WO2016129640A1 - Metal surface treatment agent - Google Patents

Metal surface treatment agent Download PDF

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Publication number
WO2016129640A1
WO2016129640A1 PCT/JP2016/053984 JP2016053984W WO2016129640A1 WO 2016129640 A1 WO2016129640 A1 WO 2016129640A1 JP 2016053984 W JP2016053984 W JP 2016053984W WO 2016129640 A1 WO2016129640 A1 WO 2016129640A1
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Prior art keywords
acid
surface treatment
metal surface
treatment agent
content
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PCT/JP2016/053984
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French (fr)
Japanese (ja)
Inventor
和史 安田
美和 内川
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日本ペイント・サーフケミカルズ株式会社
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Publication of WO2016129640A1 publication Critical patent/WO2016129640A1/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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09D201/08—Carboxyl 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
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates

Definitions

  • the present invention relates to a metal surface treatment agent.
  • Resin layer is excellent in molding processability, corrosion resistance, and barrier properties of contents, so beverage cans, food cans, design cans, capacitor cases, battery materials, etc. It is used to protect the surface of the material.
  • the metal material in which the resin layer is formed by laminating or the like has the excellent characteristics as described above, but the resin layer may be peeled off when the adhesion between the metal material and the resin layer is not sufficient. It was. Such peeling of the resin layer from the metal material has been a major cause of reducing the corrosion resistance.
  • a surface treatment layer is formed on the surface of the metal material prior to the formation of the resin layer.
  • a technique for improving the adhesiveness see, for example, Patent Documents 1 and 2). If the adhesion between the resin layer and the metal material can be improved, the corrosion resistance of the metal material on which the resin layer is formed is also improved.
  • This invention is made
  • the surface treatment film which can provide sufficient adhesiveness with a resin layer and corrosion resistance on the surface of the metal material which consists of aluminum or aluminum alloy by one process process It aims at providing the metal surface treating agent which can be formed.
  • the present invention is a metal surface treatment agent that is applied to the surface of a metal material made of aluminum or an aluminum alloy to form a surface treatment film, and contains zirconium, a phosphorus compound, and a water-soluble resin.
  • the content (C Zr ) in terms of zirconium atom of 4000 to 96000 ppm, the content (C P ) in terms of phosphorus atom of the phosphorus compound is 1250 to 22500 ppm, and the water-soluble resin is carboxy A metal surface having a group, the acid value of the water-soluble resin is 130 to 970 mg KOH / g, and the content (C R ) in terms of solid content of the water-soluble resin is 4000 to 120,000 ppm It relates to a processing agent.
  • the phosphorus compound preferably contains at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid and phytic acid.
  • the water-soluble resin comprises at least one monomer (i) selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and fumaric acid, 20-100% by mass, styrene, vinyl acetate And at least one monomer (ii) selected from the group consisting of methylstyrene, 2-hydroxy-3-allyloxypropanesulfonic acid, acrylamidomethylpropanesulfonic acid and styrenesulfonic acid is polymerized It is preferable that it is a polymer obtained by this.
  • the ratio (C P / C Zr ) of the content (C P ) of the phosphorus compound in terms of phosphorus atoms to the content (C Zr ) in terms of zirconium atoms of the zirconium is 0.08 to It is preferably 2.5.
  • At least one organic acid selected from the group consisting of maleic acid, fumaric acid, succinic acid, malic acid, acetic acid, itaconic acid, tartaric acid, ascorbic acid, glutamic acid and aspartic acid.
  • a metal surface treatment agent capable of forming a surface treatment film capable of imparting sufficient adhesion and corrosion resistance with a resin layer on the surface of a metal material made of aluminum or an aluminum alloy by a single treatment step.
  • the metal surface treatment agent according to this embodiment is a metal surface treatment agent that is applied to the surface of a metal material made of aluminum or an aluminum alloy to form a surface treatment film.
  • the material of the metal material in the present embodiment is aluminum or an aluminum alloy, but the aluminum alloy is not particularly limited as long as the aluminum alloy is an alloy mainly composed of aluminum.
  • the aluminum alloy include aluminum, aluminum-copper alloy, aluminum-manganese alloy, aluminum-silicon alloy, aluminum-magnesium alloy, aluminum-magnesium-silicon alloy, aluminum-zinc alloy, and aluminum-zinc-magnesium alloy. be able to.
  • the use of the metal material in the present embodiment is not particularly limited, but it is preferably used for beverage cans and food cans and can bodies that require high adhesion to the resin layer and high corrosion resistance.
  • the metal surface treatment agent according to this embodiment is a so-called coating type surface treatment agent.
  • the coating type surface treatment agent is used in a method in which the surface treatment agent is applied to the surface of the metal material, and then the surface of the metal material is dried without washing.
  • the metal surface treating agent according to this embodiment contains zirconium, a phosphorus compound, and a water-soluble resin.
  • Zirconium imparts corrosion resistance to the metal material.
  • Zirconium is derived from a zirconium compound.
  • the zirconium compound fluorozirconic acid, lithium of fluorozirconic acid, sodium, potassium, ammonium salt, zirconium sulfate, zirconyl sulfate, zirconium nitrate, zirconyl nitrate, zirconium fluoride, zirconium carbonate, zirconium hydrofluoride
  • the surface of the metal material can be appropriately etched by fluorine ions.
  • the content (C Zr ) of zirconium in terms of zirconium atom in the metal surface treatment agent is 4000 to 96000 ppm.
  • the content (C Zr ) is less than 4000 ppm, the corrosion resistance of the metal material is lowered.
  • the content (C Zr ) exceeds 96000 ppm the stability of the metal surface treatment agent is lowered, and the adhesion between the metal material and the resin layer is also lowered.
  • the phosphorus compound contributes to improving the adhesion between the metal material and the resin layer by coordination of unpaired electrons of phosphorus atoms to the resin component in the resin layer in the surface treatment film. By improving the adhesion between the metal material and the resin layer, the corrosion resistance of the metal material is also improved.
  • the metal surface treatment agent preferably contains at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, and phytic acid.
  • the phosphorus compound contained in the metal surface treatment agent is at least one selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, and phytic acid, thereby improving the adhesion between the metal material and the resin layer. Further, the corrosion resistance of the metal material is further improved. Further, the phosphorus compound contained in the metal surface treatment agent is more preferably phytic acid having a large number of phosphorus atoms in one molecule.
  • the content (C P ) of the phosphorus compound in terms of phosphorus atoms in the metal surface treatment agent is 1250 to 22500 ppm.
  • the content (C P ) is less than 1250 ppm, the adhesion between the metal material and the resin layer decreases.
  • the content (C P ) exceeds 22500 ppm, the stability of the metal surface treatment agent decreases, and the adhesion between the metal material and the resin layer also decreases.
  • the ratio (C P / C Zr ) of the content (C P ) of the phosphorus compound in terms of phosphorus atoms to the content (C Zr ) in terms of zirconium atoms of the zirconium is 0.08-2. 5 is preferable, and 0.3 to 1.3 is more preferable.
  • the value of the ratio (C P / C Zr ) is less than 0.08, the adhesiveness between the metal material and the resin layer tends to decrease because the content of the phosphorus compound is small.
  • the ratio value (C P / C Zr ) exceeds 2.5, the corrosion resistance of the metal material tends to decrease because the zirconium content is low.
  • Water-soluble resin contributes to improving the adhesion between the metal material and the resin layer.
  • the water-soluble resin is a resin having a carboxy group. This carboxy group coordinates to the resin component in the resin layer in the surface treatment film, and improves the adhesion between the metal material and the resin layer.
  • the water-soluble resin preferably has at least one carboxy group per unit structure.
  • water-soluble resins include polyacrylic acid, polymethacrylic acid, and polyitaconic acid. More specifically, the water-soluble resin comprises at least one monomer (i) selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and fumaric acid, 20 to 100% by mass, styrene At least one monomer (ii) selected from the group consisting of vinyl acetate, methylstyrene, 2-hydroxy-3-allyloxypropanesulfonic acid, acrylamidomethylpropanesulfonic acid and styrenesulfonic acid; It is preferable that it is a polymer obtained by superposing
  • the monomer (i) is less than 20% by mass (when the monomer (ii) exceeds 80% by mass) among the monomers used for obtaining the water-soluble resin, the carboxy contained in the water-soluble resin The number of groups is reduced. When the number of carboxy groups of the water-soluble resin decreases, the adhesion between the metal material and the resin layer tends to decrease.
  • the acid value of the water-soluble resin is 130 to 970 mgKOH / g, preferably 650 to 970 mgKOH / g, in terms of resin solid content.
  • the acid value of water-soluble resin is less than 130 mgKOH / g, the adhesiveness of a metal material and a resin layer falls.
  • the acid value of the soluble resin exceeds 970 mgKOH / g, the stability of the metal surface treatment agent decreases.
  • the content (C R ) in terms of solid content of the water-soluble resin in the metal surface treatment agent is preferably 4000 to 120,000 ppm, and more preferably 20000 to 80000 ppm.
  • the content (C R ) is less than 4000 ppm, the adhesion between the metal material and the resin layer decreases.
  • the content (C R ) exceeds 120,000 ppm, the adhesion between the metal material and the resin layer is reduced due to an increase in the thickness of the formed surface treatment film.
  • the metal surface treatment agent according to this embodiment may further contain an organic acid.
  • the organic acid is at least one selected from the group consisting of maleic acid, fumaric acid, succinic acid, malic acid, acetic acid, itaconic acid, tartaric acid, ascorbic acid, glutamic acid and aspartic acid.
  • succinic acid and malic acid are preferable from the viewpoint of improving the adhesion between the metal material and the resin layer.
  • a metal surface treating agent contains an organic acid, it is preferable to contain multiple types of organic acid from a viewpoint of improving adhesiveness and corrosion resistance.
  • the content of the organic acid is preferably 5000 to 20000 ppm.
  • the content (C 2 O 3 ) is less than 5000 ppm, the adhesion between the metal material and the resin layer tends to decrease.
  • the content (C 2 O 3 ) exceeds 20000 ppm, the stability of the metal surface treatment agent tends to decrease.
  • the solid content of the metal surface treatment agent according to this embodiment is preferably 1.85 to 11.60% by mass. If the solid content of the metal surface treatment agent is less than 1.85% by mass, it tends to be difficult to form a sufficient surface treatment film, and if it exceeds 11.60% by mass, the stability of the metal surface treatment agent Tend to decrease.
