WO2024111458A1 - Metal surface treatment agent - Google Patents
Metal surface treatment agent Download PDFInfo
- Publication number
- WO2024111458A1 WO2024111458A1 PCT/JP2023/040774 JP2023040774W WO2024111458A1 WO 2024111458 A1 WO2024111458 A1 WO 2024111458A1 JP 2023040774 W JP2023040774 W JP 2023040774W WO 2024111458 A1 WO2024111458 A1 WO 2024111458A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- surface treatment
- metal surface
- treatment agent
- compound
- metal
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 112
- 239000002184 metal Substances 0.000 title claims abstract description 112
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 73
- -1 silicic acid compound Chemical class 0.000 claims abstract description 38
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 18
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 15
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 238000004381 surface treatment Methods 0.000 claims description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 239000002738 chelating agent Substances 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 8
- 239000002585 base Substances 0.000 abstract description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 20
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
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- 238000000034 method Methods 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 5
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 5
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- 239000004115 Sodium Silicate Substances 0.000 description 3
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- 230000004888 barrier function Effects 0.000 description 2
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- WBFZBNKJVDQAMA-UHFFFAOYSA-D dipotassium;zirconium(4+);pentacarbonate Chemical compound [K+].[K+].[Zr+4].[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O WBFZBNKJVDQAMA-UHFFFAOYSA-D 0.000 description 2
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical class [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
Definitions
- the present invention relates to a metal surface treatment agent.
- Zinc phosphate treatment and zirconium-based conversion coatings have been known as technologies for imparting corrosion resistance to metal substrates such as steel.
- Zinc phosphate treatment is used as a conversion coating for paint bases, but because its coating components contain phosphorus, an element that contributes to eutrophication, and nickel, which may be carcinogenic, its use has tended to be avoided in recent years due to concerns about environmental protection and its impact on the human body.
- Zirconium-based chemical conversion coating is a technology that has traditionally been applied to aluminum-based materials, and there is still room for improvement in terms of technology that can impart high corrosion resistance to steel materials.
- Patent Document 1 The technology described in Patent Document 1 is related to surface-treated steel sheets, and the surface treatment film contains an acrylic resin emulsion.
- the main component of the surface treatment film contains a resin component such as an acrylic resin emulsion, it is difficult to raise the material temperature (PMT) during baking to a high temperature exceeding 200°C, for example, and the current situation is that sufficient heat resistance and durability of the coating film cannot be obtained, and sufficient corrosion resistance after painting cannot be obtained.
- PMT material temperature
- the present invention was made in consideration of the above, and aims to provide a metal surface treatment agent that can be baked at high temperatures and can impart high corrosion resistance to metal substrates.
- the present invention relates to a metal surface treatment agent that contains a silicate compound (A), an alkali metal salt (B) that is other than a silicate compound, a vanadium compound, and a zirconium compound, a vanadium compound (C), a zirconium compound (D), and water, and that has a silicon element content of 10 mass% or more based on the total solid content of the metal surface treatment agent.
- the present invention provides a metal surface treatment agent that can be baked at high temperatures and can impart high corrosion resistance to metal substrates.
- the following describes the metal surface treatment agent according to an embodiment of the present invention.
- the present invention is not limited to the description of the following embodiment.
- the metal surface treatment agent according to the present embodiment contains a silicic acid compound (A), an alkali metal salt (B) other than a silicic acid compound, a vanadium compound, and a zirconium compound, a vanadium compound (C), a zirconium compound (D), and water. It is also preferable that the metal surface treatment agent contains a chelating agent (E).
- the silicic acid compound (A) is the main component of the film formed by the metal surface treatment agent. By making the silicic acid compound (A), which is an inorganic compound, the main component of the film, the film can be baked at high temperatures.
- Specific examples of the silicic acid compound (A) include alkali metal silicate, colloidal silica, alkyl silicate compound, hydrolysis product of alkyl silicate compound, condensation polymerization product of alkyl silicate compound, etc., but the silicic acid compound (A) is preferably an alkali metal silicate from the viewpoint of corrosion resistance.
- silicate of the alkali metal examples include alkali metal salts of orthosilicic acid such as lithium orthosilicate, sodium orthosilicate, potassium orthosilicate, etc.; alkali metal salts of metasilicic acid such as lithium metasilicate, sodium metasilicate, potassium metasilicate, etc.; and the like.
- alkyl silicate compound examples include methyl silicate, ethyl silicate, etc.
- the silicon element content of the metal surface treatment agent of this embodiment is 10 mass% or more relative to the total solid content.
- the silicon element content is preferably 20 mass% or more and 40 mass% or less.
- PMT material target temperature
- the alkali metal salt (B) is an alkali metal salt other than a silicate compound, a vanadium compound, and a zirconium compound, and acts as a crosslinking agent.
- the alkali metal salt (B) is contained in the metal surface treatment agent, and thereby the barrier property of the formed film against water and corrosion factors (chloride ions, etc.) is improved, and as a result, the corrosion resistance imparted to the metal substrate can be improved.
- alkali metal salt (B) examples include, but are not limited to, carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; nitrites such as lithium nitrite, sodium nitrite, and potassium nitrite; and the like.
- the vanadium compound (C) acts as a rust inhibitor when added to a metal surface treatment agent.
- the vanadium compound (C) is not particularly limited, but examples thereof include vanadium pentoxide, metavanadic acid, ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride, vanadyl sulfate, magnesium vanadate, vanadium trioxide, vanadium trichloride, vanadium dioxide, vanadyl acetylacetonate, and vanadium acetylacetonate.
- the vanadium element content is preferably 0.1 to 10 mass% relative to the total solid content of the metal surface treatment agent of this embodiment.
- the vanadium element content is more preferably 0.5 to 5 mass%. If the vanadium element content is less than 0.1 mass%, sufficient rust prevention properties cannot be obtained. If the vanadium element content exceeds 10 mass%, the stability and corrosion resistance of the metal surface treatment agent decrease.
- the zirconium compound (D) acts as a crosslinking agent to improve the barrier properties of the formed coating against water and corrosion factors (chloride ions, etc.), resulting in improved corrosion resistance.
- the zirconium compound (D) is not particularly limited, but examples thereof include zirconium carbonate salts such as ammonium zirconium carbonate and potassium zirconium carbonate , alkali metal fluorozirconates such as K2ZrF6 , zirconium hydrofluoric acid ( H2ZrF6 ), ammonium zirconium fluoride (( NH4 ) 2ZrF6 ), zirconium fluoride, zirconium nitrate, zirconium oxide, and the like.
- the zirconium element content is preferably 0.1 to 10 mass% relative to the total solid content of the metal surface treatment agent of this embodiment. With the zirconium element content in this range, the stability and corrosion resistance of the metal surface treatment agent are improved.
- the zirconium element content is more preferably 0.5 to 5 mass%. If the zirconium element content is less than 0.1 mass%, the effect as a sufficient cross-linking agent is not obtained. If the zirconium element content exceeds 10 mass%, the stability and corrosion resistance of the treatment agent are reduced.
- the molar ratio (M/Si) of the alkali metal element (M) to the silicon element (Si) contained in the solid content of the metal surface treatment agent of this embodiment is preferably 0.5 to 1.2.
- the molar ratio (M/Si) is more preferably 0.6 to 1.1. If the molar ratio (M/Si) is less than 0.5, the corrosion resistance decreases. If the molar ratio (M/Si) exceeds 1.2, the stability of the metal surface treatment agent decreases.
- the alkali metal element (M) includes alkali metal elements derived from silicate compounds (A), vanadium compounds (C), zirconium compounds (D), or other compounds other than the alkali metal salt (B).
- the chelating agent (E) is added to the metal surface treatment agent to stabilize zirconium in the metal surface treatment agent.
- the chelating agent (E) is not particularly limited, but examples thereof include hydroxycarboxylic acids such as lactic acid, malic acid, tartaric acid, citric acid, and gluconic acid, ethylenediaminetetraacetic acid (EDTA), organic phosphorus compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), hydroxyamines such as triethanolamine (TEA), and salts of the above compounds.
- the chelating agent (E) may contain an organic phosphorus compound such as the above-mentioned HEDP, but from the viewpoint of reducing the environmental impact due to eutrophication, it is preferable that the metal surface treatment agent according to this embodiment does not contain inorganic phosphorus compounds such as phosphoric acids such as orthophosphoric acid (H3PO4 ) , pyrophosphoric acid ( H4P2O7 ), metaphosphoric acid ( HPO3 ), and phosphates such as ammonium phosphate and sodium phosphate.
- phosphoric acids such as orthophosphoric acid (H3PO4 )
- metaphosphoric acid ( HPO3 ) metaphosphoric acid
- phosphates such as ammonium phosphate and sodium phosphate.
- the metal surface treatment agent of this embodiment contains water as a component other than the above.
- the metal surface treatment agent may further contain other components within a range that does not inhibit the above functions.
- the other components include resin components such as acrylic resins, urethane resins, epoxy resins, olefin resins such as ethylene acrylic copolymers, polyester resins, polyolefin resins, alkyd resins, and polycarbonate resins.
- the solid content of the resin components relative to the total solid content of the metal surface treatment agent is preferably 10% by mass or less, more preferably 5% by mass or less. This allows the metal surface treatment agent to be preferably baked at high temperatures.
- other components other than the above include known components contained in surface treatment agents such as crosslinkers, rust inhibitors, leveling agents, defoamers, and pH adjusters.
- the solid content of the metal surface treatment agent of the present embodiment is preferably 0.1 to 30 mass %, and more preferably 1.0 to 25 mass %.
- the metal substrate to be surface-treated with the metal surface treatment agent of the present embodiment is not particularly limited, and examples thereof include metal steel materials such as cold-rolled steel, hot-rolled steel, stainless steel, electrogalvanized steel, hot-dip galvanized steel, zinc-aluminum alloy-based plated steel, zinc-iron alloy-based plated steel, zinc-magnesium alloy-based plated steel, zinc-aluminum-magnesium alloy-based plated steel, aluminum-based plated steel, aluminum-silicon alloy-based plated steel, tin-based plated steel, lead-tin-based plated steel, chromium-based plated steel, and Ni-based plated steel.
