[0022] 關於本發明之水性金屬表面處理劑中之各成分係描述如下，此等僅顯示為理想實施態樣之一例，而不被此等內容所侷限。 此外，於本說明書中，「質量」與「重量」為相同意義。 又，本說明書中，所謂「Ｘ及/或Ｙ」為「Ｘ及Ｙ中之至少一者」的意思。 [0023] [含胺基之丙烯酸樹脂粒子(A)] 本發明之水性金屬表面處理劑係含有含胺基之丙烯酸樹脂粒子(A)。含胺基之丙烯酸樹脂粒子(A)，係具有作為中心部之核心部、作為外殼部之殼部的核殼結構，核心部與殼部係可由各自組成相異之單體混合物而獲得。 此外，所謂核殼結構，具體為於同一微胞中，存在有相異的樹脂組成成分，且由中心部分(核心)與外殼部分(殼)相異之樹脂組成而成之結構的意思。 [0024] 上述核殼結構，通常、核心部一般係藉由殼部完全被覆之層結構，然而，依據核心部與殼部之質量比率、其他的條件等，可能有殼部不完全形成層結構之情況。於這樣的情況，如上述之完全的層結構並非必須，核心部之一部分由殼部被覆之結構亦可。 [0025] 核心部與殼部的構成比率，由分散穩定度的觀點，較佳為成為核心部：殼部＝90：10~10：90(質量比)，更佳為70：30~20：80，再更佳為70：30~30：70。 [0026] 含胺基之丙烯酸樹脂粒子(A)中之核心部比率為未滿10質量%時，有耐腐蝕性低下之情況。又，由於核心部比率超過90質量%時，分散穩定度降低，故有含胺基之丙烯酸樹脂粒子(A)之分散性降低之情況。 [0027] 用於核心部以及殼部之聚合之單體混合物皆含有聚合性不飽和單體。核心部及殼部中，關於聚合性不飽和單體，較佳係使用該種類及/或摻混比各自相異之單體混合物聚合而得。 [0028] 作為上述聚合性不飽和單體，例如，可列舉為甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、n-丙基(甲基)丙烯酸酯、i-丙基(甲基)丙烯酸酯、n-丁基(甲基)丙烯酸酯、i-丁基(甲基)丙烯酸酯、tert-丁基(甲基)丙烯酸酯、n-己基(甲基)丙烯酸酯、n-辛基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、壬基(甲基)丙烯酸酯、十三烷基(甲基)丙烯酸酯、十二烷基(甲基)丙烯酸酯、十八烷基(甲基)丙烯酸酯、異十八烷基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、甲基環己基(甲基)丙烯酸酯、tert-丁基環己基(甲基)丙烯酸酯、環十二烷基(甲基)丙烯酸酯、三環葵基(甲基)丙烯酸酯等的烷基或環烷基(甲基)丙烯酸酯；異冰片基(甲基)丙烯酸酯等的具有異冰片基之聚合性不飽和單體；金剛烷基(甲基)丙烯酸酯等之具有金剛烷基之聚合性不飽和單體；三環葵烯基(甲基)丙烯酸酯等之具有三環葵烯基之聚合性不飽和單體；苄基(甲基)丙烯酸酯、苯乙烯、α-甲基苯乙烯、乙烯基甲苯等之含有芳香環之聚合性不飽和單體；乙烯基三甲氧基矽烷、乙烯基甲基二甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基甲基二乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、乙烯基三異丙氧基矽烷、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基三乙氧基矽烷、γ-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、γ-(甲基)丙烯醯氧基丙基三甲氧基-n-丙氧基矽烷、γ-(甲基)丙烯醯氧基丙基三異丙氧基矽烷、乙烯基三乙醯氧基矽烷、β-(甲基)丙烯醯氧基乙基三甲氧基矽烷等之具有水解性矽醚基之聚合性不飽和單體；全氟丁基乙基(甲基)丙烯酸酯、全氟辛基乙基(甲基)丙烯酸酯等的全氟烷基(甲基)丙烯酸酯；氟烯烴等的具有氟化烷基之聚合性不飽和單體；N-乙烯基吡咯烷酮、乙烯、丁二烯、氯丁二烯、丙酸乙烯酯、乙酸乙烯基等的乙烯基化合物；(甲基)丙烯腈、(甲基)丙烯醯胺、亞甲基雙(甲基)丙烯醯胺、乙烯雙(甲基)丙烯醯胺、2-(甲基丙烯醯氧基)乙基三甲基氯化銨、(甲基)丙烯酸縮水甘油酯與胺類之加成物等的含氮聚合性不飽和單體；(甲基)丙烯酸縮水甘油酯、β-甲基 (甲基)丙烯酸縮水甘油酯、3,4-環氧環己基甲基(甲基)丙烯酸酯、3,4-環氧環己基乙基(甲基)丙烯酸酯、3,4-環氧環己基丙基(甲基)丙烯酸酯、丙烯基丙三基醚等的含環氧基聚合性不飽和單體；丙烯基(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯等的1分子中至少具有2個聚合性不飽和基之聚合性不飽和單體；2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、3-羥基丙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯等的(甲基)丙烯酸與碳數2~8之2價醇之單酯化物；該(甲基)丙烯酸與碳數2~8之2價醇之單酯化物的ε-己內酯改性產物；丙烯基醇等的含有烴基之聚合性不飽和單體；末端具有羥基或碳數1~3之亞烷氧基，且具有聚氧乙烯基或聚氧丙烯基之丙烯酸單體等的含有聚氧伸烷基之(甲基)丙烯酸單體。 [0029] 上述聚合性不飽和單體，可各自單獨使用或組合2種以上使用。 [0030] 此外，於本發明之各化合物中，「(甲基)丙烯酸酯」為「丙烯酸酯或丙烯酸甲酯」的意思。「(甲基)丙烯酸」為「丙烯酸或甲基丙烯酸」的意思。「(甲基)丙烯醯基」為「丙烯醯基或甲基丙烯醯基」的意思。 [0031] 於上述聚合性不飽和單體中，由附著性之觀點，較適宜係可使用含烴基之聚合性不飽和單體，由耐腐蝕性之觀點，較適宜係可使用1分子中至少含有2個聚合性不飽和基之聚合性不飽和單體。 [0032] 使用含有烴基聚合性不飽和單體之情況，作為其使用量，係於構成含胺基之丙烯酸樹脂粒子(A)之全單體成分之總量中，適宜含有0.1質量%以上，較佳為1質量%以上，再更佳為1~10質量%之範圍內。 [0033] 使用1分子中至少含有2個聚合性不飽和基之聚合性不飽和單體之情況下，作為其使用量，係於構成含胺基之丙烯酸樹脂粒子(A)之全單體成分之總量中，適宜係含0.05質量%以上，較佳為0.1質量%以上，再更佳為0.1~10質量%之範圍內。 [0034] 含胺基之丙烯酸樹脂粒子(A)係具有含胺基之陽離子性核殼結構之丙烯酸樹脂粒子。 由含胺基之丙烯酸樹脂粒子(A)之分散穩定度來看，胺基較佳係存在於殼中。 含胺基之丙烯酸樹脂粒子(A)，較佳係具有以含有含胺基之單體之單體混合物聚合而得之含有胺基之殼部。 [0035] 作為上述含有胺基之單體，例如可列舉為二甲基胺基甲基(甲基)丙烯酸酯、二乙基胺基(甲基)丙烯酸酯、二丁基胺基甲基(甲基)丙烯酸酯、二己基胺基甲基(甲基)丙烯酸酯、二甲基胺基乙基(甲基)丙烯酸酯、二異己基胺基乙基丙烯酸酯、二己基胺基丙基(甲基)丙烯酸酯、二(tert-丁基)胺基己基(甲基)丙烯酸酯等之單體。 [0036] 上述中，由分散穩定度的觀點，較佳為二甲基胺基乙基(甲基)丙烯酸酯、二乙基胺基(甲基)丙烯酸酯。 [0037] 含胺基之丙烯酸樹脂粒子(A)之胺價為14~72mgKOH/g，較佳為20~72mgKOH/g，再更佳為20~65mgKOH/g。 [0038] 此外，於本說明書中，所謂胺價(mgKOH/g)，係以將1g試料(樹脂的情況下為固體成分)中所含胺基的量，換算為氫氧化鉀時氫氧化鉀的mg數所表示者。氫氧化鉀的分子量定為56.1。 [0039] 又，於本說明書中，所謂烴基價(mgKOH/g)，係以將1g試料(樹脂的情況下為固體成分)中所含烴基的量，換算為氫氧化鉀時氫氧化鉀的mg數所表示者。氫氧化鉀的分子量定為56.1。 [0040] 作為含胺基之丙烯酸樹脂粒子(A)之製造方法，例如，可舉例為，於預先聚合之殼部的存在下，聚合以水作為主溶媒，且含有前述聚合性不飽和單體之核心部形成用單體混合物之方法。 [0041] 殼部、及核心部形成用單體混合物的加入量比，係可依照所期望之核心部/殼部的固體成分質量比，採用適宜、適當的加入比。 [0042] 於本發明之水性金屬表面處理劑中，由成膜性起因之耐腐蝕性、耐水性等的塗膜性能的觀點，較佳係使用於有機溶媒中藉由溶液聚合而合成之殼部。藉由採用藉由溶液聚合而合成之殼部，可減少使得耐水性降低之乳化劑之使用量。 [0043] 作為含胺基之丙烯酸樹脂粒子(A)聚合時可用之聚合起始劑，可採用任意合適之聚合起始劑。 [0044] 作為該聚合起始劑，脂溶性、水溶性之任一類型皆可使用，然而較適宜係可使用水溶性者。 [0045] 作為脂溶性之聚合起始劑，例如，可列舉為過氧化苯甲醯、過氧化辛醯基、過氧化月桂醯基、硬脂醯過氧化物等的有機過氧化物；偶氮二異丁腈、偶氮雙(2,4-二甲基戊腈)等的偶氮化合物等。 [0046] 作為水溶性之聚合起始劑，例如，可列舉為過氧化氫溶液；氫過氧化枯烯、tert-丁基過氧化物、tert-丁基過氧化月桂酸、tert-丁基過氧化異丙基碳酸酯、tert-丁基過氧化乙酸酯、氫過氧化二異丙苯等的有機過氧化物；偶氮雙(2-甲基丙腈)、偶氮雙(2-甲基丁腈)、4,4´-偶氮雙(4-氰基丁酸)、二甲基偶氮雙(2-甲基丙酸酯)、偶氮雙[2-甲基-N-(2-羥基乙基)-丙醯胺]、偶氮雙｛2-甲基-N-[2-(1-羥基丁基)]-丙醯胺｝等的偶氮化合物；過硫酸鉀、過硫酸銨、過硫酸鈉等的過硫酸鹽等。 [0047] 此等可為各自單獨或組合2種以上使用。 [0048] 此外，依照需要，於上述聚合起始劑中，亦可併用糖、抗壞血酸鈉、甲醛次硫酸鈉、鐵錯合物等的還原劑，形成氧化還原聚合體系。 [0049] 上述聚合起始劑，係以所使用之全單體的合計質量為基準，一般係較佳於0.1~5質量%，特佳係於0.2~3質量%之範圍內使用。該聚合起始劑之添加方法，並未有特別限制，可依據其種類或量等適宜選擇，例如，亦可預先於單體混合物或水性介質中含有，或於聚合時總括添加或滴下。 [0050] 由耐水性等的塗膜性能之觀點，較佳雖係不使用乳化劑，然而聚合含胺基之丙烯酸樹脂粒子(A)之時，可使用乳化劑。作為該乳化劑，可採用任意適宜之乳化劑。例如，可列舉為，烷基胺鹽、四級銨鹽等的陽離子性界面活性劑；聚氧乙烯壬基苯基醚等的聚氧乙烯烷基醚、山梨糖醇脂肪酸酯、聚氧乙烯脂肪酸酯、聚氧乙烯-聚氧丙烯嵌段共聚物、反應性非離子界面活性劑等之非離子性界面活性劑；(變性)聚乙烯基醇等。 [0051] 上述乳化劑，係可單獨或組合2種類以上使用。 [0052] 上述乳化劑之含量，係相對聚合含胺基之丙烯酸樹脂粒子(A)時使用之單體的總量，較佳為0.01~10質量%。更進一步，依照需要，可使用tert-十二烷基硫醇、n-辛基硫醇、n-十二烷基硫醇、巰基乙酸、巰基丙酸、2-巰基乙醇、α-甲基苯乙烯二聚物等的鏈轉移劑。 [0053] 含胺基之丙烯酸樹脂粒子(A)聚合時之聚合溫度，較佳為40~110℃，再更佳為40~90℃。聚合時間較佳為1~12小時，再更佳為1~6小時。 [0054] 上述殼部，係可藉由聚合上述聚合性不飽和單體及具有含胺基之單體之殼部形成用單體混合物而得。 [0055] 作為聚合上述殼部時使用之溶媒，可採用任意之適宜之溶媒。作為該溶媒，例如，較佳為醇類溶劑、賽路蘇類溶劑、卡必醇類溶劑等。具體的而言，例如，可列舉為，n-丁醇等的醇類溶劑；乙二醇單丁醚、乙二醇單異丙基醚、乙二醇單甲基醚、丙二醇單甲基醚、丙二醇單丙基醚、丙二醇單n-丁基醚、二丙二醇單甲基醚、二丙二醇單n-丁基醚等的賽路蘇類溶劑；二乙二醇單丁基醚、二乙二醇單乙基醚、二乙二醇單乙基醚乙酸酯等的卡必醇類溶劑等。 [0056] 又，上述以外之不與水混合之有機溶劑，亦可在不妨礙含胺基之丙烯酸樹脂粒子(A)之水分散穩定度之範圍內使用。作為這樣的有機溶劑，例如，可列舉為，甲苯、二甲苯等的芳香族烴類溶劑、乙酸乙酯、乙酸丁酯等的酯類溶劑、甲基乙基酮、環己酮等的酮類溶劑等。 [0057] 作為聚合上述殼部時可用之聚合起始劑，可採用任意之適合的聚合起始劑。作為該聚合起始劑，例如，可列舉為過氧化苯甲醯、過氧化辛醯基、過氧化月桂醯基、硬脂醯過氧化物、氫過氧化枯烯、tert-丁基過氧化物、二-tert-戊基過氧化物、tert-丁基過氧化-2-乙基己酸丁酯、tert-丁基過氧化月桂酸、tert-丁基過氧化異丙基碳酸酯、tert-丁基過氧化乙酸酯、氫過氧化二異丙苯等的有機過氧化物；偶氮二異丁腈、偶氮雙(2,4-二甲基戊腈)、偶氮雙(2-甲基丙腈)、偶氮雙(2-甲基丁腈)、4、4’-偶氮雙(4-氰基丁酸)、二甲基偶氮雙(2-甲基丙酸酯)、偶氮雙[2-甲基-N-(2-羥基乙基)-丙醯胺]、偶氮雙｛2-甲基-N-[2-(1-羥基丁基)]-丙醯胺｝等的偶氮化合物。 [0058] 此等聚合起始劑，係可單獨或2種類以上併用。 [0059] 作為聚合起始劑之摻混量，係以所使用之聚合性不飽和單體的總量為基準，由聚合反應性等的觀點來看，通常可使其成為0.01~20質量%，較佳為0.1~15質量%，再更佳為0.3~10質量%之範圍內。 [0060] 於上述殼部之聚合之聚合溫度，較佳為80~250℃，再更佳為100~210℃。聚合時間較佳為1~12小時，再更佳為2~8小時。 [0061] 上述殼部之重量平均分子量，由含胺基之丙烯酸樹脂粒子(A)之水分散性或儲藏穩定度及製造之觀點，通常較適宜係介於5,000~400,000，特別是介於10,000~200,000之範圍內。 [0062] 上述殼部，亦可含有不飽和基、環氧基、烴基、羧基、矽烷異氰酸酯基等的官能基，此等基可以公知的方法導入殼部。 [0063] 此外，本說明書中，數平均分子量及重量平均分子量，係將以膠體滲透層析儀(東曹股份公司製，商品名「HLC8120GPC」)所測定之數平均分子量及重量平均分子量，以標準聚苯乙烯之分子量為基準換算之值。於此測定中，管柱為，使用東曹股份公司製「TSKgel Super-H3000」1支，及東曹股份公司製「TSKge Super-H2500」2支(皆為商品名)，共計使用3支管柱，移動相：四氫呋喃(含三乙醇胺0.5質量%)，測定溫度；25℃、流速：0.6mL/min、偵測器：示差折射計之條件下測定。 [0064] (含胺基之丙烯酸樹脂粒子(A)之製造方法) 含胺基之丙烯酸樹脂粒子(A)，係以上述殼部作為分散穩定劑，具有上述核心部於水系介質中分散之型態之丙烯酸樹脂粒子。 [0065] 含胺基之丙烯酸樹脂粒子(A)之代表性製造方法係如下所示，然而含胺基之丙烯酸樹脂粒子(A)之製造方法並非限定於此方法者。 [0066] 1. 於水系介質中添加預先合成之作為分散穩定劑之殼部之聚合體。 [0067] 2. 接著，添加殼部胺基之中和劑及去離子水，獲得水性分散液。 [0068] 作為該中和劑，若為可中和胺基者則無特別限制，例如，可列舉為乙酸、甲酸等的有機酸或無機酸等的酸性化合物。 [0069] 此等之中和劑，係使用期望使含胺基之丙烯酸樹脂粒子(A)之水性分散液最終之pH成為4.0~8.0程度之量。 [0070] 此等之中和劑，通常，較適當係使用相對胺基等的鹼基性基為0.1~1.0當量，較佳為0.3~1.0當量。 [0071] 該水性分散液，雖可藉由一般的攪拌機分散而得，然而為了獲得粒徑更細小且均一的水性分散液，亦可使用均質混合機、均化器、分散器、混合器等。 [0072] 3. 於此水性分散液中添加構成核心部之聚合性單體混合物及自由基聚合起始劑，依據一般方法，進行構成核心部之聚合性不飽和單體之聚合反應。 [0073] 依據以上之步驟之進行，可製造含胺基之丙烯酸樹脂粒子(A)之水性分散體。 [0074] 含胺基之丙烯酸樹脂粒子(A)，由分散性及儲藏穩定度之觀點，一般可為具有10~5,000nm，較佳為10~1,000nm，更佳為20~500nm，再更佳為50~300nm之範圍內的平均粒子徑。 [0075] 於本說明書中，含胺基之丙烯酸樹脂粒子(A)之平均粒子徑，係使用次微米粒度分布測定裝置，依據常法以去離子水稀釋後於23℃下測定所得之值。作為次微米粒度分布測定裝置，例如，可使用「COULTER N5型」(商品名，beckman coulter公司製)。 [0076] 含胺基之丙烯酸樹脂粒子(A)之水性分散體中的固體成分濃度較佳為20~50質量%，更佳為30~40質量%。固體成分濃度若超過50質量%，則乳化將變得困難，而有水性分散體之獲得變得困難之情況。固體成分濃度若未滿20質量%，則由於低濃度，使溶媒(主要為水)之成分變多，例如，有變得難以用於作為水性金屬表面處理劑之構成成分之情況。 [0077] [磷酸類化合物(B)] 本發明之水性金屬表面處理劑，亦含有磷酸類化合物(B)。磷酸類化合物(B)為含有磷酸基、膦酸基或此等基之鹽，且具有水溶性之化合物。作為磷酸類化合物(B)，可為磷酸及有機膦酸以及該等之鹽。 [0078] 上述磷酸為，例如，包含正磷酸、及縮合磷酸，縮合磷酸係包含偏磷酸及聚磷酸。偏磷酸為環狀之磷酸縮合物，包含三偏磷酸、四偏磷酸、六偏磷酸等，聚磷酸為鏈狀之磷酸縮合物，包含焦磷酸、三聚磷酸、四聚磷酸等。 [0079] 作為上述有機膦酸，例如，可列舉為烴甲基二膦酸、1-烴基乙烷-1,1-二膦酸(HEDP)、1-羥基丙烷-1,1-二膦酸等的含有羥基之有機膦酸；2-羥基磷醯基乙酸、2-磷醯基丁烷-1,2,4-三羧酸 (PBTC)等的含有羧基之有機膦酸；次氮基三(亞甲基膦酸)(NTMP)、次氮基三(乙烯膦酸)、次氮基三(丙烯膦酸)、氮基雙(乙烯膦酸)單(亞甲基膦酸)、氮基雙(亞甲基膦酸)單(丙烯膦酸)等的，伸烷基為相同或相異之碳數1~4之伸烷基之次氮基三(伸烷膦酸)；乙烯二胺四亞甲基膦酸、乙烯二胺四乙烯膦酸、乙烯二胺四丙烯膦酸等的，伸烷基為碳數1~4之伸烷基之乙烯二胺四伸烷膦酸；六亞甲基二胺四亞甲基膦酸；二乙烯三胺五亞甲基膦酸等。 [0080] 作為上述磷酸及有機膦酸的鹽，例如，可列舉為鹼金屬鹽(鋰鹽、鈉鹽、鉀鹽等)、鹼土類金屬鹽(鈣鹽、鎂鹽、鋇鹽等)、銨鹽等。又，考慮溶解性，亦可使用鋅、錳、鎳等的鹽。 [0081] 磷酸類化合物(B)之1分子中，磷酸基或膦酸基為複數之情況下，該等之一部分成為鹽亦可，全部成為鹽亦可。又，磷酸基或膦酸基之活性氫原子可一部分置換為鹼金屬離子或銨離子，亦可全部置換。 [0082] 此等之磷酸類化合物(B)，可各自單獨或組合2種以上使用。 [0083] 磷酸類化合物(B)，係使本發明之表面處理劑的儲藏穩定度提升的同時，具有使表面處理皮膜的耐腐蝕性提升之效果，其中特別以正磷酸、烴甲基二膦酸、1-烴基乙烷-1,1-二膦酸為較佳。 [0084] 磷酸類化合物(B)之摻混量，由耐腐蝕性與耐水性兩立之觀點，較適宜係相對於含胺基之丙烯酸樹脂粒子(A)之固體成分總量為0.5~10質量%，較佳為3~8質量%。 [0085] [氟金屬酸及/或其鹽(C)] 於本發明之水性金屬表面處理劑中依照需要摻混之氟金屬酸及/或其鹽(C)，係以使由本發明之水系金屬表面處理劑所得之表面處理皮膜之耐腐蝕性提升等為目的而進行摻混。 [0086] 上述氟金屬酸係含有氟原子與金屬之酸，作為該金屬，例如，可為鈦、鋯、鉿、釩、鎂、錳、鋅、鎢、鉬、鋁、鎳、鈷、鈣等的金屬之1種或2種以上。這些當中，特別是鈦或鋯，由於價格便宜，作為工業用途係相較之下較容易取得，因此較佳。 [0087] 作為上述氟金屬酸，例如，可列舉為六氟鈦酸(H2
TiF6
)、六氟鋯酸(H2
ZrF6
)、六氟鉿酸(H2
HfF6
)、六氟鋁酸(H3
AlF6
)、氟硼酸(HBF4
)等。 [0088] 作為上述氟金屬酸之鹽，例如，可列舉為上述氟金屬酸之鈉鹽、鉀鹽、鋰鹽、銨鹽、胺鹽、鋅鹽等。 [0089] 作為氟金屬酸及/或其鹽(C)，可單獨使用上述各氟金屬酸及其鹽或組合2種以上使用。 [0090] 作為氟金屬酸及/或其鹽(C)，其中耐腐蝕性的點而言較適宜為六氟鈦酸(H2
TiF6
)、六氟鋯酸(H2
ZrF6