  • the pH of the metal surface treatment agent according to this embodiment is preferably less than 5.
  • the pH of the metal surface treatment agent is 5 or more, the stability of the metal surface treatment agent is lowered, and it tends to be difficult to use as the metal surface treatment agent.
  • the metal surface treatment agent according to this embodiment may contain other components as necessary. Note that many of the components of the metal surface treatment agent according to this embodiment described above are highly safe compounds that are recognized as food additives in the US FDA standards. Thus, the metal surface treatment agent according to the present embodiment can be preferably used for beverage cans and food cans because it is composed of highly safe components.
  • the surface treatment method in the present embodiment includes an application step of applying a metal surface treatment agent to the surface of the metal material, and a drying step of drying the metal surface treatment agent applied with the metal material.
  • the method for applying the metal surface treatment agent to the surface of the metal material is not particularly limited, and examples thereof include a method using a roll coating method, a bar coating method, a spray treatment method, an immersion treatment method, and the like.
  • the surface of the metal material Prior to the coating step, the surface of the metal material may be subjected to a degreasing process or an etching process as necessary.
  • the metal surface treatment agent applied to the metal material is dried after the application step, but the method for drying the metal surface treatment agent is not particularly limited.
  • the method for drying the metal surface treatment agent in the drying step include a method in which the metal material coated with the metal surface treatment agent is heated at 40 to 160 ° C. for 2 to 60 seconds.
  • the coating amount of the surface treatment film formed by the above-mentioned surface treatment method is not particularly limited, but is an amount that is 10 to 30 mg / m 2 in the total mass per unit area of zirconium and phosphorus in terms of elements. Is preferred.
  • the amount of the film is less than 10 mg / m 2 , the adhesion between the metal material and the resin layer is lowered, and the corrosion resistance of the metal material tends to be lowered.
  • the amount of the film exceeds 10 mg / m 2 , the surface treatment film becomes brittle, the adhesion between the metal material and the resin layer decreases, and the corrosion resistance of the metal material also tends to decrease. is there.
  • the total mass per unit area in terms of elements of zirconium and phosphorus can be determined, for example, by measurement using an X-ray fluorescence analyzer “XRF1700” (manufactured by Shimadzu Corporation).
  • the metal surface treating agent which concerns on this embodiment is a coating-type metal surface treating agent
  • the component ratio of solid content in a metal surface treating agent becomes a component ratio of a surface treatment film.
  • a surface treatment film can be formed very easily by a single treatment step using a coating-type metal surface treatment agent that is relatively easy to form. it can.
  • the surface treatment method according to the present embodiment uses a coating-type metal surface treatment agent, it is advantageous in that no waste liquid is generated (so-called waste water-less).
  • a resin layer is formed on the metal material on which the surface treatment film is formed.
  • the resin layer may be formed by applying a resin solution to the surface of the metal material, or may be formed by attaching a laminate film. Examples of the method for attaching the laminate film include a dry lamination method and an extrusion lamination method.
  • the resin component of the resin layer is not particularly limited. Resin components include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polycarbonate (PC), triacetyl cellulose (TAC), polyvinyl chloride (PVC), polyester, polyolefin, acrylic, etc.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PP polypropylene
  • PC polycarbonate
  • TAC triacetyl cellulose
  • PVC polyvinyl chloride
  • polyester polyolefin, acrylic, etc.
  • a plastic resin can be mentioned.
  • the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Unless otherwise specified, the unit is based on mass.
  • Dimer AC10L acid value: 750- 800 mg KOH / g, manufactured by Toa Gosei Co., Ltd.
  • C P / C Zr in Table 1 is a value of the ratio of the content (C P ) in terms of phosphorus atom of the phosphorus compound to the content (C Zr ) in terms of zirconium atom of zirconium. .
  • each metal surface treatment agent was treated in the same manner as in Example 3 except that the phosphorus compounds shown in Tables 1 and 2 were mixed so as to have the contents shown in Tables 1 and 2 instead of phytic acid. Got.
  • two types of phosphorus compounds (mass ratio is 1: 1) described in Table 1 were mixed so that it might become the total content shown in Table 1.
  • the following compounds were used as phosphorus compounds.
  • Phosphorous acid Phosphorous acid, manufactured by Terada Fine Co., Ltd.
  • Phosphonic acid Dequest 2010, manufactured by Italmatch Japan Co., Ltd.
  • Polyphosphoric acid Tripolyphosphoric acid, manufactured by Yoneyama Chemical Co., Ltd.
  • Phosphoric acid Phosphoric acid, BK Gurini Japan Co., Ltd. Company made sodium phosphate: disodium phosphate, made by Yoneyama Chemical Co., Ltd.
  • each metal surface treatment agent was obtained by further mixing the organic acids shown in Table 3 so as to have the contents shown in Table 3.
  • two types of organic acids listed in Table 3 (mass ratio is 1: 1) were mixed so that the total content shown in Table 3 was obtained.
  • the succinic acid, malonic acid, ascorbic acid, malic acid, tartaric acid, aspartic acid and fumaric acid used are all manufactured by Wako Pure Chemical Industries, Ltd.
  • Each metal surface treating agent was obtained by the same method as Example 3 except having mixed the resin shown in Table 2 instead of polyacrylic acid.
  • the following were used as resin.
  • Polyallylamine Polyallylamine 15C, Nitto Boseki Co., Ltd.
  • polyurethane PX-200, Sanyo Kasei Kogyo Co., Ltd.
  • Polyoxazoline Epochros WS700, Nippon Shokubai Co., Ltd.
  • Polyester Pesresin HSX155, Takamatsu Yushi Co., Ltd.
  • PVA Kuraray Poval 105MC , Kuraray Co., Ltd.
  • Phenol resin Shounol BRL 2854, Showa Denko Co., Ltd.
  • Melamine resin Cymel 771, Nihon Cytec Industries, Ltd.
  • a metal surface treating agent was obtained in the same manner as in Example 3 except that titanium titanium fluoride (manufactured by Morita Chemical Co., Ltd.) was mixed as a titanium source.
  • the coating amount of each metal surface treatment agent of each example, comparative example and reference example is 20 mg / m 2 (comparative example). 15 was applied so as to be 5 mg / m 2 ). Subsequently, the plate material coated with the metal surface treatment agent was dried at 80 ° C. for 20 seconds using a conveyor oven.
  • the “film amount” is the total mass per unit area in terms of elements of zirconium and phosphorus in the surface treatment film.
  • the “film amount” shown in Table 1 was determined by measurement with a fluorescent X-ray analyzer “XRF1700” (manufactured by Shimadzu Corporation).
  • a surface treatment film was formed using the metal surface treatment agent of Example 3 so as to have a film amount shown in Table 4 different from Example 3.
  • a reference example Table 2
  • "Alsurf 408” brand name, the Nippon Paint company make
  • a film quantity may be set to 20 mg / m ⁇ 2 >.
  • a chromium phosphate film was formed in the same manner as in the other Examples and Comparative Examples.
  • the “film amount” in the reference example is the mass per unit area in terms of chromium element in the surface treatment film.
  • the “film amount” of the reference example was also determined by measurement with a fluorescent X-ray analyzer “XRF1700” (manufactured by Shimadzu Corporation).
  • Solvent-type polyester paint (Flexcoat # 5000 White, manufactured by Nippon Paint Co., Ltd.) is wet-massed on the surface of the aluminum alloy plate of each Example, Comparative Example, Reference Example, and Test Example on the side where the surface treatment film is formed. It apply
  • the metal surface treatment agent of Example 3 was obtained. It turned out that the direction of the test piece obtained by using is excellent in adhesiveness and corrosion resistance. From this result, it was confirmed that when the metal surface treatment agent contains zirconium, the obtained test piece is improved in both adhesion and corrosion resistance.
  • Examples 3 and 7 to 12 were compared. It was found that the test piece obtained by using the metal surface treatment agent was superior in adhesion and corrosion resistance. Further, when the test pieces obtained using the metal surface treatment agents of Examples 3 and 7 to 12 were compared with the test pieces obtained using the metal surface treatment agent of Comparative Example 4, Examples 3 and 7 were compared. It was found that the test pieces obtained using the metal surface treatment agents of ⁇ 12 were superior in adhesion and corrosion resistance.
  • the metal surface treatment agent of Example 3 was It turned out that the direction of the test piece obtained by using is excellent in adhesiveness and corrosion resistance. From this result, it was confirmed that when the metal surface treatment agent contains a water-soluble resin having a carboxy group, the obtained test piece improves both adhesion and corrosion resistance.
  • test pieces obtained using the metal surface treatment agents of Examples 3 and 17 to 24 and the test pieces obtained using the metal surface treatment agents of Comparative Examples 12 and 13 were compared. It was found that the test pieces obtained using the metal surface treatment agents of ⁇ 24 were superior in adhesion and corrosion resistance. From these results, it can be seen that by setting the content (C R ) in terms of solid content of the water-soluble resin contained in the metal surface treatment agent to 4000 to 120,000 ppm, the obtained test piece can be improved in both adhesion and corrosion resistance. confirmed.
  • test pieces of Test Examples 3 and 4 were compared with the test pieces of Test Examples 1, 2, 5, and 6, it was found that the test pieces of Test Examples 3 and 4 were superior in adhesion and corrosion resistance. From this result, the adhesion of the test piece and the corrosion resistance are improved by setting the coating amount of the surface treatment coating to 10 to 30 mg / m 2 in terms of the total mass per unit area of zirconium and phosphorus in terms of elements. Was confirmed.

Abstract

The purpose of the present invention is to provide a metal surface treatment agent with which a surface treatment film able to impart satisfactory cohesion to a resin layer and corrosion resistance can be formed in a single treatment step, on the surface of a metal material comprising aluminum or an aluminum alloy. This metal surface treatment agent is applied to the surface of a metal material comprising aluminum or an aluminum alloy to form a surface treatment film, and contains zirconium, a phosphorus compound, and a water-soluble resin. The zirconium content (CZr), on a zirconium atom conversion basis, is 4,000-96,000 ppm, and the phosphorus compound (CP), on a phosphorus atom conversion basis, is 1,250-22,500 ppm. The water-soluble resin has carboxyl groups, the acid value of the water-soluble resin being 130-970 mgKOH/g, and the content (CR) of the water-soluble resin, on a solids conversion basis, being 4,000-120,000 ppm.