- the shape of the metal substrate is not particularly limited, and examples thereof include a plate shape.
- the metal surface treatment agent of this embodiment is a so-called coating-type metal surface treatment agent.
- the coating-type metal surface treatment agent is used in a method in which the surface treatment agent is applied to the surface of a metal substrate, and then the surface of the metal substrate is baked (dried) without rinsing with water. That is, the metal surface treatment method of this embodiment includes a coating step of applying the metal surface treatment agent to the surface of the metal substrate, and a baking step of baking the coated metal surface treatment agent on the metal substrate.
- the coating-type metal surface treatment agent of this embodiment has the advantage that the formation of a metal surface treatment film can be performed relatively easily and no waste liquid is generated.
- the method for coating the surface of the metal substrate with the metal surface treatment agent is not particularly limited, and examples of the method include roll coating, bar coating, spraying, and immersion.
- the surface of the metal substrate may be degreased, pickled, or etched, if necessary.
- the metal surface treatment agent applied to the metal substrate is baked.
- the baking method is not particularly limited.
- the baking temperature is not particularly limited, but it is preferable to set the material reachable temperature (PMT) to 200°C to 400°C, for example.
- the baking time is not particularly limited, but it can be set to, for example, 3 to 180 seconds.
- the film formed by the above-mentioned metal surface treatment method contains each component of the above-mentioned metal surface treatment agent, excluding volatile components such as water. That is, the content of silicon element contained in the metal surface treatment film is 10 mass% or more.
- the molar ratio (M/Si) of the alkali metal element (M) to the silicon element (Si) contained in the metal surface treatment film is preferably 0.5 to 1.2.
- the content of vanadium element contained in the metal surface treatment film is preferably 0.1 to 10 mass%.
- the content of zirconium element contained in the metal surface treatment film is preferably 0.1 to 10 mass%.
- the weight of the film is not particularly limited, but is preferably 0.3 to 2.0 g/ m2 , and more preferably 0.5 to 1.5 g/ m2 .
- the surface-treated metal according to the present embodiment is obtained by forming the metal surface treatment film on the surface of the metal substrate.
- the surface-treated metal may be a metal surface treatment film on which a coating film is formed.
- the paint for forming the coating film is not particularly limited, and a one-coat paint or a primer and a top coat may be used.
- Examples 1 to 36, Comparative Examples 1 to 4 The silicic acid compound (A), the alkali metal salt (B), the vanadium compound (C), the zirconium compound (D), and the chelating agent (E) were weighed out so as to obtain the solid content shown in Tables 1 to 4 below, and ion-exchanged water was added and mixed and stirred so that the total solid content concentration of these compositions in the metal surface treatment agent was 18 mass %, to obtain a metal surface treatment agent.
- the unit of the blending amount of each component shown in Tables 1 to 4 is parts by mass.
- the "Si amount”, “V amount”, and “Zr amount” shown in Tables 1 to 4 respectively indicate the contents (unit: mass %) of silicon element, vanadium element, and zirconium element relative to the total solid content of the metal surface treatment agent.
- A1 J Sodium Silicate No. 3 (sodium silicate, manufactured by Nippon Chemical Industry Co., Ltd.)
- A4 2K potassium silicate (potassium silicate, manufactured by Nippon Chemical Industry Co., Ltd.)
- A5 Hydrolysis product of Ethyl Silicate 28 (Ethyl Silicate, manufactured by Colcoat Co., Ltd.)
- Vanadium Compound (C) C1: Vanadyl sulfate C2: Ammonium metavanadate C3: Sodium metavanadate
- the metal surface treatment agents shown in Tables 1 to 4 were applied to the surfaces of the metal substrates using a bar coater so that the coating amount was 0.7 g/ m2 .
- the metal substrates after application were heated in an oven at a temperature of 550°C for 15 seconds to perform baking.
- the material reached temperature (PMT) during baking was 300°C.
- the following evaluations were performed using the test plates according to the examples and comparative examples obtained as described above.
- test plates according to the Examples have better corrosion resistance results than the test plates according to Comparative Examples 1, 3, and 4, which do not contain any specific components, and the test plate according to Comparative Example 2, which has a silicon element content of less than 10 mass%.
- the metal surface treatment agents according to the Examples have better storage stability than the surface treatment agents according to Comparative Examples 2 and 4.
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Abstract
The purpose of the present invention is to provide a metal surface treatment agent that can be baked at high temperatures and can impart high corrosion resistance to metal base materials. Provided is a metal surface treatment agent comprising a silicic acid compound (A), an alkali metal salt (B) that is different from a silicic acid compound, a vanadium compound and a zirconium compound, a vanadium compound (C), a zirconium compound (D), and water, in which the content of a silicon element is 10% by mass or more relative to the whole solid content in the metal surface treatment agent. The silicic acid compound (A) is preferably a silicic acid salt of an alkali metal.
Description
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、鉄鋼等の金属基材に対して耐食性を付与する技術として、リン酸亜鉛処理やジルコニウム系化成処理が知られている。リン酸亜鉛処理は、塗装下地用化成処理として用いられるが、富栄養化元素であるリンや、発がん性の恐れのあるニッケルを皮膜成分としていることから、近年では環境保護や人体への影響の観点から使用が避けられる傾向にある。
Conventionally, zinc phosphate treatment and zirconium-based conversion coatings have been known as technologies for imparting corrosion resistance to metal substrates such as steel. Zinc phosphate treatment is used as a conversion coating for paint bases, but because its coating components contain phosphorus, an element that contributes to eutrophication, and nickel, which may be carcinogenic, its use has tended to be avoided in recent years due to concerns about environmental protection and its impact on the human body.
ジルコニウム系化成処理は、従来アルミニウム系材料に対して適用されてきた技術であり、鉄鋼材料に対して高い耐食性を付与する技術については未だ改善の余地があるのが現状である。
Zirconium-based chemical conversion coating is a technology that has traditionally been applied to aluminum-based materials, and there is still room for improvement in terms of technology that can impart high corrosion resistance to steel materials.
特許文献１に記載された技術は、表面処理鋼板に関する技術であり、表面処理皮膜にはアクリル樹脂エマルションが含まれる。表面処理皮膜の主成分にアクリル樹脂エマルション等の樹脂成分が含まれる場合、焼付時の素材到達温度（ＰＭＴ）を例えば２００℃を超える高温とすることが困難であり、塗膜の十分な耐熱性、耐久性が得られず、塗装後の十分な耐食性も得られていないのが現状だった。
The technology described in Patent Document 1 is related to surface-treated steel sheets, and the surface treatment film contains an acrylic resin emulsion. When the main component of the surface treatment film contains a resin component such as an acrylic resin emulsion, it is difficult to raise the material temperature (PMT) during baking to a high temperature exceeding 200°C, for example, and the current situation is that sufficient heat resistance and durability of the coating film cannot be obtained, and sufficient corrosion resistance after painting cannot be obtained.
本発明は、上記に鑑みてなされたものであり、高温焼付が可能であり、かつ金属基材に対して高い耐食性を付与す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。
The present invention was made in consideration of the above, and aims to provide a metal surface treatment agent that can be baked at high temperatures and can impart high corrosion resistance to metal substrates.
（１） 本発明は、ケイ酸化合物（Ａ）と、ケイ酸化合物以外、バナジウム化合物以外、かつジルコニウム化合物以外のアルカリ金属塩（Ｂ）と、バナジウム化合物（Ｃ）と、ジルコニウム化合物（Ｄ）と、水と、を含有し、金属表面処理剤の全固形分に対し、ケイ素元素の含有量は１０質量％以上である、金属表面処理剤に関する。
(1) The present invention relates to a metal surface treatment agent that contains a silicate compound (A), an alkali metal salt (B) that is other than a silicate compound, a vanadium compound, and a zirconium compound, a vanadium compound (C), a zirconium compound (D), and water, and that has a silicon element content of 10 mass% or more based on the total solid content of the metal surface treatment agent.
（２） 前記ケイ酸化合物（Ａ）はアルカリ金属のケイ酸塩である、（１）に記載の金属表面処理剤。
(2) The metal surface treatment agent according to (1), wherein the silicate compound (A) is an alkali metal silicate.
（３） 前記金属表面処理剤の固形分に含まれるケイ素元素（Ｓｉ）に対するアルカリ金属元素（Ｍ）のモル比（Ｍ／Ｓｉ）が０．５～１．２である、（１）又は（２）に記載の金属表面処理剤。
(3) A metal surface treatment agent according to (1) or (2), in which the molar ratio (M/Si) of alkali metal element (M) to silicon element (Si) contained in the solid content of the metal surface treatment agent is 0.5 to 1.2.
（４） 前記金属表面処理剤の全固形分に対し、バナジウム元素の含有量は０．１～１０質量％であり、ジルコニウム元素の含有量は０．１～１０質量％である、（１）～（３）いずれかに記載の金属表面処理剤。
(4) A metal surface treatment agent according to any one of (1) to (3), in which the vanadium element content is 0.1 to 10 mass% and the zirconium element content is 0.1 to 10 mass% relative to the total solid content of the metal surface treatment agent.
（５） 更に、キレート剤（Ｅ）を含む、（１）～（４）いずれかに記載の金属表面処理剤。
(5) A metal surface treatment agent according to any one of (1) to (4), further comprising a chelating agent (E).
（６） （１）～（５）いずれかに記載の金属表面処理剤を硬化した、金属表面処理皮膜。
(6) A metal surface treatment film obtained by hardening a metal surface treatment agent described in any one of (1) to (5).
（７） （６）に記載の金属表面処理皮膜を有する、表面処理金属。
(7) A surface-treated metal having the metal surface treatment film described in (6).
本発明によれば、高温焼付が可能であり、かつ金属基材に対して高い耐食性を付与することができる金属表面処理剤を提供できる。
The present invention provides a metal surface treatment agent that can be baked at high temperatures and can impart high corrosion resistance to metal substrates.
