TW202006186A - Chromium-free metal surface treatment agent, metal surface treatment method using the same, and metal substrate having a mass ratio of resin solid content to silicon in a range of 1 to 5 - Google Patents

Chromium-free metal surface treatment agent, metal surface treatment method using the same, and metal substrate having a mass ratio of resin solid content to silicon in a range of 1 to 5 Download PDF

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TW202006186A
TW202006186A TW108123037A TW108123037A TW202006186A TW 202006186 A TW202006186 A TW 202006186A TW 108123037 A TW108123037 A TW 108123037A TW 108123037 A TW108123037 A TW 108123037A TW 202006186 A TW202006186 A TW 202006186A
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metal surface
chromium
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treatment agent
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中村慎太郎
三浦裕佑
山根健輔
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日商日塗表面處理化工股份有限公司
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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
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • 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
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract

The present invention provides a chromium-free metal surface treatment agent, a metal surface treatment method using the chromium-free metal surface treatment agent, and a metal substrate subjected to the surface treatment. The chromium-free metal surface treatment agent contains (A) a polysilyl-functional silane, (B) an amino-containing silane coupling agent, (C) inorganic compound particles, and (D) at least one resin selected from the group consisting of a water-based cationic urethane resin and a water-based cationic acrylic resin. The mass ratio (resin solid content/silicon) of the resin solid content in the component (D) and the silicon in the component (A) and the component (B) is in a range of from 1 to 5.

Description

無鉻金屬表面處理劑、金屬表面處理方法、及金屬基材Chromium-free metal surface treatment agent, metal surface treatment method, and metal substrate

本發明關於無鉻金屬表面處理劑、金屬表面處理方法、及金屬基材。The invention relates to a chromium-free metal surface treatment agent, a metal surface treatment method, and a metal substrate.

以往，作為用於對金屬基材賦予耐腐蝕性的表面處理劑，已知鉻酸鹽處理劑、磷酸-鉻酸鹽處理劑等鉻系金屬表面處理劑，現在仍在廣泛使用。但是，從近年的環保限制趨勢來看，由於鉻所具有的毒性、特別是致癌性，將來有可能會被限制使用。Conventionally, as surface treatment agents for imparting corrosion resistance to metal substrates, chromium-based metal surface treatment agents such as chromate treatment agents and phosphoric acid-chromate treatment agents are known, and they are still widely used today. However, from the perspective of environmental protection trends in recent years, due to the toxicity of chromium, especially carcinogenicity, it may be restricted in the future.

因此，開發了各種與鉻系金屬表面處理劑顯示同等的耐腐蝕性的無鉻金屬表面處理劑。Therefore, various chromium-free metal surface treatment agents exhibiting the same corrosion resistance as chromium-based metal surface treatment agents have been developed.

例如，專利文獻1中，作為用於預塗鋼板（PCM）的無鉻金屬表面處理劑，公開了一種金屬表面處理劑，其在1升金屬表面處理劑中，包含（a）0.01～100g/L的矽烷偶合劑及其水解縮合物、（b）0.05～100g/L的水分散性二氧化矽（固體成分）、（c）以鋯離子計為0.01～50g/L的鋯化合物和/或以鈦離子計為0.01～50g/L的鈦化合物。For example, Patent Document 1 discloses a metal surface treatment agent as a chromium-free metal surface treatment agent for pre-coated steel sheets (PCM), which contains (a) 0.01 to 100 g/in 1 liter of metal surface treatment agent L silane coupling agent and its hydrolyzed condensate, (b) 0.05-100g/L water-dispersible silica (solid content), (c) 0.01-50g/L zirconium compound in terms of zirconium ion and/or The titanium compound is 0.01-50 g/L in terms of titanium ions.

[先前技術文獻] (專利文獻) 專利文獻1：日本專利4393660號公報[Prior Technical Literature] (Patent Literature) Patent Document 1: Japanese Patent No. 4393660

[發明所欲解決的問題] 但是，在使用無鉻金屬表面處理劑在金屬基材上形成覆膜時，對於所形成的覆膜，除了要求耐腐蝕性以外，還要求對金屬基材、頂層塗裝的密合性、耐化學藥品性等。特別是，在製造預塗鋼板（PCM）時，在金屬基材成型加工前實施表面處理，因此要求加工部也顯示耐腐蝕性和密合性。[Problems to be solved by the invention] However, when a chromium-free metal surface treatment agent is used to form a coating on a metal substrate, in addition to corrosion resistance, the formed coating also requires adhesion and resistance to the coating of the metal substrate and the top layer Chemical properties, etc. In particular, when manufacturing a pre-coated steel sheet (PCM), the surface treatment is performed before the metal base material is formed. Therefore, it is required that the processed portion also exhibit corrosion resistance and adhesion.

但是，以往的無鉻金屬表面處理劑所形成的覆膜的耐腐蝕性、密合性及耐化學藥品性難以稱之為充分，存在改善的餘地。However, the corrosion resistance, adhesion, and chemical resistance of the coating formed by the conventional chromium-free metal surface treatment agent cannot be said to be sufficient, and there is room for improvement.

本發明是鑒於以上的狀況而進行，其目的在於，提供一種無鉻金屬表面處理劑，其能夠對於金屬基材形成耐腐蝕性、密合性及耐化學藥品性優異的覆膜。另外，本發明的目的在於，提供一種使用了該無鉻金屬表面處理劑的金屬表面處理方法、及實施了表面處理的金屬基板。The present invention has been made in view of the above circumstances, and its object is to provide a chromium-free metal surface treatment agent that can form a coating film excellent in corrosion resistance, adhesion, and chemical resistance to a metal substrate. In addition, an object of the present invention is to provide a metal surface treatment method using the chromium-free metal surface treatment agent, and a metal substrate subjected to surface treatment.

[解決問題的技術手段] 本發明關於一種無鉻金屬表面處理劑，其含有下述（A）成分、（B）成分、（C）成分及（D）成分； （A）多甲矽烷基官能矽烷、 （B）含有胺基之矽烷偶合劑、 （C）無機化合物粒子、 （D）選自水系陽離子胺基甲酸酯樹脂和水系陽離子丙烯酸樹脂中的至少一種樹脂， 其中，前述（A）成分和前述（B）成分中的矽與前述（D）成分中的樹脂固體成分的質量比（樹脂固體成分/矽）在1～5的範圍內。[Technical means to solve the problem] The present invention relates to a chromium-free metal surface treatment agent, which contains the following components (A), (B), (C) and (D); (A) Polysilyl functional silane, (B) Silane coupling agent containing amine groups, (C) inorganic compound particles, (D) at least one resin selected from water-based cationic urethane resins and water-based cationic acrylic resins, Among them, the mass ratio of the silicon in the component (A) and the component (B) to the resin solid content in the component (D) (resin solid content/silicon) is in the range of 1 to 5.

較佳為，前述（A）成分與前述（B）成分的質量比（（A）成分/（B）成分）在0.2～8.7的範圍內。Preferably, the mass ratio of the component (A) to the component (B) ((A) component/(B) component) is in the range of 0.2 to 8.7.