)、此等之氟金屬酸之銨鹽、胺鹽。 [0091] 氟金屬酸及/或其鹽(C)，由於在水中產生離子、於腐蝕環境中對金屬表面之腐蝕電位的控制及對氧化還原反應的控制、於金屬表面之極薄皮膜的成膜及源自與皮膜成分中的官能基的交聯反應的皮膜密度提升等，被認為具有提升耐腐蝕性的效果。 [0092] 氟金屬酸及/或其鹽(C)之摻混量，係相對於含胺基之丙烯酸樹脂粒子(A)之固體成分總量為1~5質量%，較佳為2~4質量%，由耐腐蝕性之提升及處理液之穩定度的觀點而言較適宜。 [0093] [釩化合物(D)] 本發明之於水性金屬表面處理劑中依照需要摻混之釩化合物(D)，係以本發明之水系金屬表面處理劑而得之表面處理皮膜的耐腐蝕性之提升等為目的而摻混。 [0094] 釩化合物(D)，較佳為水溶性或水分散性。又，釩化合物(D)，例如，可為碳酸鹽、磷酸鹽、硝酸鹽、硫酸鹽、乙酸鹽、氧化物等，可為酸酐亦可為水合物。 [0095] 作為釩化合物(D)，例如，可列舉為偏釩酸銨、偏釩酸鈉、偏釩酸鉀、硫酸氧釩、氧化釩等，其中，特別由對酸性水溶液之溶解性之觀點，較佳為偏釩酸銨、偏釩酸鈉、偏釩酸鉀及硫酸氧釩。 [0096] 釩化合物(D)之摻混量，係由處理液之穩定度之觀點，適宜係相對於含胺基之丙烯酸樹脂粒子(A)之固體成分總量，為0.1~5質量%，較佳為0.3~1質量%。 [0097] [矽烷偶聯劑及/或其之水解縮合物(E)] 本發明之水性金屬表面處理劑中依照需要摻混之矽烷偶聯劑及/或其之水解縮合物(E)，係有可助於其與所得之表面處理皮膜之基材表面之密著性之提升或皮膜的耐腐蝕性、耐水性之提升等之情況。 [0098] 作為上述矽烷偶聯劑，例如，可列舉為N-β(胺乙基)-γ-胺丙基三甲氧基矽烷、N-β(胺乙基)-γ-胺丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、N-β(N-乙烯基苄基胺乙基)-γ-胺丙基三甲氧基矽烷-鹽酸鹽、γ-縮水甘油氧丙基三甲氧基矽烷、γ-縮水甘油氧丙基三乙氧基矽烷、γ-縮水甘油氧丙基甲基二甲氧基矽烷、γ-縮水甘油氧丙基甲基二乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、甲基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、γ-氯丙基三甲氧基矽烷、六甲基二矽氮烷、γ-苯胺基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、十八烷基二甲基[3-(三甲氧基甲矽烷基)丙基]氯化銨、三甲基氯矽烷等。 其中，較適宜為γ-縮水甘油氧丙基三甲氧基矽烷、γ-縮水甘油氧丙基三乙氧基矽烷等的含有環氧基之矽烷偶聯劑。 [0099] 此等矽烷偶聯劑係可單獨使用1種類，亦可併用2種類以上使用。 [0100] 上述矽烷偶聯劑之所謂水解縮合物，係以矽烷偶聯劑作為原料，經水解縮合之矽烷偶聯劑之寡聚體的意思。 [0101] 矽烷偶聯劑及/或其水解縮合物(E)之摻混量，係相對於含胺基之丙烯酸樹脂粒子(A)之固體成分總量，為0.1~20質量%、較佳為2~15質量%，由表面處理劑之儲藏穩定度、所得之表面處理皮膜之耐腐蝕性及表塗密著性等的觀點而言較為適宜。 [0102] [聚烯烴蠟(F)] 本發明之水性金屬表面處理劑中，依照需要摻混之聚烯烴蠟(F)，係可賦予所得之表面處理皮膜潤滑性之成分。 [0103] 作為聚烯烴蠟(F)，例如，可列舉為聚乙烯或聚丙烯、微晶等。 [0104] 聚烯烴蠟(F)之摻混量，係由成型加工性、耐腐蝕性等的點，相對於水性金屬表面處理劑之全固體成分，作為固體成分量，適宜為0.1~10質量%，較佳為0.3~8質量%之範圍內。 [0105] 作為聚烯烴蠟(F)之平均粒子徑，由維持低動摩擦係數之觀點，係為0.1~3μm，較佳為0.5~2μm。 [0106] [溶媒、及其他成分] 本發明之水性金屬表面處理劑為水性。所謂水性，係指溶媒為以水作為主成分的意思。溶媒可僅為水，然而以調整皮膜之乾燥性、處理劑之黏度等作為目的，亦可併用 1種或2種以上1價或多價之醇、酮、醚醇類等的各種之水溶性有機溶劑。本發明之水性金屬表面處理劑，較佳係於溶媒中含有70質量%以上之水，特佳為含有80質量%以上。 [0107] 本發明之水性金屬表面處理劑，依據所求，除溶媒及上述成分以外，依照需要可摻混pH調整劑(酸或鹼基)、含有鈦之水性液、充填劑、膠態二氧化矽、著色劑、界面活性劑、消泡劑、調平劑、抗菌劑等。此為，可於不損害所得之處理皮膜之性能或表面處理劑之穩定度之範圍內添加。 [0108] 作為上述pH調整劑，例如可適宜使用乙酸、甲酸、乳酸、氨水等。 [0109] 本發明之水性金屬表面處理劑，由液體穩定度之觀點，較佳為pH3~7，更佳為pH3.5~6.5。 又，本發明之水性金屬表面處理劑的固體成分濃度，由塗裝作業性及處理液之穩定度的觀點，較佳為 5~30質量%，特佳為10~25質量%。 [0110] 上述含有鈦之水性液，亦有對於所得之處理皮膜的耐腐蝕性之提升具有效果之情況。該含有鈦之水性液係可由選自水解性鈦、水解性鈦低縮合物、氫氧化鈦及氫氧化鈦低縮合物之至少1種之鈦化合物與過氧化氫溶液反應而得(例如，參照日本國特開2006-22370號公報)。摻混含有鈦之水性液之情況，其摻混量為相對於含胺基之丙烯酸樹脂粒子(A)之固體成分之總量，由儲藏穩定度等的觀點，較適宜為固體成分量5.0質量%以下。 [0111] 作為上述充填劑，例如，可列舉為二氧化矽、滑石、氧化鋇、碳酸鈣、雲母等的微粉末，可例示作為增量劑顏料使用者。作為上述著色劑，可列舉為著色顏料、染料等。 [0112] [金屬表面處理方法] 本發明之金屬表面處理方法，係將本發明之水性金屬表面處理劑於金屬基材上塗佈、使其乾燥之金屬表面處理方法，該方法係於金屬基材表面上藉由本發明之水性金屬表面處理劑形成處理皮膜之方法。於本發明中，所謂「處理皮膜」，不僅只為連續之處理皮膜，還包含由於處理附著量少，而無法成為連續處理皮膜的不連續之處理物。 [0113] 上述所謂金屬基材，若為金屬素材則未受到任何限制，例如，可列舉為鐵、銅、鋁、錫、鋅以及含有此等金屬之合金，及藉由此等金屬之鍍鋼板或汽相沈積製品等。其中，可適宜使用源於上述金屬之金屬板。 [0114] 作為當作上述金屬基材使用之金屬板，例如，可列舉為冷軋鋼板、溶融鍍鋅鋼板、電鍍鋅鋼板、鋅合金(鋅-鐵、鋅-鋁、鋅-鎳等的合金)鍍鋼板、鋁鍍鋼板、不鏽鋼板、銅鍍鋼板、錫鍍鋼板、鋁板、銅板等。其中，鍍鋅鋼板(溶融鍍鋅鋼板、電鍍鋅鋼板皆包含)、鋅合金鍍鋼板較適宜。 [0115] 於上述金屬基材上塗佈本發明之水性金屬表面處理劑前，可將金屬基材藉由脫脂、酸洗、熱水洗、洗劑洗淨等的1或2以上進行表面調整，所有情況中，皆較佳於最後進行充足的水洗。又，塗佈時之本發明的水性金屬表面處理劑的液體溫度可為常溫，亦可依據所求冷卻或加溫。 [0116] 又，於上述金屬基材表面，亦可藉由其他表面處理形成第1層。該第1層，係為以源自本發明之水性金屬表面處理劑之處理皮膜與金屬表面之密著性的強化等為目的形成者，較佳為源自無鉻的表面處理劑者。 [0117] 於上述金屬基材上，可藉由軋輥塗佈法、噴射塗裝法、刷毛塗佈法、靜電塗裝法、浸漬法、電著塗裝法、簾幕式塗裝法、輥塗裝法等的公知方法塗裝本發明之水性金屬表面處理劑、使其乾燥，而形成表面處理皮膜。此外，上述之表面處理皮膜的形成，可僅於金屬基材的單面，亦可為兩面。 [0118] 本發明之源自水性金屬表面處理劑之處理皮膜之皮膜量，雖並未有特別限制，然而由耐腐蝕性、加工性之觀點，一般適宜介於0.4~3.6g/m2
，較佳為0.5~2.5g/m2
之範圍。處理皮膜之乾燥條件，雖適當設定即可，藉由線圈塗佈法等將經塗裝物連續性地塗佈之情況下，一般係可以成為素材到達最高溫度之60~200℃、較佳成為70~120℃之條件下，加熱5~60秒鐘而進行。以批次方式塗佈之情況中，例如，可藉由環境溫度100~180℃下，加熱1~30分而進行。 [0119] [表面處理金屬板] 本發明之表面處理金屬板，係於金屬基材表面藉由本發明之水性金屬表面處理劑進行表面處理。本發明之表面處理金屬板，其金屬基材為板狀之形狀，可藉由上述本發明之金屬表面處理方法而得。 [0120] 本發明之表面處理金屬板，本發明之源於水性金屬表面處理劑之處理皮膜之皮膜量為0.4~3.6g/m2
、較佳為0.5~2.5g/m2
之範圍，由耐腐蝕性、加工性之觀點而言較適宜。 [0121] 於本發明之表面處理金屬板之處理皮膜上，進一步以美觀性之提升、耐久性之提升，其他機能性提升等為目的，可形成著色塗膜、透明塗膜等的上層膜。此上層膜的形成，雖可於本發明之表面處理金屬板之成型加工前進行，然較佳係於成型加工後進行。 [實施例] [0122] 以下，舉出製備例、實施例及比較例，更具體的說明本發明。然而，本發明並不受這些例子的限制。 [0123] 於各例子中，「份」及「%」係除了另有說明之狀況以外，皆為以質量為基準者。又，處理皮膜之皮膜量，係以乾燥皮膜量為基準。 [0124] [含胺基之丙烯酸樹脂粒子之殼部之製備例] (含胺基之丙烯酸樹脂(S1)溶液之製造) 於具備溫度計、恆溫器、攪拌裝置、回流冷凝器、氮氣導入管及滴下裝置之反應容器中，加入丙二醇(PG)單甲基醚50份，於氮氣流中攪拌混合，升溫至105℃後，將苯乙烯(St)20份、甲基丙烯酸甲酯(MMA)45份、n-丁基丙烯酸酯(nBA)5份、2-羥基乙基丙烯酸酯(2-HEA)5份及2-(N,N-二甲胺)乙基丙烯酸甲酯(DMAEMA)25份之混合物與tert-丁基過氧化-2-乙基己酸乙酯(PBO)2份及丙二醇(PG)單甲基醚15份之混合物，於3小時間同時滴入，滴入結束後，進行1小時熟成。 [0125] 之後，以丙二醇單甲基醚稀釋，攪拌混合30分鐘，獲得固體成分濃度(NV値)45%之含胺基之丙烯酸樹脂(S1)溶液。 [0126] 所得之含胺基之丙烯酸樹脂(S1)之胺價為90mgKOH/g，烴基價為22mgKOH/g、重量平均分子量(Mw)為45,000。 [0127] (含胺基之丙烯酸樹脂(S2)~(S14)溶液之製造) 以上述相同之方法，根據下列表1及表2所示之組成，獲得含胺基之丙烯酸樹脂(S2)~(S14)溶液。 [0128][0129][0130] [Core/Shell乳化之合成例] (含胺基之丙烯酸樹脂粒子(A1)水性分散液之製造) 於具備溫度計、恆溫器、攪拌裝置、回流冷凝器、氮氣導入管及滴下裝置之反應容器中，加入固體成分濃度45%之含胺基之丙烯酸樹脂(S1)溶液111份攪拌混合，升溫至80℃後，使固體成分濃度成為69%為止，於減壓下進行去溶媒。 [0131] 接著，冷卻至60℃，於反應容器中添加苯乙烯20份、甲基丙烯酸甲酯20份、n-丁基丙烯酸酯7份、2-羥基乙基丙烯酸甲酯(2-HEMA)2.5份、丙烯基丙烯酸甲酯(AMA)0.5份、乙酸3份，攪拌混合15分鐘。 [0132] 接著，冷卻至40℃後，於1小時間滴入去離子水(DIW)180份，滴入結束後，進行15分鐘熟成。 之後升溫至60℃，添加抗壞血酸鈉0.3份與5%硫酸亞鐵水溶液0.3份後，於1小時間滴入30%過氧化氫溶液0.4份與去離子水30份之混合物，接著進行1小時之熟成，獲得具有平均粒子徑75nm[使用次微米粒度分布測定裝置「COULTER N5型」(Beckman coulter公司製)、23℃之條件下所測定之平均例子直徑]、固體成分濃度30%之含胺基之丙烯酸樹脂粒子(A1)水性分散液。 [0133] 所得之含胺基之丙烯酸樹脂粒子(A1)之胺價為45mgKOH/g，烴基價為23mgKOH/g，重量平均分子量為1,200,000。 [0134] (A2~A15之製造) 以上述相同之方法，根據下列表3及表4所示之組成，獲得含胺基之丙烯酸樹脂(A2)~(A15) 之水性分散液。 [0135] 此外，含胺基之丙烯酸樹脂粒子(A1)~(A15)中，核心部與殼部之構成比率(質量比)為，如下列所示。 (A1)~(A13)核心部：殼部＝50：50 (A14)核心部：殼部＝90：10 (A15)核心部：殼部＝10：90 [0136][0137][0138] (含胺基之丙烯酸樹脂粒子(A16)水性分散液之製造) 除使用固體成分濃度45%之含胺基之丙烯酸樹脂(S13)溶液111份、乙酸6份以外，與含胺基之丙烯酸樹脂粒子(A1)水性分散液相同，獲得平均粒子徑55nm、固體成分濃度30%之含胺基之丙烯酸樹脂粒子(A16)水性分散液。 所得之含胺基之丙烯酸樹脂粒子(A16)之胺價為90mgKOH/g，烴基價為23mgKOH/g，重量平均分子量為1,200,000。 [0139] (含胺基之丙烯酸樹脂粒子(A17)水性分散液之製造) 除使用固體成分濃度45%之含胺基之丙烯酸樹脂(S14)溶液111份、乙酸0.6份以外，與含胺基之丙烯酸樹脂粒子(A1)水性分散液相同，獲得平均粒子徑240nm、固體成分濃度30%之含胺基之丙烯酸樹脂粒子(A17)水性分散液。 所得之含胺基之丙烯酸樹脂粒子(A17)之胺價為9mgKOH/g，烴基價為23mgKOH/g，重量平均分子量為1,200,000。 [0140] (含胺基之丙烯酸樹脂粒子(A18)水性分散液之製造) 於具備溫度計、恆溫器、攪拌裝置、回流冷凝器、氮氣導入管及滴下裝置之反應容器中，加入去離子水110份、「ADEKA REASOAP ER-40」(商品名，ADEKA股份公司製，乳化劑，有效成分60%)8份，於氮氣流中攪拌混合，升溫至60℃。 [0141] 接著，將下述核心部用單體乳化物之總量中的5%的量、10%「Kayabutyl H-70」(商品名，KAYAKU AKZO股份公司製，聚合起始劑、tert-丁基過氧化氫、有效成分70%)水溶液1份及3%抗壞血酸鈉水溶液1份添加於反應容器內，於60℃下保持1小時。 [0142] 之後，將下述核心部用單體乳化物的剩餘部份，10%「Kayabutyl H-70」水溶液7份及3%抗壞血酸鈉水溶液10份於2小時間，滴入保持相同溫度之反應容器內，結束滴入之後進行1小時之熟成。 [0143] 接著，將下述殼部用單體乳化物，10%「Kayabutyl H-70」水溶液5份及3%抗壞血酸鈉水溶液10份於2小時間滴入，再熟成1小時後，將乙酸0.6份添加於反應容器內保持30分鐘。 [0144] 接著，冷卻至30℃，以去離子水稀釋，獲得具有平均粒子徑170nm、固體成分濃度30%之含胺基之丙烯酸樹脂粒子(A18)水性分散液。 [0145] 所得之含胺基之丙烯酸樹脂粒子(A18)之胺價為10mgKOH/g，烴基價為16mgKOH/g，數平均分子量為約65,000。 [0146] 殼部用單體乳化物：將去離子水20份、「ADEKA REASOAP ER-40」3.5份、苯乙烯3份、甲基丙烯酸甲酯19份、n-丁基丙烯酸甲酯(nBMA)3份、n-丁基丙烯酸酯2份、2-羥基乙基丙烯酸甲酯2份及2-(N,N-二甲基胺)乙基丙烯酸甲酯1份混合而成之單體乳化物。 [0147] 核心部用之單體乳化物：將去離子水40份、「ADEKA REASOAP ER-40」7份、甲基丙烯酸甲酯44份、n-丁基丙烯酸甲酯17份、n-丁基丙烯酸酯5份、2-羥基乙基丙烯酸甲酯2份及2-(N,N-二甲基胺)乙基丙烯酸甲酯2份混合而成之單體乳化物。 [0148] (含胺基之丙烯酸樹脂粒子(A19)水性分散液之製造) 於具備溫度計、恆溫器、攪拌裝置、回流冷凝器、氮氣導入管及滴下裝置之反應容器中，加入丙二醇單甲基醚50份，於氮氣流中攪拌混合，升溫至105℃後，將苯乙烯20份、甲基丙烯酸甲酯45份、n-丁基丙烯酸酯5份、2-羥基乙基丙烯酸酯5份、2-(N,N-二甲基胺)乙基丙烯酸甲酯25份及tert-丁基過氧化-2乙基己酸酯2份之混合物，於3小時間滴入，滴入結束後，進行1小時熟成。 [0149] 之後冷卻至60℃，於反應容器內添加乙酸14份，保持30分鐘後，以去離子水(DIW)稀釋，獲得具有平均粒子徑25nm、固體成分濃度20%之含胺基之丙烯酸樹脂粒子(A19)水性分散液。 [0150] 所得之含胺基之丙烯酸樹脂粒子(A19)之胺價為90mgKOH/g，烴基價為23mgKOH/g，重量平均分子量為45,000。 [0151] 此外，含胺基之丙烯酸樹脂粒子(A16)~(A19)為比較例用，為了方便起見，作為含胺基之丙烯酸樹脂粒子(A16)~(A19)，然而其係為不符合本發明之水性金屬表面處理劑之含胺基之丙烯酸樹脂粒子(A)之樹脂粒子。 [0152] 又，含胺基之丙烯酸樹脂粒子(A16)~(A18)中，核心部與殼部之構成比率(質量比)為，如下列所示。 (A16)~(A17)核心部：殼部＝50：50 (A18)核心部：殼部＝70：30 [0153][0154] [實施例及比較例] 依據下述表中所示之摻混比例摻混各成分，添加去離子水調整，使固體成分濃度成為15質量%，進行充足攪拌獲得各金屬表面處理劑。下述表中之摻混量係依據固體成分質量或有效成分質量。 [0155] 此外，於下述表中，含胺基之丙烯酸樹脂粒子(A)、磷酸類化合物(B)、氟金屬酸及/或其鹽(C)、釩化合物(D)、矽烷偶聯劑及/或其之水解縮合物(E)及聚烯烴蠟(F)之成分係如下列所示。 [0156] 於下述表中，含胺基之丙烯酸樹脂粒子(A)之成分 A1~A19：由上述[Core/Shell乳化之合成例]獲得，含胺基之丙烯酸樹脂粒子(A1)~(A19)水性分散液 [0157] 於下述表中，磷酸類化合物(B)之成分 B1：正磷酸 B2：1-羥基亞乙基-1,1-二膦酸 B3：次氮基三(亞甲基膦酸) [0158] 於下述表中，氟金屬酸及/或其鹽(C)之成分 C1：六氟鈦酸銨 C2：六氟鋯酸銨 C3：六氟鈦酸 C4：六氟鋯酸 C5：六氟鉿酸 [0159] 於下述表中，釩化合物(D)之成分 D1：偏釩酸銨 D2：偏釩酸鈉 D3：硫酸氧釩 [0160] 於下述表中，矽烷偶聯劑及/或其之水解縮合物(E)之成分 E1：γ-甲基丙烯醯氧基丙基三甲氧基矽烷 E2：3-縮水甘油氧丙基三甲氧基矽烷 E3：3-巰基丙基三甲氧基矽烷 [0161] 於下述表中，聚烯烴蠟(F)之成分 F1：三井化學股份公司製 CHEMIPEARL W-700 平均粒子徑1.5μm F2：股份公司岐阜Shellac製造所製 HIDISPER AC-90 平均粒子徑1.3μm F3：股份公司岐阜Shellac製造所製 HIDISPER A-206N 平均粒子徑1μm F4：股份公司岐阜Shellac製造所製 HIDISPER AG-73 平均粒子徑0.1μm F5：三井化學股份公司製 CHEMIPEARL W-500 平均粒子徑2.5μm [0162] [耐水性試驗] (表面處理金屬板之製作條件) 鍍金屬之附著量為單面20g/m2
，將板厚0.8mm之兩面電鍍鋅鋼板於濃度2%之鹼性脫脂劑(日本Cee. Bee. Chemical股份公司製、商品名「KEMICLEANER 561B」、矽酸3號之等同物)溶液中，以液溫65℃進行60秒鐘之噴塗脫脂，然後，於液溫50℃、噴塗時間20秒鐘之條件下進行熱水洗，乾燥後獲得鹼性脫脂金屬板。所得之鹼性脫脂金屬板中，將由上述[實施例及比較例]中獲得之表面處理劑以塗佈桿使乾燥皮膜重量成為0.9g/m2
之方式進行塗佈，使金屬板的最高到達溫度成為60℃之方式加熱乾燥12秒鐘，獲得各表面處理金屬板。 [0163] (評價基準) 將各表面處理金屬板於室溫下放置5分鐘，使去離子水成為直徑3cm之程度而於表面處理金屬板載置2分鐘，之後，以紗布等將水滴去除，以目視觀察處理面的外觀變化，並以下述基準進行評價，結果以下述表中顯示。 ◎：完全沒有觀察到變化。 ○：稍微變白。 ×：明顯變白。 此外，將「◎」或「○」作為實用之水準。 [0164] [硫酸銅變色試驗] (表面處理金屬板製作條件) 鍍金屬之附著量為單面20g/m2
，將板厚0.8mm之兩面電鍍鋅鋼板於濃度2%之鹼性脫脂劑(日本Cee. Bee. Chemical股份公司製、商品名「KEMICLEANER 561B」、矽酸3號之等同物)溶液中，以液溫65℃進行60秒鐘之噴塗脫脂，然後，於液溫50℃、噴塗時間20秒鐘之條件下進行熱水洗，乾燥後獲得鹼性脫脂金屬板。所得之鹼性脫脂金屬板中，將由上述[實施例及比較例]中獲得之表面處理劑以塗佈桿使乾燥皮膜重量成為0.9g/m2
之方式進行塗佈，使金屬板的最高到達溫度成為80℃之方式加熱乾燥12秒鐘，獲得各表面處理金屬板。 [0165] (評價基準) 各表面處理金屬板之處理面載置濃度5%之硫酸銅水溶液20μL，經過15秒鐘後，以紗布等將硫酸銅水溶液去除，以目視觀察處理面的外觀變化，並以下述基準進行評價，結果以下述表表示。 ◎：完全沒有觀察到變色。 ○：觀察到稍微變色。 ×：明確地觀察到變色。 此外，將「◎」或「○」作為實用之水準。 [0166] [耐腐蝕性試驗] (表面處理金屬板製作條件) 以上述硫酸銅變色試驗相同的條件及方法，獲得各表面處理金屬板。 [0167] (一般部評價基準) 將各表面處理金屬板以寬7cm、長15cm切斷，獲得耐腐蝕性試驗用之表面處理金屬試驗板。將所得之試驗板之端面部及裏面部密封，藉由依據JIS Z 2371之鹽水噴霧試驗(SST)，將處理面中鏽產生的面積根據評等編號法，將評等編號成為9為止之時間以下述基準進行評價，結果以下述表表示。 SS：評等編號成為9為止之時間為96小時以上。 S：評等編號成為9為止之時間為72小時以上、未滿96小時。 A：評等編號成為9為止之時間為48小時以上、未滿72小時。 B：評等編號成為9為止之時間為24小時以上、未滿48小時。 C：評等編號成為9為止之時間未滿24小時。 此外，將「SS」、「S」、「A」或「B」作為實用之水準。 [0168] (加工部評價基準) 將各表面處理金屬板以寬7cm、長15cm切斷，以艾利克森加工機壓出，使高度成為7mm為止，獲得具有圓頂狀之加工部之加工部耐腐蝕性試驗用表面處理金屬試驗板。將所得之試驗板之端面部及裏面部密封，藉由依據JIS Z 2371之鹽水噴霧試驗(SST)，將圓頂狀加工部之天頂部中鏽產生為止之時間以下述基準進行評價，結果以下述表表示。 S：鏽產生為止之時間為72小時以上。 A：鏽產生為止之時間為48小時以上、未滿72小時。 B：鏽產生為止之時間為24小時以上、未滿48小時。 C：鏽產生為止之時間為未滿24小時。 此外，將「S」、「A」或「B」作為實用之水準。 [0169] [耐乙醇摩擦性試驗] (表面處理金屬板製作條件) 以上述硫酸銅變色試驗相同的條件及方法，獲得各表面處理金屬板。 [0170] (評價基準) 使乙醇滲透4枚重疊之紗布後，以1kg之負重於各表面處理金屬板之處理面來回摩擦10次，以目視觀察處理面的外觀變化，並以下述基準進行評價，結果以下述表表示。 ◎：完全沒有觀察到變化。 ○：觀察到些微摩擦痕跡。 ×：明確觀察到摩擦痕跡。 此外，將「◎」或「○」作為實用之水準。 [0171] [動摩擦係數測定試驗] (表面處理金屬板製作條件) 以上述硫酸銅變色試驗相同的條件及方法，獲得各表面處理金屬板。 [0172] (評價基準) 對於各表面處理金屬板，以bowden磨耗試驗機(神鋼造機股份公司製、曾田式附著滑動試驗機、摩擦部球壓痕器3/16英吋鋼球、負重200gf、摩擦速度7來回/分)進行摩擦試驗，測定動摩擦係數。所得之動摩擦係數之值成為0.4為止之摩擦次數，以下述基準進行評價，結果以下述表表示。 S：動摩擦係數之值成為0.4為止之摩擦次數為20次以上。 A：動摩擦係數之值成為0.4為止之摩擦次數為10次以上、未滿20次。 B：動摩擦係數之值成為0.4為止之摩擦次數為5次以上、未滿10次。 C：動摩擦係數之值成為0.4為止之摩擦次數為未滿5次。 此外，將「S」、「A」或「B」作為實用之水準。 [0173][0174][0175][0176][0177][0178] 由上述實施例及比較例證實，本發明之表面處理劑所塗佈之表面處理金屬板，係於耐水性、耐腐蝕性(特別是，艾利克森加工後之表面處理金屬板之耐腐蝕性)及耐乙醇摩擦性方面優異，且為可滿足硫酸銅變色試驗及動摩擦係數等之性能者。 [0179] 雖已詳細且參照特定實施例態樣說明本發明，然而對本發明所屬技術領域中具有通常知識者而言，在不脫離本發明的精神及範圍下，可加上各種的變更或修正，係為毫無疑問之事。本申請為以2016年10月19日申請之日本專利申請(日本特願2016-205570)為基礎，其內容皆作為參照引用於此。