TW201012881A - Aqueous coating composition - Google Patents

Aqueous coating composition Download PDF

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Publication number
TW201012881A
TW201012881A TW098126755A TW98126755A TW201012881A TW 201012881 A TW201012881 A TW 201012881A TW 098126755 A TW098126755 A TW 098126755A TW 98126755 A TW98126755 A TW 98126755A TW 201012881 A TW201012881 A TW 201012881A
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Taiwan
Prior art keywords
acid
parts
mass
compound
resin
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TW098126755A
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Chinese (zh)
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TWI392711B (en
Inventor
Hideki Matsuda
Remi Kasai
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Kansai Paint Co Ltd
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Publication of TW201012881A publication Critical patent/TW201012881A/en
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Publication of TWI392711B publication Critical patent/TWI392711B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

(57) Abstract: A non-chromium water-base coating composition which can form a coating film excellent in chemical resistance, corrosion resistance of flat areas of metal sheets, corrosion resistance of worked areas or end faces of metal sheets, and adhesion; and coated metal sheets provided with coating films excellent in these properties. A water-base coating composition comprising a cationic resin (A), a polyisocyanate curing agent (B), and a rust-preventive pigment mixture (C), characterized in that the rust-preventive pigment mixture (C) has the following composition: Rust-preventive pigment mixture (C): a composition comprising at least one vanadium compound (c 1 ) selected from among divanadium pentaoxide, calcium vanadate and ammonium metavanadate, a silicon compound Act, and a calcium salt (c3) of a phosphoric acid, wherein the amounts of the vanadium compound cycle, the silicon compound Icy, the calcium salt Act, and the rust-preventive pigment mixture ECU are 1 to 30 parts by mass, 1 to 30 parts by mass, 1 to 30 parts by mass, and 3 to 90 parts by mass, respectively, per 100 parts by mass of the total solid matter of the resin (A) and the curing agent (B).

Description

201012881 六、發明說明： I：發明戶斤屬之技術領域3 發明領域 本發明係關於一種可形成耐藥品性、金屬板之平面部 的而ί姑性、金屬板之加工部和端面部的财姓性及附著性優 良的塗膜之水性塗料組成物及具有由該水性塗料組成物形 成的塗膜之塗裝金屬板。 I：先前技術3 〇 發明背景 過去以來，用線圈塗布(coil coating)等塗裝而成的預塗 . 鋼板等之預塗金屬板，被廣泛地當做建築物的屋頂、牆壁、 . 百葉窗、車庫等之建築材料，各種家電製品、配電盤、冷 凍展示櫃、鋼製傢具及廚房器具等之住宅相關商品使用。 在由預塗金屬板製成這些住宅相關商品上，通常是將 預塗金屬板切斷經加壓成型接合成。因此，在這些住宅相 關商品上，多數存在著切斷面的金屬露出部或因壓力加工 # 而產生的裂紋發生部。因為上述金屬露出部或裂紋發生 部，與其他部分相比耐蝕性容易降低，故一般是採行使預 塗金屬板的的底塗塗膜中含有鉻系防銹顏料以提昇耐蝕性 的作法。 然而，鉻系防銹顏料或含有防銹性優良的6價鉻，或者 會生成6價鉻。該6價鉻從對人體的健康面、環境保護的觀 點來看會構成問題。 截至目前為止，非鉻系防銹顏料已有磷酸鋅、三聚磷 201012881 酸銘、翻酸鋅等為數眾多的產品出現在市場上，作為組合 非鉻系顏料的底漆，則有各種產品被提出。此外，從環境 問題出發，為降低揮發性有機化合物(v〇c)，水性塗料的開 發一直受到需求。 例如，專利文獻1中記載，在環氧樹脂和酚酸樹脂的展 色劑成分中混合，矽酸鈣和釩酸磷的組合之防銹顏料，或 碳酸鈣和矽酸鈣與磷酸鋁及釩酸磷的組合之防銹顏料而成 的塗料。 另外，專利文獻2中記載，在聚醋中混合磷酸；旗與氧 化錳.氧化釩燒結物作為防銹顏料的塗料和，混舍碘酸鈣與 氧化釩的塗料。 然而，將專利文獻1及2中記載的防銹顏料應用於水性 塗料時，與使用鉻系顏料的塗料相比耐蝕性羞，尤其在 金屬板之加工部及端面部的耐蝕性不足。另外，有耐鹼性 或耐酸性等之耐藥品性或<水性差的情況。 另外，專利文獻3中記載一種塗料組成物，其係在含有 祕或環氧基的有機樹脂和硬化娜成的展色冑成分中’ 含有吸油量3G〜2〇Gml/lGGg、細孔容積〇 〇5〜丨2ml/g之二 氧化石夕微粒子的塗料，而且由該塗料形成的硬化塗膜之玻 璃轉移/皿度在4〇〜125°〇的範圍内。然而，將專利文獻3中 載之—氧化矽微粒子應用於水性塗料而獲得的塗膜，與 絡系顏料的塗料相比，耐姓性及耐藥品性差，尤其在 金屬板端面部的耐蝕性不足。 卜專利文獻4中揭示一種耐蝕性優良的無鉻塗裝鋼 201012881 板，特徵在於其係將，混合了選自磷酸鎂、磷酸鋅、磷酸 氫鎂、三聚磷酸二氫鋁、矽酸鈣的一種或兩種以上之非鉻 系防銹顏料的底塗塗膜和，混合了四烷氧矽烷的部分加水 分解縮合物（partial hydrolysis-condensation product of tetra-alkoxysilane)作為親水劑之面漆塗膜’依順積層於鍍層表 面。 另外，專利文獻5中揭示一種以含有平均粒徑〇.4〜 0.6μηι的内部凝膠化硬質聚合物粒子(a)、水分散性二氧化矽 ❹ （b)、縮水甘油氧基烧基-三烧氧基石夕貌（glycidoxyalkyl trialkoxysilanes)(c)、有機飢化合物(d)、水分散性氨醋樹脂 . (urethane resin)(e)、錯化合物（f)及填酸氣二録（g)的水性防 . 銹塗布劑組成物處理過之塗裝鍍鋅系鋼板。 但是，塗裝專利文獻4或專利文獻5中記載之含有防銹 顏料的塗料而獲得之塗膜，與塗裝含有鉻系顏料的塗料而 獲得之塗膜相比，耐蝕性及耐藥品性差’尤其在金屬板端 面部的耐性不足。 # 專利文獻1 :特開平11-61001號公報 專利文獻2 :特開2000-199〇78號公報 專利文獻3 :特開2000-129163號公報 專利文獻4 :特開2007-260953號公報 專利文獻5 :特開2008-8Π85號公報 【韻^明内容】 發明概要 發明欲解決之課題 201012881 本發明之課題在於找出—種可以形成耐藥品性、金屬 板之平面β的耐μ性、金屬板之加工部和端面部的耐触性 及附著性優良的塗狀祕$水㈣料組成物，並提供一 種具有該塗膜性能優良之塗膜的塗裝金屬板。 用以欲解決課題之手段 因此，本發明人等為解決習知之上述問題，反復專心 研究，結果發現藉由在陽離子性樹脂(Α)與多異氰酸酯硬化 劑(Β)中，添加以預定量混合特定的釩化合物（cl)、矽化合 物（c2)及磷酸系鈣鹽（C3)而成之防銹顏料混合物（c)做成水 性塗料組成物的方式，可以形成不僅耐藥品性、塗裝金屬 板之平面部的对触性’在塗裝金屬板等的加工部和端面部 之耐蝕性亦優良之塗膜，終而完成本發明。 亦即本發明係關於以下之水性塗料組成物。 1. 一種含有陽離子性樹脂(A)、多異氰酸酯硬化劑 及下述防銹顏料混合物（C)的水性塗料組成物。 防銹顏料混合物（C)由：五氧化二釩、釩酸鈣及偏釩酸 銨之中的至少1種質飢化合物（Cl)、石夕化合物（C2)及填酸系 鈣鹽(c3)組成，且相對於該樹脂(A)及該硬化劑(B)之合計固 體含量100質量份， 該釩化合物（cl)之量為1〜3〇質量份、矽酸化合物（C2) 之量為1〜30質量份及該磷酸系鈣鹽(c3)之量為1〜3〇質量 份，並且該防銹顏料混合物（C)之量為3〜90質量份。 2. 上述第1項記載之水性塗料組成物，其中陽離子性樹 脂(A)為含氨基環氧樹脂。 201012881 3. 上述第1項記載之水性塗料組成物，其付化合物 (^為’選自石夕酸金屬鹽、二氧化發微粒子及金屬離子交換 二氧化矽微粒子的至少1種。 4. 上述第1項記載之水性塗料組成物其中磷酸系鈣鹽 ⑹)為，磷酸鈣、磷酸一氫鈣、磷酸二氯药及三聚磷酸約之 中的至少1種。 5. 上述第1項記载之水性塗料組成物，其相對於陽離子 性樹脂(A)及多異氰酸酯（B)的固體含量合計，含有〇丨〜忉 Φ 質量份的Resole型酚醛樹脂。 6. —種塗膜形成方法，特徵在於，其係在金屬板上， - 形成用上述第1項記載之水性塗料組成物獲致的硬化塗 ' 膜，並在忒硬化塗膜上形成至少1種以上之面漆塗料的塗 膜。 7. —種塗裝金屬板，其具有用上述第6項記載之塗膜形 成方法獲得的塗膜。 8. —種塗裝物品，係藉加工上述第7項記載之塗裝金屬 9 板而獲得。 發明效果 本發明之含有特定的防銹顏料混合物之水性塗料組成 物，因不含鉻系防銹顏料且為水性塗料，故在環境衛生方 面是有利的。 以塗裝本發明之水性塗料組成物的方式獲得的塗膜， 耐藥品性優良，而且不僅塗裝金屬板之平面部的耐蝕性優 良，在用含有習知之非鉻系防銹顏料的水性塗料難以達成 201012881 之塗裝金屬板的加工部和端面部的耐钱性或附著性上，亦 可發揮優良的效果。 此外，在未施行化學轉化處理的熔融鍍辞鋼板(GI鋼板) 上，用塗裝本發明之水性塗料組成物並經加熱乾燥而獲得 的硬化塗膜加以被覆之塗裝鋼板，與在施行過化學轉化處 理的熔融鍍鋅鋼板(GI鋼板)上’用含有鉻酸鹽系防銹顏料的 硬化塗膜予以被覆的塗裝鋼板，可以具有同等以上的财敍 性。由此，亦可省略化學轉化處理程序（參見第丨圖），對塗 裝線的省程序化和省資源化是有利的。 圖式簡單說明 [第1圖]示意連續線圈塗裝線之一例。 [第2圖]示意含有本發明之水性塗料組成物的塗膜之 塗膜構造的一個例子。 【實施方式;1 用以實施發明之形態 本發明之水性塗料組成物係關於一種以含有特定量的 陽離子性樹脂(A)與多異氰酸酯硬化劑(B)及特定的防銹顏 料混合物（C)為特徵之水性塗料組成物。以下’將詳細敘述。 1.金屬板 作為被塗物的金屬板可舉例如，電氣鍵鋅鋼板、電氣 鍍鋅-鎳鋼板、熔融鍍鋅鋼板、熔融鍍鋅-鋁鋼板等的鍍鋅 系鋼板，熱軋鋼板、冷軋鋼板、不鏽鋼鋼板、鍍銅鋼板、 鋁板、熔融鍍錫-鋅（Sn_ 1 〇%Zn)鋼板、熔融鍍鋁鋼板、A卜Mg 合金等。 201012881 2.陽離子性樹脂(A) 陽離子性樹脂(A)為，分子中有胺基、銨基、锍鹼、鱗 鹼等可陽離子化之基團的樹脂。樹脂種類為通常所使用 者，可舉例如，環氧樹脂、丙烯酸樹脂、聚丁二烯樹脂、 醇酸樹脂、聚酯樹脂等。特別是使含有胺基的化合物在環 氧樹脂中進行加成反應而獲得的含有胺基之環氧樹脂，不 僅耐藥品性優良，且金屬板之平面部的耐蝕性優良，從提 高加工部和端面部的耐蝕性來看也是合適的。 9 上述含有胺基的環氧樹脂，可舉例如， (1)環氧樹脂與一級單-及多胺、二級單_及多胺或一、 - 二級混合多胺的加成物(例如，參見美國專利第3,984,299號 . 說明書）； • (2)環氧樹脂與含有經過酮亞胺化的一級胺基之二級 單-及多胺的加成物（例如，參見美國專利第4,〇17 438號說 明書）； (3)環氡樹脂與含有經過嗣亞胺化的一級胺基之經基 • 化合物的經醚化而獲得的反應物（例如參見，特開昭 59-43013號公報）等。 製造上述含有胺基的環氧樹脂時所使用的環氧樹脂 是’ 1分子中至少有1個環氧基，有2個以上為佳的化合物。 環氧樹脂的分子量一般適用的是有至少300，以400〜4,000 為佳，更佳的是800〜2,500之範圍内的「數量平均分子量」 及至少160g/eq，以18〇〜2,500g/eq為佳，更佳的是400〜 l，500g/eq之範圍内的環氧當量者，尤以透過多酚化合物與 201012881 環氧鹵丙烧(epihalohydrin)之反應所得者為佳。 本說明書中，「數量平均分子量」係遵循JIS κ 0124-83 中記載之方法，使用以下的4支分離管柱，用溶析液(Gpc 用四氫0夫鳴）在40°C及流速1.0ml/分鐘下，由利用RJ折射計 得到的層析圖與標準聚苯乙烯的標準曲線求算。 分離管柱：「TSKGEL4000HXL」、「TSKG3000HXL」、 「TSK G2500HXL」、「TSK G2000HXL」（每一種都是東曹 (株)製）。 為形成該環氧樹脂所使用的多盼化合物可舉例如， 2,2-雙(4-羥苯基）丙烷[雙酚A]、雙(4-羥苯基）甲烷[雙酚 F]、雙(4-羥基環己基）甲烷[氫化雙酚F]、2,2-雙(4-羥基環 . 己基）丙烷[氫化雙酚A]、4,4’-二羥基二苯甲酮、1,1-雙(4- . 羥苯基）乙烷、1,卜雙(4-羥苯基)異丁烷、2,2-雙(4-羥基-3-叔丁基-苯基）丙烷、雙（2-羥基萘）甲烷 (bis(2-hydroxynaphthyl)methane)、1，1，2,2-四（4-經苯基）曱 烧、4,4’-二經基二苯基石風、Novolac-type盼酸、曱酌裕(cresol novolac)等。 & 另外，利用多酚化合物與環氧氯丙烷的反應獲得的環 氧樹脂，其中尤以從雙酚A衍生而成的下述式之樹脂為合 適。 [化1]201012881 VI. Description of the invention: I: Technical field of the invention of the invention 3 Field of the invention The present invention relates to a kind of chemical-resistant, flat portion of a metal plate, and the processing of the metal plate and the end face An aqueous coating composition of a coating film having excellent surname and adhesion and a coated metal sheet having a coating film formed of the aqueous coating composition. I. Prior Art 3 Background of the Invention In the past, precoated steel sheets coated with coil coating or the like have been widely used as roofs, walls, and shutters of buildings. Shutters, garages Such as building materials, residential products related to various home appliances, switchboards, refrigerated display cabinets, steel furniture and kitchen appliances. In the case of these residential-related products made of pre-coated metal sheets, the pre-coated metal sheets are usually cut and joined by press molding. Therefore, in many of these residential related products, there are many metal exposed portions of the cut surface or crack generating portions due to the press working #. Since the metal exposed portion or the crack generating portion is more likely to have lower corrosion resistance than other portions, it is generally practiced to use a chromium-based rust-preventing pigment in the undercoat coating film which is used for the pre-coated metal sheet to improve corrosion resistance. However, chromium-based rust-preventive pigments or hexavalent chromium which is excellent in rust-preventing properties may generate hexavalent chromium. The hexavalent chromium poses a problem from the viewpoint of the health of the human body and environmental protection. Up to now, non-chromium anti-rust pigments have been produced on the market, such as zinc phosphate, tripolyphosphate 201012881 acid, zinc acid, etc. As a primer for combining non-chrome pigments, various products have been put forward. In addition, in order to reduce volatile organic compounds (v〇c) from environmental issues, the development of waterborne coatings has been demanded. For example, Patent Document 1 discloses an anti-rust pigment in which a combination of an epoxy resin and a phenolic resin is mixed, a combination of calcium citrate and phosphorus vanadate, or calcium carbonate and calcium silicate with aluminum phosphate and vanadium. A coating made of a combination of acid and phosphorus anti-rust pigments. Further, Patent Document 2 discloses that a phosphoric acid is mixed in a polyacetate; a flag and a manganese oxide. A vanadium oxide sintered product is used as a coating for a rust preventive pigment, and a coating of calcium iodate and vanadium oxide is mixed. However, when the rust-preventive pigments described in Patent Documents 1 and 2 are applied to an aqueous coating material, the corrosion resistance is weaker than that of the coating material using the chromium-based pigment, and the corrosion resistance of the processed portion and the end surface portion of the metal sheet is insufficient. In addition, there are cases in which chemical resistance such as alkali resistance or acid resistance or <aqueous property is poor. Further, Patent Document 3 describes a coating composition which contains an oil absorption amount of 3G to 2 〇Gml/lGGg and a pore volume 在 in an organic resin containing a secret or epoxy group and a color-developing enamel component. 〇5~丨2ml/g of the coating of the dioxide fine particles, and the glass transition/dish of the hardened coating film formed by the coating is in the range of 4 〇 to 125 ° 。. However, the coating film obtained by applying the cerium oxide microparticles contained in Patent Document 3 to an aqueous coating has poor resistance to surnames and chemical resistance, especially in the end face of the metal sheet. . Patent Document 4 discloses a chromium-free coated steel 201012881 plate excellent in corrosion resistance, characterized in that it is mixed with magnesium phosphate, zinc phosphate, magnesium hydrogen phosphate, aluminum dihydrogen phosphate, calcium citrate. A primer coating film of one or two kinds of non-chromium-based rust-preventive pigments and a partial hydrolysis-condensation product of tetra-alkoxysilane mixed with a topcoat coating film of a hydrophilic agent 'According to the surface of the coating. Further, Patent Document 5 discloses an internally gelled hard polymer particle (a) containing an average particle diameter of 44 to 0.6 μm, water-dispersible cerium oxide (b), glycidyloxyalkyl group- Glycidoxyalkyl trialkoxysilanes (c), organic hunger compounds (d), water-dispersible urethane resin (e), wrong compounds (f) and acid-filled gas (g) The water-based anti-rust coating composition is coated with a galvanized steel sheet. However, the coating film obtained by coating the coating material containing the rust preventive pigment described in Patent Document 4 or Patent Document 5 is inferior in corrosion resistance and chemical resistance as compared with the coating film obtained by coating a coating material containing a chromium-based pigment. In particular, the resistance of the end face of the metal plate is insufficient. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2000-129. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The coated portion and the end surface portion are coated with a water-soluble (four) material composition having excellent contact resistance and adhesion, and a coated metal sheet having a coating film having excellent coating film properties. In order to solve the above-mentioned problems, the present inventors have repeatedly studied intensively, and as a result, found that by adding a predetermined amount in a cationic resin and a polyisocyanate hardener (Β) The specific anti-rust pigment mixture (c) of the vanadium compound (cl), the antimony compound (c2) and the phosphoric acid calcium salt (C3) is formed into an aqueous coating composition, and can form not only chemical resistance but also coating metal. The coating of the flat portion of the sheet is excellent in the corrosion resistance of the processed portion and the end surface of the coated metal sheet, and the present invention has been completed. That is, the present invention relates to the following aqueous coating compositions. An aqueous coating composition comprising a cationic resin (A), a polyisocyanate curing agent, and the following anti-rust pigment mixture (C). The rust preventive pigment mixture (C) consists of at least one of a vanadium pentoxide, a calcium vanadate and an ammonium metavanadate (Cl), a compound (C2) and a calcium salt (c3). The amount of the vanadium compound (cl) is 1 to 3 parts by mass, and the amount of the phthalic acid compound (C2) is 100 parts by mass based on the total solid content of the resin (A) and the curing agent (B). 1 to 30 parts by mass and the amount of the calcium phosphate salt (c3) are 1 to 3 parts by mass, and the amount of the rust preventive pigment mixture (C) is 3 to 90 parts by mass. 2. The aqueous coating composition according to the above item 1, wherein the cationic resin (A) is an amino group-containing epoxy resin. 201012881 3. The aqueous coating composition according to the above item 1, wherein the compound (^ is at least one selected from the group consisting of a metal salt of a ceric acid, a oxidized oxidized fine particle, and a metal ion-exchanged cerium oxide fine particle. The aqueous coating composition according to the above aspect, wherein the phosphate-based calcium salt (6)) is at least one selected from the group consisting of calcium phosphate, monocalcium phosphate, dichlorophosphate, and tripolyphosphate. 5. The aqueous coating composition according to the above-mentioned item 1, which contains a total amount of the solid content of the cationic resin (A) and the polyisocyanate (B), and contains a Resole type phenol resin of 〇丨 part by mass. A method for forming a coating film, which is characterized in that it is formed on a metal plate, forming a hardened coating film obtained by using the aqueous coating composition according to the above item 1, and forming at least one kind on the tantalum hardening coating film. The coating film of the above topcoat paint. A coated metal sheet comprising the coating film obtained by the coating film forming method according to the above item 6. 8. A coated article obtained by processing the coated metal 9 plate described in item 7 above. EFFECT OF THE INVENTION The aqueous coating composition containing a specific rust preventive pigment mixture of the present invention is advantageous in terms of environmental hygiene because it does not contain a chromium-based rust-preventive pigment and is an aqueous coating material. The coating film obtained by coating the aqueous coating composition of the present invention is excellent in chemical resistance, and is excellent in corrosion resistance not only in the flat portion of the coated metal sheet but also in water-based coating containing a conventional non-chromium-based rust-preventing pigment. It is difficult to achieve the excellent resistance to the money or adhesion of the processed portion and the end surface of the coated metal sheet of 201012881. In addition, on a molten plated steel sheet (GI steel sheet) which is not subjected to chemical conversion treatment, a coated steel sheet coated with a hardened coating film obtained by coating the aqueous coating composition of the present invention and dried by heating is applied thereto. In the hot-dip galvanized steel sheet (GI steel sheet) subjected to the chemical conversion treatment, the coated steel sheet coated with the hardened coating film containing the chromate-based rust-preventing pigment can have the same or more profitability. Thus, the chemical conversion treatment procedure (see the figure) can be omitted, which is advantageous for the provincial programming and resource saving of the coating line. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] An example of a continuous coil coating line is illustrated. [Fig. 2] An example of a coating film structure of a coating film containing the aqueous coating composition of the present invention. [Embodiment] 1 Embodiment for carrying out the invention The aqueous coating composition of the present invention relates to a mixture containing a specific amount of a cationic resin (A) and a polyisocyanate hardener (B) and a specific rust preventive pigment (C) A waterborne coating composition characterized. The following 'will be described in detail. 1. Metal plate as a metal plate to be coated, for example, a galvanized steel plate such as an electric-bond zinc steel plate, an electric galvanized-nickel steel plate, a hot-dip galvanized steel sheet, a hot-dip galvanized-aluminum steel sheet, a hot-rolled steel sheet, or a cold Rolled steel plate, stainless steel plate, copper plated steel plate, aluminum plate, hot-dip tin-zinc (Sn_ 1 〇% Zn) steel plate, hot-dipped aluminum plate, A-M alloy. 201012881 2. Cationic resin (A) The cationic resin (A) is a resin having a cationizable group such as an amine group, an ammonium group, a decyl base or a squaraine in the molecule. The type of the resin is usually used, and examples thereof include an epoxy resin, an acrylic resin, a polybutadiene resin, an alkyd resin, and a polyester resin. In particular, an amine group-containing epoxy resin obtained by subjecting an amine group-containing compound to an addition reaction in an epoxy resin is excellent in chemical resistance and excellent in corrosion resistance in a flat portion of a metal plate, and is improved from a processing portion and The corrosion resistance of the end face is also suitable. 9 The above-mentioned epoxy group-containing epoxy resin may, for example, be an adduct of (1) an epoxy resin with a primary mono- and polyamine, a secondary mono- and polyamine or a mono-mixed polyamine (for example) , see U.S. Patent No. 3,984,299. The specification); (2) an epoxy resin and an adduct of a secondary mono- and polyamine containing a ketimine-substituted primary amine group (for example, see U.S. Patent No. 4, 〇17, 438 specification); (3) a reactant obtained by etherification of a cyclic oxime resin and a compound containing a sulfonium-imided primary amine group (see, for example, JP-A-59-43013) )Wait. The epoxy resin used in the production of the above-mentioned epoxy group-containing epoxy resin is a compound having at least one epoxy group in one molecule and preferably two or more. The molecular weight of the epoxy resin is generally suitably at least 300, preferably from 400 to 4,000, more preferably from "number average molecular weight" in the range of from 800 to 2,500, and at least 160 g/eq, from 18 Å to 2,500 g/eq. Preferably, it is preferably an epoxy equivalent in the range of 400 to 1,500 g/eq, particularly preferably obtained by reacting a polyphenol compound with 201012881 epoxy hail. In the present specification, the "number average molecular weight" is in accordance with the method described in JIS κ 0124-83, and the following four separation columns are used, and the elution solution (Gpc with tetrahydrogen) is used at 40 ° C and a flow rate of 1.0. The chromatogram obtained by using the RJ refractometer and the standard curve of standard polystyrene were calculated in ml/min. Separation column: "TSKGEL4000HXL", "TSKG3000HXL", "TSK G2500HXL", "TSK G2000HXL" (each is manufactured by Tosoh Corporation). The polypanic compound used for forming the epoxy resin may, for example, be 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] or bis(4-hydroxyphenyl)methane [bisphenol F]. Bis(4-hydroxycyclohexyl)methane [hydrogenated bisphenol F], 2,2-bis(4-hydroxycyclohexyl)propane [hydrogenated bisphenol A], 4,4'-dihydroxybenzophenone, 1 , 1-bis(4-.hydroxyphenyl)ethane, 1, bis(4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxy-3-tert-butyl-phenyl)propane , bis(2-hydroxynaphthyl)methane, 1,1,2,2-tetrakis(4-phenyl)anthracene, 4,4'-di-diphenyldiphenyl stone Novolac-type is expected to be acid, cresol novolac and the like. Further, an epoxy resin obtained by a reaction of a polyphenol compound with epichlorohydrin is used, and among them, a resin of the following formula derived from bisphenol A is particularly suitable. [Chemical 1]