以下、本発明の実施形態に係る金属表面処理剤について説明する。本発明は以下の実施形態の記載に限定されない。
The following describes the metal surface treatment agent according to an embodiment of the present invention. The present invention is not limited to the description of the following embodiment.
＜金属表面処理剤＞
本実施形態に係る金属表面処理剤は、ケイ酸化合物（Ａ）と、ケイ酸化合物以外、バナジウム化合物以外、かつジルコニウム化合物以外のアルカリ金属塩（Ｂ）と、バナジウム化合物（Ｃ）と、ジルコニウム化合物（Ｄ）と、水と、を含有する。また、キレート剤（Ｅ）を含有することが好ましい。 <Metal surface treatment agent>
The metal surface treatment agent according to the present embodiment contains a silicic acid compound (A), an alkali metal salt (B) other than a silicic acid compound, a vanadium compound, and a zirconium compound, a vanadium compound (C), a zirconium compound (D), and water. It is also preferable that the metal surface treatment agent contains a chelating agent (E).
本実施形態に係る金属表面処理剤は、ケイ酸化合物（Ａ）と、ケイ酸化合物以外、バナジウム化合物以外、かつジルコニウム化合物以外のアルカリ金属塩（Ｂ）と、バナジウム化合物（Ｃ）と、ジルコニウム化合物（Ｄ）と、水と、を含有する。また、キレート剤（Ｅ）を含有することが好ましい。 <Metal surface treatment agent>
The metal surface treatment agent according to the present embodiment contains a silicic acid compound (A), an alkali metal salt (B) other than a silicic acid compound, a vanadium compound, and a zirconium compound, a vanadium compound (C), a zirconium compound (D), and water. It is also preferable that the metal surface treatment agent contains a chelating agent (E).
（ケイ酸化合物（Ａ））
ケイ酸化合物（Ａ）は、金属表面処理剤により形成される皮膜の主成分である。皮膜の主成分を無機化合物であるケイ酸化合物（Ａ）とすることで、皮膜の高温焼付が可能となる。ケイ酸化合物（Ａ）の具体例としては、アルカリ金属のケイ酸塩、コロイダルシリカ、アルキルシリケート化合物、アルキルシリケート化合物の加水分解生成物、アルキルシリケート化合物の縮重合生成物、等が挙げられるが、ケイ酸化合物（Ａ）は耐食性の観点からアルカリ金属のケイ酸塩であることが好ましい。アルカリ金属のケイ酸塩としては、例えば、オルトケイ酸リチウム、オルトケイ酸ナトリウム、オルトケイ酸カリウム等のオルトケイ酸のアルカリ金属塩；メタケイ酸リチウム、メタケイ酸ナトリウム、メタケイ酸カリウム等のメタケイ酸のアルカリ金属塩；等が挙げられる。アルキルシリケート化合物としては、メチルシリケート、エチルシリケート等が挙げられる。 (Silicate Compound (A))
The silicic acid compound (A) is the main component of the film formed by the metal surface treatment agent. By making the silicic acid compound (A), which is an inorganic compound, the main component of the film, the film can be baked at high temperatures. Specific examples of the silicic acid compound (A) include alkali metal silicate, colloidal silica, alkyl silicate compound, hydrolysis product of alkyl silicate compound, condensation polymerization product of alkyl silicate compound, etc., but the silicic acid compound (A) is preferably an alkali metal silicate from the viewpoint of corrosion resistance. Examples of the silicate of the alkali metal include alkali metal salts of orthosilicic acid such as lithium orthosilicate, sodium orthosilicate, potassium orthosilicate, etc.; alkali metal salts of metasilicic acid such as lithium metasilicate, sodium metasilicate, potassium metasilicate, etc.; and the like. Examples of the alkyl silicate compound include methyl silicate, ethyl silicate, etc.
ケイ酸化合物（Ａ）は、金属表面処理剤により形成される皮膜の主成分である。皮膜の主成分を無機化合物であるケイ酸化合物（Ａ）とすることで、皮膜の高温焼付が可能となる。ケイ酸化合物（Ａ）の具体例としては、アルカリ金属のケイ酸塩、コロイダルシリカ、アルキルシリケート化合物、アルキルシリケート化合物の加水分解生成物、アルキルシリケート化合物の縮重合生成物、等が挙げられるが、ケイ酸化合物（Ａ）は耐食性の観点からアルカリ金属のケイ酸塩であることが好ましい。アルカリ金属のケイ酸塩としては、例えば、オルトケイ酸リチウム、オルトケイ酸ナトリウム、オルトケイ酸カリウム等のオルトケイ酸のアルカリ金属塩；メタケイ酸リチウム、メタケイ酸ナトリウム、メタケイ酸カリウム等のメタケイ酸のアルカリ金属塩；等が挙げられる。アルキルシリケート化合物としては、メチルシリケート、エチルシリケート等が挙げられる。 (Silicate Compound (A))
The silicic acid compound (A) is the main component of the film formed by the metal surface treatment agent. By making the silicic acid compound (A), which is an inorganic compound, the main component of the film, the film can be baked at high temperatures. Specific examples of the silicic acid compound (A) include alkali metal silicate, colloidal silica, alkyl silicate compound, hydrolysis product of alkyl silicate compound, condensation polymerization product of alkyl silicate compound, etc., but the silicic acid compound (A) is preferably an alkali metal silicate from the viewpoint of corrosion resistance. Examples of the silicate of the alkali metal include alkali metal salts of orthosilicic acid such as lithium orthosilicate, sodium orthosilicate, potassium orthosilicate, etc.; alkali metal salts of metasilicic acid such as lithium metasilicate, sodium metasilicate, potassium metasilicate, etc.; and the like. Examples of the alkyl silicate compound include methyl silicate, ethyl silicate, etc.
本実施形態の金属表面処理剤の全固形分に対し、ケイ素元素の含有量は１０質量％以上である。上記ケイ素元素の含有量は、２０質量％以上４０質量％以下であることが好ましい。上記ケイ素元素の含有量が１０質量％以上であることで、金属表面処理剤により形成される皮膜を、例えば素材到達度温度（ＰＭＴ）を２００℃以上の温度として高温焼付することが可能となる。上記ケイ素元素の含有量を４０質量％超とすると他の必須成分の配合量が少なくなり、金属表面処理剤の安定性や耐食性を発揮することが難しくなる。
The silicon element content of the metal surface treatment agent of this embodiment is 10 mass% or more relative to the total solid content. The silicon element content is preferably 20 mass% or more and 40 mass% or less. When the silicon element content is 10 mass% or more, it becomes possible to bake the film formed by the metal surface treatment agent at a high temperature, for example, with a material target temperature (PMT) of 200°C or more. If the silicon element content is more than 40 mass%, the amount of other essential components mixed will be reduced, making it difficult for the metal surface treatment agent to exhibit stability and corrosion resistance.
（アルカリ金属塩（Ｂ））
アルカリ金属塩（Ｂ）は、ケイ酸化合物以外、バナジウム化合物以外、かつジルコニウム化合物以外のアルカリ金属塩であり、架橋剤として作用する。アルカリ金属塩（Ｂ）が金属表面処理剤に含有されることで、形成される皮膜の水や腐食因子（塩化物イオン等）に対する遮断性が向上し、結果として金属基材に付与される耐食性を向上させることができる。アルカリ金属塩（Ｂ）の具体例としては、特に限定されないが、例えば、炭酸リチウム、炭酸ナトリウム、炭酸カリウム等の炭酸塩；炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム等の炭酸水素塩；水酸化リチウム、水酸化ナトリウム、水酸化カリウム等の水酸化物；亜硝酸リチウム、亜硝酸ナトリウム、亜硝酸カリウム等の亜硝酸塩；等が挙げられる。 (Alkali Metal Salt (B))
The alkali metal salt (B) is an alkali metal salt other than a silicate compound, a vanadium compound, and a zirconium compound, and acts as a crosslinking agent. The alkali metal salt (B) is contained in the metal surface treatment agent, and thereby the barrier property of the formed film against water and corrosion factors (chloride ions, etc.) is improved, and as a result, the corrosion resistance imparted to the metal substrate can be improved. Specific examples of the alkali metal salt (B) include, but are not limited to, carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; nitrites such as lithium nitrite, sodium nitrite, and potassium nitrite; and the like.
アルカリ金属塩（Ｂ）は、ケイ酸化合物以外、バナジウム化合物以外、かつジルコニウム化合物以外のアルカリ金属塩であり、架橋剤として作用する。アルカリ金属塩（Ｂ）が金属表面処理剤に含有されることで、形成される皮膜の水や腐食因子（塩化物イオン等）に対する遮断性が向上し、結果として金属基材に付与される耐食性を向上させることができる。アルカリ金属塩（Ｂ）の具体例としては、特に限定されないが、例えば、炭酸リチウム、炭酸ナトリウム、炭酸カリウム等の炭酸塩；炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム等の炭酸水素塩；水酸化リチウム、水酸化ナトリウム、水酸化カリウム等の水酸化物；亜硝酸リチウム、亜硝酸ナトリウム、亜硝酸カリウム等の亜硝酸塩；等が挙げられる。 (Alkali Metal Salt (B))
The alkali metal salt (B) is an alkali metal salt other than a silicate compound, a vanadium compound, and a zirconium compound, and acts as a crosslinking agent. The alkali metal salt (B) is contained in the metal surface treatment agent, and thereby the barrier property of the formed film against water and corrosion factors (chloride ions, etc.) is improved, and as a result, the corrosion resistance imparted to the metal substrate can be improved. Specific examples of the alkali metal salt (B) include, but are not limited to, carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; nitrites such as lithium nitrite, sodium nitrite, and potassium nitrite; and the like.