Description

金属表面処理剤Metal surface treatment agent
　本発明は、金属表面処理剤に関する。 The present invention relates to a metal surface treatment agent.
　従来、アルミニウム又はアルミニウム合金からなる金属材料の表面を保護し、意匠を施すために、金属材料の表面に塗装やラミネート加工等によって樹脂層が形成される。樹脂層は、成型加工性、耐食性、及び内容物のバリア性等に優れることから、飲料缶、食品缶、意匠缶、コンデンサーケース、電池材等、コイルやシート状でプレコートされる包装用の金属材料の表面を保護するために用いられている。 Conventionally, in order to protect the surface of a metal material made of aluminum or an aluminum alloy and apply a design, a resin layer is formed on the surface of the metal material by painting or laminating. Resin layer is excellent in molding processability, corrosion resistance, and barrier properties of contents, so beverage cans, food cans, design cans, capacitor cases, battery materials, etc. It is used to protect the surface of the material.
　ところで、ラミネート加工等によって樹脂層を形成した金属材料は、上述のような優れた特性を有する一方、金属材料と樹脂層との密着性が十分でない場合、樹脂層が剥離してしまうことがあった。このような、金属材料からの樹脂層の剥離は、耐食性を低下させる大きな原因となっていた。 By the way, the metal material in which the resin layer is formed by laminating or the like has the excellent characteristics as described above, but the resin layer may be peeled off when the adhesion between the metal material and the resin layer is not sufficient. It was. Such peeling of the resin layer from the metal material has been a major cause of reducing the corrosion resistance.
特許第５２３１７３８号公報Japanese Patent No. 5231338 特許第５０７７６５１号公報Japanese Patent No. 5077651
　ラミネート加工等によって樹脂層が形成された金属材料における、このような問題を解決するため、樹脂層の形成に先立って、金属材料の表面に表面処理層を形成して、樹脂層と金属材料との密着性を向上させる技術が知られている（例えば、特許文献１及び２参照）。樹脂層と金属素材との密着性を向上させることができれば、樹脂層を形成した金属材料の耐食性も向上する。 In order to solve such a problem in a metal material in which a resin layer is formed by laminating or the like, a surface treatment layer is formed on the surface of the metal material prior to the formation of the resin layer. There is known a technique for improving the adhesiveness (see, for example, Patent Documents 1 and 2). If the adhesion between the resin layer and the metal material can be improved, the corrosion resistance of the metal material on which the resin layer is formed is also improved.
　しかしながら、従来は、金属材料の表面にジルコニウムを含む化成処理剤によって化成皮膜を形成させた後に、金属表面処理剤によって樹脂層と金属素材との密着性を向上させる表面処理層を形成させていた。このように、金属材料の表面を２回の処理工程によって処理するのは煩雑であった。 However, conventionally, after forming a chemical conversion film with a chemical conversion treatment agent containing zirconium on the surface of the metal material, a surface treatment layer for improving the adhesion between the resin layer and the metal material is formed with the metal surface treatment agent. . Thus, it was complicated to treat the surface of the metal material by two treatment steps.
　本発明は、上記課題に鑑みてなされたものであり、アルミニウム又はアルミニウム合金からなる金属材料の表面に、樹脂層との十分な密着性と耐食性を付与できる表面処理皮膜を１回の処理工程によって形成させることができる金属表面処理剤を提供することを目的とする。 This invention is made | formed in view of the said subject, The surface treatment film which can provide sufficient adhesiveness with a resin layer and corrosion resistance on the surface of the metal material which consists of aluminum or aluminum alloy by one process process It aims at providing the metal surface treating agent which can be formed.
　本発明は、アルミニウム又はアルミニウム合金からなる金属材料の表面に塗布されて表面処理皮膜を形成する金属表面処理剤であって、ジルコニウムと、リン化合物と、水溶性樹脂と、を含有し、前記ジルコニウムのジルコニウム原子換算での含有量（ＣＺｒ）は、４０００～９６０００ｐｐｍであり、前記リン化合物のリン原子換算での含有量（ＣＰ）は、１２５０～２２５００ｐｐｍであり、前記水溶性樹脂は、カルボキシ基を有し、前記水溶性樹脂の酸価は、１３０～９７０ｍｇＫＯＨ／ｇであり、前記水溶性樹脂の固形分換算での含有量（ＣＲ）は、４０００～１２００００ｐｐｍである樹脂である金属表面処理剤に関する。 The present invention is a metal surface treatment agent that is applied to the surface of a metal material made of aluminum or an aluminum alloy to form a surface treatment film, and contains zirconium, a phosphorus compound, and a water-soluble resin. The content (C Zr ) in terms of zirconium atom of 4000 to 96000 ppm, the content (C P ) in terms of phosphorus atom of the phosphorus compound is 1250 to 22500 ppm, and the water-soluble resin is carboxy A metal surface having a group, the acid value of the water-soluble resin is 130 to 970 mg KOH / g, and the content (C R ) in terms of solid content of the water-soluble resin is 4000 to 120,000 ppm It relates to a processing agent.
　また、前記リン化合物はとして、リン酸、亜リン酸、ホスホン酸及びフィチン酸からなる群より選択される少なくとも一種のリン化合物を含有することが好ましい。 The phosphorus compound preferably contains at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid and phytic acid.
　前記水溶性樹脂は、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、クロトン酸及びフマル酸からなる群より選択される少なくとも一種の単量体（ｉ）２０～１００質量％と、スチレン、酢酸ビニル、メチルスチレン、２－ヒドロキシ－３－アリロキシプロパンスルホン酸、アクリルアミドメチルプロパンスルホン酸及びスチレンスルホン酸からなる群より選択される少なくとも一種の単量体（ｉｉ）０～８０質量％と、を重合して得られる重合体であることが好ましい。 The water-soluble resin comprises at least one monomer (i) selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and fumaric acid, 20-100% by mass, styrene, vinyl acetate And at least one monomer (ii) selected from the group consisting of methylstyrene, 2-hydroxy-3-allyloxypropanesulfonic acid, acrylamidomethylpropanesulfonic acid and styrenesulfonic acid is polymerized It is preferable that it is a polymer obtained by this.
　また、前記ジルコニウムのジルコニウム原子換算での含有量（ＣＺｒ）に対する、前記リン化合物のリン原子換算での含有量（ＣＰ）の比の値（ＣＰ／ＣＺｒ）は、０．０８～２．５であることが好ましい。 The ratio (C P / C Zr ) of the content (C P ) of the phosphorus compound in terms of phosphorus atoms to the content (C Zr ) in terms of zirconium atoms of the zirconium is 0.08 to It is preferably 2.5.
　また、更に、マレイン酸、フマル酸、コハク酸、リンゴ酸、酢酸、イタコン酸、酒石酸、アスコルビン酸、グルタミン酸及びアスパラギン酸からなる群より選択される少なくとも一種の有機酸を含有することが好ましい。 Furthermore, it is preferable to contain at least one organic acid selected from the group consisting of maleic acid, fumaric acid, succinic acid, malic acid, acetic acid, itaconic acid, tartaric acid, ascorbic acid, glutamic acid and aspartic acid.
　本発明によれば、アルミニウム又はアルミニウム合金からなる金属材料の表面に、樹脂層との十分な密着性と耐食性を付与できる表面処理皮膜を１回の処理工程によって形成させることができる金属表面処理剤を提供できる。 According to the present invention, a metal surface treatment agent capable of forming a surface treatment film capable of imparting sufficient adhesion and corrosion resistance with a resin layer on the surface of a metal material made of aluminum or an aluminum alloy by a single treatment step. Can provide.
本発明の実施例における、密着性の評価のために切り込みを入れた試験片を示す図である。It is a figure which shows the test piece which gave the notch | incision for the adhesive evaluation in the Example of this invention. 本発明の実施例における、テンシロン引っ張り試験機による引っ張り方を示す図である。It is a figure which shows how to pull by the Tensilon tensile testing machine in the Example of this invention. 本発明の実施例における、密着性の評価の基準（５段階）を示す図である。It is a figure which shows the reference | standard (5 steps) of adhesive evaluation in the Example of this invention.
　以下、本発明の実施形態について詳細に説明する。ただし、本発明は下記の実施形態に限定されない。なお、特に断りのない限り、単位は質量基準である。
　本実施形態に係る金属表面処理剤は、アルミニウム又はアルミニウム合金からなる金属材料の表面に塗布されて表面処理皮膜を形成する金属表面処理剤である。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiment. Unless otherwise specified, the unit is based on mass.
The metal surface treatment agent according to this embodiment is a metal surface treatment agent that is applied to the surface of a metal material made of aluminum or an aluminum alloy to form a surface treatment film.
　＜金属材料＞
　本実施形態における金属材料の素材は、アルミニウム又はアルミニウム合金であるが、アルミニウム合金はアルミニウムを主成分とする合金であれば特に限定されない。アルミニウム合金としては、例えば、アルミニウム、アルミニウム－銅合金、アルミニウム－マンガン合金、アルミニウム－珪素合金、アルミニウム－マグネシウム合金、アルミニウム－マグネシウム－珪素合金、アルミニウム－亜鉛合金、アルミニウム－亜鉛－マグネシウム合金等を挙げることができる。
　また、本実施形態における金属材料の用途は特に限定されないが、樹脂層との高い密着性や高い防食性が求められる飲料缶や食品缶の缶蓋や缶ボディに用いることが好ましい。 <Metal material>
The material of the metal material in the present embodiment is aluminum or an aluminum alloy, but the aluminum alloy is not particularly limited as long as the aluminum alloy is an alloy mainly composed of aluminum. Examples of the aluminum alloy include aluminum, aluminum-copper alloy, aluminum-manganese alloy, aluminum-silicon alloy, aluminum-magnesium alloy, aluminum-magnesium-silicon alloy, aluminum-zinc alloy, and aluminum-zinc-magnesium alloy. be able to.
In addition, the use of the metal material in the present embodiment is not particularly limited, but it is preferably used for beverage cans and food cans and can bodies that require high adhesion to the resin layer and high corrosion resistance.
＜金属表面処理剤＞
　本実施形態に係る金属表面処理剤は、いわゆる塗布型の表面処理剤である。塗布型の表面処理剤は、表面処理剤を金属材料の表面に塗布した後に、金属材料の表面を水洗せずに乾燥させる方法で使用される。
　本実施形態に係る金属表面処理剤は、ジルコニウムと、リン化合物と、水溶性樹脂と、を含有する。 <Metal surface treatment agent>
The metal surface treatment agent according to this embodiment is a so-called coating type surface treatment agent. The coating type surface treatment agent is used in a method in which the surface treatment agent is applied to the surface of the metal material, and then the surface of the metal material is dried without washing.