較佳為，前述（A）成分為1,2-雙（三乙氧基甲矽烷基）-乙烷。Preferably, the aforementioned (A) component is 1,2-bis(triethoxysilyl)-ethane.

較佳為，前述（B）成分為選自由3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷及N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷所組成之群組中的至少一種。Preferably, the aforementioned (B) component is selected from 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-amino At least one of the group consisting of propyltrimethoxysilane and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane.

較佳為，前述（C）成分為選自鋯化合物粒子和鈦化合物粒子中的至少一種。 另外，較佳為，前述（C）成分的平均粒徑為1μm以下。Preferably, the component (C) is at least one selected from zirconium compound particles and titanium compound particles. In addition, it is preferable that the average particle diameter of the component (C) is 1 μm or less.

另外，本發明關於一種金屬表面處理方法，其包含下述步驟：對金屬基材的表面賦予前述無鉻金屬表面處理劑的步驟；及，將已被賦予到前述金屬基材上的無鉻金屬表面處理劑進行乾燥而形成覆膜的步驟。In addition, the present invention relates to a metal surface treatment method including the steps of: applying the chromium-free metal surface treatment agent to the surface of the metal substrate; and, applying the chromium-free metal that has been applied to the metal substrate The step of drying the surface treatment agent to form a coating.

另外，本發明關於一種金屬基材，其具有前述無鉻金屬表面處理劑的覆膜。In addition, the present invention relates to a metal substrate having a coating film of the aforementioned chromium-free metal surface treatment agent.

[發明的效果] 根據本發明，可以提供一種無鉻金屬表面處理劑，其能夠對於金屬基材形成耐腐蝕性、密合性及耐化學藥品性優異的覆膜。另外，根據本發明，提供一種使用了該無鉻金屬表面處理劑的金屬表面處理方法、及實施了表面處理的金屬基板。[Effect of invention] According to the present invention, it is possible to provide a chromium-free metal surface treatment agent capable of forming a coating film excellent in corrosion resistance, adhesion, and chemical resistance to a metal substrate. In addition, according to the present invention, there is provided a metal surface treatment method using the chromium-free metal surface treatment agent, and a metal substrate subjected to surface treatment.

以下，對關於本實施方式的無鉻金屬表面處理劑、金屬表面處理方法、及金屬基材進行詳細說明。Hereinafter, the chromium-free metal surface treatment agent, metal surface treatment method, and metal base material of the present embodiment will be described in detail.

＜無鉻金屬表面處理劑＞ 關於本實施方式的無鉻金屬表面處理劑，其含有下述（A）成分、（B）成分、（C）成分及（D）成分； （A）多甲矽烷基官能矽烷、 （B）含有胺基之矽烷偶合劑、 （C）無機化合物粒子、 （D）選自水系陽離子胺基甲酸酯樹脂和水系陽離子丙烯酸樹脂中的至少一種樹脂， 其中，（A）成分和（B）成分中的矽與（D）成分中的樹脂固體成分的質量比（樹脂固體成分/矽）在1～5的範圍內。＜Cr-free metal surface treatment agent＞ About the chromium-free metal surface treatment agent of this embodiment, it contains the following (A) component, (B) component, (C) component, and (D) component; (A) Polysilyl functional silane, (B) Silane coupling agent containing amine groups, (C) inorganic compound particles, (D) at least one resin selected from water-based cationic urethane resins and water-based cationic acrylic resins, Among them, the mass ratio of the silicon in the components (A) and (B) to the resin solid content in the component (D) (resin solid content/silicon) is in the range of 1 to 5.

根據關於本實施方式的無鉻金屬表面處理劑，可以對於金屬基材形成耐腐蝕性、密合性及耐化學藥品性優異的覆膜。特別是，使用了關於本實施方式的無鉻金屬表面處理劑而形成的覆膜，在加工部也顯示良好的耐腐蝕性和密合性。因此，關於本實施方式的無鉻金屬表面處理劑，例如作為製造預塗鋼板（PCM）時的塗裝基底是適宜的。According to the chromium-free metal surface treatment agent of this embodiment, a coating film excellent in corrosion resistance, adhesion, and chemical resistance can be formed on a metal substrate. In particular, the coating formed using the chromium-free metal surface treatment agent of the present embodiment also shows good corrosion resistance and adhesion in the processed portion. Therefore, the chromium-free metal surface treatment agent of this embodiment is suitable as a coating base when manufacturing a pre-coated steel sheet (PCM), for example.

[（A）多甲矽烷基官能矽烷] 就作為（A）成分的多甲矽烷基官能矽烷而言，可以列舉例如具有多個能夠進行水解而生成矽烷醇基的甲矽烷基之化合物。作為較佳的多甲矽烷基官能矽烷，可以列舉例如下述式（I）所示的化合物。[(A) Polysilyl functional silane] Examples of the polysilyl functional silane as the component (A) include compounds having a plurality of silyl groups that can be hydrolyzed to generate silanol groups. Examples of preferred polysilyl functional silanes include compounds represented by the following formula (I).

Figure 02_image001
Figure 02_image001

上述式（I）中，R1 、R2 、R3 及R4 分別獨立地表示氫原子或碳數1～30的1價的有機基團。作為1價的有機基團，可以列舉：烷基、烯基、環烷基、芳基等烴基；具有羥基、環氧基、胺基等官能團之烴基等；較佳為甲基、乙基等碳數1～4的烷基。In the above formula (I), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Examples of the monovalent organic group include hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, and aryl groups; hydrocarbon groups having functional groups such as hydroxyl groups, epoxy groups, and amine groups; etc.; preferably methyl groups, ethyl groups, etc. C 1-4 alkyl.

上述式（I）中，Y表示2價的有機基團或胺。作為2價的有機基團，可以列舉伸烷基、伸烷基氧基、伸烷基硫基或包含這些基團作為部分結構的基團，較佳為伸烷基。2價的有機基團的碳數較佳為2～30，更佳為2～12。In the above formula (I), Y represents a divalent organic group or amine. Examples of the divalent organic group include an alkylene group, an alkylene oxide group, an alkylene sulfide group, or a group containing these groups as a partial structure, preferably an alkylene group. The carbon number of the divalent organic group is preferably 2-30, and more preferably 2-12.

上述式（I）中，X1 和X2 分別獨立地表示水解性基團。作為水解性基團，可以列舉碳數1～4的烷氧基，較佳為甲氧基或乙氧基。In the above formula (I), X 1 and X 2 each independently represent a hydrolyzable group. Examples of the hydrolyzable group include alkoxy groups having 1 to 4 carbon atoms, preferably methoxy or ethoxy groups.

上述式（I）中，a和b分別獨立地表示0～2的整數，0≤a+b≤2。另外，c和d分別獨立地表示0～2的整數，0≤c+d≤2。a+b和c+d較佳皆為0或1。In the above formula (I), a and b each independently represent an integer of 0 to 2, and 0≦a+b≦2. In addition, c and d each independently represent an integer of 0 to 2, and 0≦c+d≦2. Both a+b and c+d are preferably 0 or 1.