[0022] The components of the water-based metal surface treatment agent of the present invention are described below. These are only examples of ideal implementations, and are not limited by these contents. In this specification, "mass" and "weight" have the same meaning. In this specification, "X and / or Y" means "at least one of X and Y". [0023] [Amine group-containing acrylic resin particles (A)] The aqueous metal surface treatment agent of the present invention contains amine group-containing acrylic resin particles (A). The amine group-containing acrylic resin particles (A) have a core-shell structure having a core portion as a central portion and a shell portion as an outer shell portion. The core portion and the shell portion can be obtained from monomer mixtures having different compositions. In addition, the so-called core-shell structure is specifically a structure in which the same microcells have different resin composition components and are composed of resins in which the central part (core) and the outer shell part (shell) are different. [0024] Generally, the core-shell structure is generally a layer structure in which the core portion is completely covered by the shell portion. However, depending on the mass ratio of the core portion to the shell portion and other conditions, the shell portion may not form a layer structure completely. Situation. In such a case, a complete layer structure as described above is not necessary, and a structure in which a part of the core portion is covered by the shell portion is also possible. [0025] From the viewpoint of dispersion stability, the composition ratio between the core portion and the shell portion is preferably a core portion: shell portion = 90: 10 to 10:90 (mass ratio), and more preferably 70:30 to 20: 80, and even more preferably 70: 30 ~ 30: 70. [0026] When the core portion ratio in the amine group-containing acrylic resin particles (A) is less than 10% by mass, the corrosion resistance may be lowered. In addition, when the core portion ratio exceeds 90% by mass, the dispersion stability decreases, so that the dispersibility of the amine group-containing acrylic resin particles (A) may decrease. [0027] Both the monomer mixture used for the polymerization of the core portion and the shell portion contain a polymerizable unsaturated monomer. In the core portion and the shell portion, the polymerizable unsaturated monomer is preferably obtained by polymerizing a monomer mixture having a different type and / or a different blending ratio. [0028] Examples of the polymerizable unsaturated monomer include meth (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and i-propyl. (Meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) ) Acrylate, octadecyl (meth) acrylate, isooctadecyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tert-butyl Alkyl or cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, and tricyclomethylene (meth) acrylate; isobornyl (Meth) acrylic polymerizable unsaturated monomers having isobornyl groups; adamantyl (meth) acrylate polymerizable unsaturated monomers having adamantyl groups; Base) acrylic Polymerizable unsaturated monomers with tricyclic cyclene groups; polymerizable unsaturated monomers containing aromatic rings such as benzyl (meth) acrylate, styrene, α-methylstyrene, vinyl toluene, etc .; ethylene Trimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltri (2-methoxyethoxy) silane, ethylene Triisopropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (methyl ) Acrylic methoxypropyltriethoxysilane, γ- (meth) acrylic methoxypropylmethyldiethoxysilane, γ- (meth) acrylic methoxypropyltrimethoxy-n -Propoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, vinyltriethoxysilane, β- (meth) acryloxyethyltrimethoxysilane And other polymerizable unsaturated monomers having hydrolyzable silyl groups; perfluoroalkyl (meth) acrylates, perfluorooctyl ethyl (meth) acrylates, etc. ) Acrylate And other polymerizable unsaturated monomers having fluorinated alkyl groups; vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, etc .; (methyl) Acrylonitrile, (meth) acrylamide, methylenebis (meth) acrylamide, ethylene bis (meth) acrylamide, 2- (methacryloxy) ethyltrimethyl chloride Nitrogen-containing polymerizable unsaturated monomers such as ammonium, glycidyl (meth) acrylate and amine adducts; glycidyl (meth) acrylate, glycidyl beta- (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate Epoxy-based polymerizable unsaturated monomers such as propylene and glyceryl ether; propylene (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc. have at least one molecule Polymerizable unsaturated monomer with 2 polymerizable unsaturated groups; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate 4-hydroxybutyl (methyl (Meth) acrylic acid esters of monoesters of (meth) acrylic acid and divalent alcohols having 2 to 8 carbons; ε-hexane of the (mono) esters of (meth) acrylic acid and divalent alcohols having 2 to 8 carbons Modified products of lactones; polymerizable unsaturated monomers containing hydrocarbon groups such as propenyl alcohol; acrylic monomers with a hydroxyl group or an alkyleneoxy group having 1 to 3 carbon atoms at the end and a polyoxyethylene group or a polyoxypropylene group (Meth) acrylic acid monomer containing polyoxyalkylene. [0029] The polymerizable unsaturated monomers may be used singly or in combination of two or more kinds. [0030] In each compound of the present invention, "(meth) acrylate" means "acrylate or methyl acrylate". "(Meth) acrylic" means "acrylic or methacrylic". "(Meth) acrylfluorenyl" means "acrylfluorenyl or methacrylfluorenyl". [0031] Among the polymerizable unsaturated monomers, a polymerizable unsaturated monomer containing a hydrocarbon group may be preferably used from the viewpoint of adhesion, and at least one molecule may be used from a viewpoint of corrosion resistance. A polymerizable unsaturated monomer containing two polymerizable unsaturated groups. [0032] In the case of using a hydrocarbon group-containing polymerizable unsaturated monomer, the amount used is preferably 0.1% by mass or more in the total amount of all monomer components constituting the amine group-containing acrylic resin particles (A). It is preferably 1% by mass or more, and still more preferably within a range of 1 to 10% by mass. [0033] When a polymerizable unsaturated monomer containing at least two polymerizable unsaturated groups in one molecule is used, the amount used is based on the total monomer component constituting the amine group-containing acrylic resin particles (A). The total amount is preferably in a range of 0.05% by mass or more, preferably 0.1% by mass or more, and still more preferably in a range of 0.1 to 10% by mass. [0034] The amine group-containing acrylic resin particles (A) are acrylic resin particles having an amine group-containing cationic core-shell structure. From the viewpoint of the dispersion stability of the amine group-containing acrylic resin particles (A), the amine group is preferably present in the shell. The amine group-containing acrylic resin particles (A) preferably have an amine group-containing shell portion obtained by polymerizing a monomer mixture containing an amine group-containing monomer. [0035] Examples of the amine group-containing monomer include dimethylaminomethyl (meth) acrylate, diethylamino (meth) acrylate, and dibutylaminomethyl ( (Meth) acrylate, dihexylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diisohexylaminoethylacrylate, dihexylaminopropyl ( Monomers such as meth) acrylate, di (tert-butyl) aminohexyl (meth) acrylate, and the like. [0036] Among the above, from the viewpoint of dispersion stability, dimethylaminoethyl (meth) acrylate and diethylamino (meth) acrylate are preferred. [0037] The amine value of the amine group-containing acrylic resin particles (A) is 14 to 72 mgKOH / g, preferably 20 to 72 mgKOH / g, and even more preferably 20 to 65 mgKOH / g. [0038] In this specification, the amine value (mgKOH / g) refers to the amount of amine groups contained in 1 g of a sample (solid content in the case of a resin) when converted to potassium hydroxide. Expressed in mg. The molecular weight of potassium hydroxide was 56.1. [0039] In this specification, the so-called hydrocarbon group valence (mgKOH / g) refers to the amount of the potassium group in the case of potassium hydroxide when the amount of the hydrocarbon group contained in 1 g of the sample (solid content in the case of resin) is converted into potassium hydroxide. Expressed in mg. The molecular weight of potassium hydroxide was 56.1. [0040] As a method for producing the amine group-containing acrylic resin particles (A), for example, in the presence of a shell portion polymerized in advance, water is used as a main solvent for polymerization, and the polymerizable unsaturated monomer is contained. A method for forming a core mixture using a monomer. [0041] The addition ratio of the shell portion and the core portion-forming monomer mixture can be an appropriate and appropriate addition ratio in accordance with the desired solid component mass ratio of the core portion / shell portion. [0042] In the aqueous metal surface treatment agent of the present invention, from the viewpoint of coating film properties such as corrosion resistance and water resistance due to film-forming properties, it is preferred to use a shell synthesized by solution polymerization in an organic solvent. unit. By using a shell part synthesized by solution polymerization, it is possible to reduce the amount of an emulsifier that reduces water resistance. [0043] As the polymerization initiator usable in the polymerization of the amine group-containing acrylic resin particles (A), any appropriate polymerization initiator can be used. [0044] As the polymerization initiator, any of fat-soluble and water-soluble types can be used, but more preferably, water-soluble ones can be used. [0045] Examples of the fat-soluble polymerization initiator include organic peroxides such as benzamidine peroxide, octyl peroxide, lauryl peroxide, and stearyl peroxide; azobisiso Azo compounds such as butyronitrile and azobis (2,4-dimethylvaleronitrile). [0046] Examples of the water-soluble polymerization initiator include hydrogen peroxide solution; cumene hydroperoxide, tert-butyl peroxide, tert-butylperoxylauric acid, and tert-butylperoxide. Organic peroxides such as oxidized isopropyl carbonate, tert-butyl peroxyacetate, and dicumyl