The metal surface treating agent according to this embodiment contains zirconium, a phosphorus compound, and a water-soluble resin.
　ジルコニウムは、金属材料の耐食性を付与する。ジルコニウムは、ジルコニウム化合物に由来する。
　ここで、ジルコニウム化合物としては、フルオロジルコニウム酸、フルオロジルコニウム酸のリチウム、ナトリウム、カリウム、アンモニウム塩、硫酸ジルコニウム、硫酸ジルコニル、硝酸ジルコニウム、硝酸ジルコニル、フッ化ジルコニウム、炭酸ジルコニウム、フッ化水素酸ジルコニウムを挙げることができ、これらは単独で金属表面処理剤に含有させてもよく、２種以上を金属表面処理剤に含有させてもよい。なお、フッ素を含有するジルコニウム化合物を使用することで、フッ素イオンによって金属材料の表面表を適度にエッチングさせることもができる。 Zirconium imparts corrosion resistance to the metal material. Zirconium is derived from a zirconium compound.
Here, as the zirconium compound, fluorozirconic acid, lithium of fluorozirconic acid, sodium, potassium, ammonium salt, zirconium sulfate, zirconyl sulfate, zirconium nitrate, zirconyl nitrate, zirconium fluoride, zirconium carbonate, zirconium hydrofluoride These may be included in the metal surface treatment agent alone, or two or more of them may be contained in the metal surface treatment agent. Note that by using a fluorine-containing zirconium compound, the surface of the metal material can be appropriately etched by fluorine ions.
　金属表面処理剤における、ジルコニウムのジルコニウム原子換算での含有量（ＣＺｒ）は、４０００～９６０００ｐｐｍである。含有量（ＣＺｒ）が、４０００ｐｐｍ未満の場合には金属材料の耐食性が低下する。一方、含有量（ＣＺｒ）が、９６０００ｐｐｍを超えると金属表面処理剤の安定性が低下し、金属材料と樹脂層との密着性も低下する。 The content (C Zr ) of zirconium in terms of zirconium atom in the metal surface treatment agent is 4000 to 96000 ppm. When the content (C Zr ) is less than 4000 ppm, the corrosion resistance of the metal material is lowered. On the other hand, when the content (C Zr ) exceeds 96000 ppm, the stability of the metal surface treatment agent is lowered, and the adhesion between the metal material and the resin layer is also lowered.
　リン化合物は、表面処理皮膜において、リン原子の不対電子が樹脂層中の樹脂成分に配位することで、金属材料と樹脂層との密着性の向上に寄与する。金属材料と樹脂層との密着性が向上することにより、金属材料の耐食性も向上する。 The phosphorus compound contributes to improving the adhesion between the metal material and the resin layer by coordination of unpaired electrons of phosphorus atoms to the resin component in the resin layer in the surface treatment film. By improving the adhesion between the metal material and the resin layer, the corrosion resistance of the metal material is also improved.
　リン化合物としては、フィチン酸、亜リン酸、ホスホン酸、ポリリン酸、リン酸、リン酸ナトリウム等のリン酸塩等が挙げられる。金属表面処理剤は、これらのリン化合物の中でも、リン酸、亜リン酸、ホスホン酸及びフィチン酸からなる群より選択される少なくとも一種のリン化合物を含有することが好ましい。金属表面処理剤の含有するリン化合物が、リン酸、亜リン酸、ホスホン酸及びフィチン酸からなる群より選択される少なくとも一種であることで、金属材料と樹脂層との密着性がより向上し、金属材料の耐食性が更に向上する。また、金属表面処理剤の含有するリン化合物は、１分子中にリン原子を多数有するフィチン酸であることがより好ましい。 Examples of phosphorus compounds include phosphates such as phytic acid, phosphorous acid, phosphonic acid, polyphosphoric acid, phosphoric acid, and sodium phosphate. Among these phosphorus compounds, the metal surface treatment agent preferably contains at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, and phytic acid. The phosphorus compound contained in the metal surface treatment agent is at least one selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, and phytic acid, thereby improving the adhesion between the metal material and the resin layer. Further, the corrosion resistance of the metal material is further improved. Further, the phosphorus compound contained in the metal surface treatment agent is more preferably phytic acid having a large number of phosphorus atoms in one molecule.
　金属表面処理剤における、リン化合物のリン原子換算での含有量（ＣＰ）は、１２５０～２２５００ｐｐｍである。含有量（ＣＰ）が、１２５０ｐｐｍ未満の場合には金属材料と樹脂層との密着性が低下する。一方、含有量（ＣＰ）が、２２５００ｐｐｍを超える場合には金属表面処理剤の安定性の低下し、金属材料と樹脂層との密着性も低下する。 The content (C P ) of the phosphorus compound in terms of phosphorus atoms in the metal surface treatment agent is 1250 to 22500 ppm. When the content (C P ) is less than 1250 ppm, the adhesion between the metal material and the resin layer decreases. On the other hand, when the content (C P ) exceeds 22500 ppm, the stability of the metal surface treatment agent decreases, and the adhesion between the metal material and the resin layer also decreases.
　前記ジルコニウムのジルコニウム原子換算での含有量（ＣＺｒ）に対する、前記リン化合物のリン原子換算での含有量（ＣＰ）の比の値（ＣＰ／ＣＺｒ）は、０．０８～２．５であることが好ましく、０．３～１．３であることがより好ましい。比の値（ＣＰ／ＣＺｒ）が０．０８未満の場合には、リン化合物の含有量が少ないことから金属材料と樹脂層との密着性が低下する傾向にある。一方、比の値（ＣＰ／ＣＺｒ）が２．５を超える場合には、ジルコニウムの含有量が少ないことから金属材料の耐食性が低下してしまう傾向にある。 The ratio (C P / C Zr ) of the content (C P ) of the phosphorus compound in terms of phosphorus atoms to the content (C Zr ) in terms of zirconium atoms of the zirconium is 0.08-2. 5 is preferable, and 0.3 to 1.3 is more preferable. When the value of the ratio (C P / C Zr ) is less than 0.08, the adhesiveness between the metal material and the resin layer tends to decrease because the content of the phosphorus compound is small. On the other hand, when the ratio value (C P / C Zr ) exceeds 2.5, the corrosion resistance of the metal material tends to decrease because the zirconium content is low.
　水溶性樹脂は、金属材料と樹脂層との密着性の向上に寄与する。水溶性樹脂は、カルボキシ基を有する樹脂である。このカルボキシ基は、表面処理皮膜において樹脂層中の樹脂成分に配位して、金属材料と樹脂層との密着性を向上させる。水溶性樹脂は、単位構造あたり少なくとも１つのカルボキシ基を有することが好ましい。 Water-soluble resin contributes to improving the adhesion between the metal material and the resin layer. The water-soluble resin is a resin having a carboxy group. This carboxy group coordinates to the resin component in the resin layer in the surface treatment film, and improves the adhesion between the metal material and the resin layer. The water-soluble resin preferably has at least one carboxy group per unit structure.
　水溶性樹脂としては、ポリアクリル酸、ポリメタクリル酸、ポリイタコン酸等を挙げることができる。より詳しくは、水溶性樹脂は、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、クロトン酸及びフマル酸からなる群より選択される少なくとも一種の単量体（ｉ）２０～１００質量％と、スチレン、酢酸ビニル、メチルスチレン、２－ヒドロキシ－３－アリロキシプロパンスルホン酸、アクリルアミドメチルプロパンスルホン酸及びスチレンスルホン酸からなる群より選択される少なくとも一種の単量体（ｉｉ）０～８０質量％と、を重合して得られる重合体であることが好ましい。 Examples of water-soluble resins include polyacrylic acid, polymethacrylic acid, and polyitaconic acid. More specifically, the water-soluble resin comprises at least one monomer (i) selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and fumaric acid, 20 to 100% by mass, styrene At least one monomer (ii) selected from the group consisting of vinyl acetate, methylstyrene, 2-hydroxy-3-allyloxypropanesulfonic acid, acrylamidomethylpropanesulfonic acid and styrenesulfonic acid; It is preferable that it is a polymer obtained by superposing | polymerizing.
　水溶性樹脂を得る際に用いる単量体のうち単量体（ｉ）が２０質量％未満の場合（単量体（ｉｉ）が８０質量％を超える場合）には、水溶性樹脂の有するカルボキシ基の数が少なくなる。水溶性樹脂の有するカルボキシ基の数が少なくなると、金属材料と樹脂層との密着性が低下する傾向にある。 When the monomer (i) is less than 20% by mass (when the monomer (ii) exceeds 80% by mass) among the monomers used for obtaining the water-soluble resin, the carboxy contained in the water-soluble resin The number of groups is reduced. When the number of carboxy groups of the water-soluble resin decreases, the adhesion between the metal material and the resin layer tends to decrease.
　水溶性樹脂の酸価は、樹脂固形分換算で、１３０～９７０ｍｇＫＯＨ／ｇであり、６５０～９７０ｍｇＫＯＨ／ｇであることが好ましい。水溶性樹脂の酸価が、１３０ｍｇＫＯＨ／ｇ未満の場合には、金属材料と樹脂層との密着性が低下する。溶性樹脂の酸価が、９７０ｍｇＫＯＨ／ｇを超える場合には、金属表面処理剤の安定性が低下する。 The acid value of the water-soluble resin is 130 to 970 mgKOH / g, preferably 650 to 970 mgKOH / g, in terms of resin solid content. When the acid value of water-soluble resin is less than 130 mgKOH / g, the adhesiveness of a metal material and a resin layer falls. When the acid value of the soluble resin exceeds 970 mgKOH / g, the stability of the metal surface treatment agent decreases.