上述式中，η以0〜8表示者為合適。 10 201012881In the above formula, η is preferably represented by 0 to 8. 10 201012881

相關環氧樹脂的市售品可舉例如jER828EL、jER 1002、jERl004、jERl007 (Japan Epoxy Resins Co. Ltd，商 品名）、Araldite AER6099 (Asahi Ciba Co.，Ltd.製，商品名）、 EPOMIK R-309 (Mitsui Chemicals Inc.製，商品名）。 該環氧樹脂可以是和多元醇、聚喊多元醇、聚酯多元 醇、聚醯胺一胺(polyamidoamine)、多元酸、多異氰酸酯化 合物等之改質成分反應成的改質環氧樹脂，此外，也可以 是使ε-己内酯等的内酯類、丙烯酸單體等發生接枝聚合而 得的改質環氧樹脂。 再者’使上述改質成分與環氧樹脂發生反應以製造改 質環氧樹脂的方法並無特殊限定。改質成分與環氧樹脂的 反應可以透過，例如’在可溶解這些各別成分的溶劑中， 依需要在反應觸媒存在下，通常，在1〇〇〜15〇乞使之反應1 〜5小時的方式，適當地進行。 上述反應觸媒’可舉例如’四乙基溴化銨（tetra_ ethylammonium bromide)、四丁基溴化銨、三苯基苄基氣化 膦（triphenylbenzylphosphonium chloride)等之四級鹽的觸 媒，三乙胺等的胺類。 製造上述（1)之含有胺基的環氧樹脂時所使用的一級單 -及多胺、二級單-及多胺，或一、二級混合多胺，可舉例 如’單甲胺、二甲胺、單乙胺、二乙胺、一異丙胺、二異 丙胺、一丁胺、二丁胺等之單-或二-烷基胺；單乙醇胺、 二乙醇胺、單(2-羥丙基)胺、一曱胺乙醇等之烷醇胺；乙二 胺、丙二胺、丁二胺、己二胺、二乙烯三胺、三乙烯四胺 11 201012881 等之亞烷基多胺等的胺化合物。 製造上述(2)之含有胺基的環氧樹脂時所使用的具有縿 過酮亞胺化之-級胺基的二級單—及多胺，可舉例如，在製 造上述（1)之環氧樹脂胺加成物時所使用的一、二級混合聚 胺田中，例如，二乙烯三胺等中使_化合物發生反應而生 成之，胺化合物的酮亞胺化物。Commercial products of related epoxy resins include, for example, jER828EL, jER 1002, jERl004, jERl007 (Japan Epoxy Resins Co. Ltd., trade name), Araldite AER6099 (manufactured by Asahi Ciba Co., Ltd., trade name), EPOMIK R- 309 (manufactured by Mitsui Chemicals Inc., trade name). The epoxy resin may be a modified epoxy resin which is reacted with a modified component such as a polyol, a poly-polyol, a polyester polyol, a polyamidoamine, a polybasic acid or a polyisocyanate compound. Further, it may be a modified epoxy resin obtained by graft-polymerizing a lactone such as ε-caprolactone or an acrylic monomer. Further, a method of reacting the above-mentioned modified component with an epoxy resin to produce a modified epoxy resin is not particularly limited. The reaction of the modified component with the epoxy resin can be permeable, for example, in a solvent which can dissolve the respective components, if necessary, in the presence of a reaction catalyst, usually, the reaction is carried out at 1 to 15 Torr. The way of the hour is carried out as appropriate. The above reaction catalyst may, for example, be a catalyst of a quaternary salt such as tetraethylammonium bromide, tetrabutylammonium bromide or triphenylbenzylphosphonium chloride, An amine such as ethylamine. The primary mono- and polyamines, the secondary mono- and polyamines, or the first- or second-stage mixed polyamines used in the production of the amine group-containing epoxy resin of the above (1), for example, 'monomethylamine, two Mono- or di-alkylamines such as methylamine, monoethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine, etc.; monoethanolamine, diethanolamine, mono(2-hydroxypropyl) An amine such as an amine, a mercaptoethanol or the like; an amine such as an alkylene polyamine such as ethylenediamine, propylenediamine, butanediamine, hexamethylenediamine, diethylenetriamine or triethylenetetramine 11 201012881 Compound. A secondary mono- and polyamine having a ketal imidized-grade amine group used in the production of the amine group-containing epoxy resin of the above (2), for example, in the production of the above ring (1) In the first-stage mixed polyamine field used in the oxyresin amine adduct, for example, a ketimine of an amine compound which is formed by reacting a compound with diethylenetriamine or the like.

製k上述(3)之含有胺基的環氧樹脂時所使用的具有縿 過酮亞胺化之-級胺基馳基化合物，可舉例如，在製造 上述（1)之環氧樹脂胺力〇成物時所使用的一級單_及多胺、二 級單-及多胺或―、二級混合多胺之中，含有—級胺基和經 基的化β物’例如，單乙醇胺、單(2,丙基)胺等中使嗣化 口物發生應而生成的，胺化合物之含經基酮亞胺化物。The ketone imidized-grade amine-based chitin compound used in the above-mentioned (3)-containing amine group-containing epoxy resin, for example, in the production of the epoxy resin amine of the above (1) The first-stage mono- and polyamines, the second-stage mono- and polyamines or the two-stage mixed polyamines used in the composition, containing a -based amine group and a transbasic chemical substance β, for example, monoethanolamine, A monoketone (2, propyl)amine or the like which is formed by the formation of a hydrazine hydrazide, and a ketone imide containing an amine compound.

