/ou du condensat de celui-ci (C) est compris entre 0,15 et 1,5, le rapport massique [P/Zr] de la masse en termes de P du composé de phosphate (D) est compris entre 0,025 et 0,1 et le rapport massique [V/Zr] de la masse en termes de V du composé de vanadium quadrivalent (E) est compris entre 0,02 et 0,05.
PCT/JP2016/071070 2015-07-15 2016-07-15 Agent de traitement à base d'eau, matériau en acier plaqué de zinc ou matériau en acier plaqué d'un alliage de zinc et matériau en acier plaqué de zinc enrobé ou matériau en acier plaqué d'un alliage de zinc enrobé WO2017010571A1 (fr)

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JP2017528740A JP6564036B2 (ja) 2015-07-15 2016-07-15 水系処理剤、亜鉛めっき鋼材又は亜鉛合金めっき鋼材および塗装亜鉛めっき鋼材又は塗装亜鉛合金めっき鋼材
KR1020187000597A KR102043572B1 (ko) 2015-07-15 2016-07-15 수계 처리제, 아연 도금 강재 또는 아연 합금 도금 강재 및 도장 아연 도금 강재 또는 도장 아연 합금 도금 강재
MYPI2017705131A MY183818A (en) 2015-07-15 2016-07-15 Water-based treatment agent, galvanized steel material or galvannealed steel material, coated galvanized steel material or coated galvannealed steel material , and method for producing same
CN201680040716.1A CN107849696B (zh) 2015-07-15 2016-07-15 水系处理剂、镀锌钢材或镀锌合金钢材以及涂装镀锌钢材或涂装镀锌合金钢材

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WO2021235363A1 (fr) * 2020-05-20 2021-11-25 日鉄鋼板株式会社 Tôle d'acier plaquée et revêtue
WO2022186380A1 (fr) * 2021-03-04 2022-09-09 日本製鉄株式会社 Matériau d'acier traité en surface
CN115537793A (zh) * 2022-09-30 2022-12-30 安徽舜邦精细化工有限公司 一种镀锌钢板无铬钝化封闭处理方法

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JP2014055319A (ja) * 2012-09-12 2014-03-27 Kansai Paint Co Ltd 水性金属表面処理剤

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JP3857866B2 (ja) 2000-02-29 2006-12-13 日本ペイント株式会社 ノンクロメート金属表面処理剤、表面処理方法および処理された塗装鋼材
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JP2011195942A (ja) * 2010-03-24 2011-10-06 Jfe Steel Corp 表面処理鋼板
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CN115537793A (zh) * 2022-09-30 2022-12-30 安徽舜邦精细化工有限公司 一种镀锌钢板无铬钝化封闭处理方法

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MY183818A (en) 2021-03-17
CN107849696B (zh) 2020-01-14
KR20180016533A (ko) 2018-02-14

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