作為上述式（I）所示的多甲矽烷基官能矽烷的具體例，可以列舉：雙（三甲氧基甲矽烷基）甲烷、1,2-雙（三甲氧基甲矽烷基）乙烷、1,2-雙（三乙氧基甲矽烷基）乙烷、1,6-雙（三甲氧基甲矽烷基）己烷、1,6-雙（三乙氧基甲矽烷基）己烷、1,8-雙（三甲氧基甲矽烷基）辛烷、1,8-雙（三乙氧基甲矽烷基）辛烷、1,9-雙（三甲氧基甲矽烷基）壬烷、1,9-雙（三乙氧基甲矽烷基）壬烷、雙（三甲氧基甲矽烷基）胺、雙（三乙氧基甲矽烷基）胺、雙（三甲氧基甲矽烷基甲基）胺、雙（三乙氧基甲矽烷基甲基）胺、雙（三甲氧基甲矽烷基丙基）胺、雙（三乙氧基甲矽烷基丙基）胺等。這些中，從處理上的安全性、所得到的覆膜的耐腐蝕性及密合性的觀點來考量，較佳為1,2-雙（三乙氧基甲矽烷基）乙烷。Specific examples of the polysilyl functional silane represented by the above formula (I) include bis(trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1 ,2-bis(triethoxysilyl)ethane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1 ,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,9-bis(trimethoxysilyl)nonane, 1, 9-bis(triethoxysilyl)nonane, bis(trimethoxysilyl)amine, bis(triethoxysilyl)amine, bis(trimethoxysilylmethyl)amine , Bis (triethoxysilylmethyl) amine, bis (trimethoxysilylpropyl) amine, bis (triethoxysilylpropyl) amine, etc. Among these, 1,2-bis(triethoxysilyl)ethane is preferred from the viewpoints of handling safety, corrosion resistance and adhesion of the resulting coating.

這些多甲矽烷基官能矽烷可以單獨使用一種，也可以將兩種以上組合使用。另外，多甲矽烷基官能矽烷也可以部分進行了水解縮合。These polysilyl functional silanes may be used alone or in combination of two or more. In addition, polysilyl functional silanes may be partially hydrolyzed and condensed.

（A）成分的含有率沒有特別限制，在關於本實施方式的無鉻金屬表面處理劑的總量中，較佳為0.4～2.4質量%，更佳為0.6～1.7質量%。通過將（A）成分的含有率設為0.4質量%以上，有所得到的覆膜的耐腐蝕性、對金屬基材的密合性及耐化學藥品性進一步提高的傾向。另一方面，通過將（A）成分的含有率設為2.4質量%以下，有所得到的覆膜對金屬基材的密合性提高的傾向。(A) The content rate of the component is not particularly limited, and the total amount of the chromium-free metal surface treatment agent of the present embodiment is preferably 0.4 to 2.4% by mass, and more preferably 0.6 to 1.7% by mass. By setting the content rate of the component (A) to 0.4% by mass or more, there is a tendency that the corrosion resistance of the obtained coating, the adhesion to the metal substrate, and the chemical resistance are further improved. On the other hand, by setting the content rate of the component (A) to 2.4% by mass or less, there is a tendency that the adhesion of the obtained coating film to the metal base material is improved.

[（B）含有胺基之矽烷偶合劑] 就作為（B）成分的含有胺基之矽烷偶合劑而言，可以無特別限制地使用具有胺基之現有公知的矽烷偶合劑。作為含有胺基之矽烷偶合劑的具體例，可以列舉：3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、3-三乙氧基甲矽烷基-N-（1，3-二甲基-亞丁基）丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷等。這些中，較佳為3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷及N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷。[(B) Silane coupling agent containing amine groups] As the amine group-containing silane coupling agent as the component (B), a conventionally known silane coupling agent having an amine group can be used without particular limitation. Specific examples of the silane coupling agent containing an amine group include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3 -Aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3 -Aminopropylmethyl diethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-triethyl Oxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. Among these, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane is preferred And N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane.

這些含有胺基之矽烷偶合劑可以單獨使用一種，也可以將兩種以上組合使用。另外，含有胺基之矽烷偶合劑可以部分進行了水解縮合。These amine group-containing silane coupling agents may be used alone or in combination of two or more. In addition, the silane coupling agent containing an amine group may be partially hydrolyzed and condensed.

（B）成分的含有率沒有特別限制，（A）成分與（B）成分的質量比（（A）成分/（B）成分）較佳是在0.2～8.7的範圍內，更佳是在0.5～3.0的範圍內。通過將質量比（（A）成分/（B）成分）設為0.2以上，有所得到的覆膜的耐腐蝕性、對金屬基材的密合性及耐化學藥品性進一步提高的傾向。另一方面，通過將質量比（（A）成分/（B）成分）設為8.7以下，有所得到的覆膜對頂層塗裝的密合性進一步提高的傾向。(B) The content rate of the component is not particularly limited, and the mass ratio of (A) component to (B) component ((A) component/(B) component) is preferably in the range of 0.2 to 8.7, more preferably 0.5 ~3.0. By setting the mass ratio ((A) component/(B) component) to 0.2 or more, the corrosion resistance of the resulting coating, the adhesion to the metal substrate, and the chemical resistance tend to be further improved. On the other hand, by setting the mass ratio ((A) component/(B) component) to 8.7 or less, there is a tendency that the adhesion of the obtained coating to the top coating is further improved.

[（C）無機化合物粒子] 就作為（C）成分的無機化合物粒子而言，可以列舉鋯化合物粒子、鈦化合物粒子等。通過含有粒子狀的無機化合物，從而與含有非粒子狀的無機化合物的情況相比，有所得到的覆膜的耐腐蝕性和耐化學藥品性提高的傾向。[(C) inorganic compound particles] Examples of the inorganic compound particles as the component (C) include zirconium compound particles and titanium compound particles. The inclusion of the particulate inorganic compound tends to improve the corrosion resistance and chemical resistance of the resulting coating compared to the case of containing the non-particulate inorganic compound.

作為鋯化合物，可以列舉例如氧化鋯。作為鈦化合物，可以列舉例如氧化鈦。這些無機化合物粒子可以單獨使用一種，也可以將兩種以上組合使用。Examples of the zirconium compound include zirconia. Examples of titanium compounds include titanium oxide. One type of these inorganic compound particles may be used alone, or two or more types may be used in combination.

無機化合物粒子的平均粒徑（D50 ）較佳為1μm以下，更佳為10～300nm。The average particle diameter (D 50 ) of the inorganic compound particles is preferably 1 μm or less, and more preferably 10 to 300 nm.