（バナジウム化合物（Ｃ））
バナジウム化合物（Ｃ）は、金属表面処理剤に添加されることで防錆剤（インヒビター）として作用する。バナジウム化合物（Ｃ）としては、特に限定されないが、例えば、五酸化バナジウム、メタバナジン酸、メタバナジン酸アンモニウム、メタバナジン酸ナトリウム、オキシ三塩化バナジウム、硫酸バナジル、バナジン酸マグネシウム、三酸化バナジウム、三塩化バナジウム、二酸化バナジウム、バナジルアセチルアセトネート、バナジウムアセチルアセトネート等が挙げられる。 (Vanadium Compound (C))
The vanadium compound (C) acts as a rust inhibitor when added to a metal surface treatment agent. The vanadium compound (C) is not particularly limited, but examples thereof include vanadium pentoxide, metavanadic acid, ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride, vanadyl sulfate, magnesium vanadate, vanadium trioxide, vanadium trichloride, vanadium dioxide, vanadyl acetylacetonate, and vanadium acetylacetonate.
バナジウム化合物（Ｃ）は、金属表面処理剤に添加されることで防錆剤（インヒビター）として作用する。バナジウム化合物（Ｃ）としては、特に限定されないが、例えば、五酸化バナジウム、メタバナジン酸、メタバナジン酸アンモニウム、メタバナジン酸ナトリウム、オキシ三塩化バナジウム、硫酸バナジル、バナジン酸マグネシウム、三酸化バナジウム、三塩化バナジウム、二酸化バナジウム、バナジルアセチルアセトネート、バナジウムアセチルアセトネート等が挙げられる。 (Vanadium Compound (C))
The vanadium compound (C) acts as a rust inhibitor when added to a metal surface treatment agent. The vanadium compound (C) is not particularly limited, but examples thereof include vanadium pentoxide, metavanadic acid, ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride, vanadyl sulfate, magnesium vanadate, vanadium trioxide, vanadium trichloride, vanadium dioxide, vanadyl acetylacetonate, and vanadium acetylacetonate.
本実施形態の金属表面処理剤の全固形分に対し、バナジウム元素の含有量は０．１～１０質量％であることが好ましい。上記バナジウム元素の含有量は、０．５～５質量％であることがより好ましい。上記バナジウム元素の含有量が０．１質量％未満である場合、十分な防錆性が得られない。上記バナジウム元素の含有量が１０質量％を超える場合、金属表面処理剤の安定性および耐食性が低下する。
The vanadium element content is preferably 0.1 to 10 mass% relative to the total solid content of the metal surface treatment agent of this embodiment. The vanadium element content is more preferably 0.5 to 5 mass%. If the vanadium element content is less than 0.1 mass%, sufficient rust prevention properties cannot be obtained. If the vanadium element content exceeds 10 mass%, the stability and corrosion resistance of the metal surface treatment agent decrease.
（ジルコニウム化合物（Ｄ））
ジルコニウム化合物（Ｄ）は、架橋剤として作用することで、形成される皮膜の水や腐食因子（塩化物イオン等）に対する遮断性を向上させ、結果として耐食性を向上させる。ジルコニウム化合物（Ｄ）としては、特に限定されないが、例えば、炭酸ジルコニウムアンモニウム、炭酸ジルコニウムカリウム等の炭酸ジルコニウム塩；Ｋ２ＺｒＦ６等のアルカリ金属フルオロジルコネート；ジルコンフッ化水素酸（Ｈ２ＺｒＦ６）；ジルコンフッ化アンモニウム（（ＮＨ４）２ＺｒＦ６）；フッ化ジルコニウム；硝酸ジルコニウム；酸化ジルコニウム；等が挙げられる。 (Zirconium Compound (D))
The zirconium compound (D) acts as a crosslinking agent to improve the barrier properties of the formed coating against water and corrosion factors (chloride ions, etc.), resulting in improved corrosion resistance. The zirconium compound (D) is not particularly limited, but examples thereof include zirconium carbonate salts such as ammonium zirconium carbonate and potassium zirconium carbonate , alkali metal fluorozirconates such as K2ZrF6 , zirconium hydrofluoric acid ( H2ZrF6 ), ammonium zirconium fluoride (( NH4 ) 2ZrF6 ), zirconium fluoride, zirconium nitrate, zirconium oxide, and the like.
ジルコニウム化合物（Ｄ）は、架橋剤として作用することで、形成される皮膜の水や腐食因子（塩化物イオン等）に対する遮断性を向上させ、結果として耐食性を向上させる。ジルコニウム化合物（Ｄ）としては、特に限定されないが、例えば、炭酸ジルコニウムアンモニウム、炭酸ジルコニウムカリウム等の炭酸ジルコニウム塩；Ｋ２ＺｒＦ６等のアルカリ金属フルオロジルコネート；ジルコンフッ化水素酸（Ｈ２ＺｒＦ６）；ジルコンフッ化アンモニウム（（ＮＨ４）２ＺｒＦ６）；フッ化ジルコニウム；硝酸ジルコニウム；酸化ジルコニウム；等が挙げられる。 (Zirconium Compound (D))
The zirconium compound (D) acts as a crosslinking agent to improve the barrier properties of the formed coating against water and corrosion factors (chloride ions, etc.), resulting in improved corrosion resistance. The zirconium compound (D) is not particularly limited, but examples thereof include zirconium carbonate salts such as ammonium zirconium carbonate and potassium zirconium carbonate , alkali metal fluorozirconates such as K2ZrF6 , zirconium hydrofluoric acid ( H2ZrF6 ), ammonium zirconium fluoride (( NH4 ) 2ZrF6 ), zirconium fluoride, zirconium nitrate, zirconium oxide, and the like.
本実施形態の金属表面処理剤の全固形分に対し、ジルコニウム元素の含有量は０．１～１０質量％であることが好ましい。ジルコニウム元素の含有量がこの範囲にあることで、金属表面処理剤の安定性および耐食性が向上する。上記ジルコニウム元素の含有量は、０．５～５質量％であることがより好ましい。上記ジルコニウム元素の含有量が０．１質量％未満である場合、十分な架橋剤としての効果が得られない。上記ジルコニウム元素の含有量が１０質量％を超える場合、処理剤の安定性および耐食性が低下する。
The zirconium element content is preferably 0.1 to 10 mass% relative to the total solid content of the metal surface treatment agent of this embodiment. With the zirconium element content in this range, the stability and corrosion resistance of the metal surface treatment agent are improved. The zirconium element content is more preferably 0.5 to 5 mass%. If the zirconium element content is less than 0.1 mass%, the effect as a sufficient cross-linking agent is not obtained. If the zirconium element content exceeds 10 mass%, the stability and corrosion resistance of the treatment agent are reduced.
本実施形態の金属表面処理剤の固形分に含まれるケイ素元素（Ｓｉ）に対するアルカリ金属元素（Ｍ）のモル比（Ｍ／Ｓｉ）は、０．５～１．２であることが好ましい。上記モル比（Ｍ／Ｓｉ）は、０．６～１．１であることがより好ましい。上記モル比（Ｍ／Ｓｉ）が０．５未満である場合、耐食性が低下する。上記モル比（Ｍ／Ｓｉ）が１．２を超える場合、金属表面処理剤の安定性が低下する。なお、上記アルカリ金属元素（Ｍ）は、アルカリ金属塩（Ｂ）以外のケイ酸化合物（Ａ）、バナジウム化合物（Ｃ）、ジルコニウム化合物（Ｄ）、又はその他の化合物由来のアルカリ金属元素を含む。
The molar ratio (M/Si) of the alkali metal element (M) to the silicon element (Si) contained in the solid content of the metal surface treatment agent of this embodiment is preferably 0.5 to 1.2. The molar ratio (M/Si) is more preferably 0.6 to 1.1. If the molar ratio (M/Si) is less than 0.5, the corrosion resistance decreases. If the molar ratio (M/Si) exceeds 1.2, the stability of the metal surface treatment agent decreases. The alkali metal element (M) includes alkali metal elements derived from silicate compounds (A), vanadium compounds (C), zirconium compounds (D), or other compounds other than the alkali metal salt (B).
（キレート剤（Ｅ））
キレート剤（Ｅ）は、金属表面処理剤に添加されることで、金属表面処理剤中のジルコニウムを安定化させる。キレート剤（Ｅ）としては、特に限定されないが、例えば、乳酸、リンゴ酸、酒石酸、クエン酸、グルコン酸等のヒドロキシカルボン酸；エチレンジアミン四酢酸（ＥＤＴＡ）；１－ヒドロキシエタン－１，１－ジホスホン酸（ＨＥＤＰ）等の有機リン化合物；トリエタノールアミン（ＴＥＡ）等のヒドロキシアミン；及び上記化合物の塩；等が挙げられる。 (Chelating Agent (E))
The chelating agent (E) is added to the metal surface treatment agent to stabilize zirconium in the metal surface treatment agent. The chelating agent (E) is not particularly limited, but examples thereof include hydroxycarboxylic acids such as lactic acid, malic acid, tartaric acid, citric acid, and gluconic acid, ethylenediaminetetraacetic acid (EDTA), organic phosphorus compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), hydroxyamines such as triethanolamine (TEA), and salts of the above compounds.
キレート剤（Ｅ）は、金属表面処理剤に添加されることで、金属表面処理剤中のジルコニウムを安定化させる。キレート剤（Ｅ）としては、特に限定されないが、例えば、乳酸、リンゴ酸、酒石酸、クエン酸、グルコン酸等のヒドロキシカルボン酸；エチレンジアミン四酢酸（ＥＤＴＡ）；１－ヒドロキシエタン－１，１－ジホスホン酸（ＨＥＤＰ）等の有機リン化合物；トリエタノールアミン（ＴＥＡ）等のヒドロキシアミン；及び上記化合物の塩；等が挙げられる。 (Chelating Agent (E))
The chelating agent (E) is added to the metal surface treatment agent to stabilize zirconium in the metal surface treatment agent. The chelating agent (E) is not particularly limited, but examples thereof include hydroxycarboxylic acids such as lactic acid, malic acid, tartaric acid, citric acid, and gluconic acid, ethylenediaminetetraacetic acid (EDTA), organic phosphorus compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), hydroxyamines such as triethanolamine (TEA), and salts of the above compounds.