　金属表面処理剤における、水溶性樹脂の固形分換算での含有量（ＣＲ）は、４０００～１２００００ｐｐｍであることが好ましく、２００００～８００００ｐｐｍであることがより好ましい。含有量（ＣＲ）が、４０００ｐｐｍ未満である場合には金属材料と樹脂層との密着性が低下する。一方、含有量（ＣＲ）が、１２００００ｐｐｍを超える場合には形成される表面処理皮膜の膜厚が厚くなることに起因して、金属材料と樹脂層との密着性が低下する。 The content (C R ) in terms of solid content of the water-soluble resin in the metal surface treatment agent is preferably 4000 to 120,000 ppm, and more preferably 20000 to 80000 ppm. When the content (C R ) is less than 4000 ppm, the adhesion between the metal material and the resin layer decreases. On the other hand, when the content (C R ) exceeds 120,000 ppm, the adhesion between the metal material and the resin layer is reduced due to an increase in the thickness of the formed surface treatment film.
　本実施形態に係る金属表面処理剤は、更に有機酸を含有していてもよい。有機酸は、マレイン酸、フマル酸、コハク酸、リンゴ酸、酢酸、イタコン酸、酒石酸、アスコルビン酸、グルタミン酸及びアスパラギン酸からなる群より選択される少なくとも一種である。金属表面処理剤がこれらの有機酸を含有することで金属材料と樹脂層との密着性が向上し、金属材料の耐食性も向上する。金属表面処理剤の含有する有機酸としては、金属材料と樹脂層との密着性を向上させる観点から、コハク酸及びリンゴ酸が好ましい。また、金属表面処理剤が有機酸を含有する場合には、密着性及び耐食性を向上させる観点から、複数種類の有機酸を含有させるのが好ましい。 The metal surface treatment agent according to this embodiment may further contain an organic acid. The organic acid is at least one selected from the group consisting of maleic acid, fumaric acid, succinic acid, malic acid, acetic acid, itaconic acid, tartaric acid, ascorbic acid, glutamic acid and aspartic acid. When the metal surface treatment agent contains these organic acids, the adhesion between the metal material and the resin layer is improved, and the corrosion resistance of the metal material is also improved. As the organic acid contained in the metal surface treatment agent, succinic acid and malic acid are preferable from the viewpoint of improving the adhesion between the metal material and the resin layer. Moreover, when a metal surface treating agent contains an organic acid, it is preferable to contain multiple types of organic acid from a viewpoint of improving adhesiveness and corrosion resistance.
　金属表面処理剤が有機酸を含有する場合には、有機酸の含有量は、５０００～２００００ｐｐｍであることが好ましい。含有量（ＣＯ）が、５０００ｐｐｍ未満である場合には金属材料と樹脂層との密着性が低下する傾向にある。一方、含有量（ＣＯ）が、２００００ｐｐｍを超える場合には、金属表面処理剤の安定性が低下する傾向にある。 When the metal surface treatment agent contains an organic acid, the content of the organic acid is preferably 5000 to 20000 ppm. When the content (C 2 O 3 ) is less than 5000 ppm, the adhesion between the metal material and the resin layer tends to decrease. On the other hand, when the content (C 2 O 3 ) exceeds 20000 ppm, the stability of the metal surface treatment agent tends to decrease.
　本実施形態に係る金属表面処理剤の固形分含有量は、１．８５～１１．６０質量％であることが好ましい。金属表面処理剤の固形分含有量が、１．８５質量％未満の場合、十分な表面処理皮膜を形成し難くなる傾向にあり、１１．６０質量％を超える場合、金属表面処理剤の安定性が低下する傾向にある。 The solid content of the metal surface treatment agent according to this embodiment is preferably 1.85 to 11.60% by mass. If the solid content of the metal surface treatment agent is less than 1.85% by mass, it tends to be difficult to form a sufficient surface treatment film, and if it exceeds 11.60% by mass, the stability of the metal surface treatment agent Tend to decrease.
　本実施形態に係る金属表面処理剤のｐＨは、５未満であることが好ましい。金属表面処理剤のｐＨが、５以上である場合、金属表面処理剤の安定性が低下し、金属表面処理剤として使用し難くなる傾向にある。 The pH of the metal surface treatment agent according to this embodiment is preferably less than 5. When the pH of the metal surface treatment agent is 5 or more, the stability of the metal surface treatment agent is lowered, and it tends to be difficult to use as the metal surface treatment agent.
　本実施形態に係る金属表面処理剤は、必要に応じて他の成分を含有してもよい。なお、上述した本実施形態に係る金属表面処理剤の成分の多くは、米国ＦＤＡ規格において、食品添加物として認められている安全性の高い化合物である。このように、本実施形態に係る金属表面処理剤は、安全性の高い成分によって構成されていることから飲料缶や食料缶に対して好ましく用いることができる。 The metal surface treatment agent according to this embodiment may contain other components as necessary. Note that many of the components of the metal surface treatment agent according to this embodiment described above are highly safe compounds that are recognized as food additives in the US FDA standards. Thus, the metal surface treatment agent according to the present embodiment can be preferably used for beverage cans and food cans because it is composed of highly safe components.
＜表面処理方法＞
　続いて、本実施形態に係る金属表面処理剤による金属材料の表面処理方法について説明する。
　本実施形態における表面処理方法は、金属材料の表面に金属表面処理剤を塗布する塗布工程と、金属材料の塗布した金属表面処理剤を乾燥させる乾燥工程と、を備える。 <Surface treatment method>
Then, the surface treatment method of the metal material by the metal surface treating agent which concerns on this embodiment is demonstrated.
The surface treatment method in the present embodiment includes an application step of applying a metal surface treatment agent to the surface of the metal material, and a drying step of drying the metal surface treatment agent applied with the metal material.
　塗布工程において、金属材料の表面に金属表面処理剤を塗布する方法は特に限定されず、例えば、ロールコート法、バーコート法、スプレー処理法、浸漬処理法等による方法が挙げられる。なお、塗布工程に先立って、必要に応じて金属材料の表面に脱脂処理やエッチング処理を施してもよい。 In the application step, the method for applying the metal surface treatment agent to the surface of the metal material is not particularly limited, and examples thereof include a method using a roll coating method, a bar coating method, a spray treatment method, an immersion treatment method, and the like. Prior to the coating step, the surface of the metal material may be subjected to a degreasing process or an etching process as necessary.
　乾燥工程では、塗布工程の後に、金属材料に塗布した金属表面処理剤を乾燥させるが、金属表面処理剤を乾燥させる方法は特に限定されない。乾燥工程において、金属表面処理剤を乾燥させる方法としては、金属表面処理剤を塗布した金属材料を４０～１６０℃で、２～６０秒加熱する方法が挙げられる。 In the drying step, the metal surface treatment agent applied to the metal material is dried after the application step, but the method for drying the metal surface treatment agent is not particularly limited. Examples of the method for drying the metal surface treatment agent in the drying step include a method in which the metal material coated with the metal surface treatment agent is heated at 40 to 160 ° C. for 2 to 60 seconds.
　上述の表面処理方法により形成される表面処理皮膜の皮膜量は、特に限定されないが、ジルコニウム及びリンの元素換算での単位面積当たりの合計質量において、１０～３０ｍｇ／ｍ２となる量であることが好ましい。上記の皮膜量が、１０ｍｇ／ｍ２未満となる量の場合、金属材料と樹脂層との密着性が低下して、金属材料の耐食性が低下する傾向にある。一方、上記の皮膜量が、１０ｍｇ／ｍ２を超える量の場合、表面処理皮膜が脆くなることで金属材料と樹脂層との密着性が低下して、やはり金属材料の耐食性が低下する傾向にある。 The coating amount of the surface treatment film formed by the above-mentioned surface treatment method is not particularly limited, but is an amount that is 10 to 30 mg / m 2 in the total mass per unit area of zirconium and phosphorus in terms of elements. Is preferred. When the amount of the film is less than 10 mg / m 2 , the adhesion between the metal material and the resin layer is lowered, and the corrosion resistance of the metal material tends to be lowered. On the other hand, when the amount of the film exceeds 10 mg / m 2 , the surface treatment film becomes brittle, the adhesion between the metal material and the resin layer decreases, and the corrosion resistance of the metal material also tends to decrease. is there.
　ジルコニウム及びリンの元素換算での単位面積当たりの合計質量は、例えば、蛍光Ｘ線分析装置「ＸＲＦ１７００」（株式会社島津製作所製）による測定によって求めることができる。
　なお、本実施形態に係る金属表面処理剤は、塗布型の金属表面処理剤であるので、金属表面処理剤における固形分の成分比は、表面処理皮膜の成分比となる。本実施形態に係る表面処理方法によれば、表面処理皮膜を形成するのが比較的簡便な塗布型の金属表面処理剤による、１回の処理工程だけで、非常に容易に表面処理皮膜を形成できる。また、本実施形態に係る表面処理方法は、塗布型の金属表面処理剤を用いるので、廃液を生じない点でも有利である（いわゆる廃水レス）。 The total mass per unit area in terms of elements of zirconium and phosphorus can be determined, for example, by measurement using an X-ray fluorescence analyzer “XRF1700” (manufactured by Shimadzu Corporation).
In addition, since the metal surface treating agent which concerns on this embodiment is a coating-type metal surface treating agent, the component ratio of solid content in a metal surface treating agent becomes a component ratio of a surface treatment film. According to the surface treatment method according to the present embodiment, a surface treatment film can be formed very easily by a single treatment step using a coating-type metal surface treatment agent that is relatively easy to form. it can. Moreover, since the surface treatment method according to the present embodiment uses a coating-type metal surface treatment agent, it is advantageous in that no waste liquid is generated (so-called waste water-less).
　表面処理皮膜を形成させた金属材料には、樹脂層を形成する。樹脂層は、樹脂溶液を金属材料の表面に塗布することによって形成してもよいし、ラミネートフィルムの貼り付けることで形成してもよい。ラミネートフィルムの貼り付け方法としては、ドライラミネート法、押出ラミネート法を挙げることができる。樹脂層の樹脂成分は特に限定されない。樹脂成分としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリプロピレン（ＰＰ）、ポリカーボネート（ＰＣ）、トリアセチルセルロース（ＴＡＣ）、ポリ塩化ビニル（ＰＶＣ）、ポリエステル、ポリオレフィン、アクリル等の熱可塑性の樹脂を挙げることができる。 A resin layer is formed on the metal material on which the surface treatment film is formed. The resin layer may be formed by applying a resin solution to the surface of the metal material, or may be formed by attaching a laminate film. Examples of the method for attaching the laminate film include a dry lamination method and an extrusion lamination method. The resin component of the resin layer is not particularly limited. Resin components include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polycarbonate (PC), triacetyl cellulose (TAC), polyvinyl chloride (PVC), polyester, polyolefin, acrylic, etc. A plastic resin can be mentioned.