作為無機化合物粒子，也可以使用市售品。作為鋯化合物粒子的市售品，可以列舉“ZSL-20N”、“ZSL-10A”、“ZSL-10T”、“EP氧化鋯”、“UEP氧化鋯”、“UEP-100氧化鋯”（以上為第一稀元素化學工業股份有限公司製造）等。另外，作為鈦化合物粒子的市售品，可以列舉：“CSB”、“CSB-M”、“SSP-25”、“SSP-20”、“SSP-M”、“STA-100A”（以上為堺化學工業股份有限公司製造）；“DC-Ti”、“DCN-Ti”、“DCB-Ti”（以上為富士鈦工業股份有限公司製造）等。As the inorganic compound particles, commercially available products can also be used. Examples of commercially available products of zirconium compound particles include "ZSL-20N", "ZSL-10A", "ZSL-10T", "EP zirconia", "UEP zirconia", and "UEP-100 zirconia" (above) For the first rare element Chemical Industry Co., Ltd.) etc. In addition, as commercially available products of titanium compound particles, "CSB", "CSB-M", "SSP-25", "SSP-20", "SSP-M", "STA-100A" (the above are (Sakai Chemical Industry Co., Ltd.); "DC-Ti", "DCN-Ti", "DCB-Ti" (above manufactured by Fuji Titanium Industry Co., Ltd.), etc.

（C）成分的含有率沒有特別限制，相對於關於本實施方式的無鉻金屬表面處理劑的總固體成分量，較佳為9.0～16.0質量%。通過將（C）成分的含有率設為9.0質量%以上，有所得到的覆膜的耐化學藥品性提高的傾向。另一方面，通過將（C）成分的含有率設為16.0質量%以下，有所得到的覆膜的耐腐蝕性和對金屬基材的密合性提高的傾向。(C) The content rate of the component is not particularly limited, and it is preferably 9.0 to 16.0% by mass relative to the total solid content of the chromium-free metal surface treatment agent of the present embodiment. By setting the content rate of the component (C) to 9.0% by mass or more, there is a tendency that the chemical resistance of the obtained film is improved. On the other hand, by setting the content rate of the component (C) to 16.0% by mass or less, there is a tendency that the corrosion resistance of the obtained film and the adhesion to the metal substrate are improved.

[（D）選自水系陽離子胺基甲酸酯樹脂和水系陽離子丙烯酸樹脂中的至少一種樹脂] 作為（D）成分的水系陽離子胺基甲酸酯樹脂和水系陽離子丙烯酸樹脂，其分子結構中具有伯胺基～叔胺基、銨基、鋶基、鏻基等在水性介質中可陽離子化的陽離子性官能團。作為陽離子性官能團的具體例，可以列舉：胺基、甲基胺基、乙基胺基、二甲基胺基、二乙基胺基、三甲基銨基、三乙基銨基等。[(D) At least one resin selected from water-based cationic urethane resin and water-based cationic acrylic resin] As the component (D), the water-based cationic urethane resin and the water-based cationic acrylic resin have primary to tertiary amine groups, ammonium groups, ammonium groups, phosphonium groups, etc. that can be cationized in an aqueous medium. Cationic functional group. Specific examples of the cationic functional group include amine groups, methylamino groups, ethylamino groups, dimethylamino groups, diethylamine groups, trimethylammonium groups, triethylammonium groups, and the like.

水系陽離子胺基甲酸酯樹脂和水系陽離子丙烯酸樹脂，較佳為以微細地分散於水中的乳液形式添加到無鉻金屬表面處理劑中。The water-based cationic urethane resin and the water-based cationic acrylic resin are preferably added to the chromium-free metal surface treatment agent in the form of an emulsion finely dispersed in water.

作為水系陽離子胺基甲酸酯樹脂，可以列舉：在使聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚己內酯多元醇、蓖麻油多元醇等多元醇與脂肪族、脂環式或芳香族多異氰酸酯聚合而得到的胺基甲酸酯樹脂中，使用通過被伯胺基～叔胺基、銨基等陽離子性官能團置換的多元醇作為多元醇的一部分而得到的樹脂。Examples of the water-based cationic urethane resin include polyether polyols such as polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, and castor oil polyols. In the urethane resin obtained by polymerizing a cyclic or aromatic polyisocyanate, a polyhydric alcohol substituted with a cationic functional group such as a primary amine group, a tertiary amine group, or an ammonium group is used as a part of the polyhydric alcohol.

作為水系陽離子胺基甲酸酯樹脂，也可以使用市售品。作為水系陽離子胺基甲酸酯樹脂的市售品，可以列舉：“F-2667D”、“SUPERFLEX 650”（以上為第一工業製藥股份有限公司製造）；“TECH COAT WH-1515”（股份有限公司京絹化成製造）等。As the aqueous cationic urethane resin, commercially available products can also be used. Examples of commercially available products of water-based cationic urethane resins include: "F-2667D" and "SUPERFLEX 650" (above manufactured by Daiichi Pharmaceutical Co., Ltd.); "TECH COAT WH-1515" (share limited Company Beijing Silk Chemical Manufacturing) and so on.

作為水系陽離子丙烯酸樹脂，可以列舉：含有胺基之（甲基）丙烯酸酯、含有季銨基之（甲基）丙烯酸酯等具有陽離子性官能團之（甲基）丙烯酸酯與其它聚合性不飽和單體的共聚物。作為含有胺基之（甲基）丙烯酸酯，可以列舉：（甲基）丙烯酸N,N-二甲基胺基乙酯、（甲基）丙烯酸N,N-二甲基胺基丙酯、（甲基）丙烯酸N-甲基胺基乙酯、（甲基）丙烯酸N-甲基胺基丙酯等。作為含有季銨基之（甲基）丙烯酸酯，可以列舉（甲基）丙烯醯氧基乙基三甲基氯化銨等。Examples of the water-based cationic acrylic resins include (meth)acrylates containing cationic functional groups such as (meth)acrylates containing amine groups, (meth)acrylates containing quaternary ammonium groups, and other polymerizable unsaturated monomers. Copolymer. Examples of (meth)acrylates containing amine groups include N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, ( N-methylaminoethyl meth)acrylate, N-methylaminopropyl (meth)acrylate, etc. Examples of (meth)acrylates containing quaternary ammonium groups include (meth)acryloyloxyethyltrimethylammonium chloride.

作為水系陽離子丙烯酸樹脂，也可以使用市售品。作為水系陽離子丙烯酸樹脂的市售品，可以列舉：“UW-550CS”、“UW-600”（以上為大成精細化工股份有限公司製造）；“ACE-6”（股份有限公司村山化學研究所製造）等。As the water-based cationic acrylic resin, commercially available products can also be used. Examples of commercially available products of water-based cationic acrylic resins include: "UW-550CS" and "UW-600" (above manufactured by Dacheng Fine Chemical Co., Ltd.); "ACE-6" (manufactured by Murayama Chemical Research Institute Co., Ltd. )Wait.