特別疋’在含胺基環氧樹脂之中，從提高預塗鋼板中 的加工部之耐歸的觀點來看，較佳的樹脂可以舉例如， 將胺化合物等加成到碳數4〜36的脂肪族多元酸與環氧樹 脂反應成之改質環氧樹脂而形成之，脂肪族多元酸改質之 3胺基f氧樹&，其他，像是將胺化合物等加成到多異氮 酸醋化合物與環氧樹脂反應成的改質環氧樹脂 而形成之， 二異氛酸醋化合物改質之含胺基環氧樹脂。 上物數4〜36的脂肪族多元酸，以6〜36的飽和 飽和脂職多讀純，可舉·，六氫間苯二甲酸(1 Μ油0PhthaUC啊、六氣對笨二甲酸（he_ te哪她alic acid)、六氫鄰苯二甲酸伽吻加咖 ㈣、甲基六氫鄰笨二甲酸、甲基六氫對苯二甲酸' 12 201012881 氫鄰苯二甲酸、2-四氫鄰苯二甲酸、3-四氫鄰苯二甲酸、 4-四氫鄰苯二甲酸、卜四氫間苯二甲酸、2-四氫間苯二甲 酸、3-四氫間苯二甲酸、4-四氫間苯二甲酸、1-四氫對苯 二甲酸、2-四氫對苯二甲酸、甲基四氫鄰苯二甲酸、内亞 甲基四氫鄰苯二甲酸（endomethylene tetrahydrophthalic acid)、甲基内亞甲基四氫鄰苯二曱酸、六氣内亞曱基四氫 鄰笨二甲酸等之脂環式二羧酸基其酸酐；琥珀酸、戊二酸、 己二酸、壬二酸、癸二酸、十二烷二酸、十四烷二酸、辛 二酸、庚二酸、順丁稀二酸(maleic acid)、反丁稀二酸 (fumaric acid)、亞甲基丁二酸(Itaconic acid)、十三烧二酸 (brassylic acid)、甲基順丁稀二酸(citraconic acid)、氣順丁 . 稀二酸(chloromaleic acid)、二聚酸等之脂肪族二竣酸及其 酸針；六氫苯三甲酸(hexahydrotrimellitic acid)等之3價以上 的脂肪族多元酸；如這些酸的曱酯、乙酯之低級烷酯等。 上述的多異氰酸醋化合物，可舉例如，甲苯二異氰酸 酯（tolylene diisocyanate)、二苯甲二異氰酸酯（Xyiyiene 9 diisocyanate)、苯二異氰酸酯（phenylene diisocyanate)、二苯 甲烷-2,2’-二異氰酸酯、二苯曱烷-2,4’-二異氰酸酯、二苯 甲烷-4,4’-二異氰酸酯、粗MDI[多亞甲基多苯基異氰酸酯 (polymethylene polyphenyl isocyanate)]、二（異氰酸根合甲 基）環己院(bis(isocyanatomethyl)-Cyclohexane)、四亞甲基二 異氰酸酯、六亞甲基二異氰酸酯、亞甲基二異氰酸酯 (methylene diisocyanate)、異佛爾酮二異氰酸酯等之芳香 族、脂肪族或脂環族多異氰酸酯化合物；這些多異氰酸酯 13 201012881 化合物的環化聚合物或縮二脲；或其等之组合。 尤其，六亞曱基二異氰酸酯從提高加工部和端面部的 而寸姓性方面來看是合適的。 再者，製造含胺基環氧樹脂時，對於環氧樹脂（改質環 乳樹脂）’及含胺基化合物的加成反應，通常可以在適當的 溶劑中，宜在80〜170°C(較佳為90〜15〇。〇之溫度，進行1 〜6小時(較佳為1〜5小時）。上述溶劑可舉例如，甲苯、二 甲笨、環己烷、正己烷等之烴系溶劑；醋酸甲酯、醋酸乙 酯、醋酸丙酯等之酯系溶劑；丙酮、甲乙鲷、甲基異丁酮、 參 甲基戊基甲酮(methyl amyl ketone)等之酿I系溶劑；二甲基曱 酿胺、二f基乙醯胺等之醯胺系溶劑；甲醇、乙醇、正丙 醇、異丙醇等之醇系溶劑；或其等之混合物等。 _ 上述加成反應中的各反應成分之使用比例，雖無嚴密 限制可適纽變’惟鱗氧_(改„氧細旨)與含麟① 'In particular, among the amine-containing epoxy resins, from the viewpoint of improving the resistance of the processed portion in the precoated steel sheet, a preferred resin may be, for example, an amine compound or the like added to a carbon number of 4 to 36. The aliphatic polybasic acid and epoxy resin are reacted to form a modified epoxy resin, and the aliphatic polybasic acid is modified by a 3-amino-based oxygen tree and other, such as adding an amine compound to the like. An amine-containing epoxy resin modified by a diisoleic acid vinegar compound modified by a modified epoxy resin formed by reacting a nitrite compound with an epoxy resin. An aliphatic polybasic acid with a number of 4 to 36, which is 6 to 36 saturated saturated fat, and can be read, hexahydroisophthalic acid (1 Μ oil 0PhthaUC ah, six gas to stupi dicarboxylic acid (he_) Te which she alic acid), hexahydrophthalic acid gamma plus gamma (four), methyl hexahydro phthalic acid, methyl hexahydroterephthalic acid ' 12 201012881 hydrogen phthalic acid, 2-tetrahydroortene Phthalic acid, 3-tetrahydrophthalic acid, 4-tetrahydrophthalic acid, tetrahydroisophthalic acid, 2-tetrahydroisophthalic acid, 3-tetrahydroisophthalic acid, 4- Tetrahydroisophthalic acid, 1-tetrahydroterephthalic acid, 2-tetrahydroterephthalic acid, methyltetrahydrophthalic acid, endomethylene tetrahydrophthalic acid, An alicyclic dicarboxylic acid anhydride such as methyl endomethylenetetrahydrophthalic acid or a hexaqilidene tetrahydron-benzoic acid; succinic acid, glutaric acid, adipic acid, hydrazine Diacid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, suberic acid, pimelic acid, maleic acid, fumaric acid, methylene Succinic acid (Itaconic a Cid), trisuccinic acid, citraconic acid, cis-butyl, chloromaleic acid, dimer acid, etc. a needle; a trivalent or higher aliphatic polybasic acid such as hexahydrotrimellitic acid; a decyl ester of these acids; a lower alkyl ester of an ethyl ester; and the above-mentioned polyisocyanate compound, for example, Tolylene diisocyanate, Xyiyiene 9 diisocyanate, phenylene diisocyanate, diphenylmethane-2,2'-diisocyanate, diphenylnonane-2,4'-di Isocyanate, diphenylmethane-4,4'-diisocyanate, crude MDI [polymethylene polyphenyl isocyanate], bis(isocyanatomethyl)- Cyclohexane), an aromatic, aliphatic or alicyclic polyisocyanate compound such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate or isophorone diisocyanate; Cyclic polymers or biuret these polyisocyanates 13201012881 compound;. Or etc. combination in particular, hexamethylene Yue-yl diisocyanate thereby inches name of improving the processing portion and the end face of view are suitable. Further, when the amine-containing epoxy resin is produced, the addition reaction of the epoxy resin (modified cyclic latex resin) and the amine-containing compound can be usually carried out in a suitable solvent, preferably at 80 to 170 ° C ( It is preferably 90 to 15 Torr. The temperature of the hydrazine is 1 to 6 hours (preferably 1 to 5 hours). The solvent may, for example, be a hydrocarbon solvent such as toluene, dimethyl benzene, cyclohexane or n-hexane. An ester solvent such as methyl acetate, ethyl acetate or propyl acetate; a solvent based on acetone, methyl ethyl hydrazine, methyl isobutyl ketone, methyl amyl ketone, etc.; a guanamine-based solvent such as an amine-based amine or a di-f-acetamide; an alcohol-based solvent such as methanol, ethanol, n-propanol or isopropanol; or a mixture thereof, etc. _ each of the above addition reactions The proportion of the reaction components used, although there is no strict restriction, can be changed to the newest 'square oxygen _ (change „ oxygen thin purpose) and contain lin 1 '

。物之合4固體含量質量做基準，環氧樹脂宜使用7〇〜97 質量％’較佳為70〜95質量％，更佳的是8〇〜95質量％;含 胺基化合物宜使用3〜30質量％，較佳為5〜_量％，更# Q 的是在5〜20質量％之範圍内。 另外，含胺基化合物之使用量從提高水分散性與塗膜 耐餘性的面來看，本發明之最終生成物的陽離子性樹脂之 胺價為1〇〜8〇mgK〇H/g’以落在〜7〇mgKOH/g的範圍内 為佳^。 3·多異氰酸酯硬化劑(B) 本發明的水性塗料組成物為，在陽離子性樹脂⑷中混 14 201012881 合多異氰酸酯硬化劑(B)而成的熱硬化性塗料。 在多異氰酸酯硬化劑（B)中所使用的多異氰酸酯化合 物，可以使用公知化合物，例如，甲苯二異氰酸酯、苯二 甲基二異氰酸酯、亞苯基二異氰酸酯、二苯甲烷-2,2’-二異 氰酸酯、二笨甲烷-2,4’-二異氰酸酯、二苯曱烷-4,4’-二異 氰酸酯、粗MDI[多亞甲基多苯基異氰酸酯]、二(異氰酸根 合甲基)環己烷、四亞甲基二異氰酸酯、六亞甲基二異氰酸 酯、亞曱基二異氰酸酯、異佛爾酮二異氰酸酯等之芳香族、 〇 脂肪族或脂環族多異氰酸酯化合物；此等多異氰酸酯化合 物的環化聚合物或縮二脲；或其等之組合。 . 尤其，甲苯二異氰酸酯、苯二甲基二異氰酸酯、亞苯 . 基二異氰酸酯、二苯甲烷-2,4’-二異氰酸酯、二苯甲烷-4,4’- 二異氰酸酯、粗MDI等的芳香族多異氰酸酯化合物，從金 屬板之平面部的耐蝕性觀點來看特別合適。 特別是，異氰酸酯的種類用六亞曱基二異氰酸酯時， 因為可以提高硬化性並賦予塗膜柔軟性，所以對提高預塗 ® 鋼板的加工部和端面部之耐蝕性是較佳的。 另外，本發明中，多異氰酸酯硬化劑(B)，可以適當地 使用使前述多異氰酸酯化合物與異氰酸酯封閉劑以接近化 學理論量進行加成反應而得到的封閉型多異氰酸酯化合 物。 前述異氰酸酯封閉劑係加成於多異氰酸酯化合物的異 氰酸酯基而將其封閉者。藉加成而生成之封閉型多異氰酸 酯化合物在常溫下是安定的，但是在加熱到塗膜的燒結溫 15 201012881 度（通常為100〜200°c)時，希望異氰酸酯封閉劑可以解離再 生成游離的異氰酸酯基。 前述異氰酸δ旨封閉劑，可舉例如，甲乙酿I躬^ (methyl-ethylketoxime)、曱戊酮肪(methylamylketoxime)、環己酮將 等之肟系化合物；苯酚、對叔丁基苯酚、甲酚等之酚系化 合物；正丁醇、2-乙基己醇等的脂肪族醇類；苯甲醇、曱 基苯甲醇等之芳香族烷醇類；乙二醇單丁醚、二乙二醇單 ***等之醚醇系化合物；ε-己内醯胺、γ-丁内醯胺等之内 醯胺系化合物等等。 前述陽離子性樹脂(Α)及多異氰酸酯硬化劑(Β)之混合 比例，以上述成分(Α)及成分(Β)的固體含量合計質量為基 準，宜取成分(Α)為60〜95質量％，較佳為70〜90質量％， 取成分(Β)為5〜40質量％為佳，較佳為10〜30質量％之範圍 内，從塗料安定性與硬化性的面看是合適的。 在製造本發明之水性塗料組成物時，除陽離子性樹脂 (Α)及多異氰酸酯硬化劑（Β)外，在充分混合界面活性劑、表 面調整劑和Re s ο 1 e型酚醛樹脂的等各種添加劑和有機溶劑 等以製成調合樹脂後，可以將上述調合樹脂用醋酸、磷酸、 甲酸、丙酸、乳酸等之有機羧酸；鹽酸、硫酸等之無機酸 等加以水溶化或水分散化而獲得乳液。 上述Resole型酚醛樹脂亦包含，在反應觸媒的存在下， 使苯酚或雙酚A等的酚類與甲醛等的醛類發生縮合反應，導 入羥甲基而形成的酚醛樹脂，或以碳數6以下的醇使被導入 的羥曱基之一部分發生烷基醚化而形成者。 16 201012881. The content of the solid content of the material 4 is used as a reference, and the epoxy resin is preferably used in an amount of 7 to 97% by mass, preferably 70 to 95% by mass, more preferably 8 to 95% by mass; and the amine-containing compound is preferably used in 3 to 3 30% by mass, preferably 5 to _% by volume, more preferably #5 is in the range of 5 to 20% by mass. Further, the amount of the amine group-containing compound used is from the viewpoint of improving water dispersibility and coating film durability, and the amine resin of the final product of the present invention has an amine price of 1 〇 8 〇 mg K 〇 H / g ' It is better to fall within the range of ~7〇mgKOH/g. 3. Polyisocyanate curing agent (B) The aqueous coating composition of the present invention is a thermosetting coating material obtained by mixing 14 201012881 polyisocyanate curing agent (B) with a cationic resin (4). As the polyisocyanate compound used in the polyisocyanate hardener (B), a known compound such as toluene diisocyanate, benzodimethylisocyanate, phenylene diisocyanate, diphenylmethane-2,2'-di can be used. Isocyanate, dimethane-2,4'-diisocyanate, diphenylnonane-4,4'-diisocyanate, crude MDI [polymethylene polyphenyl isocyanate], di(isocyanatomethyl) ring An aromatic, hydrazine aliphatic or alicyclic polyisocyanate compound such as hexane, tetramethylene diisocyanate, hexamethylene diisocyanate, fluorenylene diisocyanate or isophorone diisocyanate; such polyisocyanate compounds a cyclized polymer or a biuret; or a combination thereof. In particular, aromatics such as toluene diisocyanate, benzodimethyl diisocyanate, phenylene diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, crude MDI, etc. The polyisocyanate compound is particularly suitable from the viewpoint of corrosion resistance of the flat portion of the metal plate. In particular, when hexamethylene diisocyanate is used as the type of isocyanate, since the curability is improved and the flexibility of the coating film is imparted, it is preferable to improve the corrosion resistance of the processed portion and the end surface portion of the precoated steel sheet. Further, in the present invention, as the polyisocyanate curing agent (B), a blocked polyisocyanate compound obtained by subjecting the polyisocyanate compound and the isocyanate blocking agent to an addition reaction amount close to a theoretical amount of the chemical can be suitably used. The above isocyanate blocking agent is added to the isocyanate group of the polyisocyanate compound to be blocked. The blocked polyisocyanate compound formed by the addition is stable at normal temperature, but when heated to a sintering temperature of the coating film of 15 201012881 degrees (usually 100 to 200 ° C), it is desirable that the isocyanate blocking agent can be dissociated and regenerated. Isocyanate group. The above isocyanate δ is a blocking agent, and examples thereof include a fluorene compound such as methyl-ethylketoxime, methylamylketoxime, and cyclohexanone; phenol and p-tert-butylphenol; a phenolic compound such as cresol; an aliphatic alcohol such as n-butanol or 2-ethylhexanol; an aromatic alkanol such as benzyl alcohol or mercaptobenzyl alcohol; ethylene glycol monobutyl ether; An ether alcohol compound such as an alcohol monoethyl ether; an indoleamine compound such as ε-caprolactam or γ-butylimamine; and the like. The mixing ratio of the cationic resin and the polyisocyanate curing agent is preferably 60 to 95% by mass based on the total mass of the solid content of the component (Α) and the component (Β). Preferably, it is 70 to 90% by mass, and the component (Β) is preferably 5 to 40% by mass, preferably 10 to 30% by mass, and is suitable from the viewpoint of coating stability and hardenability. In the production of the aqueous coating composition of the present invention, in addition to the cationic resin and the polyisocyanate curing agent, various surfactants, surface conditioners, and Res s 1 e phenol resins are sufficiently mixed. After the additive and the organic solvent are used to prepare the blended resin, the blended resin may be hydrolyzed or water-dispersed with an organic carboxylic acid such as acetic acid, phosphoric acid, formic acid, propionic acid or lactic acid; or an inorganic acid such as hydrochloric acid or sulfuric acid. Obtain an emulsion. The Resole type phenol resin further includes a phenol resin formed by a condensation reaction between a phenol such as phenol or bisphenol A and an aldehyde such as formaldehyde in the presence of a reaction catalyst, or a phenol resin formed by introducing a methylol group, or a carbon number. The alcohol of 6 or less is formed by alkyl etherification of a part of the introduced hydroxyl group. 16 201012881

Resole型紛醛樹脂的數量平均分子量（注〖），以2〇〇〜 1，〇〇〇為佳，較佳的是在300〜900之範圍内，而且每丨苯核 的經甲基之平均數為0.3〜2.5個’以0.3〜2.〇個的範圍内為 佳。藉使用上述Resole型酚醛樹脂，可形成密封性等之塗膜 性能優良的塗膜。 (注1)關於數量平均分子量’係如前述之「陽離子性樹 脂(A)」中所做的說明。 上述Resole型盼搭樹脂的市售產品，可舉例如，Sumime ❹ Resin PR—55317(SUmit〇m〇 Bakelite製，商品名）、sh〇n〇1 BKS-316 等0 前述Resole型酚醛樹脂的混合量，以上述成分(A)及成 分(B)的固體含量合計質量為基準，從膜附著性與塗膜安定 性的點來看，以1〜20質量％為佳，2〜7質量％較佳。 4.防銹顏料混合物（〇 本發明之水性塗料組成物因含有一定量的特定防銹顏 料混合物（C)而可以獲得耐藥品性、平面部之耐蝕性、加工 部和端面部之耐蝕性及附著性優良的塗裴金屬板。防銹顏 料混合物(C)由，飢化合物(ci)、矽化合物(c2)及鱗酸系約鹽 (c3)組成。另外，防銹顏料混合物(c)亦可含有前述釩化合 物(cl)、矽化合物(C2)及磷酸系鈣鹽(c3)以外的化合物。 以下將做詳細記載。 4-1.飢化合物（cl) 釩化合物（cl)為五氧化二釩、釩酸鈣及偏釩酸銨中之至 少1種釩化合物。五氧化二釩、釩酸鈣及偏釩酸銨，利用5 17 201012881 價釩粒子對水的溶出性優異，從釩化合物(cl)釋出的5價釩 粒子或與材料金屬反應，或與來自其他防銹顏料混合物的 離子反應’藉而發揮提高耐蝕性的效果。其中特別是五氧 化二飢提高财蚀性的效果明顯。 4-2 •«夕化合物（c2) 石夕化合物(c2)含有選自矽酸金屬鹽、二氧化矽微粒子、 金屬離子交換二氧化矽微粒子之至少丨種化合物。The number average molecular weight of Resole type aldehyde resin is preferably 2 〇〇 1 , 〇〇〇, preferably in the range of 300 to 900, and the average of methyl groups per benzene nucleus. The number is 0.3 to 2.5, which is preferably in the range of 0.3 to 2. By using the above-mentioned Resole type phenol resin, it is possible to form a coating film having excellent coating properties such as sealing properties. (Note 1) The number average molecular weight ' is as described in the above-mentioned "cationic resin (A)". The commercially available product of the above-mentioned Resole type resin may, for example, be a mixture of the above-mentioned Resole type phenol resin, such as Sumime® Resin PR-55317 (manufactured by SUmit〇m〇Bakelite, trade name), sh〇n〇1 BKS-316, and the like. The amount is preferably from 1 to 20% by mass, and from 2 to 7% by mass, based on the total mass of the solid content of the component (A) and the component (B), from the viewpoint of film adhesion and film stability. good. 4. Anti-rust pigment mixture (The aqueous coating composition of the present invention can obtain chemical resistance, corrosion resistance at a flat portion, corrosion resistance of a processed portion and an end portion due to a certain amount of a specific antirust pigment mixture (C) A coated metal plate having excellent adhesion. The anti-rust pigment mixture (C) is composed of a hungry compound (ci), a bismuth compound (c2), and a squaric acid-based salt (c3). In addition, the anti-rust pigment mixture (c) is also The compound other than the vanadium compound (cl), the ruthenium compound (C2), and the phosphate calcium salt (c3) may be contained in the following. 4-1. The hunger compound (cl) The vanadium compound (cl) is pentoxide. At least one vanadium compound of vanadium, calcium vanadate and ammonium metavanadate. Vanadium pentoxide, calcium vanadate and ammonium metavanadate, using vanadium particles of 5 17 201012881 for excellent solubility in water, from vanadium compounds ( Cl) The released vanadium vanadium particles react with the material metal or react with ions from other anti-rust pigment mixtures to enhance the corrosion resistance. 4-2 • «Night compound (c2) Shi Xi compound (c 2) At least a compound selected from the group consisting of a metal salt of ruthenic acid, cerium oxide microparticles, and metal ion-exchanged cerium oxide microparticles.