hydroperoxide; azobis (2-methylpropionitrile), azobis (2-methyl Butyronitrile), 4,4´-azobis (4-cyanobutanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- ( Azo compounds such as 2-hydroxyethyl) -propylamine], azobisfluorene 2-methyl-N- [2- (1-hydroxybutyl)]-propylamine, etc .; potassium persulfate, Persulfates such as ammonium sulfate and sodium persulfate. [0047] These can be used individually or in combination of two or more kinds. [0048] In addition, according to need, in the polymerization initiator, reducing agents such as sugar, sodium ascorbate, sodium formaldehyde sulfoxylate, and iron complexes may be used in combination to form a redox polymerization system. [0049] The above-mentioned polymerization initiator is based on the total mass of all the monomers used, and is generally preferably 0.1 to 5% by mass, and particularly preferably used in the range of 0.2 to 3% by mass. The method for adding the polymerization initiator is not particularly limited, and may be appropriately selected according to the type or amount thereof. For example, it may be contained in a monomer mixture or an aqueous medium in advance, or may be added or dropped collectively during polymerization. [0050] From the viewpoint of coating film performance such as water resistance, although an emulsifier is not used, it is preferred to use an emulsifier when polymerizing amine group-containing acrylic resin particles (A). As the emulsifier, any suitable emulsifier can be used. Examples include cationic surfactants such as alkylamine salts and quaternary ammonium salts; polyoxyethylene alkyl ethers such as polyoxyethylene nonylphenyl ether; sorbitol fatty acid esters; and polyoxyethylene Nonionic surfactants such as fatty acid esters, polyoxyethylene-polyoxypropylene block copolymers, reactive nonionic surfactants; (denatured) polyvinyl alcohols, and the like. [0051] The emulsifier may be used alone or in combination of two or more kinds. [0052] The content of the emulsifier is preferably 0.01 to 10% by mass relative to the total amount of monomers used when polymerizing the amine group-containing acrylic resin particles (A). Furthermore, as required, tert-dodecyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, α-methylbenzene can be used. Chain transfer agents such as ethylene dimers. [0053] The polymerization temperature at the time of polymerization of the amine group-containing acrylic resin particles (A) is preferably 40 to 110 ° C, and even more preferably 40 to 90 ° C. The polymerization time is preferably 1 to 12 hours, and even more preferably 1 to 6 hours. [0054] The shell part is obtained by polymerizing the polymerizable unsaturated monomer and a monomer mixture for forming a shell part having a monomer having an amine group. [0055] As the solvent used when polymerizing the shell portion, any appropriate solvent can be used. As the solvent, for example, an alcohol-based solvent, a cyrus solvent, a carbitol-based solvent, and the like are preferable. Specific examples include alcohol solvents such as n-butanol; ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether. , Propylene glycol monopropyl ether, propylene glycol mono n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono n-butyl ether, and other Cyrus solvents; diethylene glycol monobutyl ether, diethylene glycol Carbitol solvents such as alcohol monoethyl ether and diethylene glycol monoethyl ether acetate. [0056] In addition to the above, organic solvents that are not mixed with water may be used within a range that does not hinder the water dispersion stability of the amine group-containing acrylic resin particles (A). Examples of such an organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone and cyclohexanone. Solvents, etc. [0057] As the polymerization initiator usable when polymerizing the above-mentioned shell portion, any appropriate polymerization initiator can be used. Examples of the polymerization initiator include benzamidine peroxide, octyl peroxide, lauryl peroxide, stearyl peroxide, cumene hydroperoxide, tert-butyl peroxide, and -tert-pentyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxylaurate, tert-butylperoxyisopropyl carbonate, tert-butyl Organic peroxides such as peracetate, dicumyl hydroperoxide; azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), azobis (2-methyl Propionitrile), azobis (2-methylbutyronitrile), 4,4'-azobis (4-cyanobutanoic acid), dimethylazobis (2-methylpropionate), azo Azabis [2-methyl-N- (2-hydroxyethyl) -propylamine], azobisfluorene 2-methyl-N- [2- (1-hydroxybutyl)]-propylamine And other azo compounds. [0058] These polymerization initiators can be used alone or in combination of two or more kinds. [0059] The blending amount of the polymerization initiator is based on the total amount of the polymerizable unsaturated monomers used. From the viewpoint of polymerization reactivity and the like, it can be generally 0.01 to 20% by mass. It is preferably within a range of 0.1 to 15% by mass, and even more preferably within a range of 0.3 to 10% by mass. [0060] The polymerization temperature of the above-mentioned shell polymerization is preferably 80 to 250 ° C, and even more preferably 100 to 210 ° C. The polymerization time is preferably 1 to 12 hours, and even more preferably 2 to 8 hours. [0061] The weight-average molecular weight of the above-mentioned shell part is generally more preferably between 5,000 and 400,000, especially between 10,000, from the viewpoint of water dispersibility or storage stability and manufacturing of the amine group-containing acrylic resin particles (A). Within the range of ~ 200,000. [0062] The shell portion may contain functional groups such as an unsaturated group, an epoxy group, a hydrocarbon group, a carboxyl group, and a silane isocyanate group. These groups may be introduced into the shell portion by a known method. [0063] In this specification, the number average molecular weight and the weight average molecular weight are the number average molecular weight and the weight average molecular weight measured by a colloidal permeation chromatography (manufactured by Tosoh Corporation, trade name "HLC8120GPC"). The molecular weight of standard polystyrene is a value converted from a standard. In this measurement, the column used 1 TSKgel Super-H3000 manufactured by Tosoh Corporation and 2 TSKge Super-H2500 manufactured by Tosoh Corporation (both trade names). A total of 3 columns were used. , Mobile phase: tetrahydrofuran (containing 0.5% by mass of triethanolamine), measurement temperature; 25 ° C, flow rate: 0.6mL / min, detector: differential refractometer. [0064] (Manufacturing method of amine group-containing acrylic resin particles (A)) The amine group-containing acrylic resin particles (A) use the shell portion as a dispersion stabilizer, and have a type in which the core portion is dispersed in an aqueous medium. Acrylic resin particles. [0065] A representative method for producing the amine group-containing acrylic resin particles (A) is shown below, but the method for producing the amine group-containing acrylic resin particles (A) is not limited to this method. [0066] 1. A polymer in the shell part which is previously synthesized as a dispersion stabilizer is added to an aqueous medium. [0067] 2. Next, a shell amine neutralizing agent and deionized water were added to obtain an aqueous dispersion. [0068] The neutralizing agent is not particularly limited as long as it can neutralize an amine group, and examples thereof include an acidic compound such as an organic acid or an inorganic acid such as acetic acid and formic acid. [0069] These neutralizers are used in such an amount that the final pH of the aqueous dispersion of the amine group-containing acrylic resin particles (A) is desired to be about 4.0 to 8.0. [0070] In general, the neutralizing agent is more preferably 0.1 to 1.0 equivalent, preferably 0.3 to 1.0 equivalent, relative to a basic group such as an amine group. [0071] Although this aqueous dispersion can be obtained by dispersing with a general mixer, in order to obtain an aqueous dispersion with a finer and more uniform particle diameter, a homomixer, homogenizer, disperser, mixer, etc. can also be used. . [0072] 3. A polymerizable monomer mixture and a radical polymerization initiator constituting a core portion are added to this aqueous dispersion, and a polymerization reaction of a polymerizable unsaturated monomer constituting the core portion is performed according to a general method. [0073] According to the above steps, an aqueous dispersion of the amine group-containing acrylic resin particles (A) can be produced. [0074] From the viewpoint of dispersibility and storage stability, the acrylic resin particles (A) containing an amine group may generally have 10 to 5,000 nm, preferably 10 to 1,000 nm, more preferably 20 to 500 nm, and even more The average particle diameter is preferably in the range of 50 to 300 nm. [0075] In the present specification, the average particle diameter of the amine group-containing acrylic resin particles (A) is a value measured at 23 ° C. after dilution with deionized water in accordance with a conventional method using a submicron particle size distribution measuring device. As the sub-micron particle size distribution measuring device, for example, "COULTER N5 type" (trade name, manufactured by Beckman Coulter) can be used. The solid content concentration in the aqueous dispersion of the amine group-containing acrylic resin particles (A) is preferably 20 to 50% by mass, and more preferably 30 to 40% by mass. When the solid content concentration exceeds 50% by mass, emulsification becomes difficult, and obtaining of an aqueous dispersion may become difficult. If the solid content