　以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。なお、特に断りのない限り、単位は質量基準である。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Unless otherwise specified, the unit is based on mass.
＜実施例１の金属表面処理剤の調製＞
　ジルコニウム源としてのジルコンフッ化アンモニウム（森田化学工業株式会社製）、リン化合物としてのフィチン酸（築野食品工業株式会社）、及び、水溶性樹脂としてのポリアクリル酸（ジュリマーＡＣ１０Ｌ、酸価：７５０～８００ｍｇＫＯＨ／ｇ、東亜合成株式会社製）を、それぞれ表１に示す含有量（単位：ｐｐｍ）となるように水に混合し、実施例１の金属表面処理剤を得た。なお、表１における「ＣＰ／ＣＺｒ」は、ジルコニウムのジルコニウム原子換算での含有量（ＣＺｒ）に対する、前記リン化合物のリン原子換算での含有量（ＣＰ）の比の値である。 <Preparation of Metal Surface Treatment Agent of Example 1>
Zircon ammonium fluoride as a zirconium source (manufactured by Morita Chemical Co., Ltd.), phytic acid as a phosphorus compound (Tsukino Food Industry Co., Ltd.), and polyacrylic acid as a water-soluble resin (Durimer AC10L, acid value: 750- 800 mg KOH / g, manufactured by Toa Gosei Co., Ltd.) was mixed with water so that the content (unit: ppm) shown in Table 1 was obtained, and the metal surface treating agent of Example 1 was obtained. In addition, “C P / C Zr ” in Table 1 is a value of the ratio of the content (C P ) in terms of phosphorus atom of the phosphorus compound to the content (C Zr ) in terms of zirconium atom of zirconium. .
＜実施例２～１２、１７～２０及び比較例１～４、１２の金属表面処理剤の調製＞
　各成分の含有量を表１に示す含有量となるように混合した以外は実施例１と同様の方法で各金属表面処理剤を得た。 <Preparation of Metal Surface Treatment Agents of Examples 2-12, 17-20 and Comparative Examples 1-4, 12>
Each metal surface treating agent was obtained in the same manner as in Example 1 except that the content of each component was mixed so as to be the content shown in Table 1.
＜実施例１３～１６、２１～２４及び比較例１３の金属表面処理剤の調製＞
　リン化合物として、フィチン酸に代えて、表１及び２に示したリン化合物を、表１及び２に示した含有量となるよう混合した以外は実施例３と同様の方法で各金属表面処理剤を得た。なお、実施例１６については、表１に記載した２種類のリン化合物（質量比は１：１）を、表１に示す合計含有量となるよう混合した。なお、リン化合物としては以下のものを用いた。
　亜リン酸：亜リン酸、寺田ファイン株式会社製
　ホスホン酸：ディクエスト２０１０、イタルマッチジャパン株式会社製
　ポリリン酸：トリポリリン酸、米山化学工業株式会社製
　リン酸：リン酸、ビーケー・ギューリニ・ジャパン株式会社製
　リン酸ナトリウム：リン酸２ナトリウム、米山化学工業株式会社製 <Preparation of Metal Surface Treatment Agents of Examples 13 to 16, 21 to 24, and Comparative Example 13>
As the phosphorus compound, each metal surface treatment agent was treated in the same manner as in Example 3 except that the phosphorus compounds shown in Tables 1 and 2 were mixed so as to have the contents shown in Tables 1 and 2 instead of phytic acid. Got. In addition, about Example 16, two types of phosphorus compounds (mass ratio is 1: 1) described in Table 1 were mixed so that it might become the total content shown in Table 1. The following compounds were used as phosphorus compounds.
Phosphorous acid: Phosphorous acid, manufactured by Terada Fine Co., Ltd. Phosphonic acid: Dequest 2010, manufactured by Italmatch Japan Co., Ltd. Polyphosphoric acid: Tripolyphosphoric acid, manufactured by Yoneyama Chemical Co., Ltd. Phosphoric acid: Phosphoric acid, BK Gurini Japan Co., Ltd. Company made sodium phosphate: disodium phosphate, made by Yoneyama Chemical Co., Ltd.
＜実施例２５～３８の金属表面処理剤の調製＞
　実施例３の金属表面処理剤において、更に、表３に示した有機酸を表３に示した含有量となるように混合することで各金属表面処理剤を得た。なお、実施例３２～３８については、表３に記載した２種類の有機酸（質量比は１：１）を、表３に示す合計含有量となるよう混合した。用いたコハク酸、マロン酸、アスコルビン酸、リンゴ酸、酒石酸、アスパラギン酸及びフマル酸は、全て和光純薬株式会社製である。 <Preparation of metal surface treatment agents of Examples 25 to 38>
In the metal surface treatment agent of Example 3, each metal surface treatment agent was obtained by further mixing the organic acids shown in Table 3 so as to have the contents shown in Table 3. For Examples 32 to 38, two types of organic acids listed in Table 3 (mass ratio is 1: 1) were mixed so that the total content shown in Table 3 was obtained. The succinic acid, malonic acid, ascorbic acid, malic acid, tartaric acid, aspartic acid and fumaric acid used are all manufactured by Wako Pure Chemical Industries, Ltd.
＜実施例３９及び４０の金属表面処理剤の調製＞
　実施例３の金属表面処理剤において、ポリアクリル酸に代えて表３に示した水溶性樹脂を表３に示した含有量となるように混合し、更に、表３に示した２種類の有機酸（質量比は１：１）を表３に示した合計含有量となるように混合することで各金属表面処理剤を得た。なお、水溶性樹脂としては以下のものを用いた。
　ポリアクリル酸－マレイン酸共重合体：アクアリックＴＬ３００（株式会社日本触媒製）
　ポリアクリル酸－スルホン酸共重合体：アロン　Ａ１２ＳＬ（東亜合成株式会社製） <Preparation of Metal Surface Treatment Agents of Examples 39 and 40>
In the metal surface treating agent of Example 3, in place of polyacrylic acid, the water-soluble resin shown in Table 3 was mixed so as to have the content shown in Table 3, and two kinds of organic compounds shown in Table 3 were further mixed. Each metal surface treating agent was obtained by mixing acid (mass ratio is 1: 1) so that it may become the total content shown in Table 3. In addition, the following were used as water-soluble resin.
Polyacrylic acid-maleic acid copolymer: Aqualic TL300 (manufactured by Nippon Shokubai Co., Ltd.)
Polyacrylic acid-sulfonic acid copolymer: Aron A12SL (manufactured by Toa Gosei Co., Ltd.)
＜比較例５～１１の金属表面処理剤の調製＞
　ポリアクリル酸に代えて、表２に示した樹脂を混合した以外は、実施例３と同様の方法で各金属表面処理剤を得た。なお、樹脂としては以下のものを用いた。
　ポリアリルアミン：ポリアリルアミン１５Ｃ、日東紡績株式会社製
　ポリウレタン：ＰＸ－２００、三洋化成工業株式会社製
　ポリオキサゾリン：エポクロスＷＳ７００、株式会社日本触媒製
　ポリエステル：ペスレジンＨＳＸ１５５、高松油脂株式会社製
　ＰＶＡ：クラレポバール１０５ＭＣ、株式会社クラレ製
　フェノール樹脂：ショウノールＢＲＬ２８５４、昭和電工株式会社製
　メラミン樹脂：サイメル７７１、日本サイテックインダストリーズ株式会社製 <Preparation of metal surface treatment agents of Comparative Examples 5 to 11>
Each metal surface treating agent was obtained by the same method as Example 3 except having mixed the resin shown in Table 2 instead of polyacrylic acid. In addition, the following were used as resin.
Polyallylamine: Polyallylamine 15C, Nitto Boseki Co., Ltd. polyurethane: PX-200, Sanyo Kasei Kogyo Co., Ltd. Polyoxazoline: Epochros WS700, Nippon Shokubai Co., Ltd. Polyester: Pesresin HSX155, Takamatsu Yushi Co., Ltd. PVA: Kuraray Poval 105MC , Kuraray Co., Ltd. Phenol resin: Shounol BRL 2854, Showa Denko Co., Ltd. Melamine resin: Cymel 771, Nihon Cytec Industries, Ltd.
＜比較例１４の金属表面処理剤の調製＞
　ジルコンフッ化アンモニウムに代えて、チタン源としてチタンフッ化アンモニウム（森田化学工業株式会社製）を混合した以外は実施例３と同様の方法で金属表面処理剤を得た。 <Preparation of Metal Surface Treatment Agent of Comparative Example 14>
Instead of zircon ammonium fluoride, a metal surface treating agent was obtained in the same manner as in Example 3 except that titanium titanium fluoride (manufactured by Morita Chemical Co., Ltd.) was mixed as a titanium source.
＜比較例１５の金属表面処理剤の調製＞
　ジルコンフッ化アンモニウムを添加しなかった以外は実施例３と同様の方法で金属表面処理剤を得た。 <Preparation of metal surface treatment agent of Comparative Example 15>
A metal surface treating agent was obtained in the same manner as in Example 3 except that no zircon ammonium fluoride was added.
＜表面処理皮膜の形成＞
　各実施例、比較例及び参考例の金属表面処理剤を、厚さ０．２８ｍｍのアルミニウム合金３００４板材の表面に、リバースロールコーターを用いて、皮膜量が片面当たり、２０ｍｇ／ｍ２（比較例１５については５ｍｇ／ｍ２）となるように塗布した。続いて、金属表面処理剤を塗布した板材を、コンベア式オーブンを用いて８０℃で、２０秒間乾燥させた。ここで、「皮膜量」とは、表面処理皮膜における、ジルコニウム及びリンの元素換算での単位面積当たりの合計質量である。表１に示す「皮膜量」については、蛍光Ｘ線分析装置「ＸＲＦ１７００」（株式会社島津製作所製）による測定によって求めた。 <Formation of surface treatment film>
Using the reverse surface coater on the surface of an aluminum alloy 3004 plate having a thickness of 0.28 mm, the coating amount of each metal surface treatment agent of each example, comparative example and reference example is 20 mg / m 2 (comparative example). 15 was applied so as to be 5 mg / m 2 ). Subsequently, the plate material coated with the metal surface treatment agent was dried at 80 ° C. for 20 seconds using a conveyor oven. Here, the “film amount” is the total mass per unit area in terms of elements of zirconium and phosphorus in the surface treatment film. The “film amount” shown in Table 1 was determined by measurement with a fluorescent X-ray analyzer “XRF1700” (manufactured by Shimadzu Corporation).