石夕酸金屬鹽係由二氧化矽與金屬氧化物形成的鹽可 為正矽酸鹽、聚矽酸鹽等的任一種皆可。矽酸鹽可舉例如， 矽酸辞 '矽酸鋁、正矽酸鋁、水合矽酸鋁、矽酸鋁鈣、矽 酸鋁鈉、矽酸鋁鈹、矽酸鈉、正矽酸鈣、偏矽酸鈣、矽酸 辦納、石夕酸錄、正石夕酸鎂、偏石夕酸鎮、妙酸鎮！弓、石夕酸猛、 碎酸鎖、撖視石、石權石、銃纪石（thortveitite)、異極礦、 -錐礦(benitoite)、柱星葉石(neptunite)、綠柱石、透輝石、The metal salt of the oleic acid is a salt of cerium oxide and a metal oxide, and may be any of a ruthenate or a polyphthalate. The bismuth salt can be exemplified by, for example, bismuth citrate 'aluminum citrate, aluminum orthosilicate, aluminum hydrated aluminum citrate, calcium aluminum citrate, sodium aluminum citrate, aluminum bismuth citrate, sodium citrate, calcium ortho citrate, partial Calcium citrate, citric acid, sodium sulphate, sulphate, magnesium sulphate, sulphuric acid town, wonderful acid town! Bow, Lixi acid, broken acid lock, squint stone, stone stone, thirveitite, heteropolar ore, benitoite, neptunite, beryl, diopside ,

夕灰石、薔薇輝石、透閃石、硬石夕飼石（xonotlite)、滑石、 魚眼:、㈣酸鹽、卿酸鹽、鈹賴鹽、長石、沸石等。 其等田中，作為矽酸金屬鹽尤以，正矽酸鈣、偏矽酸鈣、 偏夕酸鎂、料銘為佳，正㈣飼、偏料約特別合適。 一氧切微粒子只要是二氧切微粒子即可以無特殊 限制地使用，可泉 ‘’、 』举例如，表面無處理的二氧化矽微粉末、 ^面用有機物處理過的二氧化賴粉末、觸子交換二氧 ，子有機溶劑分散性膠體二氧化石夕等。 ‘’、、處理或以有機物處理過的二氧化矽微粒子可舉 平均粒杈以〇·5〜15Km為佳，較佳為1〜ΙΟμπ!之二氧 18 201012881 化碎微粉末。. 二氧化矽微粉末的吸油量為30〜350ml/100g、可以適 當地使用在30〜150ml/100g之範圍内者。市售品可舉例Umbrella, rhodochrosite, tremolite, hard cemetery (xonotlite), talc, fisheye: (4) acid salt, acid salt, bismuth salt, feldspar, zeolite, etc. In the middle of the field, as a metal citrate, calcium orthosilicate, calcium citrate, magnesium citrate, and the material are good, and the (four) feeding and eccentric materials are particularly suitable. The oxygen-cutting microparticles can be used without any particular limitation as long as they are dioxo-microparticles, for example, a non-treated cerium oxide micropowder, an organic-treated cerium oxide powder, and a touch. Sub-exchange dioxane, sub-organic solvent dispersible colloidal dioxide, etc. The cerium oxide microparticles which are treated with or treated with organic matter may preferably have an average particle size of 〇5 to 15 Km, preferably 1 to ΙΟμπ! dioxin 18 201012881. The cerium oxide micropowder has an oil absorption of 30 to 350 ml/100 g and can be suitably used in the range of 30 to 150 ml/100 g. Commercial products can be exemplified

如 ’ Sylysia 710、Sylysia 740、Sylysia 550、Aerosil R 972(以 上’母一種都是Fuji Silysia chemical Ltd.製）、MIZUKASIL P-73(水澤化學工業（株）製）、Gasil綱DF(Cr〇sfield Chemical Inc.製）等。 有機/谷劑刀散性黟體一乳化石夕亦稱為有機氧化石夕溶膠 (OrganosUicaSol)，係在醇類、二醇類、醚類等之有機溶劑 中’安定地分散粒㈣為5〜12GnmA右的二氧化碎微粒子 而成，市f品可舉例如奥斯卡(0SCAL)系列(觸媒化成(株） 製）、有機溶膠（日產化學(株)製）等。 金屬離子交換一氧化梦微粒子，係透過離子交換將金 屬離子導人微細的多孔質二氧切_之二氧切微粒 子。具體'言’係導人了約或鎂的二氧切微粒子。飼離 子交換二氧化矽的市售產品可舉例如，犯肌順 (Shield，註冊商標）C303、SHIELDEX ac_3、畑助以 C_5 (以上每一種皆由W· R. Grace & c〇公司製）等。 由金屬離子交換二氧切釋出的驗土類金屬離子，與 電化學仙或各種鹽的生成作用相關，可有效地提高雜 性。另外，被固定在塗膜中的二氧切，在脑氛圍下有 效地抑制塗膜剝離。 4-3.磷酸系鈣鹽(C3) 磷酸系飼鹽⑼係含有約作為金屬元素的碟酸鹽，可舉 19 201012881 例如，磷酸鈣、磷酸鈣銨、磷酸氫鈣、磷酸二氫鈣、氣氟 碟酸約、三聚猶料^餐系触(e3)釋出的嶙酸離^ 及#5離子有效地提高耐飯性。 本發明之水性塗料組成物中，相對於前述陽離子性樹 脂(A)及多異氰酸酯硬化劑(B)的合計固體含量1〇〇質量份， 防銹顏料混合物（c)的上述釩化合物（cl)與矽化合物（c2)及 磷酸系鈣鹽(c3)在下述範圍内。 鈒化合物(cl) : 1〜30質量份，以1〜2〇質量份為佳，For example, 'Sylysia 710, Sylysia 740, Sylysia 550, Aerosil R 972 (above 'Mother is made by Fuji Silysia Chemical Co., Ltd.), MIZUKASIL P-73 (made by Mizusawa Chemical Industry Co., Ltd.), Gasil DF (Cr〇sfield) Chemical Inc.) and the like. Organic/Valental granules 散 一 乳化 乳化 乳化 亦 亦 亦 Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or Or For example, the Oscar (0SCAL) series (manufactured by Catalyst Chemical Co., Ltd.) or the organosol (manufactured by Nissan Chemical Co., Ltd.) can be used. The metal ion exchange-oxidizes the dream microparticles by introducing the metal ions into the fine porous dioxo-diode microparticles by ion exchange. The specific 'words' lead to about or magnesium dioxide cut-off particles. Commercially available products of ion-exchanged cerium oxide include, for example, Shield (registered trademark) C303, SHIELDEX ac_3, and C_5 (each of which is manufactured by W. R. Grace & c〇) Wait. The soil-like metal ions released by metal ion exchange dioxo are related to the formation of electrochemical or various salts, and can effectively improve the impurity. Further, the dioxin which is fixed in the coating film effectively suppresses peeling of the coating film under a brain atmosphere. 4-3. Phosphate-based calcium salt (C3) The phosphate-based feed salt (9) contains a disc salt as a metal element, and may be exemplified by 19, 2010, 881, for example, calcium phosphate, calcium calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, gas The sulphuric acid is about to be triad, and the bismuth acid and #5 ions released by the meal (e3) effectively improve the resistance to rice. In the aqueous coating composition of the present invention, the vanadium compound (cl) of the rust preventive pigment mixture (c) is 1 part by mass based on the total solid content of the cationic resin (A) and the polyisocyanate curing agent (B). The ruthenium compound (c2) and the phosphate calcium salt (c3) are within the following ranges.鈒 compound (cl): 1 to 30 parts by mass, preferably 1 to 2 parts by mass,

矽化合物(c2) : 1〜30質量份’以1〜2〇質量份為佳， 磷酸系鈣鹽(c3) : 1〜30質量份，以1〜2〇質量份為佳。 另外，釩化合物(cl)、矽化合物卜2)、磷酸系鈣鹽(e3) 之混合比率（質量基準），以3〜20/3〜20/5〜20為佳，較 佳為5〜15/5〜15/10〜20。在上述範圍内時，因不僅可 獲得耐藥品性、金屬板平面部的耐蝕性，還可獲得金屬板 之加工部和端面部的耐蝕性及附著性優良的塗膜，故而合 適。The hydrazine compound (c2): 1 to 30 parts by mass is preferably 1 to 2 parts by mass, and the calcium phosphate salt (c3): 1 to 30 parts by mass, preferably 1 to 2 parts by mass. Further, the mixing ratio (mass basis) of the vanadium compound (cl), the bismuth compound 2), and the calcium phosphate salt (e3) is preferably 3 to 20/3 to 20/5 to 20, preferably 5 to 15 /5~15/10~20. When it is in the above range, not only chemical resistance but also corrosion resistance of the flat portion of the metal plate can be obtained, and a coating film having excellent corrosion resistance and adhesion of the processed portion and the end surface portion of the metal plate can be obtained.