水系陽離子胺基甲酸酯樹脂和水系陽離子丙烯酸樹脂中，較佳為在結構中具有雙鍵之水系陽離子胺基甲酸酯樹脂。分子結構中具有雙鍵之水系陽離子胺基甲酸酯樹脂，由於疏水性較高，因此有所得到的覆膜的耐腐蝕性、與頂層塗裝的密合性等進一步提高的傾向。 需要說明的是，作為結構中具有雙鍵之水系陽離子胺基甲酸酯樹脂的市售品，可列舉“F-2667D”（第一工業製藥股份有限公司製造）等。Among water-based cationic urethane resins and water-based cationic acrylic resins, water-based cationic urethane resins having a double bond in the structure are preferred. The water-based cationic urethane resin having a double bond in the molecular structure tends to further improve the corrosion resistance of the resulting coating and the adhesion to the top coating due to its high hydrophobicity. In addition, as a commercial item of the water-based cationic urethane resin which has a double bond in a structure, "F-2667D" (made by Daiichi Pharmaceutical Co., Ltd.) etc. are mentioned.

以（A）成分和（B）成分中的矽與（D）成分中的樹脂固體成分的質量比（樹脂固體成分/矽）在1～5的範圍內的量來含有（D）成分。通過將質量比（樹脂固體成分/矽）設為1以上，有所得到的覆膜的耐腐蝕性、密合性及耐化學藥品性（特別是耐鹼性）進一步提高的傾向。另一方面，通過將質量比（樹脂固體成分/矽）設為5以下，有所得到的覆膜的耐化學藥品性（特別是耐酸性）進一步提高的傾向。The (D) component is contained in an amount in which the mass ratio of the silicon in the (A) component and the (B) component to the resin solid component in the (D) component (resin solid component/silicon) is in the range of 1 to 5. By setting the mass ratio (resin solid content/silicon) to 1 or more, the corrosion resistance, adhesiveness, and chemical resistance (especially alkali resistance) of the obtained coating tend to be further improved. On the other hand, by setting the mass ratio (resin solid content/silicon) to 5 or less, there is a tendency that the chemical resistance (especially acid resistance) of the obtained film is further improved.

關於本實施方式的無鉻金屬表面處理劑，可以進一步含有除水系陽離子胺基甲酸酯樹脂和水系陽離子丙烯酸樹脂以外之其它樹脂。其中，相對於樹脂的總量，其它樹脂的含有率，較佳為20質量%以下，更佳為10質量%以下，進一步更佳為0質量%。The chromium-free metal surface treatment agent of this embodiment may further contain resins other than the water-based cationic urethane resin and the water-based cationic acrylic resin. Among them, the content of other resins relative to the total amount of resins is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 0% by mass.

[其它成分] 關於本實施方式的無鉻金屬表面處理劑，除了上述各成分以外，可以進一步含有其它成分。作為其它成分，可以列舉：促進樹脂固化的樹脂交聯劑、用於調平用途的表面調整劑、用於抑泡用途的消泡劑等。[Other ingredients] The chromium-free metal surface treatment agent of this embodiment may contain other components in addition to the above-mentioned components. Examples of other components include resin crosslinking agents that promote curing of resins, surface conditioners for leveling applications, and defoaming agents for foam suppression applications.

[無鉻金屬表面處理劑的pH] 關於本實施方式的無鉻金屬表面處理劑的pH，較佳為7以下，更佳為4～7。通過將無鉻金屬表面處理劑的pH設為7以下，儲存穩定性進一步提高，並且有所得到的覆膜的耐化學藥品性（特別是耐鹼性）進一步提高的傾向。[PH of chromium-free metal surface treatment agent] The pH of the chromium-free metal surface treatment agent of the present embodiment is preferably 7 or less, and more preferably 4 to 7. By setting the pH of the chromium-free metal surface treatment agent to 7 or less, the storage stability is further improved, and the chemical resistance (especially alkali resistance) of the resulting coating tends to be further improved.

＜金屬表面處理方法＞ 關於本實施方式的金屬表面處理方法，包含下述步驟：對金屬基材的表面賦予關於上述的本實施方式的無鉻金屬表面處理劑的步驟（以下也稱為“賦予步驟”。）；及，將已被賦予到金屬基材上的無鉻金屬表面處理劑進行乾燥而形成覆膜的步驟（以下也稱為“乾燥步驟”。）。<Metal surface treatment method> The metal surface treatment method of this embodiment includes the following steps: a step of applying the above-mentioned chromium-free metal surface treatment agent of the present embodiment to the surface of the metal base material (hereinafter also referred to as "application step"); and The step of drying the chromium-free metal surface treatment agent that has been applied to the metal substrate to form a coating (hereinafter also referred to as "drying step").

賦予步驟中，將關於上述的本實施方式的無鉻金屬表面處理劑賦予到金屬基材上。In the application step, the chromium-free metal surface treatment agent of the present embodiment described above is applied to the metal substrate.

作為金屬基材，可以列舉：熔融鍍鋅鋼材、電鍍鍍鋅鋼材、鍍鋁鋅合金鋼材、鋁材、不銹鋼等。 將無鉻金屬表面處理劑賦予到金屬材料的方法沒有特別限定，可列舉：輥塗機塗裝、刷塗塗裝、輥塗塗裝、棒塗器塗裝、淋塗塗裝等方法。Examples of the metal substrate include hot-dip galvanized steel materials, electro-galvanized steel materials, aluminum-zinc alloy coated steel materials, aluminum materials, and stainless steel. The method for applying the chromium-free metal surface treatment agent to the metal material is not particularly limited, and examples include methods such as roll coater coating, brush coating, roller coating, bar coater coating, and shower coating.

乾燥步驟中，將已被賦予到金屬基材上的無鉻金屬表面處理劑進行乾燥而形成覆膜。In the drying step, the chromium-free metal surface treatment agent applied to the metal substrate is dried to form a coating.

乾燥溫度例如較佳為50～150℃，更佳為60～100℃。The drying temperature is preferably, for example, 50 to 150°C, and more preferably 60 to 100°C.

賦予步驟與乾燥步驟可以同時並列進行。例如，可以對預先進行了加熱的金屬基材賦予無鉻金屬表面處理劑，利用餘熱使無鉻金屬表面處理劑乾燥。The imparting step and the drying step can be performed in parallel at the same time. For example, a chromium-free metal surface treatment agent may be applied to a metal substrate that has been previously heated, and the chromium-free metal surface treatment agent may be dried using waste heat.

覆膜的附著量較佳為例如0.01～1.0g/m2 ，更佳為0.04～0.6/m2 。通過將附著量設為0.01g/m2 以上，有耐腐蝕性和耐化學藥品性進一步提高的傾向。另外，通過將附著量設為1.0g/m2 以下，有耐腐蝕性（特別是加工部的耐腐蝕性）和密合性進一步提高的傾向。The adhesion amount of the coating film is preferably, for example, 0.01 to 1.0 g/m 2 , and more preferably 0.04 to 0.6/m 2 . By setting the adhesion amount to 0.01 g/m 2 or more, the corrosion resistance and the chemical resistance tend to be further improved. In addition, by setting the adhesion amount to 1.0 g/m 2 or less, the corrosion resistance (particularly the corrosion resistance of the processed portion) and the adhesion tend to be further improved.