concentration is less than 20% by mass, the concentration of the solvent (mainly water) increases due to the low concentration. For example, it may become difficult to use it as a constituent component of an aqueous metal surface treatment agent. [Phosphate Compound (B)] The aqueous metal surface treatment agent of the present invention also contains a phosphate compound (B). The phosphoric acid-based compound (B) is a compound containing a phosphate group, a phosphonic acid group, or a salt thereof, and having water solubility. Examples of the phosphoric acid-based compound (B) include phosphoric acid, organic phosphonic acid, and salts thereof. [0078] The phosphoric acid includes, for example, orthophosphoric acid and condensed phosphoric acid, and the condensed phosphoric acid system includes metaphosphoric acid and polyphosphoric acid. Metaphosphoric acid is a cyclic phosphoric acid condensate including trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, and the like, and polyphosphoric acid is a chain-shaped phosphoric acid condensate including pyrophosphoric acid, tripolyphosphoric acid, and tetrapolyphosphoric acid. [0079] Examples of the organic phosphonic acid include a hydrocarbon methyl diphosphonic acid, a 1-hydrocarbylethane-1,1-diphosphonic acid (HEDP), and a 1-hydroxypropane-1,1-diphosphonic acid. Hydroxyl-containing organic phosphonic acids; 2-hydroxyphosphorylacetic acid, 2-phosphorylbutane-1,2,4-tricarboxylic acid (PBTC), and other carboxyl-containing organic phosphonic acids; nitrilotris (Methylenephosphonic acid) (NTMP), nitrilotris (vinylphosphonic acid), nitrilotris (propylenephosphonic acid), nitrogenbis (vinylphosphonic acid) mono (methylenephosphonic acid), nitrogen Bis (methylene phosphonic acid) mono (propylene phosphonic acid) and the like, the alkylene group is the same or different carbon number of 1 to 4 alkylene tris (trialkylene phosphonic acid); ethylene diamine Tetramethylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, ethylenediaminetetrapropylenephosphonic acid, etc., whose alkylene group is ethylenediaminetetraalkylenephosphonic acid having 1 to 4 carbon atoms; hexamethylene Methyldiaminetetramethylenephosphonic acid; diethylenetriaminepentamethylenephosphonic acid and the like. [0080] Examples of the salts of phosphoric acid and organic phosphonic acid include alkali metal salts (such as lithium, sodium, and potassium salts), alkaline earth metal salts (such as calcium, magnesium, and barium salts), and ammonium. Salt, etc. In addition, considering solubility, salts such as zinc, manganese, and nickel may also be used. [0081] In a case where the phosphate group or the phosphonic acid group is plural in one molecule of the phosphoric acid-based compound (B), one of these may be a salt, and all may be a salt. Moreover, a part of active hydrogen atoms of a phosphate group or a phosphonic acid group may be substituted with an alkali metal ion or an ammonium ion, or all of them may be substituted. [0082] These phosphate compounds (B) can be used alone or in combination of two or more kinds. [0083] The phosphoric acid-based compound (B) has the effect of improving the corrosion resistance of the surface-treated film while improving the storage stability of the surface-treating agent of the present invention. Among them, orthophosphoric acid and hydrocarbon methyl diphosphine are particularly effective. Acids and 1-hydrocarbylethane-1,1-diphosphonic acid are preferred. [0084] The blending amount of the phosphoric acid-based compound (B) is more preferably 0.5 to 10 with respect to the total solid content of the acrylic resin particles (A) containing amine groups from the standpoint of both corrosion resistance and water resistance. Mass%, preferably 3 to 8 mass%. [0084] [Fluorometallic acid and / or its salt (C)] The fluorometallic acid and / or its salt (C), which is blended as necessary in the aqueous metal surface treatment agent of the present invention, is such that the aqueous system of the present invention The surface treatment film obtained by the metal surface treatment agent is blended for the purpose of improving the corrosion resistance and the like. [0086] The fluorometal acid is an acid containing a fluorine atom and a metal. Examples of the metal include titanium, zirconium, hafnium, vanadium, magnesium, manganese, zinc, tungsten, molybdenum, aluminum, nickel, cobalt, and calcium. One or more metals. Among these, titanium or zirconium is particularly preferable because it is inexpensive and relatively easy to obtain as an industrial application. [0087] Examples of the fluorometal acid include hexafluorotitanic acid (H 2 TiF 6 ), hexafluorozirconic acid (H 2 ZrF 6 ), hexafluoroarsanoic acid (H 2 HfF 6 ), and hexafluoroaluminum. Acid (H 3 AlF 6 ), fluoboric acid (HBF 4 ), and the like. [0088] Examples of the salt of the fluorometal acid include the sodium salt, potassium salt, lithium salt, ammonium salt, amine salt, and zinc salt of the fluorometal acid. [0089] As the fluorometal acid and / or its salt (C), each of the above-mentioned fluorometal acids and their salts can be used alone or in combination of two or more. [0090] Among the fluorometal acids and / or their salts (C), hexafluorotitanic acid (H 2 TiF 6 ), hexafluorozirconic acid (H 2 ZrF 6 ), or the like is more suitable in terms of corrosion resistance. And other ammonium and amine salts of fluorometal acids. [0091] Fluorometallic acid and / or its salt (C), due to the generation of ions in water, the control of the corrosion potential of the metal surface in a corrosive environment, and the control of the redox reaction, the formation of an extremely thin film on the metal surface The density of a film and a film derived from a cross-linking reaction with a functional group in a film component is considered to have an effect of improving corrosion resistance. [0092] The blending amount of the fluorometal acid and / or its salt (C) is 1 to 5 mass% with respect to the total solid content of the amine group-containing acrylic resin particles (A), and preferably 2 to 4 Mass% is suitable from the viewpoints of improvement of corrosion resistance and stability of the treatment liquid. [Vanadium Compound (D)] The vanadium compound (D), which is blended in the aqueous metal surface treatment agent according to need, of the present invention is a corrosion-resistant surface treatment film obtained by using the water-based metal surface treatment agent of the present invention. Enhancement of sexuality, etc. The vanadium compound (D) is preferably water-soluble or water-dispersible. The vanadium compound (D) may be, for example, a carbonate, a phosphate, a nitrate, a sulfate, an acetate, or an oxide, or may be an acid anhydride or a hydrate. [0095] Examples of the vanadium compound (D) include ammonium metavanadate, sodium metavanadate, potassium metavanadate, vanadyl sulfate, vanadium oxide, and the like. Among them, from the viewpoint of solubility in an acidic aqueous solution, among others, , Preferably ammonium metavanadate, sodium metavanadate, potassium metavanadate, and vanadyl sulfate. [0096] The blending amount of the vanadium compound (D) is from the viewpoint of the stability of the treatment liquid, and is preferably 0.1 to 5% by mass relative to the total solid content of the amine group-containing acrylic resin particles (A). It is preferably 0.3 to 1% by mass. [Silane coupling agent and / or its hydrolyzed condensate (E)] The silane coupling agent and / or its hydrolyzed condensate (E) as required in the aqueous metal surface treatment agent of the present invention, It is the case that it can help to improve the adhesion with the surface of the substrate of the obtained surface-treated film, or to improve the corrosion resistance and water resistance of the film. [0098] Examples of the silane coupling agent include N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) -γ-aminopropylmethyl. Dimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane-hydrochloride, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylmethyldi Ethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethyl ether Oxysilane, hexamethyldisilazane, γ-anilinepropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, octadecyldimethyl [3- (trimethyl Oxysilyl) propyl] ammonium chloride, trimethylchlorosilane and the like. Among these, epoxy-containing silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane are more suitable. [0099] These silane coupling agents may be used alone or in combination of two or more kinds. [0100] The so-called hydrolyzed condensate of the above-mentioned silane coupling agent means an oligomer of the silane coupling agent which is hydrolyzed and condensed using the silane coupling agent as a raw material. [0101] The blending amount of the silane coupling agent and / or its hydrolyzed condensate (E) is 0.1 to 20% by mass relative to the total solid content of the amine group-containing acrylic resin particles (A), preferably It is 2 to 15% by mass, and is more suitable from the viewpoints of storage stability of the surface treatment agent, corrosion resistance of the obtained surface treatment film, and surface coating adhesion. [Polyolefin Wax (F)] In the aqueous metal surface treatment agent of the present invention, the polyolefin wax (F) blended as necessary is a component that can impart lubricity to the obtained surface-treated film. [0103] Examples of the polyolefin wax (F) include polyethylene, polypropylene, and microcrystals. [0104] The blending amount of the polyolefin wax (F) is from the point of molding processability, corrosion resistance, etc., and is preferably 0.1 to 10 masses relative to the total solid content of the aqueous metal surface treatment agent