上述飢化合物（cl)與矽化合物（C2)及鱗酸系鈣鹽（c3)之 添加量在上述範圍内時，不僅可獲得耐藥品性、金屬板平 面部的耐蝕性’還可獲得金屬板之加工部和端面部的耐钱 性及附著性優良的塗膜，故而合適。 此外，本發明之水性塗料組成物中，相對於前述陽離 子性樹脂(Α)及多異氰酸酯硬化劑(Β)的合計固體含量1〇〇質 量份，防銹顏料混合物(C)之量為3〜90質量份，以9〜60質 量伤為佳。防銹顏料混合物(C)之量在前述範圍内時，不僅 20 201012881 可獲得耐藥品性、金屬板平面部的对钱性，還可獲得金屬 板之加工部和端面部的耐蝕性及附著性優良的塗膜’故而 合適。 本發明之水性塗料組成物，可透過將這些釩化合物 (cl)、矽化合物(c2)及磷酸系鈣鹽(C3)按預定量組合的方式 形成防銹顏料混合物(C)，相乘地提高耐蚀性。防銹顏料混 合物(C)雖無特別限定，惟以含有五氧化二釩、偏矽酸鈣及 磷酸鈣的混合物為佳，從耐蝕性的觀點，五氧化二釩、偏 參 矽酸約及填酸約的組合特別合適。 再者，將相對於前述陽離子性樹脂(A)及多異氰酸酯硬 化劑(B)之合計固體含量100質量份所混合的’構成防鎊顏 料混合物(C)之釩化合物（cl)、矽酸鹽化合物（C2)及該磷酸系 鈣鹽(c3)的混合物((ci)〜(c3)的混合量在前述範圍内）’添加 到25 C之5質量％氣化鈉水溶液丨〇 〇〇〇質量份中，挽拌6小 時，過濾在25°C靜置48小時後的上清液所得到的濾液，其 pH以3〜8為佳，較佳為4〜6。前述濾液之pH在前述範圍 φ 時，從叙化合物(cl)、矽酸鹽化合物（C2)及磷酸系鈣鹽（c3) 對水的溶解性及防銹顏料之溶解液與金屬板的反應性之觀 點’或者耐蝕性之觀點來看是適當的。 亦即’得到上述pH測定的濾液是，相對於25°C的5質量 %氣化納水溶液10,〇〇〇質量份，添加釩化合物(C1)1〜30質量 份之範圍内的任意量，石夕化合物(〇!〜3〇質量份之範圍内 的任意量，以及磷酸系鈣鹽(C3)i〜30質量份之範圍内的任 意量，經溶解而得之溶解液的濾液。 21 201012881 製造本發明之水性塗料組成物時’係將前述之防銹顏 料混合物(c)和，依需要，顏料分散用樹脂、著色顏料、體 質顏料、有機錫化合物、紫外線吸收劑、紫外線安定劑、 有機溶劑、矽烷耦合劑、防沉劑、消泡劑、塗面調整劑等 自過去以來所公知的塗料用添加劑、中和劑（例如酸類，具 體而言，可舉例如醋酸、磷酸、乳酸，或其等之混合物等）、 鈒化合物（cl)、石夕化合物（c2)、鱗酸系約鹽(c3)以外的防錢 劑加以混合，並在球磨機、砂磨機、卵石磨機等之分散混 合機中施行分散處理以混合成所獲得之顏料分散漿。 另外，添加釩化合物(cl)、石夕化合物(c2)、麟酸系飼鹽 (c3)以外的防銹劑時’可以在不阻礙防銹顏料混合物（c)之 添加效果的程度的量下做添加。 前述顏料分散用樹脂可以使用公知者，例如可以使用 含有羥基及陽離子性基的基體樹脂，或三級胺型環氧樹 脂、四級銨鹽型環氧樹脂、三級锍鹽型環氧樹脂等的樹脂。 上述顏料分散用樹脂的使用量，對每100質量份的顏料成分 為1〜150質量份，特別是⑺叫⑻質量份之範圍内為合適。 上述著色顏料可舉例如，酞菁藍、酞菁綠、偶氮系或 喹丫啶酮(qumacridone)系等之有機紅色顏料等的有機著色 顏料；鈦白、鈦黃、鐵丹、碳黑、各種燒結顏料等的無機 ¥色顏料’其中尤其可以適當地使用鈦白。 上述體質顏料可舉例如，滑石、枯土、二氧化石夕 '雲 母、氧化鋁、碳酸鈣、硫酸鋇等。 上述著色顏料及體質顏料的添加量並無特別限定惟 22 201012881 例如，相對於前述陽離子性樹脂(A)及多異氰酸酯硬化劑(B) 之合計固體含量100質量份，分別為1〜100質量份左右。 上述有機錫化合物可以適當地使用二丁基二苯甲酸錫 (dibutyl tin dibenzoate)、二辛基氧化錫、二丁基氧化錫等。 前述有機溶劑係為改善本發明之水性塗料組成物的塗 裝性等而根據需要混合者，可以使用能夠溶解乃至於分散 陽離子性樹脂(A)及多氰酸酯硬化劑(B)的有機溶劑。具體而 言，可舉例如，甲苯、二甲苯、高沸點石油系烴等烴系溶 ❹ 劑、甲乙酮、甲基異丁酮、環己酮、異佛酮等的酮系溶劑， 醋酸乙酯、醋酸丁酯、乙二醇單***醋酸酯、二乙二醇單 ***醋酸酯等的酯系溶劑，甲醇、乙醇、異丙醇、丁醇等 . 的醇系溶劑，乙二醇單***、乙二醇單丁醚、二乙二醇單 丁醚等的醚醇系溶劑等，可以將它們單獨或混合2種以上使 用。 前述之矽烷偶合劑可舉例如，β-(3,4-環氧環己基）乙基 三曱氧基矽烷、γ-縮水甘油醚丙基三甲氧基矽烷 (γ-glycidoxypropyltrimethoxysilane)、γ-縮水甘油醚丙基甲 基二乙氧基矽烷、γ-縮水甘油醚丙基三乙氧基矽烧、Ν-β(胺 乙基)γ-胺丙基甲基二甲氧基矽烷、Ν-β(胺乙基)γ-胺丙基三 曱氧基矽烷、Ν-β(胺乙基)γ-胺丙基三甲氧基矽烷、γ_胺丙 基三曱氧基石夕烧、β-胺丙基三乙氧基石夕院、Ν-苯基-γ-胺丙 基三甲氧基矽烷、Ν-(乙烯基苄胺)-β-胺乙基-γ-胺丙基三 甲氧基矽烷等，可以將它們單獨或混合2種以上使用。 可以利用將含有如上所述之防銹顏料混合物（C)的顏 23 201012881 料分散漿加到前述的乳液中’並以水調整的方式來調整水 性塗料組成物。 5.塗膜形成方法 本發明之水性塗料組成物，可以透過塗裝在金屬板上 並使之硬化的作法而獲得塗裝金屬板。被塗裝的金屬板可 舉例如前述之金屬板。另外，這些金屬板的表面，亦可施 以化學轉化處理（前處理）。 第1圖為，用本發明之水性塗料組成物作為底塗塗料時 之塗裝線的模式圖。此處，因為於熔融錢鋅鋼板上塗裝本 發明之水性塗料組成物而獲得的塗膜，即使不施行化學轉 化處理(前處理）’也可獲得耐祕優良之㈣，故在塗㈣ 中亦可省略化學轉化處理(前處理）的程序，對於省i程和冑 資源化也可有所貢獻。 ’ 另外，可依需要而施行的化學轉化處理(前處理），可U ' 舉例如，磷酸鋅處理或磷酸鐵處理等之魏鹽處理、複合 乳化膜處理、碟酸絡處理、絡酸鹽處理等。 使用本發明之水性塗料組成物的塗裝可在上述金$ ❿ 板上，利用滾筒式塗布法、淋幕式塗布朴—n fl〇w coating)、喷塗法、毛刷塗布法、浸潰法等公知的方法來進 行塗裝。 由水性塗料組成物獲得之塗膜的硬化膜厚度並無特殊 限疋，通常在0.5〜ΙΟμιη、宜在2〜7μηι之範圍使用。 塗膜的硬化’只要依據使用的樹脂之種類等做適當設 疋即可，在連續燒結利用線圏塗布法等塗裝成的塗膜時， 24 201012881 是在材料到達的最高溫度為100〜250°C，以達到180〜 230C為佳之條件下，燒結15〜6〇秒。批次式燒結的情形， 則亦可在80〜200。(：燒結1〇〜3〇分鐘。 本發明之水性塗料組成物塗裝於金屬板上，所形成的 塗膜不僅在金屬板之平面部，在金屬板之加工部和端面 部也表現出優良的耐蝕性。 其理由考慮有以下3點。 1·在腐蚀環境下’因氯化物離子等造成素材金屬的溶 ® 解而生成之金屬離子’與5價的釩離子(V(V或V043-的釩酸 離子）不經歷氧化還原反應而直接生成沉澱性的鹽，5價釩 離子與素材金屬之因氧化還原反應而生成的3價釩離子及 . 素材金屬離子，和矽酸離子有效地生成沉澱性的鹽或化合 • 物’藉而有效地被覆素材露出面。此外，認為是因為同時 溶出的磷酸離子，使得腐蝕進行部位及其周邊被調整成特 別適合於5價釩離子與素材金屬進行氧化還原反應的pH範 圍。 ® 2.本水性塗料組成物中防銹劑有一部分溶解而以金屬 離子狀態存在。將本水性塗料組成物塗裝於金屬素材並加 熱乾燥形成塗膜時，該溶解成分在素材金屬的界面上有效 地發生反應，於前述塗膜之下，形成發揮如化學轉化處理 皮膜的作用之氧化皮膜。而且，即使該皮膜上之塗膜受損， 依然可以從塗膜中，因防銹顏料混合物(C)的金屬離子溶出 而形成具有保護該損傷之作用（自我修復性）的塗膜。上述的 「皮膜與塗膜」之形成，可通過1次塗裝與加熱乾燥獲得， 25 201012881 這點推測對於獲得耐蝕性優良之塗裝物品大有幫助。 3.藉併用構成防銹顏料混合物的前述釩化合物（cl)、 矽酸鹽化合物(c2)及該磷酸系鈣鹽(c3)，可以有效地節制前 述(cl)、（c2)及(C3)各自具有的耐酸性或耐鹼性及耐水性的 薄弱部分。此外，因為鈣離子在超過pH 10之素材金屬易於 溶解的強驗氛圍下，具有抑制素材金屬溶解的作用，故可 同時實現優良的耐藥品性和耐水性。以這些防鎊顏料混合 物為基礎的作用之相乘效果發揮了很大功能，推斷這也對 本水性塗料之優良耐蝕性大有幫助。 參 再者，由本發明之水性塗料組成物獲得的硬化塗膜之 玻璃轉移溫度為40〜115°C，從塗膜之耐蝕性、耐酸性及加 工性等的點來看，以50〜1〇5。(：為佳。 . 而’塗膜的玻璃轉移溫度是使用DINAMIC VISCO-EL ASTO METER MODEL VIBRON (振動子型動態 粘彈譜 儀）DDV-IIEA型（ToyoBaldwinCo.製，自動動態粘彈性測 定儀）’根據在頻率110Hz中之溫度分散測定所得到的tan5 之變化所求得的極大值溫度^ ❿ 在燒結乾燥水性塗料組成物所得的塗膜之上，依需要 亦可配設面漆塗膜（參見第2圖面漆塗膜之膜厚為5〜 ΙΟμιη，以 10〜50μιη為佳。 上述之面漆塗料可舉例如，作為預塗鋼板之公知的聚 Θ旨樹脂系、醇酸樹脂系、矽酮改質聚酯（siHc〇ne modified polyester)樹脂系、石夕酮改質丙烯酸樹脂系、氟樹脂系等的 面漆塗料。面漆塗料之種類並不限於上述種類。此外，在 26 201012881 特別重視加工性之情形中，可使用高度加工用的聚醋系面 漆塗料，藉以獲得加工性特別優良的塗裝金屬板。 此外’使用鑛鋅鋼板、触-鋅合金鋼板作為被塗物的 t屬板時’金屬板平面部的耐齡大為提高，不過，截至 s岫的技術’在切斷的端面部和經過成型加工的加工部， 财蚀性部都疋不足的。然而，藉塗裝本發明之水性塗料組 成’可以獲得具有耐藥品性，而且無論是在金屬板之平面 部、端面部、加工部，均可以體現優良耐姓性的塗膜。 ❹ 實施例 以下’將藉製造例、實施例及比較例更詳細地說明本 - 發明，但本發明不限於此。各例中之「份」表示質量份、「％」 . 表示質量％。 陽離子性樹脂(Α)的製造 製造例1陽離子性環氧樹脂No. 1之製造例(環氧樹脂系） 用裝有攪拌器、溫度計、氮氣導入管及回流冷卻器的 燒瓶，將jER1004(雙酚A型環氧樹脂，環氧值〇1〇8 ® m〇l/l〇〇g ’ 數量平均分子量 1，65〇，Japan Epoxy Resins Co.，When the amount of the above-mentioned hunger compound (cl), the cerium compound (C2), and the scaly calcium salt (c3) is within the above range, not only chemical resistance but also corrosion resistance of the flat portion of the metal plate can be obtained. It is suitable for the coating film having excellent durability and adhesion of the processed portion and the end surface portion. Further, in the aqueous coating composition of the present invention, the amount of the antirust pigment mixture (C) is 3 to 3 parts by mass based on the total solid content of the cationic resin (Α) and the polyisocyanate curing agent (Β). 90 parts by mass, preferably 9 to 60 quality wounds. When the amount of the rust preventive pigment mixture (C) is within the above range, not only 20 201012881 can obtain chemical resistance, the surface of the metal sheet, but also the corrosion resistance and adhesion of the processed portion and the end surface of the metal sheet. An excellent coating film is suitable. The aqueous coating composition of the present invention can form a rust preventive pigment mixture (C) by combining these vanadium compound (cl), bismuth compound (c2) and phosphoric acid calcium salt (C3) in a predetermined amount, and multiply the mixture. Corrosion resistance. Although the rust preventive pigment mixture (C) is not particularly limited, it is preferably a mixture containing vanadium pentoxide, calcium metasilicate, and calcium phosphate. From the viewpoint of corrosion resistance, vanadium pentoxide, bismuth citrate, and A combination of acids is particularly suitable. In addition, the vanadium compound (cl) constituting the anti-pound pigment mixture (C) and the cerium salt are mixed with respect to 100 parts by mass of the total solid content of the cationic resin (A) and the polyisocyanate curing agent (B). a mixture of the compound (C2) and the phosphate-based calcium salt (c3) (the amount of (ci) to (c3) is within the above range) 'added to 25 C of a 5 mass% sodium carbonate aqueous solution 丨〇〇〇〇 mass The mixture was stirred for 6 hours, and the filtrate obtained by filtering the supernatant after standing at 25 ° C for 48 hours had a pH of preferably 3 to 8, preferably 4 to 6. When the pH of the filtrate is in the above range φ, the solubility of the compound (cl), the citrate compound (C2), and the phosphate calcium salt (c3) in water and the reactivity of the rust preventive pigment solution with the metal plate are obtained. The viewpoint 'or the viewpoint of corrosion resistance is appropriate. In other words, the filtrate obtained by the above-mentioned pH measurement is an amount of the vanadium compound (C1) in an amount of from 1 to 30 parts by mass, based on 5 parts by mass of the vaporized sodium solution 10 at 25 ° C, and the amount of the vanadium compound (C1). Any amount within the range of 石!~3〇 parts by mass and any amount within the range of i to 30 parts by mass of the phosphate calcium salt (C3), dissolved in the filtrate of the solution. 21 201012881 When the aqueous coating composition of the present invention is produced, the anti-rust pigment mixture (c) and, if necessary, the resin for pigment dispersion, the coloring pigment, the extender pigment, the organotin compound, the ultraviolet absorber, the ultraviolet stabilizer, and the organic An additive for a coating material, a neutralizing agent (for example, an acid, such as acetic acid, phosphoric acid, lactic acid, or the like, which is known from the past, such as a solvent, a decane coupling agent, an anti-settling agent, an antifoaming agent, and a coating surface adjusting agent. a mixture such as a mixture thereof, a ruthenium compound (cl), a ruthenium compound (c2), or a tartar-based salt (c3), and is dispersed in a ball mill, a sand mill, a pebble mill, or the like. Dispersion in the mixer In addition, when the rust inhibitor other than the vanadium compound (cl), the stone compound (c2), and the linonic acid salt (c3) is added, the rust preventive pigment mixture can be prevented. (c) The amount of the additive effect may be added. The pigment dispersion resin may be a known one. For example, a base resin containing a hydroxyl group and a cationic group, or a tertiary amine type epoxy resin or a quaternary ammonium salt may be used. The resin used for the pigment dispersion resin is used in an amount of 1 to 150 parts by mass per 100 parts by mass of the pigment component, and particularly (7) is called (8) parts by mass. The coloring pigment may, for example, be an organic coloring pigment such as an organic red pigment such as phthalocyanine blue, phthalocyanine green, azo or quinacridone; titanium white, titanium yellow, and iron dan In particular, titanium black may be suitably used among the inorganic black pigments such as carbon black and various sintered pigments. The above-mentioned extender pigments may, for example, be talc, dry earth, silica dioxide mica, alumina, calcium carbonate, barium sulfate. Wait The amount of the coloring pigment and the extender pigment is not particularly limited, and it is, for example, 1 to 100 parts by mass per 100 parts by mass of the total solid content of the cationic resin (A) and the polyisocyanate curing agent (B), respectively. The above organotin compound may suitably use dibutyl tin dibenzoate, dioctyltin oxide, dibutyltin oxide, etc. The organic solvent is used to improve the aqueous coating composition of the present invention. An organic solvent capable of dissolving or dispersing the cationic resin (A) and the polycyanate curing agent (B) may be used as the coating property, etc. Specific examples thereof include toluene and xylene. a hydrocarbon-based solvent such as a high-boiling petroleum hydrocarbon, a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or isophorone; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and An ester solvent such as ethylene glycol monoethyl ether acetate, an alcohol solvent such as methanol, ethanol, isopropanol or butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether Ether Based solvent may be used singly or as a mixture of two or more use. The above-mentioned decane coupling agent may, for example, be β-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, γ-glycidoxypropyltrimethoxysilane, γ-glycidol. Ethyl propyl methyl diethoxy decane, γ-glycidyl ether propyl triethoxy oxime, Ν-β (aminoethyl) γ-aminopropyl methyl dimethoxy decane, Ν-β ( Amine ethyl) γ-aminopropyl trimethoxy decane, Ν-β (aminoethyl) γ-aminopropyl trimethoxy decane, γ-aminopropyl trimethoxy oxy-stone, β-aminopropyl Triethoxy zeshi, Ν-phenyl-γ-aminopropyltrimethoxydecane, Ν-(vinylbenzylamine)-β-amineethyl-γ-aminopropyltrimethoxydecane, etc. These can be used individually or in mixture of 2 or more types. The aqueous coating composition can be adjusted by a water-adjusting method by using a pigment dispersion slurry containing the rust-preventive pigment mixture (C) as described above in the emulsion described above. 5. Coating film forming method The aqueous coating composition of the present invention can be obtained by coating a metal plate and hardening it. The coated metal plate can be exemplified by the aforementioned metal plate. In addition, the surface of these metal plates may be subjected to chemical conversion treatment (pretreatment). Fig. 1 is a schematic view showing a coating line when the aqueous coating composition of the present invention is used as a primer. Here, since the coating film obtained by coating the water-based paint composition of the present invention on the molten zinc-zinc steel sheet can be obtained without the chemical conversion treatment (pretreatment), it is excellent in the resistance (4), so in the coating (four) It is also possible to omit the procedure of the chemical conversion treatment (pre-treatment), and contribute to the saving of the process and the resource utilization. In addition, chemical conversion treatment (pretreatment) can be carried out as needed, for example, Wei salt treatment, composite emulsion membrane treatment, dish acid treatment, and complex acid treatment for zinc phosphate treatment or iron phosphate treatment. Wait. The coating of the aqueous coating composition of the present invention can be applied to the above-mentioned gold ❿ board by a roll coating method, a curtain coating method, a spray coating method, a brush coating method, and a dipping A known method such as a method is used for coating. The thickness of the cured film of the coating film obtained from the aqueous coating composition is not particularly limited, and is usually used in the range of 0.5 to ΙΟμηη, preferably 2 to 7 μm. The curing of the coating film can be appropriately set according to the type of the resin to be used, and when the coating film is applied by continuous coating or the like, 24 201012881 is the highest temperature at which the material reaches 100 to 250. °C, to achieve 180~230C for better conditions, sintering 15~6 〇 seconds. In the case of batch sintering, it can also be in the range of 80 to 200. (: Sintering 1 〇 to 3 〇 minutes. The aqueous coating composition of the present invention is coated on a metal plate, and the formed coating film is excellent not only in the flat portion of the metal plate but also in the processed portion and the end surface portion of the metal plate. Corrosion resistance. The reasons for this are as follows: 1. In the corrosive environment, 'metal ions generated by dissolution of metal ions due to chloride ions, etc.' and pentavalent vanadium ions (V (V or V043-) The vanadic acid ion directly forms a precipitated salt without undergoing a redox reaction, and the trivalent vanadium ion and the metal ion generated by the redox reaction of the pentavalent vanadium ion and the material metal are efficiently generated. The precipitated salt or the compound's material can effectively cover the material to expose the surface. In addition, it is considered that the phosphate ion is dissolved at the same time, so that the corrosion progressing portion and its periphery are adjusted to be particularly suitable for the pentavalent vanadium ion and the material metal. The pH range of the redox reaction. 2. The rust inhibitor in the aqueous coating composition is partially dissolved and exists in the state of metal ions. The waterborne coating composition is applied to the metal material and added. When the coating film is formed by thermal drying, the dissolved component is effectively reacted at the interface of the material metal, and an oxide film which functions as a chemical conversion treatment film is formed under the coating film. Further, even if the film is coated on the film In addition, it is possible to form a coating film having a function of protecting the damage (self-healing property) by eluting the metal ions of the rust-preventing pigment mixture (C) from the coating film. The formation of the above-mentioned "film and coating film", It can be obtained by one coat and heat drying, 25 201012881 This is presumably helpful for obtaining coated articles excellent in corrosion resistance. 3. By using the above-mentioned vanadium compound (cl) and citrate compound which constitute a mixture of rust preventive pigments (c2) and the phosphate-based calcium salt (c3) can effectively control the weak portions of the acid resistance, alkali resistance, and water resistance of each of the above (cl), (c2), and (C3). In a strong atmosphere where the material of the material exceeding pH 10 is easy to dissolve, it has the effect of inhibiting the dissolution of the metal of the material, so that excellent chemical resistance and water resistance can be achieved at the same time. The multiplication effect of the basic function exerts a great function, and it is inferred that this also contributes greatly to the excellent corrosion resistance of the water-based paint. Further, the glass transition temperature of the hardened coating film obtained from the aqueous paint composition of the present invention is 40~ 115 ° C, from the point of view of the corrosion resistance, acid resistance and processability of the coating film, 50 to 1 〇 5. (: is better. . . 'The glass transition temperature of the coating film is to use DINAMIC VISCO-EL ASTO METER MODEL VIBRON (Vibration type dynamic viscoelastic spectrometer) DDV-IIEA type (manufactured by ToyoBaldwin Co., automatic dynamic viscoelasticity meter) 'maximum value obtained from the variation of tan5 obtained by temperature dispersion measurement at a frequency of 110 Hz Value temperature ^ ❿ On the coating film obtained by sintering and drying the water-based paint composition, a top coat film may be provided as needed (see the film thickness of the top coat film in Fig. 2 is 5~ ΙΟμιη, with 10~50μιη as good. The above-mentioned top coat paint may, for example, be a known polyether-based resin, an alkyd resin, an oxime-modified polyester resin, or a linalo-modified acrylic resin. A topcoat paint such as a fluororesin or the like. The type of the top coat is not limited to the above types. In addition, in the case of 26 201012881, when processing is particularly important, a highly processed urethane-based topcoat can be used to obtain a coated metal sheet having particularly excellent workability. In addition, 'the use of mineral zinc steel plate and touch-zinc alloy steel plate as the t-plate of the coated object' is greatly improved in the flatness of the flat portion of the metal plate, but the technique of the s岫 is cut off at the end face and molded. The processing department and the financial department are insufficient. However, by coating the water-based paint composition of the present invention, it is possible to obtain a coating film which is excellent in resistance to the surname regardless of the flat portion, the end surface portion, and the processed portion of the metal sheet. EMBODIMENT EXAMPLES Hereinafter, the present invention will be described in more detail by way of Production Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In each case, "parts" means parts by mass and "%". It means mass%. Production Example 1 of a cationic resin (Α) Production Example of a cationic epoxy resin No. 1 (epoxy resin) A jER1004 (double) was used with a flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a reflux condenser. Phenolic A type epoxy resin, epoxy value 〇1〇8 ® m〇l/l〇〇g ' number average molecular weight 1,65〇, Japan Epoxy Resins Co.,