需要說明的是，在製造預塗鋼板（PCM）時，例如可以將底層塗料賦予在所形成的覆膜上，然後賦予頂塗塗料。作為底層塗料和頂塗塗料，較佳皆為無鉻的塗料。In addition, when manufacturing a pre-coated steel sheet (PCM), for example, a primer can be applied to the formed coating, and then a top coating can be applied. As the primer coating and the top coating, both are preferably chrome-free coatings.

＜金屬基材＞ 關於本實施方式的金屬基材，具有關於上述的本實施方式的無鉻金屬表面處理劑的覆膜。關於本實施方式的金屬基材，可以通過關於上述的本實施方式的金屬表面處理方法而得到。<Metal base material> The metal substrate of the present embodiment has a coating on the chromium-free metal surface treatment agent of the present embodiment described above. The metal substrate of this embodiment can be obtained by the metal surface treatment method of this embodiment described above.

[實施例] 以下，基於實施例更詳細地說明本發明，但本發明不受這些實施例限定。[Example] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

＜無鉻金屬表面處理劑的製備＞ [實施例1～17、24～33、比較例1～14] 相對於離子交換水100g(克)，混合表1、2所示的種類和量（單位：g）的（A）成分，用乙酸將pH調節為6。向得到的溶液中依次混合（B）成分、（C）成分、（D）成分並進行攪拌，從而得到實施例1～17、24～33、比較例1～14的各無鉻金屬表面處理劑。<Preparation of chromium-free metal surface treatment agent> [Examples 1 to 17, 24 to 33, Comparative Examples 1 to 14] The type and amount (unit: g) of component (A) shown in Tables 1 and 2 were mixed with respect to 100 g (g) of ion-exchanged water, and the pH was adjusted to 6 with acetic acid. To the obtained solution, component (B), component (C), and component (D) were sequentially mixed and stirred to obtain each of the chromium-free metal surface treatment agents of Examples 1 to 17, 24 to 33, and Comparative Examples 1 to 14. .

[實施例18～23] 相對於離子交換水100g，混合表1所示的種類和量（單位：g）的（A）成分，用乙酸將pH調節為6。向得到的溶液中依次混合（B）成分、（C）成分、（D）成分並攪拌。進一步，用乙酸或25質量%氨水調節成表1所示的pH，從而得到實施例18～23的各無鉻金屬表面處理劑。[Examples 18 to 23] The type and amount (unit: g) of component (A) shown in Table 1 were mixed with respect to 100 g of ion-exchanged water, and the pH was adjusted to 6 with acetic acid. To the resulting solution, component (B), component (C), and component (D) were sequentially mixed and stirred. Furthermore, the pH shown in Table 1 was adjusted with acetic acid or 25 mass% ammonia water, and each chromium-free metal surface treatment agent of Examples 18-23 was obtained.

[表1]

Figure 02_image003
[Table 1]
Figure 02_image003

[表2]

Figure 02_image005
[Table 2]
Figure 02_image005

需要說明的是，表1、2中的縮寫的意思如下。 （多甲矽烷基官能矽烷） A1：1,2-雙（三乙氧基甲矽烷基）乙烷（信越化學工業股份有限公司製造、“KBE-3026”（商品名）） A2：乙烯基三甲氧基矽烷（信越化學工業股份有限公司製造、“KBM-1003”）It should be noted that the meanings of the abbreviations in Tables 1 and 2 are as follows. (Polysilyl functional silane) A1: 1,2-bis(triethoxysilyl)ethane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBE-3026" (trade name)) A2: Vinyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-1003")

（矽烷偶合劑） B1：3-胺基丙基三乙氧基矽烷（信越化學工業股份有限公司製造、“KBE-903”） B2：3-胺基丙基三甲氧基矽烷（信越化學工業股份有限公司製造、“KBM-903”） B3：N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷（信越化學工業股份有限公司製造、“KBM-603”） B4：N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷（信越化學工業股份有限公司製造、“KBM-602”） B5：乙烯基三甲氧基矽烷（信越化學工業股份有限公司製造、“KBM-1003”） B6：3-環氧丙氧基丙基三甲氧基矽烷（信越化學工業股份有限公司製造、“KBM-403”）(Silane coupling agent) B1: 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBE-903") B2: 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-903") B3: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-603") B4: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-602") B5: Vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-1003") B6: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403")

（無機化合物） C1：鋯化合物粒子（第一稀元素化學股份有限公司製造、“ZSL-20N”、粒徑：60～105nm、固體成分濃度：20質量%） C2：鈦化合物粒子（堺化學工業股份有限公司製造、“CSB-M”、粒徑：7nm、固體成分濃度：30質量%） C3：鋯化合物粒子（第一稀元素化學股份有限公司製造、“EP氧化鋯”、平均粒徑：1.5～2.5μm、固體成分濃度：100質量%） C4：鋯化合物（第一稀元素化學股份有限公司製造、“ZIRCOZOLE AC-7”、固體成分濃度：20質量%） C5：二氧化矽粒子（股份有限公司ADEKA製造、“ADELITE AT-20A”、粒徑：10～20nm、固體成分濃度：20質量%）(Inorganic compound) C1: Zirconium compound particles (manufactured by First Dilute Element Chemical Co., Ltd., "ZSL-20N", particle size: 60 to 105 nm, solid content concentration: 20% by mass) C2: Titanium compound particles (Sakai Chemical Industry Co., Ltd., "CSB-M", particle size: 7 nm, solid content concentration: 30% by mass) C3: Zirconium compound particles (manufactured by First Dilute Element Chemical Co., Ltd., "EP zirconia", average particle diameter: 1.5 to 2.5 μm, solid content concentration: 100% by mass) C4: Zirconium compound (manufactured by Daiichi Element Chemical Co., Ltd., "ZIRCOZOLE AC-7", solid content concentration: 20% by mass) C5: Silicon dioxide particles (made by ADEKA Co., Ltd., "ADELITE AT-20A", particle size: 10 to 20 nm, solid content concentration: 20% by mass)

（樹脂） D1：水系陽離子胺基甲酸酯樹脂（第一工業製藥股份有限公司製造、“F-2667D”、固體成分濃度：25質量%） D2：水系陽離子胺基甲酸酯樹脂（第一工業製藥股份有限公司製造、“SUPERFLEX 650”、固體成分濃度：26質量%） D3：水系陽離子丙烯酸樹脂（大成精細化工股份有限公司製造、“UW-550CS”、固體成分濃度：34質量%） D4：水系陰離子胺基甲酸酯樹脂（股份有限公司ADEKA製造、“HUX-320”、固體成分濃度：32質量%） D5：水系非離子胺基甲酸酯樹脂（第一工業製藥股份有限公司製造、“SUPERFLEX 500M”、固體成分濃度：45質量%） D6：水系陰離子丙烯酸類樹脂（SAIDEN化學股份有限公司製造、“AD-7”、固體成分濃度：39質量%）(Resin) D1: Water-based cationic urethane resin (manufactured by Daiichi Pharmaceutical Co., Ltd., "F-2667D", solid content concentration: 25% by mass) D2: Water-based cationic carbamate resin (manufactured by Daiichi Pharmaceutical Co., Ltd., "SUPERFLEX 650", solid content concentration: 26% by mass) D3: Water-based cationic acrylic resin (made by Dacheng Fine Chemical Co., Ltd., "UW-550CS", solid content concentration: 34% by mass) D4: Water-based anionic urethane resin (made by ADEKA Co., Ltd., "HUX-320", solid content concentration: 32% by mass) D5: Aqueous nonionic urethane resin (made by Daiichi Pharmaceutical Co., Ltd., "SUPERFLEX 500M", solid content concentration: 45% by mass) D6: Water-based anionic acrylic resin (manufactured by SAIDEN Chemical Co., Ltd., "AD-7", solid content concentration: 39% by mass)