　なお、表４の試験例１～６については、実施例３の金属表面処理剤を用いて、実施例３とは異なる表４に示す皮膜量となるように、表面処理皮膜を形成した。
　また、参考例（表２）については、クロム化合物・リン酸系化成処理剤である「アルサーフ４０８」（商品名、日本ペイント社製）を用いて、皮膜量を２０ｍｇ／ｍ２となるように調整した以外は、他の実施例及び比較例と同様の方法でリン酸クロム皮膜を形成させた。参考例の「皮膜量」は、表面処理皮膜における、クロムの元素換算での単位面積当たりの質量である。参考例の「皮膜量」も、蛍光Ｘ線分析装置「ＸＲＦ１７００」（株式会社島津製作所製）による測定によって求めた。 For Test Examples 1 to 6 in Table 4, a surface treatment film was formed using the metal surface treatment agent of Example 3 so as to have a film amount shown in Table 4 different from Example 3.
Moreover, about a reference example (Table 2), using "Alsurf 408" (brand name, the Nippon Paint company make) which is a chromium compound and phosphoric acid type | system | group chemical conversion treatment agent, so that a film quantity may be set to 20 mg / m < 2 >. Except for the adjustment, a chromium phosphate film was formed in the same manner as in the other Examples and Comparative Examples. The “film amount” in the reference example is the mass per unit area in terms of chromium element in the surface treatment film. The “film amount” of the reference example was also determined by measurement with a fluorescent X-ray analyzer “XRF1700” (manufactured by Shimadzu Corporation).
　＜樹脂層の形成＞
　各実施例、比較例、参考例及び試験例のアルミニウム合金板の、表面処理皮膜を形成した側の表面に、溶剤型ポリエステル塗料（フレキコート＃５０００ホワイト、日本ペイント株式会社製）を、ウェット質量１５ｇ／ｍ２となるようにバーコーターを用いて塗布した。続いて、このアルミニウム合金板を、コンベア式オーブンを用いて温度２６０℃、風速１～３０ｍ／分の条件下、６０秒間加熱することで樹脂層を形成した。 <Formation of resin layer>
Solvent-type polyester paint (Flexcoat # 5000 White, manufactured by Nippon Paint Co., Ltd.) is wet-massed on the surface of the aluminum alloy plate of each Example, Comparative Example, Reference Example, and Test Example on the side where the surface treatment film is formed. It apply | coated using the bar coater so that it might become 15 g / m < 2 >. Subsequently, the aluminum alloy plate was heated for 60 seconds under the conditions of a temperature of 260 ° C. and a wind speed of 1 to 30 m / min using a conveyor oven to form a resin layer.
　＜密着性（フェザリング性）の評価＞
　樹脂層を形成した各アルミニウム合金板を、７０ｍｍ×５０ｍｍのサイズに切り出して試験片１を得た。続いて、図１に示すように、試験片１の非塗装面２２に、ＮＴカッターでＶ字の切り込み２１をｂ－ｃ－ｂに沿って入れた。そして、試験片１を１２５℃で３０分間ロトマト処理して、Ｖ字の切り込み２１の裾を金切はさみで、試験片の端から５ｍｍ、ａ－ｂに沿って切断した。
　次いで、図２のようにＶ字の切り込みの部分の裾と、その両端部を逆方向に、テンシロン引っ張り試験機にて５０ｍｍ／分の速度で引っ張って分離させた。そして、切断面の塗膜残存状態を、目視にて図３に示す５段階で評価した。評価結果を表１～４に示す。評価結果が４又は５である場合を以って合格とする。
　１；塗膜が残る
　２；やや塗膜が残る
　３；塗膜片が残る
　４；塗膜片がほとんど残らない
　５；塗膜残りが無い <Evaluation of adhesion (feathering)>
Each aluminum alloy plate on which the resin layer was formed was cut into a size of 70 mm × 50 mm to obtain a test piece 1. Subsequently, as shown in FIG. 1, V-shaped cuts 21 were made along the line bcb on the non-painted surface 22 of the test piece 1 with an NT cutter. Then, the test piece 1 was subjected to rotomato treatment at 125 ° C. for 30 minutes, and the hem of the V-shaped cut 21 was cut along the line ab by 5 mm from the end of the test piece with gold cutting scissors.
Next, as shown in FIG. 2, the hem of the V-shaped cut portion and both ends thereof were separated in the opposite direction by pulling them at a speed of 50 mm / min with a Tensilon tensile tester. And the coating-film residual state of a cut surface was evaluated in five steps visually shown in FIG. The evaluation results are shown in Tables 1 to 4. A case where the evaluation result is 4 or 5 is regarded as acceptable.
1; paint film remains 2; some paint film remains 3; paint film piece remains 4; paint film piece hardly remains 5; no paint film remains
　＜耐食性Ａ（圧延加工耐食）の評価＞
　樹脂層を形成した各アルミニウム合金板を、２５ｍｍ×７０ｍｍのサイズに切り出して試験片を得た。試験片の非塗装面にバックシールを施して、被塗装面にデュポン式落下衝撃試験機を用いて衝撃を加えた（落下高さ２０ｃｍ、重り５００ｇ）。続いて、試験片を、６０℃の環境下、密閉容器中において清涼飲料（コーラ、コカ・コーラ社製）に５６時間浸漬し、腐食の程度を以下の基準で評価した。評価結果を表１～４に示す。評価結果が４又は５である場合を以って合格とする。
　１；評価面積の３０％未満の領域が腐食なし
　２；評価面積の３０％以上６０％未満の領域が腐食なし
　３；評価面積の６０％以上９０％未満の領域が腐食なし
　４；評価面積の９０％以上の領域が腐食なし
　５；全面腐食なし  <Evaluation of corrosion resistance A (rolling corrosion resistance)>
Each aluminum alloy plate on which the resin layer was formed was cut into a size of 25 mm × 70 mm to obtain a test piece. A back seal was applied to the non-coated surface of the test piece, and an impact was applied to the surface to be coated using a DuPont drop impact tester (drop height 20 cm, weight 500 g). Subsequently, the test piece was immersed in a soft drink (Cola, manufactured by Coca-Cola) for 56 hours in an airtight container in an environment of 60 ° C., and the degree of corrosion was evaluated according to the following criteria. The evaluation results are shown in Tables 1 to 4. A case where the evaluation result is 4 or 5 is regarded as acceptable.
1; Area of less than 30% of evaluation area has no corrosion 2; Area of 30% to less than 60% of evaluation area has no corrosion 3; Area of 60% to less than 90% of evaluation area has no corrosion 4; 90% or more of the area does not corrode 5; No overall corrosion
　＜耐食性Ｂ（クロスカット耐食）の評価＞
　樹脂層を形成したアルミニウム合金板を、７０ｍｍ×５０ｍｍのサイズに切り出して試験片を得た。試験片の非塗装面にバックシールを施して、塗装面にＮＴカッターで５０ｍｍ×５０ｍｍのクロスカットを施した。続いて、試験片を、７０℃の環境下、密閉容器中において塩化ナトリウムとクエン酸の混合水溶液（それぞれ１質量％）に７２時間浸漬し、腐食の程度を以下の基準で評価した。評価結果を表１～４に示す。評価結果が４又は５である場合を以って合格とする。
　１；評価面積の３０％未満の領域が腐食なし
　２；評価面積の３０％以上６０％未満の領域が腐食なし
　３；評価面積の６０％以上９０％未満の領域が腐食なし
　４；評価面積の９０％以上の領域が腐食なし
　５；全面腐食なし <Evaluation of corrosion resistance B (cross cut corrosion resistance)>
The aluminum alloy plate on which the resin layer was formed was cut into a size of 70 mm × 50 mm to obtain a test piece. A back seal was applied to the non-painted surface of the test piece, and a 50 mm × 50 mm cross cut was applied to the painted surface with an NT cutter. Subsequently, the test piece was immersed in a mixed aqueous solution of sodium chloride and citric acid (each 1% by mass) in an airtight container at 70 ° C. for 72 hours, and the degree of corrosion was evaluated according to the following criteria. The evaluation results are shown in Tables 1 to 4. A case where the evaluation result is 4 or 5 is regarded as acceptable.
1; Area of less than 30% of evaluation area has no corrosion 2; Area of 30% to less than 60% of evaluation area has no corrosion 3; Area of 60% to less than 90% of evaluation area has no corrosion 4; 90% or more of the area does not corrode 5; No overall corrosion
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　実施例３の金属表面処理剤を用いて得られた試験片と、比較例１４、１５の金属表面処理剤を用いて得られた試験片とを比較すると、実施例３の金属表面処理剤を用いて得られた試験片の方が密着性及び耐食性に優れることが分かった。この結果から、金属表面処理剤がジルコニウムを含有することで、得られる試験片は密着性、耐食性ともに向上することが確認された。 When the test piece obtained using the metal surface treatment agent of Example 3 and the test piece obtained using the metal surface treatment agent of Comparative Examples 14 and 15 were compared, the metal surface treatment agent of Example 3 was obtained. It turned out that the direction of the test piece obtained by using is excellent in adhesiveness and corrosion resistance. From this result, it was confirmed that when the metal surface treatment agent contains zirconium, the obtained test piece is improved in both adhesion and corrosion resistance.
　実施例１～６の金属表面処理剤を用いて得られた試験片と、比較例１の金属表面処理剤を用いて得られた試験片とを比較すると、実施例１～６の金属表面処理剤を用いて得られた試験片の方が耐食性に優れることが分かった。また、実施例１～６の金属表面処理剤を用いて得られた試験片と、比較例２の金属表面処理剤を用いて得られた試験片とを比較すると、実施例１～６の金属表面処理剤を用いて得られた試験片の方が密着性及び耐食性に優れることが分かった。これらの結果から、金属表面処理剤の含有するジルコニウムのジルコニウム原子換算での含有量（ＣＺｒ）を４０００～９６０００ｐｐｍとすることによって、得られる試験片は密着性、耐食性ともに向上することが確認された。 When the test pieces obtained using the metal surface treatment agents of Examples 1 to 6 and the test pieces obtained using the metal surface treatment agent of Comparative Example 1 were compared, the metal surface treatments of Examples 1 to 6 were compared. It was found that the test piece obtained using the agent was superior in corrosion resistance. In addition, when the test pieces obtained using the metal surface treatment agents of Examples 1 to 6 and the test pieces obtained using the metal surface treatment agent of Comparative Example 2 were compared, the metals of Examples 1 to 6 were compared. It was found that the test piece obtained using the surface treatment agent was superior in adhesion and corrosion resistance. From these results, it was confirmed that by setting the content (C Zr ) of zirconium contained in the metal surface treatment agent to 4000 to 96000 ppm, both the adhesion and the corrosion resistance of the obtained specimen are improved. It was.