Ltd.製）100份與 ’ 3-甲氧基乙酸丁醋（3_methoxybutyl acetate) 25份在l〇〇°C加溫混合。 確認已均勻溶解後，添加單乙醇胺2.75份，就這樣反 應2小時。確認環氧值達到0.018 mol/100g後，添加二乙醇 胺1.89份’再繼續反應2小時。如果環氧值降到0.005 mol/100g以下，就用預先混合成甲乙酮肪/二甲苯/丁醇 =1/1八的混合溶劑稀釋，獲得固體含量65%的陽離子性環 27 201012881 氧樹脂No. 1。而，獲得的陽離子性環氧樹脂Νο· i的胺價 為35.1 mgKOH/g。 製造例2陽離子性環氧樹脂No. 2之製造例（二異氰酸酯 化合物改質系） 用裝有授拌器、溫度計、氮氣導入管及回流冷卻器的 燒瓶’將jER1004 (雙酚a型環氧樹脂，環氧值〇.108 mol/l〇〇g ’ 數量平均分子量 i，65〇，japan EpOXy Resins Co·,100 parts of <3-methoxybutyl acetate" made by Ltd. was mixed and warmed at 10 °C. After confirming that it was uniformly dissolved, 2.75 parts of monoethanolamine was added, and the reaction was carried out for 2 hours. After confirming that the epoxy value reached 0.018 mol/100 g, 1.89 parts of diethanolamine was added, and the reaction was further continued for 2 hours. If the epoxy value falls below 0.005 mol/100g, it is diluted with a mixed solvent premixed with methyl ethyl ketone/xylene/butanol = 1/1 8 to obtain a cationic ring of 65% solids. 201012881 Oxygen resin No. 1. Further, the obtained cationic epoxy resin Νο· i had an amine value of 35.1 mgKOH/g. Production Example 2 Production Example of Cationic Epoxy Resin No. 2 (Diisocyanate Compound Modification System) jER1004 (bisphenol a type epoxy) was used in a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux cooler. Resin, epoxy value 〇.108 mol/l〇〇g ' number average molecular weight i, 65 〇, japan EpOXy Resins Co·,

Ltd.製)和，3-甲氧基乙酸丁酯25份在1〇(rc加溫混合。 確認已均勻溶解後’添加n_甲基乙醇胺6 75份，就這 麵 樣反應2小時。確認環氧值達到〇 〇18 mol/100g後，添加預 先混合成甲乙酮肟/二曱笨=1/丨的混合溶劑丨丨丨份，並將反 應溫度冷卻至40°C為止。 確認均勻溶解後，添加六亞甲基二異氰酸酯7 56份， 就這樣反應1小時。之後，再度將反應溫度加溫至100°c， 添加二乙醇胺1.89份，再繼續反應丨小時。如果環氧值降到 0.005 mol/l〇〇g以下，就用預先混合成甲乙酮肟/二甲苯/丁 醇= 1/1/1的混合溶劑稀釋，獲得固體含量65%的二異氰酸 © 酯化合物改質的陽離子性環氧樹脂No. 2。而，所獲得的陽 離子性環氧樹脂No. 2的胺價為53 0 mgKOH/g。 製造例3陽離子性環氧樹脂No. 3之製造例（二元酸改質 系） 用裝有擾掉器、溫度計、氮氣導入管及回流冷卻器的 燒瓶’將jER1004(雙酚a型環氧樹脂、環氧值0.108 mol/100g ’ 數量平均分子量 i，65〇，Japan Epoxy Resins Co.， 28 201012881Ltd.) and 25 parts of 3-methoxyacetic acid butyl ester were mixed at 1 Torr (rc was heated. After confirming that it had been uniformly dissolved, '75 parts of n-methylethanolamine was added, and the reaction was carried out for 2 hours. After the epoxy value reaches 〇〇18 mol/100g, a mixed solvent mixture pre-mixed to methyl ethyl ketone oxime / dioxane = 1 / 丨 is added, and the reaction temperature is cooled to 40 ° C. After confirming uniform dissolution, Adding 56 parts of hexamethylene diisocyanate, reacting for 1 hour, then heating the reaction temperature to 100 ° C again, adding 1.89 parts of diethanolamine, and continuing the reaction for a few hours. If the epoxy value drops to 0.005 mol /l〇〇g or less, diluted with a mixed solvent previously mixed with methyl ethyl ketone oxime / xylene / butanol = 1 / 1 / 1 to obtain a cationic ring modified with a diisocyanate compound having a solid content of 65%. Oxygen resin No. 2. The amine resin of the obtained cationic epoxy resin No. 2 was 530 mg KOH/g. Production Example 3 Production Example of cationic epoxy resin No. 3 (dibasic acid modification system) ) Using a flask equipped with a scrambler, thermometer, nitrogen inlet tube and reflux cooler 'jER1004 (bisphenol a type) Epoxy resin, epoxy value 0.108 mol/100g ′ number average molecular weight i, 65〇, Japan Epoxy Resins Co., 28 201012881

Ltd.製）100份’與3-甲氧基乙酸丁酯25份在1〇〇。(：加溫混合。 確認已均勻溶解後，添加Tsunodime 205(二聚酸、築野 食品工業社(TSUNO CO.，LTD.)製）1〇份，就這樣反應2小 時。確認酸價達到〇_5 mgKOH/g以下之後，添加單乙醇胺 2.36份’再繼續保持這樣地反應2小時。確認環氧值達到 0.018 mol/100g後，添加二乙醇胺189份，再反應丨小時。 環氧值如果降到0.005mol/100g以下，就用預先混合成曱乙 酮肟/二甲苯/丁醇=1/1/1的混合溶劑稀釋，獲得固體含量 Φ 65%的二聚酸改質的陽離子性環氧樹脂No. 3。而，所得陽 離子性環氧樹脂No. 3的胺價為28.9 mgKOH/g。 水性塗料用乳液的製造 ' 製造例4 乳膠No. 1之製造例 , 將在製造例1製得的陽離子性環氧樹脂No. 1 (固體含 量 80 份）123.1 份、Desmodur BL-3175 (Sumitomo Bayer Urethane Co., Ltd.製，用甲乙酮肟封閉的六亞甲基二異氰酸 酯型多異氰酸酯化合物溶液，固體含量約75%) 26.7份（固體 ® 含量20份）、乙二醇單丁醚20份加以混合，再混合10%醋酸 3〇·3份並攪拌混勻後，將去離子水133.2份邊強烈攪拌邊以 大約30分鐘滴下’獲得樹脂固體含量30%的乳液No. 1。 製造例5〜10 乳膠No. 2〜No. 7之製造例 除表1的混合内容以外，與製造例4同樣地處理，獲得 乳液No. 2〜No. 7。 29 201012881 [表1] 製造例 4 5 6 7 8 9 10 乳液 No.l No.2 Νο.3 Νο.4 Νο.5 Νο.6 Νο·7 混 合 物 質 陽離子性環氧樹脂Νο·1 固體含量65% 123.1 (8〇) 123.1 (80) 123.1 (80) 123.1 (80) 153.8 (100) 陽離子性環氧樹脂No_2 固體含量65% 123.1 (80) 陽離子性環氧樹脂Νο.3 固體含量65% 123.1 (80) 乙二酵單丁醚 20 20 20 20 20 20 20 Desmodur BL-3175 固體含量75% (註2) 26.7 (2〇) 26.7 (20) 26.7 (2〇) 26.7 (20) Duranate MF-K60X 固體含量60% (註 333 (20) 33.3 (20) 10%醋酸 <當量> 30.3 <1.0> 34.7 <0.67> 212 <1.0> 30.3 <1.0 15.1 <0.5> 15.1 <0.5> 30.3 <1.0 1〇°/4 酸 <當量> 24.8 <0.5> 24.8 <0.5> 去離子水 133.2 128.8 136.3 126.6 123.6 117 129.2 30%乳液的合計量 333.3 (100) 333.3 (100) 333.3 (1〇〇) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 混合中0内之數字表示固體含量。 參 (注2) Desmodur BL-3175 : Sumitomo Bayer Urethane Co.，Ltd.) 100 parts 'with 3 parts of 3-methoxyacetic acid butyl ester at 1 Torr. (: Warming and mixing. After confirming that it has been uniformly dissolved, one part of Tsunodime 205 (dimerized acid, manufactured by TSUNO CO., LTD.) was added, and the reaction was carried out for 2 hours. After _5 mgKOH/g or less, 2.36 parts of monoethanolamine was added, and the reaction was continued for 2 hours. After confirming that the epoxy value reached 0.018 mol/100 g, 189 parts of diethanolamine was added, and the reaction was further carried out for a few hours. To 0.005 mol/100 g or less, it is diluted with a mixed solvent pre-mixed with ethyl ketone ketone/xylene/butanol = 1/1/1 to obtain a dimer acid-modified cationic epoxy having a solid content of Φ 65%. Resin No. 3. The amine valence of the obtained cationic epoxy resin No. 3 was 28.9 mgKOH/g. Production of Emulsion for Aqueous Coatings Manufactured Example 4 A manufacturing example of Latex No. 1 was produced in Production Example 1. Cationic epoxy resin No. 1 (solid content: 80 parts), 123.1 parts, Desmodur BL-3175 (manufactured by Sumitomo Bayer Urethane Co., Ltd., a solution of hexamethylene diisocyanate type polyisocyanate compound blocked with methyl ethyl ketone oxime, Solid content about 75%) 26.7 parts (solids content 20 parts) 20 parts of ethylene glycol monobutyl ether was mixed, and then mixed with 10% acetic acid 3 〇·3 parts and stirred and mixed, 133.2 parts of deionized water was vigorously stirred and dropped for about 30 minutes to obtain a resin solid content of 30%. The emulsion No. 1 was produced in the same manner as in Production Example 4 except that the contents of the mixing of Table 1 were obtained, and the emulsion No. 2 to No. 7 were obtained. 29 201012881 [ Table 1] Production Example 4 5 6 7 8 9 10 Emulsion No.l No.2 Νο.3 Νο.4 Νο.5 Νο.6 Νο·7 Mixed substance cationic epoxy resin Νο·1 Solid content 65% 123.1 ( 8〇) 123.1 (80) 123.1 (80) 123.1 (80) 153.8 (100) Cationic epoxy resin No_2 Solid content 65% 123.1 (80) Cationic epoxy resin Νο.3 Solid content 65% 123.1 (80) B Diacetate monobutyl ether 20 20 20 20 20 20 20 Desmodur BL-3175 Solids content 75% (Note 2) 26.7 (2〇) 26.7 (20) 26.7 (2〇) 26.7 (20) Duranate MF-K60X Solid content 60% (Note 333 (20) 33.3 (20) 10% acetic acid <Equivalent> 30.3 <1.0> 34.7 <0.67> 212 <1.0> 30.3 <1.0 15.1 <0.5> 15.1 ≪ 0.5 > 30.3 < 1.0 1 〇 ° / 4 acid < equivalents > 24.8 <0.5 > 24.8 <0.5> Deionized water 133.2 128.8 136.3 126.6 123.6 117 129.2 Total amount of 30% emulsion 333.3 ( 100) 333.3 (100) 333.3 (1〇〇) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) The number in 0 in the mixture indicates the solid content. Reference (Note 2) Desmodur BL-3175 : Sumitomo Bayer Urethane Co.,