キレート剤（Ｅ）としては、上記ＨＥＤＰのような有機リン化合物を含んでいてもよいが、本実施形態に係る金属表面処理剤は、富栄養化による環境影響低減の観点から、オルトリン酸（Ｈ３ＰＯ４）、ピロリン酸（Ｈ４Ｐ２Ｏ７）、メタリン酸（ＨＰＯ３）等のリン酸類、及びリン酸アンモニウム、リン酸ナトリウム等のリン酸塩類等の無機リン化合物を含まないことが好ましい。
The chelating agent (E) may contain an organic phosphorus compound such as the above-mentioned HEDP, but from the viewpoint of reducing the environmental impact due to eutrophication, it is preferable that the metal surface treatment agent according to this embodiment does not contain inorganic phosphorus compounds such as phosphoric acids such as orthophosphoric acid (H3PO4 ) , pyrophosphoric acid ( H4P2O7 ), metaphosphoric acid ( HPO3 ), and phosphates such as ammonium phosphate and sodium phosphate.
（その他の成分）
本実施形態の金属表面処理剤には、上記以外の成分として水が含まれる。また、金属表面処理剤には、上記の機能を阻害しない範囲で、更にその他の成分が含まれていてもよい。その他の成分としては、例えば、アクリル系樹脂、ウレタン系樹脂、エポキシ系樹脂、エチレンアクリル共重合体等のオレフィン系樹脂、ポリエステル系樹脂、ポリオレフィン系樹脂、アルキド系樹脂、ポリカーボネート系樹脂等の樹脂成分が挙げられる。上記樹脂成分が金属表面処理剤に含まれる場合、樹脂成分の金属表面処理剤の全固形分に対する固形分含有量が１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。これにより、金属表面処理剤の高温焼付を好ましく行うことができる。上記以外のその他の成分としては、架橋剤、防錆剤、レベリング剤、消泡剤、ｐＨ調整剤等の表面処理剤に含まれる公知の成分が挙げられる。 (Other ingredients)
The metal surface treatment agent of this embodiment contains water as a component other than the above. In addition, the metal surface treatment agent may further contain other components within a range that does not inhibit the above functions. Examples of the other components include resin components such as acrylic resins, urethane resins, epoxy resins, olefin resins such as ethylene acrylic copolymers, polyester resins, polyolefin resins, alkyd resins, and polycarbonate resins. When the resin components are contained in the metal surface treatment agent, the solid content of the resin components relative to the total solid content of the metal surface treatment agent is preferably 10% by mass or less, more preferably 5% by mass or less. This allows the metal surface treatment agent to be preferably baked at high temperatures. Examples of other components other than the above include known components contained in surface treatment agents such as crosslinkers, rust inhibitors, leveling agents, defoamers, and pH adjusters.
本実施形態の金属表面処理剤には、上記以外の成分として水が含まれる。また、金属表面処理剤には、上記の機能を阻害しない範囲で、更にその他の成分が含まれていてもよい。その他の成分としては、例えば、アクリル系樹脂、ウレタン系樹脂、エポキシ系樹脂、エチレンアクリル共重合体等のオレフィン系樹脂、ポリエステル系樹脂、ポリオレフィン系樹脂、アルキド系樹脂、ポリカーボネート系樹脂等の樹脂成分が挙げられる。上記樹脂成分が金属表面処理剤に含まれる場合、樹脂成分の金属表面処理剤の全固形分に対する固形分含有量が１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。これにより、金属表面処理剤の高温焼付を好ましく行うことができる。上記以外のその他の成分としては、架橋剤、防錆剤、レベリング剤、消泡剤、ｐＨ調整剤等の表面処理剤に含まれる公知の成分が挙げられる。 (Other ingredients)
The metal surface treatment agent of this embodiment contains water as a component other than the above. In addition, the metal surface treatment agent may further contain other components within a range that does not inhibit the above functions. Examples of the other components include resin components such as acrylic resins, urethane resins, epoxy resins, olefin resins such as ethylene acrylic copolymers, polyester resins, polyolefin resins, alkyd resins, and polycarbonate resins. When the resin components are contained in the metal surface treatment agent, the solid content of the resin components relative to the total solid content of the metal surface treatment agent is preferably 10% by mass or less, more preferably 5% by mass or less. This allows the metal surface treatment agent to be preferably baked at high temperatures. Examples of other components other than the above include known components contained in surface treatment agents such as crosslinkers, rust inhibitors, leveling agents, defoamers, and pH adjusters.
（固形分量）
本実施形態の金属表面処理剤の固形分量は、０．１～３０質量％であることが好ましく、１．０～２５質量％であることがより好ましい。 (Solid content)
The solid content of the metal surface treatment agent of the present embodiment is preferably 0.1 to 30 mass %, and more preferably 1.0 to 25 mass %.
本実施形態の金属表面処理剤の固形分量は、０．１～３０質量％であることが好ましく、１．０～２５質量％であることがより好ましい。 (Solid content)
The solid content of the metal surface treatment agent of the present embodiment is preferably 0.1 to 30 mass %, and more preferably 1.0 to 25 mass %.
＜金属基材＞
本実施形態の金属表面処理剤により表面処理される対象である金属基材としては、特に限定されないが、例えば、冷延鋼材、熱延鋼材、ステンレス、電気亜鉛めっき鋼材、溶融亜鉛めっき鋼材、亜鉛－アルミニウム合金系めっき鋼材、亜鉛－鉄合金系めっき鋼材、亜鉛－マグネシウム合金系めっき鋼材、亜鉛－アルミニウム－マグネシウム合金系めっき鋼材、アルミニウム系めっき鋼材、アルミニウム－シリコン合金系めっき鋼材、錫系めっき鋼材、鉛－錫系めっき鋼材、クロム系めっき鋼材、Ｎｉ系めっき鋼材等の金属鋼材が挙げられる。金属基材の形状としては、特に限定されないが、例えば、板状等が挙げられる。 <Metal substrate>
The metal substrate to be surface-treated with the metal surface treatment agent of the present embodiment is not particularly limited, and examples thereof include metal steel materials such as cold-rolled steel, hot-rolled steel, stainless steel, electrogalvanized steel, hot-dip galvanized steel, zinc-aluminum alloy-based plated steel, zinc-iron alloy-based plated steel, zinc-magnesium alloy-based plated steel, zinc-aluminum-magnesium alloy-based plated steel, aluminum-based plated steel, aluminum-silicon alloy-based plated steel, tin-based plated steel, lead-tin-based plated steel, chromium-based plated steel, and Ni-based plated steel. The shape of the metal substrate is not particularly limited, and examples thereof include a plate shape.
本実施形態の金属表面処理剤により表面処理される対象である金属基材としては、特に限定されないが、例えば、冷延鋼材、熱延鋼材、ステンレス、電気亜鉛めっき鋼材、溶融亜鉛めっき鋼材、亜鉛－アルミニウム合金系めっき鋼材、亜鉛－鉄合金系めっき鋼材、亜鉛－マグネシウム合金系めっき鋼材、亜鉛－アルミニウム－マグネシウム合金系めっき鋼材、アルミニウム系めっき鋼材、アルミニウム－シリコン合金系めっき鋼材、錫系めっき鋼材、鉛－錫系めっき鋼材、クロム系めっき鋼材、Ｎｉ系めっき鋼材等の金属鋼材が挙げられる。金属基材の形状としては、特に限定されないが、例えば、板状等が挙げられる。 <Metal substrate>
The metal substrate to be surface-treated with the metal surface treatment agent of the present embodiment is not particularly limited, and examples thereof include metal steel materials such as cold-rolled steel, hot-rolled steel, stainless steel, electrogalvanized steel, hot-dip galvanized steel, zinc-aluminum alloy-based plated steel, zinc-iron alloy-based plated steel, zinc-magnesium alloy-based plated steel, zinc-aluminum-magnesium alloy-based plated steel, aluminum-based plated steel, aluminum-silicon alloy-based plated steel, tin-based plated steel, lead-tin-based plated steel, chromium-based plated steel, and Ni-based plated steel. The shape of the metal substrate is not particularly limited, and examples thereof include a plate shape.
＜金属表面処理方法＞
本実施形態の金属表面処理剤は、いわゆる塗布型の金属表面処理剤である。塗布型の金属表面処理剤は、表面処理剤を金属基材の表面に塗布した後に、金属基材の表面を水洗せずに焼付（乾燥）する方法で使用される。即ち、本実施形態における金属表面処理方法は、金属基材の表面に金属表面処理剤を塗布する塗布工程と、金属基材の塗布した金属表面処理剤を焼付ける焼付工程と、を備える。本実施形態の塗布型の金属表面処理剤は、金属表面処理皮膜の形成を比較的簡便に行うことができ、かつ廃液を生じない利点を有する。 <Metal surface treatment method>
The metal surface treatment agent of this embodiment is a so-called coating-type metal surface treatment agent. The coating-type metal surface treatment agent is used in a method in which the surface treatment agent is applied to the surface of a metal substrate, and then the surface of the metal substrate is baked (dried) without rinsing with water. That is, the metal surface treatment method of this embodiment includes a coating step of applying the metal surface treatment agent to the surface of the metal substrate, and a baking step of baking the coated metal surface treatment agent on the metal substrate. The coating-type metal surface treatment agent of this embodiment has the advantage that the formation of a metal surface treatment film can be performed relatively easily and no waste liquid is generated.
本実施形態の金属表面処理剤は、いわゆる塗布型の金属表面処理剤である。塗布型の金属表面処理剤は、表面処理剤を金属基材の表面に塗布した後に、金属基材の表面を水洗せずに焼付（乾燥）する方法で使用される。即ち、本実施形態における金属表面処理方法は、金属基材の表面に金属表面処理剤を塗布する塗布工程と、金属基材の塗布した金属表面処理剤を焼付ける焼付工程と、を備える。本実施形態の塗布型の金属表面処理剤は、金属表面処理皮膜の形成を比較的簡便に行うことができ、かつ廃液を生じない利点を有する。 <Metal surface treatment method>
The metal surface treatment agent of this embodiment is a so-called coating-type metal surface treatment agent. The coating-type metal surface treatment agent is used in a method in which the surface treatment agent is applied to the surface of a metal substrate, and then the surface of the metal substrate is baked (dried) without rinsing with water. That is, the metal surface treatment method of this embodiment includes a coating step of applying the metal surface treatment agent to the surface of the metal substrate, and a baking step of baking the coated metal surface treatment agent on the metal substrate. The coating-type metal surface treatment agent of this embodiment has the advantage that the formation of a metal surface treatment film can be performed relatively easily and no waste liquid is generated.