＜評價＞ 使用實施例1～33、比較例1～14的無鉻金屬表面處理劑，如下所述地評價耐腐蝕性、密合性、耐化學藥品性及儲存穩定性。將結果示於表3、4。<Evaluation> Using the chromium-free metal surface treatment agents of Examples 1 to 33 and Comparative Examples 1 to 14, the corrosion resistance, adhesion, chemical resistance, and storage stability were evaluated as follows. The results are shown in Tables 3 and 4.

[試驗板的製作] 對於表3、4所示的鋼板，用鹼性脫脂劑（Nippon Paint Surf Chemical股份有限公司製造、“Surf cleaner 155”），以60℃進行1分鐘噴霧處理，從而進行脫脂。將脫脂後的鋼板水洗，然後乾燥。接著，對鋼板的表面，用棒塗器塗布實施例1～33、比較例1～14的無鉻金屬表面處理劑，使得覆膜的附著量成為表1、2所示的值，然後進行烘烤乾燥至鋼板的到達溫度為90℃為止。接著，分別塗裝無鉻的底層塗料和頂塗塗料（皆為Nippon Paint Industrial Coatings股份有限公司製造），得到塗裝鋼板。[Production of breadboard] The steel plates shown in Tables 3 and 4 were degreased using an alkaline degreasing agent (Nippon Paint Surf Chemical Co., Ltd., "Surf cleaner 155") at 60°C for 1 minute. Wash the degreased steel plate with water and then dry it. Next, on the surface of the steel plate, the chromium-free metal surface treatment agents of Examples 1 to 33 and Comparative Examples 1 to 14 were applied with a bar coater so that the amount of coating adhered to the values shown in Tables 1 and 2, followed by baking. Bake and dry until the steel plate reaches a temperature of 90°C. Next, a chromium-free primer coating and a top coating (both manufactured by Nippon Paint Industrial Coatings Co., Ltd.) were applied separately to obtain a coated steel sheet.

[耐腐蝕性的評價] 對塗裝鋼板的塗裝面噴霧35℃的5w/v%食鹽水。在食鹽水噴霧開始1000小時之後，通過目視確認產生白鏽的面積的比例（%）而評價耐腐蝕性。對平面部和彎曲加工部兩處進行評價，所述彎曲加工部是將2個板向其間對折進行折彎加工（2T加工）而成的。 評價基準如下所述。如果按照該評價基準為3分以上則為合格。 -評價基準- 4分：無白鏽產生 3分：產生了白鏽的面積小於10% 2分：產生了白鏽的面積為10%以上且小於30% 1分：產生了白鏽的面積為30%以上[Evaluation of corrosion resistance] Spray 5w/v% saline solution at 35°C on the coated surface of the coated steel plate. After 1000 hours from the start of the salt water spray, the corrosion resistance was evaluated by visually confirming the ratio (%) of the area where white rust was generated. Evaluation was performed on two parts, the flat part and the bent part, which was formed by bending the two plates in half (2T). The evaluation criteria are as follows. If it is 3 points or more according to this evaluation criterion, it is considered as a pass. -Evaluation criteria- 4 points: No white rust 3 points: The area where white rust is generated is less than 10% 2 points: The area where white rust is generated is 10% or more and less than 30% 1 point: The area where white rust is generated is more than 30%

[密合性的評價] 對塗裝鋼板進行180°折彎加工（0T加工）。然後，在折彎加工部的塗裝面粘貼膠帶後，將其剝離，通過目視確認塗裝被剝離的面積的比例（%）而評價密合性。 評價基準如下所述。如果按照該評價基準為3分以上則為合格。 -評價基準- 4分：無剝離 3分：剝離的面積小於25% 2分：剝離的面積為26%以上且小於50% 1分：剝離的面積為50%以上[Evaluation of adhesion] Carry out 180° bending processing (0T processing) on the coated steel plate. Then, after sticking the adhesive tape on the coating surface of the bending process part, it was peeled off, and the adhesiveness was evaluated by visually confirming the ratio (%) of the area where the coating was peeled off. The evaluation criteria are as follows. If it is 3 points or more according to this evaluation criterion, it is considered as a pass. -Evaluation criteria- 4 points: no stripping 3 points: the peeled area is less than 25% 2 points: the peeled area is more than 26% and less than 50% 1 point: the peeled area is more than 50%

[耐化學藥品性的評價] a）耐酸性的評價 將塗裝鋼板在25℃的5w/v%硫酸水溶液中浸漬24小時，通過目視確認塗膜產生膨脹的面積的比例（%）而評價耐酸性。 評價基準如下所述。如果按照該評價基準為3分以上則為合格。 -評價基準- 4分：無膨脹 3分：產生膨脹的面積小於25% 2分：產生膨脹的面積為25%以上且小於50% 1分：產生膨脹的面積為50%以上[Evaluation of chemical resistance] a) Evaluation of acid resistance The coated steel sheet was immersed in a 5w/v% sulfuric acid aqueous solution at 25°C for 24 hours, and the acid resistance was evaluated by visually confirming the ratio (%) of the area where the coating film swelled. The evaluation criteria are as follows. If it is 3 points or more according to this evaluation criterion, it is considered as a pass. -Evaluation criteria- 4 points: no swelling 3 points: the area where the expansion occurs is less than 25% 2 points: the area where expansion occurs is more than 25% and less than 50% 1 point: the area where expansion occurs is more than 50%

b）耐鹼性的評價 將塗裝鋼板在25℃的5w/v%氫氧化鈉水溶液中浸漬24小時，通過目視確認塗膜產生膨脹的面積的比例（%）而評價耐鹼性。 評價基準如下所述。如果按照該評價基準為3分以上則為合格。 -評價基準- 4分：無膨脹 3分：產生膨脹的面積小於25% 2分：產生膨脹的面積為25%以上且小於50% 1分：產生膨脹的面積為50%以上b) Evaluation of alkali resistance The coated steel plate was immersed in a 5 w/v% sodium hydroxide aqueous solution at 25° C. for 24 hours, and the alkali resistance was evaluated by visually confirming the ratio (%) of the area where the coating film swelled. The evaluation criteria are as follows. If it is 3 points or more according to this evaluation criterion, it is considered as a pass. -Evaluation criteria- 4 points: no swelling 3 points: the area where the expansion occurs is less than 25% 2 points: the area where expansion occurs is more than 25% and less than 50% 1 point: the area where expansion occurs is more than 50%