Ltd.製，用甲乙酮肟封閉的六亞甲基二異氰酸酯型多異氰酸 酯化合物溶液，固體含量約75% (注 3) Duranate MF-K60X : Asahi Kasei Chemicals Corp. 製，活性亞甲基封閉的六亞甲基二異氰酸酯之樹脂溶液， 馨 固艎含量60% 製造例11 顏料分散用樹脂之製造例 將390份的雙酚A，240份的Plaxel 212 (聚己醯内酯二 醇，Daicel Chemical Industries Ltd.，商品名，重量平均分 子量約 1，250)及 0.2份的二甲基苄胺（dimethylbenzylamine) 加到1010份的jER828EL(注4)，在130°C反應直至環氧當量 成為約1,090 g/eq為止。 30 201012881 接著’加入134份的二甲基乙醇胺及15〇份之9〇%乳酸 水溶液，在UOt：反應4小時。接著，加入甲基異丁基酮調 整固體含量，獲得固體含量6G%的銨鹽型樹脂之顏料分散 用樹脂。上述分散用樹脂的銨鹽濃度為〇 78 mm〇1/g。 G主4) jER828EL.商品名’環氧樹脂，Japan Ep〇Xy Resins c〇 , Ltd.製 ’’ 製造例12顏料分散聚No. 1之製造例 加入在製造例11中獲得之固體含量6〇%的顏料分散用 樹脂8.3份（固體含量5份）、五氧化二釩2份、偏矽酸鈣丨份、 磷酸鈣2份、鈦白20份、氧化鋇(硫酸鋇)2〇份及去離子水37 6 份，用球磨機分散20小時，施行顏料分散直至粒子（顏料粗 粒子的粒徑）成為20μηι以下，獲得固體含量55%的顏料分散 漿 No. 1。 對25°C的5質量％氣化鈉水溶液1〇 〇〇〇份，添加構成防 銹顏料混合物(C)的五氧化二釩2份、偏矽酸鈣丨份、磷酸鈣 2份的混合物並攪拌6小時，測定過濾在2Γ(：靜置了 48小時 的上清液而得到之濾液的pH。濾液的pH為5.5。 製造例13〜21 除表2的混合内容以外，與製造例12同樣地處理製得 顏料分散漿No· 2〜No. 10。另外，以和製造例12同樣的方 法，將測定化合物(cl)〜(c3)混合物的氣化鈉水溶液濾液之 pH的結果示於表2。 31 201012881 [表2] 製造例 12 13 14 15 16 17 18 19 20 21 顏料分散漿 No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 No. 10 顏料分散用樹脂 8.3 8.3 83 8.3 8.3 8.3 8.3 8.3 8.3 8.3 (5) (5) ⑸ (5) (5) (5) (5) (5) (5) (5) 五氧化二釩 2 10 20 30 20 20 20 20 (cl) 偏釩酸敍 20 釩酸約 20 混 偏矽酸約 1 5 5 20 10 10 石夕化合物 偏矽酸錢 5 .(c2) 矽酸銘 5 shieldexC303 20 20 20 20 20 20 sylysia710 10 20 合 成始备征BA 磷酸約 2 10 20 30 20 20 (c3) 磷酸一氣約 20 20 20 三聚磷酸转 20 著色顏料 鈦白 20 20 20 20 20 20 20 20 20 20 體質顏料 氧化鋇 20 20 20 20 20 20 20 20 20 20 去離子水 37.6 54 86.7 107.2 86.7 86.7 90.8 90.8 82.6 82.6 顏料分散漿 90.9 127.3 200 245.5 200 200 209.1 209.1 190.9 190.9 固想含量55% (50) (70) (110) (135) (110) (110) (115) (115) (105) (105) 防銹顏料混合物(c)的合計量 5 25 65 90 65 65 70 70 60 60 濾液的pH 5.5 5.5 6.0 7.0 5.5 5.5 5.8 6.0 7.8 7.7 數值表示混合質量份，0表示固體含量。 表2中之「sylysia 710」、「shieldex C303」如下。 sylysia 710 :二氧化石夕微粉末，平均粒徑2·8μιη，吸油量190 ml/100g、BET比表面積700 m2/g，Fuji Silysia Chemical Ltd·製 shieldex C303 :妈離子交換二氧化砍，W. R. Grace & Co. 社製 比較製造例1〜10 除表3的混合内容以外，與製造例12同樣地處理，製得 顏料分散漿No. 11〜No. 20。另外’以和製造例12同樣的 方法，將測定化合物(el)〜（c3)混合物的氣化鈉水溶液濾液 之pH的結果示於表3。 201012881 [表3] 比較製造例 1 2 3 4 5 6 7 8 9 10 顏料分散漿 No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 No. 19 No. 20 混 合 顏料分散用樹脂 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 叙化合物(cl) 五氧化二釩 0 40 50 20 20 0 20 20 偏釩酸敍 釩酸奸 矽化合物(c2) 偏矽酸約 0 40 20 50 20 20 0 20 偏矽酸錢 矽酸鋁 磷酸系鈣鹽(c3) 磷酸約 0 40 20 20 50 20 20 0 磷酸一氫約 三聚磷酸約 著色染料 欽白 20 20 20 20 20 20 20 20 20 20 體質染料 氧化鋇 20 20 20 20 20 20 20 20 20 20 鉻酸锶 50 90 去離子水 33.5 131.7 107.2 107.2 107.2 66.2 66.2 662 74.4 107.2 顏料分散漿 固體含量55% 81.8 (45) 300 (165) 245.5 (135) 245.5 (135) 245.5 (135) 154.5 (85) 154.5 (85) 154.5 (85) 172.7 (95) 245.5 (135) 防銹顏料C成分之合計 0 120 90 90 90 40 40 40 0 0 濾液的pH - 8.2 4.8 9.1 8.0 11.2 4.3 8.3 7.7 8.1 數值表示混合質量份，（)表示固體含量。Co., Ltd., a solution of hexamethylene diisocyanate type polyisocyanate compound blocked with methyl ethyl ketone oxime, solid content of about 75% (Note 3) Duranate MF-K60X: Asahi Kasei Chemicals Corp., active methylene-closed six Resin solution of methyl diisocyanate, saponin content 60% Production Example 11 Production Example of Pigment Dispersion Resin 390 parts of bisphenol A, 240 parts of Plaxel 212 (polycaprolactone diol, Daicel Chemical Industries Ltd) ., trade name, weight average molecular weight about 1,250) and 0.2 parts of dimethylbenzylamine were added to 1010 parts of jER828EL (Note 4), and reacted at 130 ° C until the epoxy equivalent became about 1,090 g / Eq until now. 30 201012881 Next, 134 parts of dimethylethanolamine and 15 parts by weight of a 9% aqueous solution of lactic acid were added, and the reaction was carried out at UOt for 4 hours. Next, methyl isobutyl ketone was added to adjust the solid content to obtain a pigment dispersion resin of an ammonium salt type resin having a solid content of 6 G%. The ammonium salt concentration of the above dispersion resin is 〇78 mm〇1/g. G main 4) jER828EL. trade name 'epoxy resin, manufactured by Japan Ep〇Xy Resins c〇, Ltd.'. Production Example 12 Pigment Dispersion Poly No. 1 Production Example The solid content obtained in Production Example 11 was added. % of pigment dispersion resin 8.3 parts (solid content 5 parts), vanadium pentoxide 2 parts, calcium bismuth citrate, 2 parts of calcium phosphate, 20 parts of titanium dioxide, 2 parts of cerium oxide (barium sulphate) and 37 parts of ionized water was dispersed in a ball mill for 20 hours, and pigment dispersion was carried out until the particles (particle diameter of the pigment coarse particles) became 20 μm or less to obtain a pigment dispersion slurry No. 1 having a solid content of 55%. To a mixture of 5 parts by mass of a sodium carbonated aqueous solution at 25 ° C for 1 part, a mixture of 2 parts of vanadium pentoxide constituting the rust preventive pigment mixture (C), calcium bismuth citrate, and 2 parts of calcium phosphate was added. The mixture was stirred for 6 hours, and the pH of the filtrate obtained by filtration of the supernatant liquid at room temperature for 48 hours was measured. The pH of the filtrate was 5.5. Production Examples 13 to 21 were the same as in Production Example 12 except for the contents of the mixing in Table 2. In the same manner as in Production Example 12, the results of measuring the pH of the filtrate of the sodium carbonate aqueous solution of the mixture of the compounds (cl) to (c3) are shown in the table. 2. 31 201012881 [Table 2] Production Example 12 13 14 15 16 17 18 19 20 21 Pigment Dispersion Pulp No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 6 No. 8 No. No. 10 Resin for pigment dispersion 8.3 8.3 83 8.3 8.3 8.3 8.3 8.3 8.3 8.3 (5) (5) (5) (5) (5) (5) (5) (5) (5) (5) Vanadium pentoxide 2 10 20 30 20 20 20 20 (cl) Metavanadic acid 20 20 Vanadium acid about 20 mixed bismuth acid about 1 5 5 20 10 10 Shi Xi compound partial bismuth acid 5 . (c2) 矽酸铭5 shieldexC303 20 20 20 20 20 20 sylysia710 10 20 Synthetic starting point BA Phosphoric acid about 2 10 20 30 20 20 (c3) Phosphoric acid one gas about 20 20 20 Tripolyphosphate to 20 coloring pigment titanium white 20 20 20 20 20 20 20 20 20 20 Body pigment bismuth oxide 20 20 20 20 20 20 20 20 20 20 Deionized water 37.6 54 86.7 107.2 86.7 86.7 90.8 90.8 82.6 82.6 Pigment dispersion slurry 90.9 127.3 200 245.5 200 200 209.1 209.1 190.9 190.9 Solid content 55% (50) ( 70) (110) (135) (110) (110) (115) (115) (105) (105) Total amount of anti-rust pigment mixture (c) 5 25 65 90 65 65 70 70 60 60 pH 5.5 of the filtrate 5.5 6.0 7.0 5.5 5.5 5.8 6.0 7.8 7.7 The value indicates the mixed mass fraction and 0 indicates the solid content. "sylysia 710" and "shieldex C303" in Table 2 are as follows. Sylysia 710: SiO2 powder, average particle size 2·8μιη, oil absorption 190 ml/100g, BET specific surface area 700 m2/g, shieldex C303 manufactured by Fuji Silysia Chemical Ltd.: MM ion exchange oxidized cut, WR Grace Comparative Production Examples 1 to 10 In the same manner as in Production Example 12 except that the contents of the mixing in Table 3 were used, pigment dispersions No. 11 to No. 20 were obtained. Further, the results of measuring the pH of the filtrate of the sodium carbonate aqueous solution of the mixture of the compounds (el) to (c3) in the same manner as in Production Example 12 are shown in Table 3. 201012881 [Table 3] Comparative Production Example 1 2 3 4 5 6 7 8 9 10 Pigment Dispersion No. 11 No. 12 No. 12 No. 14 No. 14 No. 16 No. 16 No. 20 Mixed pigment dispersion resin 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) Compound (cl) Vanadium pentoxide 0 40 50 20 20 0 20 20 Metavanadic acid, vanadic acid, cockroach compound (c2) Heteroic acid, about 0 40 20 50 20 20 0 20 Heteroic acid, aluminum citrate, calcium phosphate (c3) Phosphoric acid about 0 40 20 20 50 20 20 0 monohydrogen phosphate about tripolyphosphate about coloring dye white 20 20 20 20 20 20 20 20 20 20 body dye cerium oxide 20 20 20 20 20 20 20 20 20 20 strontium chromate 50 90 Deionized water 33.5 131.7 107.2 107.2 107.2 66.2 66.2 662 74.4 107.2 Pigment dispersion Solids content 55% 81.8 (45) 300 (165) 245.5 (135) 245.5 (135) 245.5 (135) 154.5 (85) 154.5 (85) 154.5 (85) 172.7 (95) 245.5 (135) Total anti-rust pigment C composition 0 120 90 90 90 40 40 40 0 0 pH of the filtrate - 8.2 4.8 9.1 8.0 11.2 4.3 8.3 7.7 8.1 Values indicate mixed mass parts, and () indicates solid content.

製造例22 Resole型酚醛樹脂交聯劑溶液之製造 於反應容器中’混合1〇〇份的雙酚A、178份的37%甲醛 水溶液及1份的氫氧化鈉，在60°C使其反應3小時後，在減 壓下，50°C脫水1小時。接著，加入正丁醇1〇〇份和磷酸3份， 在110〜120°C反應2小時。反應結束後，過濾所得溶液並濾 掉生成的磷酸鈉，獲得固體含量約50%的Resole型酚醛樹脂 交聯劑溶液。所得樹脂之數量平均分子量為880，每1苯核 的平均羥曱基數為0.4個以及平均烷氧甲基數為1.0個。 實施例1 水性塗料組成物No. 1之製造 混合333.3份（固體含量1〇〇份)在製造例4製得的乳膠No. 1，90.9份（固體含量50份)在製造例丨2製得的顏料分散漿及 75.8份的去離子水，製得固體含量30%的水性塗料組成物 33 201012881Production Example 22 Resole-type phenolic resin cross-linking agent solution was prepared by mixing 1 part of bisphenol A, 178 parts of 37% aqueous formaldehyde solution and 1 part of sodium hydroxide in a reaction vessel, and reacting at 60 ° C. After 3 hours, it was dehydrated at 50 ° C for 1 hour under reduced pressure. Next, 1 part of n-butanol and 3 parts of phosphoric acid were added, and the mixture was reacted at 110 to 120 ° C for 2 hours. After completion of the reaction, the resulting solution was filtered and the resulting sodium phosphate was filtered off to obtain a Resole type phenol resin crosslinker solution having a solid content of about 50%. The obtained resin had a number average molecular weight of 880, an average number of hydroxymethyl groups per one benzene nucleus of 0.4, and an average number of alkoxymethyl groups of 1.0. Example 1 Preparation of Aqueous Coating Composition No. 1 333.3 parts (solid content: 1 part) Latex No. 1, 90.9 parts (solid content: 50 parts) obtained in Production Example 4 was produced in Production Example 2 A pigment dispersion slurry and 75.8 parts of deionized water to obtain an aqueous coating composition having a solid content of 30% 33 201012881

No」。 實施例2〜18 水性塗料組成物No. 2〜No. 18之製造 除下述表4及表5所示的混合以外，與實施例1同樣地處 理，獲得水性塗料組成物No. 2〜No. 18。 [表4] 1mm 實施例2 侧列3 實施例4 實施例5 實施例6 實施例7 例 8 實施例9 實施例10 水性塗料减物 No.l No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 No. 10 混 合 物 質 獅 No. 1 333.3 a〇〇) 333.3 (100) 3333 _ No. 2 333.3 _ No. 3 333.3 (100) 娜 No. 4 333.3 (100) 倾 No. 5 3333 (100) iL#No. 6 333.3 (100) |L^No.7 90.9 (50) 赚^1N0.2 127.3 (70) 齡^®ΛΝ0.3 200 (HO) 200 (110) 200 (110) 200 (Π0) 200 (Π0) 200 (HO) 245.5 (135) »^«No.5 200 (110) 去離子水 75.8 106.1 166.7 166.7 166.7 166.7 166.7 166.7 204.5 166.7 水11塗料緘物 固想含量30% 500 (150) 566.7 070) 700 (210) 700 (210) 700 (210) 700 (210) 700 (210) 700 (210) 7833 (235) 700 (210) 數值表示混合質量份，（)表示固體含量。 34 201012881 [表5] 實施例11 倾列12 實施例13 實施例14 實施例15 實施例16 實施例17 實施例18 水1±塗料組成物 No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 混 合 物 質 瓣 No_ 1 3333 (100) 3333 (100) 3333 (100) 333.3 000) 3333 (100) 333.3 000) 333.3 (100) 333.3 (100) 顏料錄漿No. 3 200 010) 200 αΐ〇) 200 (110) 顏料分散漿No. 6 200 (110) 顏#^綠漿No.7 209.1 015) 顏奸綠漿漏 209.1 015) 顏价綠漿No_9 190.9 005) 顏料分散漿No. 10 190.9 (105) Resoled酌链樹脂交 聯劑緘固體Φ150% __ 10 ⑶ 10 (5) 10 ⑶ 去離子水 166.7 174.3 174.3 159.1 159.1 173.4 173.4 173.4 水性塗料組成物 固體含量30% 700 (210) 716.7 (215) 716.7 (215) 683.3 (205) 6833 (205) 716.7 (215) 716.7 (215) 716.7 (215) 數值表示混合質量份，（)表示固體含量。 比較例1〜10 除做成示於下述表6的混合外，與實施例1同樣地處 理，製得水性塗料組成物No. 19〜No. 28。No". Example 2 to 18 Aqueous coating composition No. 2 to No. 18 was produced in the same manner as in Example 1 except that the mixing shown in Tables 4 and 5 below was carried out to obtain an aqueous coating composition No. 2 to No. 18. [Table 4] 1 mm Example 2 Side row 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Water-based paint subtraction No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 No. 6 Mixed material lion No. 1 333.3 a〇〇) 333.3 (100) 3333 _ No. 2 333.3 _ No. 3 333.3 (100) Na No. 4 333.3 ( 100) Pour No. 5 3333 (100) iL#No. 6 333.3 (100) | L^No.7 90.9 (50) Earn ^1N0.2 127.3 (70) Age ^®ΛΝ0.3 200 (HO) 200 ( 110) 200 (110) 200 (Π0) 200 (Π0) 200 (HO) 245.5 (135) »^«No.5 200 (110) Deionized water 75.8 106.1 166.7 166.7 166.7 166.7 166.7 166.7 204.5 166.7 Water 11 paint Solid content 30% 500 (150) 566.7 070) 700 (210) 700 (210) 700 (210) 700 (210) 700 (210) 700 (210) 7833 (235) 700 (210) The numerical value indicates the mass of the mixture, () indicates the solid content. 34 201012881 [Table 5] Example 11 Tipping 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Water 1 ± Coating Composition No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 Mixed material flap No_ 1 3333 (100) 3333 (100) 3333 (100) 333.3 000) 3333 (100) 333.3 000) 333.3 (100) 333.3 (100) Pigment recording No. 3 200 010) 200 αΐ〇) 200 (110) Pigment Dispersion Pulp No. 6 200 (110) 颜#^绿浆No.7 209.1 015) 颜奸绿浆漏209.1 015) 颜绿绿浆No_9 190.9 005) Pigment Dispersion slurry No. 10 190.9 (105) Resoled chain resin crosslinker 缄solid Φ150% __ 10 (3) 10 (5) 10 (3) Deionized water 166.7 174.3 174.3 159.1 159.1 173.4 173.4 173.4 Aqueous coating composition solid content 30% 700 ( 210) 716.7 (215) 716.7 (215) 683.3 (205) 6833 (205) 716.7 (215) 716.7 (215) 716.7 (215) The values indicate the mixed mass parts, and () indicates the solid content. Comparative Examples 1 to 10 were treated in the same manner as in Example 1 except that the mixing shown in Table 6 below was carried out to obtain aqueous coating compositions No. 19 to No. 28.

35 201012881 [表6] 峨例1 tbfe^J3 tbfe#J5 tb^J6 t賺J7 fcbft你J9 比較例10 水性塗料組成物 No. 19 No. 20 No. 21 No. 22 No. 23 No. 24 No. 25 No. 26 No. 27 No. 28 混 合 内 容 导 LfifNo.l 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) ίΙ^Νο.7 顏辦綠__3 顏11 81.8 (45) 12 300 (165) 顏#^ifNo. 13 2455 (m 顏^14 245.5 035) «♦mttNo.15 245.5 (135) 顏料分散iNo. 16 154.5 (85) 顏料錄《Νο· 17 1545 (85) 顏料分散tNo. 18 154.5 (85) 19 172.7 (95) 顏Ϋ4^_·20 2455 (135) 去離子水 77.9 250 2M5 204*5 204.5 128.9 128.9 128.9 144 2045 水性塗料物 固體含量30% 493 (145) 8833 (265) 7833 (235) 7833 (235) 7833 (235) 616.7 (185) 616.7 Π85) 616.7 (185) 650 (195) 7833 (235)35 201012881 [Table 6] Example 1 tbfe^J3 tbfe#J5 tb^J6 t earn J7 fcbft you J9 Comparative Example 10 Water-based paint composition No. 19 No. 20 No. 21 No. 22 No. 23 No. 24 No 25 No. 26 No. 27 No. 28 Mixed content guide LfifNo.l 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) 3333 (100) ίΙ^Νο.7 颜办绿__3 颜11 81.8 (45) 12 300 (165) 颜#^ifNo. 13 2455 (m 颜^14 245.5 035) «♦mttNo.15 245.5 ( 135) Pigment dispersion iNo. 16 154.5 (85) Pigment record "Νο· 17 1545 (85) Pigment dispersion tNo. 18 154.5 (85) 19 172.7 (95) Yan Yan 4^_·20 2455 (135) Deionized water 77.9 250 2M5 204*5 204.5 128.9 128.9 128.9 144 2045 Waterborne coatings Solids content 30% 493 (145) 8833 (265) 7833 (235) 7833 (235) 7833 (235) 616.7 (185) 616.7 Π85) 616.7 (185) 650 ( 195) 7833 (235)