　実施例３、７～１２の金属表面処理剤を用いて得られた試験片と、比較例３の金属表面処理剤を用いて得られた試験片とを比較すると、実施例３、７～１２の金属表面処理剤を用いて得られた試験片の方が密着性及び耐食性に優れることが分かった。また、実施例３、７～１２の金属表面処理剤を用いて得られた試験片と、比較例４の金属表面処理剤を用いて得られた試験片とを比較すると、実施例３、７～１２の金属表面処理剤を用いて得られた試験片の方が密着性及び耐食性に優れることが分かった。これらの結果から、金属表面処理剤の含有するリン化合物のリン原子換算での含有量（ＣＰ）を、１２５０～２２５００ｐｐｍとすることによって、得られる試験片は密着性、耐食性ともに向上することが確認された。 When comparing the test pieces obtained using the metal surface treatment agents of Examples 3 and 7 to 12 with the test pieces obtained using the metal surface treatment agent of Comparative Example 3, Examples 3 and 7 to 12 were compared. It was found that the test piece obtained by using the metal surface treatment agent was superior in adhesion and corrosion resistance. Further, when the test pieces obtained using the metal surface treatment agents of Examples 3 and 7 to 12 were compared with the test pieces obtained using the metal surface treatment agent of Comparative Example 4, Examples 3 and 7 were compared. It was found that the test pieces obtained using the metal surface treatment agents of ˜12 were superior in adhesion and corrosion resistance. From these results, it can be seen that by setting the content (C P ) in terms of phosphorus atom of the phosphorus compound contained in the metal surface treatment agent to 1250 to 22500 ppm, the obtained test piece is improved in both adhesion and corrosion resistance. confirmed.
　実施例３の金属表面処理剤を用いて得られた試験片と、比較例５～１１の金属表面処理剤を用いて得られた試験片とを比較すると、実施例３の金属表面処理剤を用いて得られた試験片の方が密着性及び耐食性に優れることが分かった。この結果から、金属表面処理剤に、カルボキシ基を有する水溶性樹脂を含有させることによって、得られる試験片は密着性、耐食性ともに向上することが確認された。 When the test pieces obtained using the metal surface treatment agent of Example 3 and the test pieces obtained using the metal surface treatment agents of Comparative Examples 5 to 11 were compared, the metal surface treatment agent of Example 3 was It turned out that the direction of the test piece obtained by using is excellent in adhesiveness and corrosion resistance. From this result, it was confirmed that when the metal surface treatment agent contains a water-soluble resin having a carboxy group, the obtained test piece improves both adhesion and corrosion resistance.
　実施例３、１７～２４の金属表面処理剤を用いて得られた試験片と、比較例１２、１３の金属表面処理剤を用いて得られた試験片とを比較すると、実施例３、１７～２４の金属表面処理剤を用いて得られた試験片の方が密着性及び耐食性に優れることが分かった。この結果から、金属表面処理剤の含有する水溶性樹脂の固形分換算での含有量（ＣＲ）を、４０００～１２００００ｐｐｍとすることによって、得られる試験片は密着性、耐食性ともに向上することが確認された。 The test pieces obtained using the metal surface treatment agents of Examples 3 and 17 to 24 and the test pieces obtained using the metal surface treatment agents of Comparative Examples 12 and 13 were compared. It was found that the test pieces obtained using the metal surface treatment agents of ˜24 were superior in adhesion and corrosion resistance. From these results, it can be seen that by setting the content (C R ) in terms of solid content of the water-soluble resin contained in the metal surface treatment agent to 4000 to 120,000 ppm, the obtained test piece can be improved in both adhesion and corrosion resistance. confirmed.
　実施例３の金属表面処理剤を用いて得られた試験片及び実施例２５～３８の金属表面処理剤を用いて得られた試験片の密着性及び耐食性は、同等であることが確認された。この結果から、金属表面処理剤が各種の有機酸を含有する場合にも、得られる試験片は密着性、耐食性ともに高いことが確認された。 The adhesion and corrosion resistance of the test piece obtained using the metal surface treatment agent of Example 3 and the test piece obtained using the metal surface treatment agent of Examples 25 to 38 were confirmed to be equivalent. . From this result, even when the metal surface treatment agent contains various organic acids, it was confirmed that the obtained test piece had high adhesion and corrosion resistance.
　試験例３、４の試験片と、試験例１、２、５、６の試験片とを比較すると、試験例３、４の試験片の方が密着性及び耐食性に優れることが分かった。この結果から、表面処理皮膜の皮膜量を、ジルコニウム及びリンの元素換算での単位面積当たりの合計質量において、１０～３０ｍｇ／ｍ２とすることで、試験片は密着性、耐食性ともに向上することが確認された。 When the test pieces of Test Examples 3 and 4 were compared with the test pieces of Test Examples 1, 2, 5, and 6, it was found that the test pieces of Test Examples 3 and 4 were superior in adhesion and corrosion resistance. From this result, the adhesion of the test piece and the corrosion resistance are improved by setting the coating amount of the surface treatment coating to 10 to 30 mg / m 2 in terms of the total mass per unit area of zirconium and phosphorus in terms of elements. Was confirmed.
　１　試験片
　２１　切り込み
　２２　非塗装面 1 Test piece 21 Notch 22 Non-painted surface

Claims (5)

  1. 　アルミニウム又はアルミニウム合金からなる金属材料の表面に塗布されて表面処理皮膜を形成する金属表面処理剤であって、
    　ジルコニウムと、リン化合物と、水溶性樹脂と、を含有し、
    　前記ジルコニウムのジルコニウム原子換算での含有量（ＣＺｒ）は、４０００～９６０００ｐｐｍであり、
    　前記リン化合物のリン原子換算での含有量（ＣＰ）は、１２５０～２２５００ｐｐｍであり、
    　前記水溶性樹脂は、カルボキシ基を有し、
    　前記水溶性樹脂の酸価は、１３０～９７０ｍｇＫＯＨ／ｇであり、
    　前記水溶性樹脂の固形分換算での含有量（ＣＲ）は、４０００～１２００００ｐｐｍである樹脂である金属表面処理剤。     A metal surface treatment agent that is applied to the surface of a metal material made of aluminum or an aluminum alloy to form a surface treatment film,
    Containing zirconium, a phosphorus compound, and a water-soluble resin,
    The zirconium content in terms of zirconium atoms (C Zr ) is 4000 to 96000 ppm,
    The phosphorus compound content (C P ) of the phosphorus compound is 1250 to 22500 ppm,
    The water-soluble resin has a carboxy group,
    The acid value of the water-soluble resin is 130 to 970 mg KOH / g,
    The content in terms of solids of the water-soluble resin (C R) is a metal surface treatment agent is a resin which is 4000 ~ 120000ppm.
  2. 　前記リン化合物として、リン酸、亜リン酸、ホスホン酸及びフィチン酸からなる群より選択される少なくとも一種のリン化合物を含有する請求項１記載の金属表面処理剤。 The metal surface treatment agent according to claim 1, comprising at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid and phytic acid as the phosphorus compound.
  3. 　前記水溶性樹脂は、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、クロトン酸及びフマル酸からなる群より選択される少なくとも一種の単量体（ｉ）２０～１００質量％と、スチレン、酢酸ビニル、メチルスチレン、２－ヒドロキシ－３－アリロキシプロパンスルホン酸、アクリルアミドメチルプロパンスルホン酸及びスチレンスルホン酸からなる群より選択される少なくとも一種の単量体（ｉｉ）０～８０質量％と、を重合して得られる重合体である請求項１又は２記載の金属表面処理剤。 The water-soluble resin comprises at least one monomer (i) selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and fumaric acid, 20-100% by mass, styrene, vinyl acetate And at least one monomer (ii) selected from the group consisting of methylstyrene, 2-hydroxy-3-allyloxypropanesulfonic acid, acrylamidomethylpropanesulfonic acid and styrenesulfonic acid is polymerized The metal surface treating agent according to claim 1 or 2, which is a polymer obtained by the above process.
  4. 　前記ジルコニウムのジルコニウム原子換算での含有量（ＣＺｒ）に対する、前記リン化合物のリン原子換算での含有量（ＣＰ）の比の値（ＣＰ／ＣＺｒ）は、０．０８～２．５である請求項１から３のいずれか記載の金属表面処理剤。 The ratio (C P / C Zr ) of the content (C P ) of the phosphorus compound in terms of phosphorus atoms to the content (C Zr ) in terms of zirconium atoms of the zirconium is 0.08-2. The metal surface treating agent according to any one of claims 1 to 3, which is 5.
  5. 　更に、マレイン酸、フマル酸、コハク酸、リンゴ酸、酢酸、イタコン酸、酒石酸、アスコルビン酸、グルタミン酸及びアスパラギン酸からなる群より選択される少なくとも一種の有機酸を含有する請求項１から４のいずれか記載の金属表面処理剤。 Furthermore, at least 1 type of organic acid selected from the group which consists of maleic acid, fumaric acid, succinic acid, malic acid, acetic acid, itaconic acid, tartaric acid, ascorbic acid, glutamic acid, and aspartic acid is contained. Or a metal surface treatment agent as described above.
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JPWO2018139328A1 (en) * 2017-01-25 2019-11-07 Ｄｉｃ株式会社 Active energy ray-curable aqueous resin composition and undercoat agent for inorganic material thin film
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JPWO2018139328A1 (en) * 2017-01-25 2019-11-07 Ｄｉｃ株式会社 Active energy ray-curable aqueous resin composition and undercoat agent for inorganic material thin film
JPWO2018139329A1 (en) * 2017-01-25 2019-12-19 Dic株式会社 (Meth) acryloyl group-containing acrylic-modified alkyd resin and undercoat agent for inorganic material thin film
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CN111234633A (en) * 2020-03-25 2020-06-05 攀钢集团攀枝花钢铁研究院有限公司 Water-based transparent corrosion-resistant coating steel rail and preparation method thereof
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