塗布工程において、金属基材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、必要に応じて金属基材の表面に脱脂処理や酸洗、エッチング処理を施してもよい。
In the coating process, the method for coating the surface of the metal substrate with the metal surface treatment agent is not particularly limited, and examples of the method include roll coating, bar coating, spraying, and immersion. Prior to the coating process, the surface of the metal substrate may be degreased, pickled, or etched, if necessary.
焼付工程において、塗布工程の後に、金属基材に塗布した金属表面処理剤を焼付ける。上記焼付ける方法としては特に限定されない。焼付温度は、特に制限されないが、例えば素材到達温度（ＰＭＴ）で２００℃～４００℃とすることが好ましい。焼付時間は、特に制限されないが、例えば３～１８０秒とすることができる。
In the baking process, after the application process, the metal surface treatment agent applied to the metal substrate is baked. The baking method is not particularly limited. The baking temperature is not particularly limited, but it is preferable to set the material reachable temperature (PMT) to 200°C to 400°C, for example. The baking time is not particularly limited, but it can be set to, for example, 3 to 180 seconds.
＜金属表面処理皮膜＞
上記金属表面処理方法により形成される皮膜（以下、単に「皮膜」と記載する場合がある）は、上述の金属表面処理剤の各成分のうち、水等の揮発成分を除く各成分を含む。即ち、金属表面処理皮膜に含まれるケイ素元素の含有量は１０質量％以上である。金属表面処理皮膜に含まれるケイ素元素（Ｓｉ）に対するアルカリ金属元素（Ｍ）のモル比（Ｍ／Ｓｉ）が０．５～１．２であることが好ましい。金属表面処理皮膜に含まれるバナジウム元素の含有量は０．１～１０質量％であることが好ましい。金属表面処理皮膜に含まれるジルコニウム元素の含有量は０．１～１０質量％であることが好ましい。皮膜重量としては特に限定されないが、０．３～２．０ｇ／ｍ２であることが好ましく、０．５～１．５ｇ／ｍ２であることがより好ましい。 <Metal surface treatment film>
The film formed by the above-mentioned metal surface treatment method (hereinafter, sometimes simply referred to as "film") contains each component of the above-mentioned metal surface treatment agent, excluding volatile components such as water. That is, the content of silicon element contained in the metal surface treatment film is 10 mass% or more. The molar ratio (M/Si) of the alkali metal element (M) to the silicon element (Si) contained in the metal surface treatment film is preferably 0.5 to 1.2. The content of vanadium element contained in the metal surface treatment film is preferably 0.1 to 10 mass%. The content of zirconium element contained in the metal surface treatment film is preferably 0.1 to 10 mass%. The weight of the film is not particularly limited, but is preferably 0.3 to 2.0 g/ m2 , and more preferably 0.5 to 1.5 g/ m2 .
上記金属表面処理方法により形成される皮膜（以下、単に「皮膜」と記載する場合がある）は、上述の金属表面処理剤の各成分のうち、水等の揮発成分を除く各成分を含む。即ち、金属表面処理皮膜に含まれるケイ素元素の含有量は１０質量％以上である。金属表面処理皮膜に含まれるケイ素元素（Ｓｉ）に対するアルカリ金属元素（Ｍ）のモル比（Ｍ／Ｓｉ）が０．５～１．２であることが好ましい。金属表面処理皮膜に含まれるバナジウム元素の含有量は０．１～１０質量％であることが好ましい。金属表面処理皮膜に含まれるジルコニウム元素の含有量は０．１～１０質量％であることが好ましい。皮膜重量としては特に限定されないが、０．３～２．０ｇ／ｍ２であることが好ましく、０．５～１．５ｇ／ｍ２であることがより好ましい。 <Metal surface treatment film>
The film formed by the above-mentioned metal surface treatment method (hereinafter, sometimes simply referred to as "film") contains each component of the above-mentioned metal surface treatment agent, excluding volatile components such as water. That is, the content of silicon element contained in the metal surface treatment film is 10 mass% or more. The molar ratio (M/Si) of the alkali metal element (M) to the silicon element (Si) contained in the metal surface treatment film is preferably 0.5 to 1.2. The content of vanadium element contained in the metal surface treatment film is preferably 0.1 to 10 mass%. The content of zirconium element contained in the metal surface treatment film is preferably 0.1 to 10 mass%. The weight of the film is not particularly limited, but is preferably 0.3 to 2.0 g/ m2 , and more preferably 0.5 to 1.5 g/ m2 .
＜表面処理金属＞
本実施形態に係る表面処理金属は、上記金属基材の表面に上記金属表面処理皮膜が形成されてなる。表面処理金属は、上記金属表面処理皮膜の上に塗膜が形成されたものであってもよい。塗膜を形成する塗料としては、特に限定されず、１コート用塗料を用いてもよいし、プライマー及びトップコートを用いてもよい。 <Surface-treated metal>
The surface-treated metal according to the present embodiment is obtained by forming the metal surface treatment film on the surface of the metal substrate. The surface-treated metal may be a metal surface treatment film on which a coating film is formed. The paint for forming the coating film is not particularly limited, and a one-coat paint or a primer and a top coat may be used.
本実施形態に係る表面処理金属は、上記金属基材の表面に上記金属表面処理皮膜が形成されてなる。表面処理金属は、上記金属表面処理皮膜の上に塗膜が形成されたものであってもよい。塗膜を形成する塗料としては、特に限定されず、１コート用塗料を用いてもよいし、プライマー及びトップコートを用いてもよい。 <Surface-treated metal>
The surface-treated metal according to the present embodiment is obtained by forming the metal surface treatment film on the surface of the metal substrate. The surface-treated metal may be a metal surface treatment film on which a coating film is formed. The paint for forming the coating film is not particularly limited, and a one-coat paint or a primer and a top coat may be used.
以下、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、実施例に限定されるものではない。
The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
＜金属表面処理剤の調製＞
［実施例１～３６、比較例１～４］
以下の表１～表４に記載の固形分含有量となるように、ケイ酸化合物（Ａ）、アルカリ金属塩（Ｂ）、バナジウム化合物（Ｃ）、ジルコニウム化合物（Ｄ）、キレート剤（Ｅ）を計量し、金属表面処理剤におけるこれら組成物の合計の固形分濃度が１８質量％となるようにイオン交換水を添加して混合撹拌し、金属表面処理剤を得た。表１～表４に記載した各成分の配合量の単位は、質量部を示す。表１～表４に記載した「Ｓｉ量」「Ｖ量」「Ｚｒ量」は、それぞれ、金属表面処理剤の全固形分に対する、ケイ素元素、バナジウム元素、ジルコニウム元素の含有量（単位：質量％）を示す。 <Preparation of Metal Surface Treatment Agent>
[Examples 1 to 36, Comparative Examples 1 to 4]
The silicic acid compound (A), the alkali metal salt (B), the vanadium compound (C), the zirconium compound (D), and the chelating agent (E) were weighed out so as to obtain the solid content shown in Tables 1 to 4 below, and ion-exchanged water was added and mixed and stirred so that the total solid content concentration of these compositions in the metal surface treatment agent was 18 mass %, to obtain a metal surface treatment agent. The unit of the blending amount of each component shown in Tables 1 to 4 is parts by mass. The "Si amount", "V amount", and "Zr amount" shown in Tables 1 to 4 respectively indicate the contents (unit: mass %) of silicon element, vanadium element, and zirconium element relative to the total solid content of the metal surface treatment agent.
［実施例１～３６、比較例１～４］
以下の表１～表４に記載の固形分含有量となるように、ケイ酸化合物（Ａ）、アルカリ金属塩（Ｂ）、バナジウム化合物（Ｃ）、ジルコニウム化合物（Ｄ）、キレート剤（Ｅ）を計量し、金属表面処理剤におけるこれら組成物の合計の固形分濃度が１８質量％となるようにイオン交換水を添加して混合撹拌し、金属表面処理剤を得た。表１～表４に記載した各成分の配合量の単位は、質量部を示す。表１～表４に記載した「Ｓｉ量」「Ｖ量」「Ｚｒ量」は、それぞれ、金属表面処理剤の全固形分に対する、ケイ素元素、バナジウム元素、ジルコニウム元素の含有量（単位：質量％）を示す。 <Preparation of Metal Surface Treatment Agent>
[Examples 1 to 36, Comparative Examples 1 to 4]
The silicic acid compound (A), the alkali metal salt (B), the vanadium compound (C), the zirconium compound (D), and the chelating agent (E) were weighed out so as to obtain the solid content shown in Tables 1 to 4 below, and ion-exchanged water was added and mixed and stirred so that the total solid content concentration of these compositions in the metal surface treatment agent was 18 mass %, to obtain a metal surface treatment agent. The unit of the blending amount of each component shown in Tables 1 to 4 is parts by mass. The "Si amount", "V amount", and "Zr amount" shown in Tables 1 to 4 respectively indicate the contents (unit: mass %) of silicon element, vanadium element, and zirconium element relative to the total solid content of the metal surface treatment agent.
表１～表４に記載した原料の種類の詳細を以下に示す。
Details of the types of raw materials listed in Tables 1 to 4 are shown below.
（ケイ酸化合物（Ａ））
Ａ１：Ｊ珪酸ソーダ３号（ケイ酸ナトリウム、日本化学工業（株）製）
Ａ２：珪酸リチウム３５（ケイ酸リチウム、ＳｉＯ２／Ｌｉ２Ｏ（モル比）＝３．５、日本化学工業（株）製）
Ａ３：珪酸リチウム７５（ケイ酸リチウム、ＳｉＯ２／Ｌｉ２Ｏ（モル比）＝７．５、日本化学工業（株）製）
Ａ４：２Ｋ珪酸カリ（ケイ酸カリウム、日本化学工業（株）製）
Ａ５：エチルシリケート２８（エチルシリケート、コルコート（株）製）の加水分解生成物 (Silicate Compound (A))
A1: J Sodium Silicate No. 3 (sodium silicate, manufactured by Nippon Chemical Industry Co., Ltd.)