as the solid content amount. %, Preferably in the range of 0.3 to 8% by mass. [0105] The average particle diameter of the polyolefin wax (F) is from 0.1 to 3 μm, and preferably from 0.5 to 2 μm from the viewpoint of maintaining a low dynamic friction coefficient. [Solvent and Other Components] The aqueous metal surface treatment agent of the present invention is aqueous. The term "water-based" means that the solvent contains water as a main component. The solvent may be only water, but for the purpose of adjusting the dryness of the film and the viscosity of the treatment agent, it is also possible to use one or two or more kinds of monovalent or polyvalent alcohols, ketones, ether alcohols, and other water-soluble substances Organic solvents. The aqueous metal surface treating agent of the present invention preferably contains 70% by mass or more of water in the solvent, and particularly preferably contains 80% by mass or more. [0107] The aqueous metal surface treatment agent of the present invention may be blended with a pH adjuster (acid or base), an aqueous solution containing titanium, a filler, and a colloidal two, as required, in addition to the solvent and the components described above. Silicon oxide, colorant, surfactant, antifoaming agent, leveling agent, antibacterial agent, etc. In this case, it can be added within a range that does not impair the performance of the obtained treatment film or the stability of the surface treatment agent. [0108] As the pH adjusting agent, for example, acetic acid, formic acid, lactic acid, ammonia, and the like can be suitably used. [0109] From the viewpoint of liquid stability, the aqueous metal surface treatment agent of the present invention is preferably pH 3 to 7, and more preferably pH 3.5 to 6.5. The solid content concentration of the aqueous metal surface treatment agent of the present invention is preferably from 5 to 30% by mass, and particularly preferably from 10 to 25% by mass from the viewpoints of coating workability and stability of the treatment liquid. [0110] The above-mentioned aqueous solution containing titanium may be effective in improving the corrosion resistance of the obtained treated film. The titanium-containing aqueous liquid system can be obtained by reacting at least one titanium compound selected from hydrolyzable titanium, hydrolyzable titanium low condensate, titanium hydroxide, and titanium hydroxide low condensate with a hydrogen peroxide solution (for example, refer to (Japanese Patent Laid-Open No. 2006-22370). In the case of blending an aqueous solution containing titanium, the blending amount is preferably 5.0 mass by mass with respect to the total solid content of the amine group-containing acrylic resin particles (A) from the viewpoint of storage stability and the like. %the following. [0111] Examples of the filler include fine powders of silicon dioxide, talc, barium oxide, calcium carbonate, mica, and the like, and examples thereof include users of extender pigments. Examples of the colorant include colored pigments and dyes. [Metal surface treatment method] The metal surface treatment method of the present invention is a metal surface treatment method in which the aqueous metal surface treatment agent of the present invention is coated on a metal substrate and dried. The method is based on a metal substrate. A method for forming a treatment film on the surface of a material by the aqueous metal surface treatment agent of the present invention. In the present invention, the "treatment film" is not only a continuous treatment film, but also includes a discontinuous treatment product that cannot be a continuous treatment film due to a small amount of treatment adhesion. [0113] The above-mentioned so-called metal substrate is not subject to any restrictions as long as it is a metal material, and examples thereof include iron, copper, aluminum, tin, zinc, and alloys containing these metals, and plated steel sheets using such metals. Or vapor deposition products. Among them, metal plates derived from the above metals can be suitably used. [0114] Examples of the metal plate used as the metal substrate include cold-rolled steel sheets, molten galvanized steel sheets, galvanized steel sheets, and zinc alloys (zinc-iron, zinc-aluminum, zinc-nickel and other alloys). ) Plated steel, aluminum plated steel, stainless steel plate, copper plated steel plate, tin plated steel plate, aluminum plate, copper plate, etc. Among them, a galvanized steel sheet (including both a molten galvanized steel sheet and an electrogalvanized steel sheet) and a zinc alloy plated steel sheet are more suitable. [0115] Before coating the aqueous metal surface treatment agent of the present invention on the above-mentioned metal substrate, the metal substrate may be surface-adjusted by 1 or 2 or more, such as degreasing, pickling, hot water washing, washing agent washing, etc. In all cases, sufficient water washing is preferred over the end. In addition, the liquid temperature of the aqueous metal surface treatment agent of the present invention at the time of coating may be normal temperature, or it may be cooled or warmed as required. [0116] The first layer may be formed on the surface of the metal substrate by other surface treatment. The first layer is formed for the purpose of enhancing the adhesion between the treatment film and the metal surface derived from the aqueous metal surface treatment agent of the present invention, and is preferably a chromium-free surface treatment agent. [0117] On the above metal substrate, a roll coating method, a spray coating method, a bristle coating method, an electrostatic coating method, a dipping method, an electro-painting method, a curtain coating method, and a roll can be used. A known method such as a coating method is to coat and dry the aqueous metal surface treatment agent of the present invention to form a surface-treated film. In addition, the surface treatment film may be formed on only one side of the metal substrate or on both sides. [0118] Although the film amount of the treatment film derived from the aqueous metal surface treatment agent of the present invention is not particularly limited, from the viewpoint of corrosion resistance and processability, it is generally suitable to be between 0.4 and 3.6 g / m 2 . The range of 0.5 to 2.5 g / m 2 is preferred. Although the drying conditions of the processing film may be appropriately set, in the case where the coated article is continuously coated by a coil coating method or the like, generally, the material can reach 60 to 200 ° C, which is the highest temperature of the material. It is heated at 70 to 120 ° C for 5 to 60 seconds. In the case of applying by a batch method, for example, it can be performed by heating at an ambient temperature of 100 to 180 ° C. for 1 to 30 minutes. [Surface-treated metal plate] The surface-treated metal plate of the present invention is surface-treated on the surface of a metal substrate with the aqueous metal surface-treating agent of the present invention. The surface-treated metal plate of the present invention has a metal substrate having a plate-like shape and can be obtained by the above-mentioned metal surface treatment method of the present invention. [0120] In the surface-treated metal plate of the present invention, the film amount of the treatment film derived from the water-based metal surface treatment agent of the present invention is in the range of 0.4 to 3.6 g / m 2 , preferably 0.5 to 2.5 g / m 2 , from From a viewpoint of corrosion resistance and processability, it is suitable. [0121] On the treatment film of the surface-treated metal plate of the present invention, for the purpose of improving the aesthetics, improving the durability, and improving other functions, etc., an upper film such as a colored coating film, a transparent coating film, or the like can be formed. Although the formation of the upper layer film may be performed before the forming process of the surface-treated metal plate of the present invention, it is preferably performed after the forming process. [Examples] [0122] Hereinafter, the present invention will be described more specifically with reference to Preparation Examples, Examples and Comparative Examples. However, the present invention is not limited by these examples. [0123] In each example, "parts" and "%" are based on quality, except for the conditions stated otherwise. The film amount of the treated film is based on the dry film amount. [0124] [Preparation Example of Shell of Acrylic Resin Particles Containing Amine Group] (Production of Amine-Containing Acrylic Resin (S1) Solution) A thermometer, thermostat, stirring device, reflux condenser, nitrogen introduction tube, and In the reaction vessel of the dropping device, 50 parts of propylene glycol (PG) monomethyl ether was added, and the mixture was stirred and mixed in a nitrogen stream. After raising the temperature to 105 ° C, 20 parts of styrene (St) and methyl methacrylate (MMA) 45 Parts, 5 parts of n-butyl acrylate (nBA), 5 parts of 2-hydroxyethyl acrylate (2-HEA), and 25 parts of 2- (N, N-dimethylamine) ethyl acrylate (DMAEMA) The mixture was mixed with 2 parts of tert-butylperoxy-2-ethylhexanoate ethyl ester (PBO) and 15 parts of propylene glycol (PG) monomethyl ether, and dropped into the mixture at the same time for 3 hours. It is aged for 1 hour. [0125] Then, it was diluted with propylene glycol monomethyl ether, and stirred and mixed for 30 minutes to obtain an amino group-containing acrylic resin (S1) solution having a solid content concentration (NV 値) of 45%. The amine value of the obtained amine group-containing acrylic resin (S1) was 90 mgKOH / g, the hydrocarbon group value was 22 mgKOH / g, and the weight average molecular weight (Mw) was 45,000. [Production of amine group-containing acrylic resin (S2) to (S14) solution] In the same manner as above, according to the composition shown in the following Table 1 and Table 2, an amine group-containing acrylic resin (S2) ~ (S14) solution. [0128] [0129] [0130] [Synthesis Example of Core / Shell Emulsification] (Production of Amine-containing Acrylic Resin Particles (A1) Aqueous Dispersion Liquid) A thermometer, a thermostat, a stirring device, a reflux condenser, a nitrogen introduction tube, and a dropping device are provided. In the reaction container, 111 parts of the amine group-containing acrylic resin (S1) solution with a solid content concentration of 45% was added, and the mixture was stirred and heated to 80 ° C. until the solid content concentration became 69%, and the solvent was removed under reduced pressure. [0131] Next, it was cooled to 60 ° C, and 20 parts of styrene, 20 parts of methyl methacrylate, 7 parts of n-butyl acrylate, and 2-hydroxyethyl acrylate (2-HEMA) were added to the reaction vessel. 