[儲存穩定性的評價] 將實施例1～33、比較例1～14的無鉻金屬表面處理劑，在40℃的恒溫裝置內儲存3個月，通過目視觀察凝膠化和沉澱的狀態而評價儲存穩定性。 評價基準如下所述。如果按照該評價基準為2分則為合格。 -評價基準- 2分：未確認到凝膠化和沉澱 1分：確認到凝膠化或沉澱[Evaluation of storage stability] The chromium-free metal surface treatment agents of Examples 1 to 33 and Comparative Examples 1 to 14 were stored in a thermostat at 40°C for 3 months, and the storage stability was evaluated by visually observing the state of gelation and precipitation. The evaluation criteria are as follows. If it is 2 points according to this evaluation criterion, it is considered as a pass. -Evaluation criteria- 2 points: Gelation and precipitation are not confirmed 1 point: Confirmation of gelation or precipitation

[表3]

Figure 02_image007
[table 3]
Figure 02_image007

[表4]

Figure 02_image009
[Table 4]
Figure 02_image009

需要說明的是，表3、4中的縮寫為如下意思。 （鋼板） GL：鍍鋁鋅合金鋼板（Al：55質量%） GI：熔融鍍鋅鋼板 GF：鍍鋁鋅合金鋼板（Al：5質量%） EG：電鍍鍍鋅鋼板 SUS：不銹鋼板 AL：鋁板In addition, the abbreviations in Tables 3 and 4 have the following meanings. (Steel plate) GL: aluminum-zinc alloy steel plate (Al: 55% by mass) GI: hot-dip galvanized steel sheet GF: Aluminum-zinc alloy steel plate (Al: 5 mass%) EG: Galvanized steel plate SUS: stainless steel plate AL: Aluminum plate

如表3、4所示，實施例1～33使用了一種無鉻金屬表面處理劑，其含有（A）多甲矽烷基官能矽烷、（B）含有胺基之矽烷偶合劑、（C）無機化合物粒子及（D）選自水系陽離子胺基甲酸酯樹脂和水系陽離子丙烯酸樹脂中的至少一種，並且，（A）成分和（B）成分中的矽與（D）成分中的樹脂固體成分的質量比（樹脂固體成分/矽）在1～5的範圍內，因此實施例1~33的耐腐蝕性、密合性、耐化學藥品性及儲存穩定性皆優異。與此相對，使用了不滿足一部分條件的無鉻金屬表面處理劑的比較例1～14，其耐腐蝕性、密合性、耐化學藥品性和儲存穩定性中至少1種的評價比實施例1～33差。As shown in Tables 3 and 4, Examples 1 to 33 used a chromium-free metal surface treatment agent containing (A) polysilyl functional silane, (B) amine group-containing silane coupling agent, (C) inorganic The compound particles and (D) are at least one selected from the group consisting of water-based cationic urethane resins and water-based cationic acrylic resins, and the silicon in the components (A) and (B) and the resin solid component in the component (D) The mass ratio (resin solid content/silicon) is in the range of 1 to 5, so Examples 1 to 33 are excellent in corrosion resistance, adhesion, chemical resistance, and storage stability. On the other hand, Comparative Examples 1 to 14 using a chromium-free metal surface treatment agent that does not satisfy some of the conditions, the evaluation ratio of at least one of corrosion resistance, adhesion, chemical resistance, and storage stability is compared to Examples 1 to 33 poor.

無no

國內寄存資訊 (請依寄存機構、日期、號碼順序註記) 無Domestic storage information (please note in order of storage institution, date, number) no

國外寄存資訊 (請依寄存國家、機構、日期、號碼順序註記) 無Overseas hosting information (please note in order of hosting country, institution, date, number) no

Claims (8)

一種無鉻金屬表面處理劑，其含有下述（A）成分、（B）成分、（C）成分及（D）成分； （A）多甲矽烷基官能矽烷、 （B）含有胺基之矽烷偶合劑、 （C）無機化合物粒子、 （D）選自水系陽離子胺基甲酸酯樹脂和水系陽離子丙烯酸樹脂中的至少一種樹脂， 其中，前述（A）成分和前述（B）成分中的矽與前述（D）成分中的樹脂固體成分的質量比也就是樹脂固體成分/矽在1～5的範圍內。A chromium-free metal surface treatment agent, which contains the following components (A), (B), (C) and (D); (A) Polysilyl functional silane, (B) Silane coupling agent containing amine groups, (C) inorganic compound particles, (D) at least one resin selected from water-based cationic urethane resins and water-based cationic acrylic resins, Among them, the mass ratio of the silicon in the component (A) and the component (B) to the resin solid component in the component (D), that is, the resin solid content/silicon is in the range of 1 to 5. 如請求項1所述之無鉻金屬表面處理劑，其中，前述（A）成分與前述（B）成分的質量比也就是（A）成分/（B）成分在0.2～8.7的範圍內。The chromium-free metal surface treatment agent according to claim 1, wherein the mass ratio of the component (A) to the component (B), that is, the component (A)/(B) is in the range of 0.2 to 8.7. 如請求項1或2所述之無鉻金屬表面處理劑，其中，前述（A）成分為1,2-雙（三乙氧基甲矽烷基）乙烷。The chromium-free metal surface treatment agent according to claim 1 or 2, wherein the component (A) is 1,2-bis(triethoxysilyl)ethane. 如請求項1或2所述之無鉻金屬表面處理劑，其中，前述（B）成分為選自由3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷及N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷所組成之群組中的至少一種。The chromium-free metal surface treatment agent according to claim 1 or 2, wherein the component (B) is selected from 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N -2-(aminoethyl)-3-aminopropyltrimethoxysilane and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane At least one of them. 如請求項1或2所述之無鉻金屬表面處理劑，其中，前述（C）成分為選自鋯化合物粒子和鈦化合物粒子中的至少一種。The chromium-free metal surface treatment agent according to claim 1 or 2, wherein the component (C) is at least one selected from the group consisting of zirconium compound particles and titanium compound particles. 如請求項1或2所述之無鉻金屬表面處理劑，其中，前述（C）成分的平均粒徑為1μm以下。The chromium-free metal surface treatment agent according to claim 1 or 2, wherein the average particle diameter of the component (C) is 1 μm or less. 一種金屬表面處理方法，其包含下述步驟：對金屬基材的表面賦予如請求項1至6中任一項所述之無鉻金屬表面處理劑的步驟；及， 將已被賦予到前述金屬基材上的無鉻金屬表面處理劑進行乾燥而形成覆膜的步驟。A metal surface treatment method, comprising the steps of: applying a chromium-free metal surface treatment agent according to any one of claims 1 to 6 to the surface of a metal substrate; and, The step of drying the chromium-free metal surface treatment agent that has been applied to the aforementioned metal substrate to form a coating. 一種金屬基材，其具有請求項1至6中任一項所述之無鉻金屬表面處理劑的覆膜。A metal substrate having a coating film of a chromium-free metal surface treatment agent according to any one of claims 1 to 6.
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