A2: Lithium silicate 35 (lithium silicate, SiO 2 /Li 2 O (molar ratio) = 3.5, manufactured by Nippon Chemical Industry Co., Ltd.)
A3: Lithium silicate 75 (lithium silicate, SiO 2 /Li 2 O (molar ratio) = 7.5, manufactured by Nippon Chemical Industry Co., Ltd.)
A4: 2K potassium silicate (potassium silicate, manufactured by Nippon Chemical Industry Co., Ltd.)
A5: Hydrolysis product of Ethyl Silicate 28 (Ethyl Silicate, manufactured by Colcoat Co., Ltd.)
Ａ１：Ｊ珪酸ソーダ３号（ケイ酸ナトリウム、日本化学工業（株）製）
Ａ２：珪酸リチウム３５（ケイ酸リチウム、ＳｉＯ２／Ｌｉ２Ｏ（モル比）＝３．５、日本化学工業（株）製）
Ａ３：珪酸リチウム７５（ケイ酸リチウム、ＳｉＯ２／Ｌｉ２Ｏ（モル比）＝７．５、日本化学工業（株）製）
Ａ４：２Ｋ珪酸カリ（ケイ酸カリウム、日本化学工業（株）製）
Ａ５：エチルシリケート２８（エチルシリケート、コルコート（株）製）の加水分解生成物 (Silicate Compound (A))
A1: J Sodium Silicate No. 3 (sodium silicate, manufactured by Nippon Chemical Industry Co., Ltd.)
A2: Lithium silicate 35 (lithium silicate, SiO 2 /Li 2 O (molar ratio) = 3.5, manufactured by Nippon Chemical Industry Co., Ltd.)
A3: Lithium silicate 75 (lithium silicate, SiO 2 /Li 2 O (molar ratio) = 7.5, manufactured by Nippon Chemical Industry Co., Ltd.)
A4: 2K potassium silicate (potassium silicate, manufactured by Nippon Chemical Industry Co., Ltd.)
A5: Hydrolysis product of Ethyl Silicate 28 (Ethyl Silicate, manufactured by Colcoat Co., Ltd.)
（アルカリ金属塩（Ｂ））
Ｂ１：水酸化ナトリウム
Ｂ２：炭酸水素ナトリウム
Ｂ３：炭酸ナトリウム
Ｂ４：水酸化リチウム・一水和物
Ｂ５：水酸化カリウム
Ｂ６：亜硝酸ナトリウム
Ｂ７：亜硝酸リチウム (Alkali Metal Salt (B))
B1: Sodium hydroxide B2: Sodium bicarbonate B3: Sodium carbonate B4: Lithium hydroxide monohydrate B5: Potassium hydroxide B6: Sodium nitrite B7: Lithium nitrite
Ｂ１：水酸化ナトリウム
Ｂ２：炭酸水素ナトリウム
Ｂ３：炭酸ナトリウム
Ｂ４：水酸化リチウム・一水和物
Ｂ５：水酸化カリウム
Ｂ６：亜硝酸ナトリウム
Ｂ７：亜硝酸リチウム (Alkali Metal Salt (B))
B1: Sodium hydroxide B2: Sodium bicarbonate B3: Sodium carbonate B4: Lithium hydroxide monohydrate B5: Potassium hydroxide B6: Sodium nitrite B7: Lithium nitrite
（バナジウム化合物（Ｃ））
Ｃ１：硫酸バナジル
Ｃ２：メタバナジン酸アンモニウム
Ｃ３：メタバナジン酸ナトリウム (Vanadium Compound (C))
C1: Vanadyl sulfate C2: Ammonium metavanadate C3: Sodium metavanadate
Ｃ１：硫酸バナジル
Ｃ２：メタバナジン酸アンモニウム
Ｃ３：メタバナジン酸ナトリウム (Vanadium Compound (C))
C1: Vanadyl sulfate C2: Ammonium metavanadate C3: Sodium metavanadate
（ジルコニウム化合物（Ｄ））
Ｄ１：炭酸ジルコニウムアンモニウム
Ｄ２：炭酸ジルコニウムカリウム
Ｄ３：ＡＺコート５８００ＭＴ（炭酸ジルコニウムアンモニウム４５％液、サンノプコ（株）製）
Ｄ４：ＺＳＬ－１０Ａ（酸化ジルコニウムゾル、ｐＨ７．７、第一稀元素化学工業（株）製）
Ｄ５：ジルコンフッ化アンモニウム
Ｄ６：硝酸ジルコニウム (Zirconium Compound (D))
D1: Ammonium zirconium carbonate D2: Potassium zirconium carbonate D3: AZ Coat 5800MT (45% ammonium zirconium carbonate solution, manufactured by San Nopco Ltd.)
D4: ZSL-10A (zirconium oxide sol, pH 7.7, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.)
D5: Ammonium zirconate fluoride D6: Zirconium nitrate
Ｄ１：炭酸ジルコニウムアンモニウム
Ｄ２：炭酸ジルコニウムカリウム
Ｄ３：ＡＺコート５８００ＭＴ（炭酸ジルコニウムアンモニウム４５％液、サンノプコ（株）製）
Ｄ４：ＺＳＬ－１０Ａ（酸化ジルコニウムゾル、ｐＨ７．７、第一稀元素化学工業（株）製）
Ｄ５：ジルコンフッ化アンモニウム
Ｄ６：硝酸ジルコニウム (Zirconium Compound (D))
D1: Ammonium zirconium carbonate D2: Potassium zirconium carbonate D3: AZ Coat 5800MT (45% ammonium zirconium carbonate solution, manufactured by San Nopco Ltd.)
D4: ZSL-10A (zirconium oxide sol, pH 7.7, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.)
D5: Ammonium zirconate fluoride D6: Zirconium nitrate
（キレート剤（Ｅ））
Ｅ１：クエン酸
Ｅ２：グルコン酸
Ｅ３：１－ヒドロキシエチリデン－１，１－ジホスホン酸
Ｅ４：トリエタノールアミン
Ｅ５：エチレンジアミン四酢酸 (Chelating Agent (E))
E1: Citric acid E2: Gluconic acid E3: 1-hydroxyethylidene-1,1-diphosphonic acid E4: Triethanolamine E5: Ethylenediaminetetraacetic acid
Ｅ１：クエン酸
Ｅ２：グルコン酸
Ｅ３：１－ヒドロキシエチリデン－１，１－ジホスホン酸
Ｅ４：トリエタノールアミン
Ｅ５：エチレンジアミン四酢酸 (Chelating Agent (E))
E1: Citric acid E2: Gluconic acid E3: 1-hydroxyethylidene-1,1-diphosphonic acid E4: Triethanolamine E5: Ethylenediaminetetraacetic acid
［貯蔵安定性試験］
４０℃のインキュベータで７日間、表１～表４に示す金属表面処理剤を静置した後、以下の判定基準で、貯蔵安定性を目視評価し、２を合格とした。結果を表５及び表６に示す。
２：金属表面処理剤の内容物が沈降していない
１：金属表面処理剤の内容物が沈降している [Storage stability test]
The metal surface treatment agents shown in Tables 1 to 4 were allowed to stand in an incubator at 40° C. for 7 days, and then the storage stability was visually evaluated according to the following criteria, with a score of 2 being acceptable. The results are shown in Tables 5 and 6.
2: The contents of the metal surface treatment agent have not settled. 1: The contents of the metal surface treatment agent have settled.
４０℃のインキュベータで７日間、表１～表４に示す金属表面処理剤を静置した後、以下の判定基準で、貯蔵安定性を目視評価し、２を合格とした。結果を表５及び表６に示す。
２：金属表面処理剤の内容物が沈降していない
１：金属表面処理剤の内容物が沈降している [Storage stability test]
The metal surface treatment agents shown in Tables 1 to 4 were allowed to stand in an incubator at 40° C. for 7 days, and then the storage stability was visually evaluated according to the following criteria, with a score of 2 being acceptable. The results are shown in Tables 5 and 6.
2: The contents of the metal surface treatment agent have not settled. 1: The contents of the metal surface treatment agent have settled.
＜試験板の作製＞
表１～表４に示す金属表面処理剤を用い、金属基材としてのＪＩＳ Ｇ３１３５に規定される冷間圧延鋼板（ＳＰＣＣ２７０ＳＤ、株式会社パルテック製）に対してそれぞれ表面処理を行った。表面処理は、以下の手順で行った。まず、日本ペイント・サーフケミカルズ株式会社製、サーフクリーナー５３ＮＦを２％の濃度に調製した溶液に上記金属基材を４５℃で２分間浸漬させ、脱脂処理を行った。脱脂処理後の金属基材を水洗後、乾燥を行った。次いで、表１～表４に示す金属表面処理剤を、バーコーターを用いて、上記金属基材表面に、皮膜量が０．７ｇ／ｍ２となるように塗布した。次いで、上記塗布後の金属基材をオーブンにて温度５５０℃で１５秒間加熱し焼付を行った。焼付時の素材到達温度（ＰＭＴ）は３００℃であった。上記により得られた各実施例及び比較例に係る試験板を用いて以下の評価を行った。 <Preparation of test plate>
Using the metal surface treatment agents shown in Tables 1 to 4, surface treatment was performed on cold-rolled steel sheets (SPCC270SD, manufactured by Paltec Co., Ltd.) specified in JIS G3135 as metal substrates. The surface treatment was performed according to the following procedure. First, the metal substrates were immersed in a solution prepared by preparing Surf Cleaner 53NF manufactured by Nippon Paint Surf Chemicals Co., Ltd. at a concentration of 2% at 45°C for 2 minutes to perform degreasing treatment. The metal substrates after degreasing treatment were washed with water and then dried. Next, the metal surface treatment agents shown in Tables 1 to 4 were applied to the surfaces of the metal substrates using a bar coater so that the coating amount was 0.7 g/ m2 . Next, the metal substrates after application were heated in an oven at a temperature of 550°C for 15 seconds to perform baking. The material reached temperature (PMT) during baking was 300°C. The following evaluations were performed using the test plates according to the examples and comparative examples obtained as described above.