2.5 parts, 0.5 parts of methyl acrylate (AMA), 3 parts of acetic acid, and stirred for 15 minutes. [0132] Next, after cooling to 40 ° C., 180 parts of deionized water (DIW) was added dropwise over a period of one hour. After the dropwise addition was completed, aging was performed for 15 minutes. Thereafter, the temperature was raised to 60 ° C, and 0.3 parts of sodium ascorbate and 0.3 parts of a 5% ferrous sulfate aqueous solution were added. Then, a mixture of 0.4 parts of a 30% hydrogen peroxide solution and 30 parts of deionized water was added dropwise over a period of one hour, followed by 1 hour. Matured to obtain an amine group having an average particle diameter of 75 nm [average example diameter measured under conditions of 23 ° C using a submicron particle size distribution measuring device "COULTER N5" (manufactured by Beckman Coulter)] and a solid content concentration of 30% Aqueous dispersion of acrylic resin particles (A1). The amine value of the obtained amine group-containing acrylic resin particles (A1) was 45 mgKOH / g, the hydrocarbon group value was 23 mgKOH / g, and the weight average molecular weight was 1,200,000. [Production of A2 to A15] In the same manner as above, according to the composition shown in Tables 3 and 4 below, an aqueous dispersion of an amine group-containing acrylic resin (A2) to (A15) was obtained. [0134] In the amine group-containing acrylic resin particles (A1) to (A15), the composition ratio (mass ratio) between the core portion and the shell portion is as follows. (A1) ~ (A13) Core: Shell = 50: 50 (A14) Core: Shell = 90: 10 (A15) Core: Shell = 10: 90 [0136] [0137] [Production of Amino Group-Containing Acrylic Resin Particles (A16) Aqueous Dispersion Liquid] Except using 111 parts of an amino group-containing acrylic resin (S13) solution with a solid content concentration of 45% and 6 parts of acetic acid, The acrylic resin particle (A1) aqueous dispersion was the same, and an amine group-containing acrylic resin particle (A16) aqueous dispersion having an average particle diameter of 55 nm and a solid content concentration of 30% was obtained. The obtained amine group-containing acrylic resin particles (A16) had an amine value of 90 mgKOH / g, a hydrocarbon group value of 23 mgKOH / g, and a weight average molecular weight of 1,200,000. [Production of Amino Group-Containing Acrylic Resin Particles (A17) Aqueous Dispersion Liquid] Except using 111 parts of an amino group-containing acrylic resin (S14) solution with a solid content concentration of 45% and 0.6 parts of acetic acid, The acrylic resin particle (A1) aqueous dispersion was the same, and an amine group-containing acrylic resin particle (A17) aqueous dispersion having an average particle diameter of 240 nm and a solid content concentration of 30% was obtained. The amine value of the obtained amine group-containing acrylic resin particles (A17) was 9 mgKOH / g, the hydrocarbon group value was 23 mgKOH / g, and the weight average molecular weight was 1,200,000. [Production of Amine-containing Acrylic Resin Particles (A18) Aqueous Dispersion Liquid] In a reaction vessel equipped with a thermometer, a thermostat, a stirring device, a reflux condenser, a nitrogen introduction tube, and a dropping device, deionized water 110 was added. 8 parts of "ADEKA REASOAP ER-40" (trade name, made by ADEKA Co., Ltd., emulsifier, active ingredient 60%), stirred and mixed in a nitrogen stream, and heated to 60 ° C. [0141] Next, the amount of 5% of the total amount of the monomer emulsion for the core portion described below, 10% of "Kayabutyl H-70" (trade name, manufactured by KAYAKU AKZO Corporation, polymerization initiator, tert- 1 part of butyl hydroperoxide, 70% of active ingredient) aqueous solution and 1 part of 3% sodium ascorbate aqueous solution were added to the reaction container, and kept at 60 ° C. for 1 hour. [0142] After that, 7 parts of 10% "Kayabutyl H-70" aqueous solution and 10 parts of 3% sodium ascorbate aqueous solution were added to the remainder of the monomer emulsion for the core part described below for 2 hours, and the solution was dropped at the same temperature. In the reaction container, aging was performed for 1 hour after the completion of the dropping. [0143] Next, 5 parts of a monomer emulsion for the following shell part, 10% of "Kayabutyl H-70" aqueous solution and 10 parts of 3% sodium ascorbate aqueous solution were added dropwise over 2 hours, and after ripening for 1 hour, acetic acid was added. 0.6 parts were added to the reaction container and kept for 30 minutes. [0144] Next, it was cooled to 30 ° C. and diluted with deionized water to obtain an amino group-containing acrylic resin particle (A18) aqueous dispersion liquid having an average particle diameter of 170 nm and a solid content concentration of 30%. The amine value of the obtained amine group-containing acrylic resin particles (A18) was 10 mgKOH / g, the hydrocarbon group value was 16 mgKOH / g, and the number average molecular weight was about 65,000. Monomer Emulsion for Shell: 20 parts of deionized water, 3.5 parts of "ADEKA REASOAP ER-40", 3 parts of styrene, 19 parts of methyl methacrylate, n-butyl methyl acrylate (nBMA ) 3 parts, 2 parts of n-butyl acrylate, 2 parts of methyl 2-hydroxyethyl acrylate, and 1 part of 2- (N, N-dimethylamine) ethyl methacrylate. Thing. Monomer emulsion for core: 40 parts of deionized water, 7 parts of "ADEKA REASOAP ER-40", 44 parts of methyl methacrylate, 17 parts of n-butyl methyl acrylate, and n-butyl A monomer emulsion made by mixing 5 parts of methacrylate, 2 parts of methyl 2-hydroxyethyl acrylate, and 2 parts of 2- (N, N-dimethylamine) ethyl acrylate. [Production of Amine-containing Acrylic Resin Particles (A19) Aqueous Dispersion Liquid] In a reaction vessel equipped with a thermometer, a thermostat, a stirring device, a reflux condenser, a nitrogen introduction tube, and a dropping device, propylene glycol monomethyl was added. 50 parts of ether were stirred and mixed in a nitrogen stream, and after raising the temperature to 105 ° C, 20 parts of styrene, 45 parts of methyl methacrylate, 5 parts of n-butyl acrylate, 5 parts of 2-hydroxyethyl acrylate, A mixture of 25 parts of methyl 2- (N, N-dimethylamine) ethyl acrylate and 2 parts of tert-butylperoxy-2 ethylhexanoate was added dropwise over a period of 3 hours. It is aged for 1 hour. [0149] After cooling to 60 ° C, 14 parts of acetic acid was added to the reaction container and kept for 30 minutes, and then diluted with deionized water (DIW) to obtain amine-containing acrylic acid having an average particle diameter of 25 nm and a solid content concentration of 20%. Resin particle (A19) aqueous dispersion. The amine value of the obtained amine group-containing acrylic resin particles (A19) was 90 mgKOH / g, the hydrocarbon group value was 23 mgKOH / g, and the weight average molecular weight was 45,000. [0151] In addition, the amine group-containing acrylic resin particles (A16) to (A19) are used for comparison. For convenience, the amine group-containing acrylic resin particles (A16) to (A19) are used, but they are not The resin particles of the amine group-containing acrylic resin particles (A) of the aqueous metal surface treating agent according to the present invention. [0152] In the amine group-containing acrylic resin particles (A16) to (A18), the composition ratio (mass ratio) between the core portion and the shell portion is as follows. (A16) ~ (A17) Core: Shell = 50:50 (A18) Core: Shell = 70:30 [0153] [Examples and Comparative Examples] Each component was blended in accordance with the blending ratio shown in the following table, adjusted by adding deionized water so that the solid content concentration became 15% by mass, and sufficient stirring was performed to obtain each metal surface treatment agent. . The blending amounts in the following tables are based on the mass of solid ingredients or the mass of active ingredients. In the following table, amine group-containing acrylic resin particles (A), phosphoric acid-based compounds (B), fluorometal acids and / or their salts (C), vanadium compounds (D), and silane coupling The components of the agent and / or its hydrolyzed condensate (E) and polyolefin wax (F) are as follows. In the following table, the components A1 to A19 of the amine group-containing acrylic resin particles (A) are obtained from the above [Core / Shell emulsified synthesis example], and the amine group-containing acrylic resin particles (A1) to ( A19) Aqueous dispersion [0157] In the following table, the component B1 of the phosphoric acid-based compound (B): orthophosphoric acid B2: 1-hydroxyethylene-1,1-diphosphonic acid B3: nitrilotris Methylphosphonic acid) [0158] In the following table, the components of the fluorometallic acid and / or its salt (C) are C1: ammonium hexafluorotitanate C2: ammonium hexafluorozirconate C3: hexafluorotitanate C4: six Fluorozirconic acid C5: Hexafluorophosphonic acid [0159] In the following table, the component D1 of the vanadium compound (D): ammonium metavanadate D2: sodium metavanadate D3: vanadyl sulfate [0160] In the following table , Silane coupling agent and / or its hydrolyzed condensate (E), component E1: γ-methacryloxypropyltrimethoxysilane E2: 3-glycidoxypropyltrimethoxysilane E3: 3 -Mercaptopropyltrimethoxysilane [0161] In the following table, the component F1 of the polyolefin wax (F): CHEMIPEARL W-700 manufactured by Mitsui Chemicals Co., Ltd. Average particle diameter 1.5 μm F2: manufactured by Gifu Shellac Manufacturing Co., Ltd. HIDISPER AC-90 average particle diameter 1.3 μm F 3: HIDISPER A-206N manufactured by Gifu Shellac Manufacturing Co., Ltd. average particle diameter 1 μm F4: HIDISPER AG-73 manufactured by Gifu Shellac Manufacturing Co., Ltd. average particle diameter 0.1 μm F5: CHEMIPEARL W-500 manufactured by Mitsui Chemicals Co., Ltd. average particle diameter 2.5 μm [0162] [Water resistance test] (Production conditions of surface-treated metal plate) The adhesion amount of metal plating is 20g / m 2 on one side, and the two sides of galvanized steel plate with a thickness of 0.8mm are alkaline degreasing agents at a concentration of 2%. (Made by Japan Cee. Bee. Chemical Co., Ltd. under the trade name "KEMICLEANER 561B", equivalent to Silicic Acid No. 3) spray degreasing at a liquid temperature of 65 ° C for 60 seconds, and then at a liquid temperature of 50 ° C, Wash with hot water under the spraying time of 20 seconds, and obtain an alkaline degreased metal plate after drying. In the obtained alkaline degreased metal plate, the surface treatment agent obtained in the above-mentioned [Examples and Comparative Examples] was coated with a coating rod so that the dry film weight became 0.9 g / m 2 so that the maximum value of the metal plate reached It heat-dried for 12 seconds so that temperature might become 60 degreeC, and each surface-treated metal plate was obtained. [0163] (Evaluation Criteria) Each surface-treated metal plate was left at room temperature for 5 minutes, and deionized water was placed on the surface-treated metal plate to a diameter of 3 cm, and then the water droplets were removed with gauze or the like. The change in the appearance of the treated surface was visually observed, and evaluation was performed on the following criteria, and the results are shown in the following table. ：: No change was observed at all. ○: Slightly whitened. ×: Significantly whitened. In addition, use "◎" or "○" as a practical level. [Copper sulfate discoloration test] (Surface treatment metal plate manufacturing conditions) The amount of metal plating adhered was 20 g / m 2 on one side, and the two sides of the galvanized steel sheet with a thickness of 0.8 mm were coated with an alkaline degreaser at a concentration of 2% ( Cee. Bee. Chemical Co., Ltd. (trade name: "KEMICLEANER 561B", equivalent to Silicic Acid No. 3), spray-degreased at a liquid temperature of 65 ° C for 60 seconds, and then sprayed at a liquid temperature of 50 ° C. Wash with hot water under the condition of 20 seconds, and obtain an alkaline degreased metal plate after drying. In the obtained alkaline degreased metal plate, the surface treatment agent obtained in the above-mentioned [Examples and Comparative Examples] was coated with a coating rod so that the dry film weight became 0.9 g / m 2 so that the maximum value of the metal plate reached It heat-dried for 12 seconds so that temperature might become 80 degreeC, and each surface-treated metal plate was obtained. [0165] (Evaluation criteria) On the treated surface of each surface-treated metal plate, 20 μL of a copper sulfate aqueous solution with a concentration of 5% was placed. After 15 seconds, the copper sulfate aqueous solution was removed with gauze or the like, and the appearance change of the treated surface was visually observed. The evaluation was performed on the following criteria, and the results are shown in the following table. ：: No discoloration was observed at all. ○: Slight discoloration was observed. ×: Discoloration was clearly observed. In addition, use "◎" or "○" as a practical level. [Corrosion resistance test] (Surface-treated metal plate manufacturing conditions) Each surface-treated metal plate was obtained under the same conditions and methods as the copper sulfate discoloration test described above. [0167] (General part evaluation criteria) Each surface-treated metal plate was cut at a width of 7 cm and a length of 15 cm to obtain a surface-treated metal test plate for a corrosion resistance test. The end surface and the back surface of the obtained test plate were sealed, and the area where rust was generated in the treated surface was evaluated by the salt number spray method (SST) in accordance with JIS Z 2371, and the rating number was 9 Evaluation was performed on the following criteria, and the results are shown in the following table. SS: The time from the rating number to 9 is 96 hours or more. S: The time from the rating number to 9 is 72 hours or more and less than 96 hours. A: The time from the rating number to 9 is 48 hours or more and less than 72 hours. B: The time from the rating number to 9 is 24 hours or more and less than 48 hours. C: The time until the rating number becomes 9 is less than 24 hours. Also, use "SS", "S", "A", or "B" as a practical level. [0168] (Evaluation Criteria for the Processing Section) Each surface-treated metal plate was cut with a width of 7 cm and a length of 15 cm, and was extruded with an Eriksson processing machine to a height of 7 mm to obtain a processing section having a dome-shaped processing section. Surface treatment metal test plate for corrosion resistance test. The end surface and the back surface of the obtained test plate were sealed, and the time until rust was generated in the top of the dome-shaped processed portion was evaluated by the following criteria by the salt water spray test (SST) according to JIS Z 2371. The results are as follows:表表 描述。 Table representation. S: The time until rust is generated is 72 hours or more. A: The time until rust is generated is 48 hours or more and less than 72 hours. B: The time until the occurrence of rust is 24 hours or more and less than 48 hours. C: The time until the occurrence of rust is less than 24 hours. Also, use "S", "A", or "B" as a practical level. [0169] [Alcohol friction resistance test] (Surface treatment metal plate production conditions) Each surface treatment metal plate was obtained under the same conditions and methods as the above-mentioned copper sulfate discoloration test. [Evaluation Criteria] After permeating 4 overlapping gauze with ethanol, rubbing back and forth 10 times with a load of 1 kg on the treatment surface of each surface-treated metal plate, visually observing changes in the appearance of the treatment surface, and evaluating based on the following criteria The results are shown in the following table. ：: No change was observed at all. ○: Slight friction marks were observed. ×: Marks of friction were clearly observed. In addition, use "◎" or "○" as a practical level. [Dynamic Friction Coefficient Measurement Test] (Surface Treatment Metal Plate Production Conditions) Each surface treatment metal plate was obtained under the same conditions and methods as the above-mentioned copper sulfate discoloration test. (Evaluation Criteria) For each surface-treated metal plate, a bowden abrasion tester (manufactured by Kobelco Kogyo Co., Ltd., Zonda-type adhesion sliding tester, friction part ball indenter 3/16 inch steel ball, 200gf load, A friction test was performed at a friction speed of 7 rounds / minutes), and a dynamic friction coefficient was measured. The number of times of friction obtained until the value of the obtained dynamic friction coefficient became 0.4 was evaluated on the following basis, and the results are shown in the following table. S: The number of frictions until the value of the dynamic friction coefficient reaches 0.4 is 20 or more. A: The number of times of friction until the value of the dynamic friction coefficient reaches 0.4 is 10 times or more and less than 20 times. B: The number of times of friction until the value of the dynamic friction coefficient reaches 0.4 is 5 or more and less than 10 times. C: The number of times of friction until the value of the dynamic friction coefficient is 0.4 is less than 5 times. Also, use "S", "A", or "B" as a practical level. [0173] [0174] [0175] [0176] [0177] [0178] From the above examples and comparative examples, the surface-treated metal plate coated with the surface-treating agent of the present invention is based on water resistance and corrosion resistance (especially, the surface-treated metal plate processed by Eriksson) Corrosion resistance) and ethanol friction resistance are excellent, and it can meet the performance of copper sulfate discoloration test and dynamic friction coefficient. [0179] Although the present invention has been described in detail and with reference to specific embodiments, those skilled in the art to which the present invention pertains may add various changes or modifications without departing from the spirit and scope of the present invention. It is a matter of no doubt. This application is based on the Japanese patent application (Japanese Patent Application No. 2016-205570) filed on October 19, 2016, the contents of which are incorporated herein by reference.