表１～表４に示す金属表面処理剤を用い、金属基材としてのＪＩＳ Ｇ３１３５に規定される冷間圧延鋼板（ＳＰＣＣ２７０ＳＤ、株式会社パルテック製）に対してそれぞれ表面処理を行った。表面処理は、以下の手順で行った。まず、日本ペイント・サーフケミカルズ株式会社製、サーフクリーナー５３ＮＦを２％の濃度に調製した溶液に上記金属基材を４５℃で２分間浸漬させ、脱脂処理を行った。脱脂処理後の金属基材を水洗後、乾燥を行った。次いで、表１～表４に示す金属表面処理剤を、バーコーターを用いて、上記金属基材表面に、皮膜量が０．７ｇ／ｍ２となるように塗布した。次いで、上記塗布後の金属基材をオーブンにて温度５５０℃で１５秒間加熱し焼付を行った。焼付時の素材到達温度（ＰＭＴ）は３００℃であった。上記により得られた各実施例及び比較例に係る試験板を用いて以下の評価を行った。 <Preparation of test plate>
Using the metal surface treatment agents shown in Tables 1 to 4, surface treatment was performed on cold-rolled steel sheets (SPCC270SD, manufactured by Paltec Co., Ltd.) specified in JIS G3135 as metal substrates. The surface treatment was performed according to the following procedure. First, the metal substrates were immersed in a solution prepared by preparing Surf Cleaner 53NF manufactured by Nippon Paint Surf Chemicals Co., Ltd. at a concentration of 2% at 45°C for 2 minutes to perform degreasing treatment. The metal substrates after degreasing treatment were washed with water and then dried. Next, the metal surface treatment agents shown in Tables 1 to 4 were applied to the surfaces of the metal substrates using a bar coater so that the coating amount was 0.7 g/ m2 . Next, the metal substrates after application were heated in an oven at a temperature of 550°C for 15 seconds to perform baking. The material reached temperature (PMT) during baking was 300°C. The following evaluations were performed using the test plates according to the examples and comparative examples obtained as described above.
＜評価＞
［耐食性（塩水噴霧試験（ＳＳＴ））］
各試験板をＪＩＳ Ｚ２３１７に示される塩水噴霧腐食試験機に４時間、８時間及び１６時間投入し、赤錆の発生面積を目視で以下の基準に従って評価し、２以上を合格とした。結果を表５及び表６に示した。
４：ＳＳＴ１６時間後の赤錆の発生面積が、試験板の面積の５％以下
３：ＳＳＴ８時間後の赤錆の発生面積が、試験板の面積の５％以下
２：ＳＳＴ４時間後の赤錆の発生面積が、試験板の面積の５％以下
１：ＳＳＴ４時間後の赤錆の発生面積が、試験板の面積の５％超 <Evaluation>
[Corrosion resistance (salt spray test (SST))]
Each test plate was placed in a salt spray corrosion tester according to JIS Z2317 for 4, 8 and 16 hours, and the area of red rust was visually evaluated according to the following criteria, with a score of 2 or more being considered a pass. The results are shown in Tables 5 and 6.
4: After 16 hours of SST, the area of red rust is 5% or less of the test plate area. 3: After 8 hours of SST, the area of red rust is 5% or less of the test plate area. 2: After 4 hours of SST, the area of red rust is 5% or less of the test plate area. 1: After 4 hours of SST, the area of red rust is more than 5% of the test plate area.
［耐食性（塩水噴霧試験（ＳＳＴ））］
各試験板をＪＩＳ Ｚ２３１７に示される塩水噴霧腐食試験機に４時間、８時間及び１６時間投入し、赤錆の発生面積を目視で以下の基準に従って評価し、２以上を合格とした。結果を表５及び表６に示した。
４：ＳＳＴ１６時間後の赤錆の発生面積が、試験板の面積の５％以下
３：ＳＳＴ８時間後の赤錆の発生面積が、試験板の面積の５％以下
２：ＳＳＴ４時間後の赤錆の発生面積が、試験板の面積の５％以下
１：ＳＳＴ４時間後の赤錆の発生面積が、試験板の面積の５％超 <Evaluation>
[Corrosion resistance (salt spray test (SST))]
Each test plate was placed in a salt spray corrosion tester according to JIS Z2317 for 4, 8 and 16 hours, and the area of red rust was visually evaluated according to the following criteria, with a score of 2 or more being considered a pass. The results are shown in Tables 5 and 6.
4: After 16 hours of SST, the area of red rust is 5% or less of the test plate area. 3: After 8 hours of SST, the area of red rust is 5% or less of the test plate area. 2: After 4 hours of SST, the area of red rust is 5% or less of the test plate area. 1: After 4 hours of SST, the area of red rust is more than 5% of the test plate area.
表５及び表６の結果から、以下の結果が明らかである。実施例に係る試験板はそれぞれ特定の成分を含まない比較例１、３、４に係る試験板、及びケイ素元素の含有量が１０質量％未満である比較例２に係る試験板よりも耐食性の結果が優れている。また、実施例に係る金属表面処理剤は、比較例２、４に係る表面処理剤よりも貯蔵安定性に優れている。
The results in Tables 5 and 6 make the following clear: The test plates according to the Examples have better corrosion resistance results than the test plates according to Comparative Examples 1, 3, and 4, which do not contain any specific components, and the test plate according to Comparative Example 2, which has a silicon element content of less than 10 mass%. In addition, the metal surface treatment agents according to the Examples have better storage stability than the surface treatment agents according to Comparative Examples 2 and 4.
Claims (7)
- ケイ酸化合物（Ａ）と、
ケイ酸化合物以外、バナジウム化合物以外、かつジルコニウム化合物以外のアルカリ金属塩（Ｂ）と、
バナジウム化合物（Ｃ）と、
ジルコニウム化合物（Ｄ）と、
水と、を含有し、
金属表面処理剤の全固形分に対し、ケイ素元素の含有量は１０質量％以上である、金属表面処理剤。 A silicic acid compound (A),
an alkali metal salt (B) other than a silicate compound, a vanadium compound, and a zirconium compound;
A vanadium compound (C),
A zirconium compound (D),
Water;
A metal surface treatment agent, the silicon content of which is 10 mass% or more based on the total solid content of the metal surface treatment agent. - 前記ケイ酸化合物（Ａ）はアルカリ金属のケイ酸塩である、請求項１に記載の金属表面処理剤。 The metal surface treatment agent according to claim 1, wherein the silicate compound (A) is an alkali metal silicate.
- 前記金属表面処理剤の固形分に含まれるケイ素元素（Ｓｉ）に対するアルカリ金属元素（Ｍ）のモル比（Ｍ／Ｓｉ）が０．５～１．２である、請求項１又は２に記載の金属表面処理剤。 The metal surface treatment agent according to claim 1 or 2, wherein the molar ratio (M/Si) of alkali metal element (M) to silicon element (Si) contained in the solid content of the metal surface treatment agent is 0.5 to 1.2.
- 前記金属表面処理剤の全固形分に対し、バナジウム元素の含有量は０．１～１０質量％であり、ジルコニウム元素の含有量は０．１～１０質量％である、請求項１又は２に記載の金属表面処理剤。 The metal surface treatment agent according to claim 1 or 2, wherein the vanadium element content is 0.1 to 10 mass % and the zirconium element content is 0.1 to 10 mass % relative to the total solid content of the metal surface treatment agent.
- 更に、キレート剤（Ｅ）を含む、請求項１又は２に記載の金属表面処理剤。 The metal surface treatment agent according to claim 1 or 2, further comprising a chelating agent (E).
- 請求項１又は２に記載の金属表面処理剤を硬化した、金属表面処理皮膜。 A metal surface treatment film obtained by hardening the metal surface treatment agent according to claim 1 or 2.
- 請求項６に記載の金属表面処理皮膜を有する、表面処理金属。 A surface-treated metal having the metal surface treatment film according to claim 6.
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| JP2022-188237 | 2022-11-25 | ||
| JP2022188237 | 2022-11-25 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008088553A (en) * | 2006-09-08 | 2008-04-17 | Nippon Paint Co Ltd | Method of treating surface of metal base, metallic material treated by the surface treatment method, and method of coating the metallic material |
| JP2009114500A (en) * | 2007-11-07 | 2009-05-28 | Jfe Galvanizing & Coating Co Ltd | Method for manufacturing surface-treated steel sheet and surface-treated steel sheet |
| JP2011068996A (en) * | 2010-12-07 | 2011-04-07 | Nippon Parkerizing Co Ltd | Composition for surface treatment of metallic material, and treatment method |
| JP2020186456A (en) * | 2019-05-16 | 2020-11-19 | Ｊｆｅ鋼板株式会社 | Surface-treated steel sheet |
| WO2021065485A1 (en) * | 2019-10-04 | 2021-04-08 | 日鉄鋼板株式会社 | Surface-treated steel material |
-
2023
- 2023-11-13 WO PCT/JP2023/040774 patent/WO2024111458A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008088553A (en) * | 2006-09-08 | 2008-04-17 | Nippon Paint Co Ltd | Method of treating surface of metal base, metallic material treated by the surface treatment method, and method of coating the metallic material |
| JP2009114500A (en) * | 2007-11-07 | 2009-05-28 | Jfe Galvanizing & Coating Co Ltd | Method for manufacturing surface-treated steel sheet and surface-treated steel sheet |
| JP2011068996A (en) * | 2010-12-07 | 2011-04-07 | Nippon Parkerizing Co Ltd | Composition for surface treatment of metallic material, and treatment method |
| JP2020186456A (en) * | 2019-05-16 | 2020-11-19 | Ｊｆｅ鋼板株式会社 | Surface-treated steel sheet |
| WO2021065485A1 (en) * | 2019-10-04 | 2021-04-08 | 日鉄鋼板株式会社 | Surface-treated steel material |
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