數值表示混合質量份，0表示固體含量。 [試驗用塗裝板的製作] 利用上述實施例1〜18、比較例1〜10中製得的各水性 塗料組成物No· 1〜No. 28及面漆塗料，以下述的塗裝要求 1、塗裝要求2及塗裝要求3，塗裝各素材並進行燒結，製得 各試驗用塗裝板。 塗裝要求1 在施行過無鉻系化學轉化處理（前處理）的鍵鋁鋅鋼板 (Galvalume Steel)(板厚0 35mm，鍍層被覆量為 15〇 g/m2， 表中表不為「GL鋼板」。）上，將由實施例及比較例製得的 36 201012881 各水性塗料組成物’用刮棒塗布機塗裝成乾燥膜厚3μιη， 在140°C (素材到達的最高溫度）用鏈條式平爐（conveyor oven)加熱乾燥20秒鐘。 接著，於剛才的塗裝面（正面）之相反面，塗裝和正面同 樣的水性塗料組成物形成乾燥膜厚度3 ，在21 〇°c (素材到 達的最高溫度）用鏈條式平爐加熱乾燥4〇秒鐘，製得各底漆 塗裝板。 冷卻後’在這些底漆塗裝板上(正面），用刮棒塗布機將 ❹ KP Color 158〇B4〇(Kansai Paint Co” Ltd.製，商品名，聚g旨 系面漆塗料，藍色，硬化塗膜的玻璃轉移溫度約為7〇〇c)塗 - 裝成乾燥膜厚度約15μιη，以素材到達的最高溫度22〇°c燒 ，· 結40秒鐘，製得各試驗用板GL-1〜GL-28(以正面供作試 驗）。 塗裝要求2 在未施行化學轉化處理的熔融鍍鋅鋼板（板厚 〇.35mm ’鍍鋅鍍層被覆量為250g/m2、表中略稱為「〇1鋼 ® 板」）上，將由實施例及比較例製得的各水性塗料組成物， 用刮棒塗布機塗裝成乾燥膜厚3μιη，在14〇t(素材到達的最 兩溫度）用鏈條式平爐加熱乾燥15秒鐘。 接著，於剛才的塗裝面（正面）之相反面，將和正面同樣 的水性塗料組成物，用刮棒塗布機塗裝成乾燥膜厚度 3μπι，在140°C(素材到達的最高溫度）用鏈條式平爐加熱乾 燥15秒鐘’製得各底漆塗裝板。 冷卻後，在這些底漆塗裝板上(正面），用刮棒塗布機將 37 201012881 KPcolorl510(KansaiPaintCo” Ltd.製，商品名，古八子 酯系面漆塗料，茶色，硬化塗膜的破璃轉移溫度約為 塗裝成乾燥膜厚度約15μηι，用鏈條式平爐在22〇。〇（素材， 達的最高溫度）燒結40秒鐘，製得各試驗用板Gli〜 GI-28(以正面供作試驗）。 塗裝要求3Values indicate mixed mass parts and 0 indicates solid content. [Preparation of Test Coating Sheet] Each of the aqueous coating compositions No. 1 to No. 28 and the topcoat paints obtained in the above Examples 1 to 18 and Comparative Examples 1 to 10 were subjected to the following coating requirements 1 , coating requirements 2 and coating requirements 3, coating each material and sintering, to obtain each test coated plate. Coating Requirements 1 Galvalume Steel (Galvalume Steel) with a chromium-free chemical conversion treatment (pretreatment) (plate thickness 0 35 mm, plating coverage 15 〇g/m2, table not shown as "GL steel sheet" In the above, the 36 201012881 water-based paint compositions prepared in the examples and the comparative examples were coated with a bar coater to a dry film thickness of 3 μm, and at 140 ° C (the highest temperature at which the material reached), a chain type open hearth furnace was used. (Conveyor oven) Heat and dry for 20 seconds. Next, on the opposite side of the painted surface (front side), the same aqueous coating composition as the front surface is applied to form a dry film thickness of 3, and dried at a temperature of 21 ° C (the highest temperature at which the material reaches) in a chain type open hearth furnace. In each second, each primer coating plate was prepared. After cooling, 'on these primer coating plates (front side), ❹KP Color 158〇B4〇 (manufactured by Kansai Paint Co. Ltd., trade name, poly g-based topcoat paint, blue) with a bar coater The glass transition temperature of the hardened coating film is about 7 〇〇 c) coating - the thickness of the dried film is about 15 μm, and the maximum temperature reached by the material is 22 ° C, and the junction is 40 seconds to prepare each test plate GL. -1~GL-28 (for the test on the front side). Coating requirements 2 In the case of a hot-dip galvanized steel sheet that has not been subjected to chemical conversion treatment (thickness 〇.35mm' galvanized coating coverage is 250g/m2, abbreviated in the table On the "〇1 Steel® plate", each of the aqueous coating compositions prepared in the examples and the comparative examples was coated with a bar coater to a dry film thickness of 3 μm at 14 〇t (the two temperatures at which the material reached). It was dried by heating in a chain type open hearth for 15 seconds. Next, on the opposite side of the coating surface (front side), the same aqueous coating composition as the front surface was coated with a bar coater to a dry film thickness of 3 μm, at 140 ° C (the highest temperature at which the material reached). Each of the primer coating plates was prepared by heating and drying the chain type open hearth for 15 seconds. After cooling, on these primer coating plates (front side), using a bar coater, 37 201012881 KPcolorl 510 (KansaiPaintCo" Ltd., trade name, ancient octame ester topcoat paint, brown, hardened film The transfer temperature was approximately 15 μηη thick coated with a dry film, and was sintered in a chain-type open hearth at 22 〇. (material, the highest temperature reached) for 40 seconds to prepare test plates Gli~GI-28 (for front side) For testing). Painting requirements 3

在施行過磷酸辞化學轉化處理的冷軋鋼板（板厚〇·8 mm、表中表示為「SPC鋼板」）上，將由實施例及比較例製 得的各水性塗料組成物，用刮棒塗布機塗裝成乾燥膜厚 8μιη ’在180C(素材到達的最高溫度）用鏈條式平爐乾燥30 秒鐘。 接著，於剛才的塗裝面（正面）之相反面，將和正面同樣 的水性塗料組成物，用刮棒塗布機塗裝成乾燥膜厚度 20μιη，在180°C (素材到達的最高溫度）用鏈條式平爐加熱乾 燥30分鐘，獲得各試驗用塗裝板sp-i〜sp—28(以正面供作 試驗）。 塗膜性能試驗 針對使用上述實施例1〜18、比較例1〜1 〇中製得之各 水性塗料組成物塗裝過的各試驗用塗裝板GL-1〜GL-28、 GI-1〜GI-28、SP-1〜SP-28 ’依據下述試驗方法，進行耋 膜性能試驗。試驗結果不於表7〜表9。 38 201012881 [表7] 1 料例 2 倾例 3 4 1m例 5 tm 6 秋例 7 热例 8 tm\ 9 料例 10 水性塗钭^^ Ναΐ Νο.2 Νο.3 No. 4 Νο.5 Νο.6 Νο.7 Νο.8 Νο.9 No. 10 mm GL-1 Gh2 Gb3 GL4 GLr5 GL·^ GL7 GL·^ Gh9 GUO 雜 (>±5) ◎ ◎ ◎ 〇 〇 ◎ Ο 〇 〇 〇 mm m ◎ ◎ ◎ 〇 〇 ◎ 〇 Ο 〇 〇 塗裝要拟 对祕 (注7) 〇 ◎ 〇 Ο 〇 〇 〇 ο 〇 〇 (Gum ^m± (m 〇 〇 Ο 〇 〇 〇 ◎ 〇 〇 〇 複擁環 4T加工部 〇 Ο 〇 ◎ ◎ 〇 〇 〇 ◎ Ο 親部 Ο ο 〇 ◎ ◎ 〇 ◎ ◎ ◎ Ο (>i9) 5txl_ ο 〇 〇 〇 〇 Ο ◎ ◎ ◎ 〇 0*1 GI-2 α-3 (Η-4 GI-5 Gl-6 CH-7 GI-8 GW CH-10 雜 (>±5) Ο 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐雜 m Ο 〇 〇 〇 〇 〇 Ο 〇 〇 〇 塗裝要 (注7) 〇 〇 Ο 〇 〇 〇 ο 〇 〇 〇 (Gwm (M) ο 〇 〇 Ο 〇 Ο 〇 〇 Ο 〇 複練環 4ΤΛαΧ部 ο 〇 〇 ◎ ◎ 〇 〇 Ο 〇 ο 腐mm 猶部 〇 〇 〇 ◎ ◎ ο ο ο 〇 〇 (必） 5UU1 腺部 〇 〇 〇 〇 〇 〇 ◎ ◎ ◎ 〇 mm SP-1 SP-2 SP-3 SP4 SP-5 SP-7 SPS SP-9 SP-10 m 〇 Ο Ο 〇 Ο 〇 〇 Ο 〇 〇 塗裝要彩 耐雜 _ ο 〇 〇 Ο Ο 〇 ο 〇 〇 〇 (SPC觸 (注7) 〇 Γ 〇 〇 〇 〇 Γ ο 〇 ο Ο Γ ο m) 〇 ο 〇 〇 〇 〇 Ο 〇 ο 〇 鹽水條谢 (注10) ο 〇 〇 〇 ο Ο Ο 〇 ◎ ο [表8] tmn 11 獅例 12 13 imn 14 攸例 15 imm 16 1mm Ι7 18 极塗料^^7 Noll No. 12 Νο.13 No. 14 Να 15 Ndl6 Νο.17 Ναΐ8 GUI GM2 GL-13 GW4 GM5 GL·^ GL-17 Cir】8 雜 ㈣ 〇 〇 〇 〇 Ο ◎ ◎ ◎ m 〇 Ο 〇 〇 〇 ◎ ◎ (S) 魏要41 (注7) Ο 〇 Ο 〇 〇 ◎ ◎ (6) (GUSfe) 脚 〇 〇 ο 〇 ο ◎ ◎ ◎ mm 腐mm m 4TA〇x部 ο 〇 〇 Ο ο ◎ ◎ ◎ 槪部 〇 〇 ο 〇 ο ◎ ◎ ◎ itXl'M-SP ο ◎ ◎ 〇 ο ◎ ◎ GI-11 GI-12 GI-13 GI-14 GI-15 GH6 GH7 Q-18 娜附署fi (>±5) Ο 〇 〇 〇 Ο ◎ ◎ (S) 邮微 （脚 〇 〇 〇 〇 Ο ◎ ◎ ◎ 塗裝要和 <^11 (注7) 〇 「〇 「〇 〇 Ο 〇 〇 〇 (G峨 脚 Ο 〇 〇 〇 〇 ◎ ◎ (5) 複^#環 4ΤΛ〇Χ部 Ο 〇 〇 〇 Ο 〇 Ο 〇 (>i9) 雜部 〇 〇 Ο 〇 Ο 〇 Ο ◎ ^^慨部 〇 〇 〇 Ο Ο 〇 〇 ◎ . 9Μ1 SP-12 SP-14 SM5 SP-16 SP-17 SP-1R (>is) 〇 Ο Ο 〇 〇 ◎ ◎ ◎ 塗裝要衫 *r雜 脚 Ο Ο 〇 〇 〇 ◎ ◎ ◎ (SPC綱 (注7) 〇 〇 〇 〇 〇 ◎ ◎ β) (；i8) 〇 ο ο 〇 ο 〇 〇 〇 m〇) 〇 〇 〇 ◎ ◎ 〇 Ο ◎ 39 201012881 [表9] tbfe^J 1 峨例 2 3 4 5 tfc^J 6 tbW 7 8 tb^-J 9 10 水性塗物 Να 19 No. 20 Νο.21 No. 22 Νο.23 No. 24 Να25 No. 26 Να 27 No. 28 Gir\9 GL-20 Gh-21 GL-72. 0^23 Ca^-24 GL-25 GL-26 GL*27 GL-28 雖 (>i5) ◎ X 〇 Ο 〇 〇 〇 〇 〇 X 时;♦水性 脚 ◎ X Ο 〇 Ο Ο 〇 〇 〇 X 塗裝要求 1 (Gum (注7) 〇 ο Δ 〇 ο 〇 X 〇 〇 〇 m) Ο ο 〇 A 〇 X Δ 〇 〇 Δ 複雜環 4T加工部 A X Λ X Δ 〇 Δ Δ 〇 ◎ 躲部 X 〇 〇 Δ Δ X X Δ 〇 ◎ (>i9) itxt懺部 X 〇 〇 Δ Λ Δ X Δ 〇 ◎ GH9 GI-20 GI-21 α-η α-23 ¢3-24 G1-25 GK26 GI-27 Q-28 奢l± ㈣ Ο X Δ A Δ 〇 〇 Ο 〇 X 时弗水n (>i6) ο X Δ Δ Δ 〇 〇 〇 〇 X 魏要和 (>i7) ο Δ X Δ Δ Δ X ο 〇 〇 mm. ㈣ ο Δ Δ X Δ X △ ο Ο A mm. 4TA〇i部 X Δ Δ X Δ X X Δ ο ◎ 躲部 X Δ Ο X Δ X X X ο ◎ ㈣ 部 X Λ 〇 X Λ X Λ V 〇 〇 SP-I9 SP-20 SP-21 SP-22 SP-23 SP-24 SP-25 SP-26 ^-27 SP-28 taw雜 (>i5) 〇 X X X Δ 〇 Ο 〇 〇 X 塗裝要勒 时脉性 ㈣ 〇 X X X Δ 〇 ο 〇 〇 X (SPC_ 礙n (注7) Δ X X Δ Λ Δ A Ο 〇 〇 _ X X X X Λ X 〇 〇 〇 X 狀噴霧試驗 （注l〇) X 〇 Δ 〇 Ο Λ Δ Δ 〇 〇 試驗方法 (注5)塗膜附著性：遵循JIS K-5600-5-6 (1999)劃格 法，切痕的間隙間隔設為1mm，製作丨00個網格，在其表面 黏貼透明膠帶，調查在急劇剝離後塗面上所殘存的網格數。 ◎:塗膜無發生膨脹、白化等的異常，殘存網格數1〇〇 個， 〇：塗膜無發生膨脹、白化等的異常，殘存網格數91 〜99個， △:塗膜上稍微確認到發生膨脹或白化等的異常殘 存網格數91〜99個，或者塗膜雖無發生膨脹、白化等的異 常，惟殘存網格數為71〜90個， X:塗膜上相當程度或明顯確認到膨脹的發生，或者 40 201012881 殘存網格數在70個以下 (注6)耐沸水性：將切斷成5em雜岐大小的 塗裝板，在約10(TC的彿水中浸潰2小時後#出評估表面 (正面)侧的塗膜外觀’同時進行劃格附著試驗的評估。劃格 附著試驗係遵細Κ-5600_5—6⑽9)劃格法，將切痕的間 隙間隔設為！_，製作刚個網格，在其表面黏貼透明勝 帶，調查在急劇剝離後塗面上所殘存的網格數。 ◎:塗膜無發生膨腸、白化等的異常，殘存網格數謂 個， 〇：塗膜無發生膨脹' 白化等的異常，殘存網格數91 〜99個， △.塗膜上龍確認到義的發生或白化等的異常， 殘存網格數91〜99個，或者塗膜雖無雜的發生、白化等 的異常，惟殘存網格數為71〜9〇個， X .相當程度或明顯確則塗媒上發生膨脹或者殘 存網格數在70個以下 (注7)耐驗性：用防錄塗料密封切斷成5_1〇啦之大小 的各試驗用塗裝板背面及切斷面，並在塗裝板的表面側中 央部切入深達基材的劃痕。評價將該塗裝板在贼的5%氨 氧化納水溶液浸潰24小時後，取出洗淨，並於室温乾燥過 的塗裝板之表面側的塗膜外觀’同時在劃格部用透明膠帶 =貼’評估急劇剝離後’從塗膜的切痕部分剝離的寬度(單 ◎.未發生膨脹，膠帶自切痕部分剝離的寬度在15_ 41 201012881 以下， 〇：未發生膨脹，膠帶自切痕部分剝離的寬度超過 1.5mm，在3mm以下， △:確認有些膨脹的發生，惟膠帶自切痕部分剝離的 寬度在3mm以下，或者未確認到膨脹的發生，惟膠帶自切 痕部分剝離的寬度超過3mm。 X :確認膨脹的發生，而立膠帶自切痕部分剝離的寬 度超過3mm。Each of the aqueous coating compositions prepared in the examples and the comparative examples was coated with a doctor bar on a cold-rolled steel sheet (plate thickness: 8 mm, indicated as "SPC steel sheet" in the table) subjected to a chemical conversion treatment of phosphoric acid. The machine was painted to a dry film thickness of 8 μm and was dried in a chain open hearth at 180 C (the highest temperature reached by the material) for 30 seconds. Next, on the opposite side of the coating surface (front side), the same aqueous coating composition as the front surface was coated with a bar coater to a dry film thickness of 20 μm, and used at 180 ° C (the highest temperature at which the material reached). The chain type open hearth was heated and dried for 30 minutes to obtain test plates sp-i to sp-28 for each test (for test on the front side). Film Coating Performance Test Each of the test coated sheets GL-1 to GL-28 and GI-1 which were coated with each of the aqueous coating compositions prepared in the above Examples 1 to 18 and Comparative Examples 1 to 1 was used. GI-28, SP-1 to SP-28 'The decidual performance test was carried out according to the following test method. The test results are not in Tables 7 to 9. 38 201012881 [Table 7] 1 Material Example 2 Pour Example 3 4 1m Case 5 tm 6 Autumn Case 7 Heat Example 8 tm\ 9 Material Example 10 Water-based coating 钭^^ Ναΐ Νο.2 Νο.3 No. 4 Νο.5 Νο .6 Νο.7 Νο.8 Νο.9 No. 10 mm GL-1 Gh2 Gb3 GL4 GLr5 GL·^ GL7 GL·^ Gh9 GUO Miscellaneous (>±5) ◎ ◎ ◎ 〇〇 ◎ Ο 〇〇〇mm m ◎ ◎ ◎ 〇〇 〇Ο 〇Ο 〇〇 要 要 要 ( 注 (Note 7) 〇 ◎ 〇Ο 〇〇〇 〇〇 〇〇 (Gum ^ m ± (m 〇〇Ο 〇〇〇 ◎ 〇〇〇 拥 环4T processing department 〇Ο ◎ ◎ 〇〇〇 ◎ Ο 亲 ο ο ◎ ◎ 〇 ◎ ◎ ◎ Ο (>i9) 5txl_ ο 〇〇〇〇Ο ◎ ◎ ◎ 〇0*1 GI-2 α-3 (Η-4 GI-5 Gl-6 CH-7 GI-8 GW CH-10 Miscellaneous (>±5) Ο 〇〇〇〇〇〇〇〇〇 杂 m m Ο 〇〇〇〇〇Ο 〇〇〇 Painting (Note 7) 〇〇Ο 〇〇〇ο 〇〇〇 (Gwm (M) ο 〇〇Ο 〇Ο 〇〇Ο 〇 Rehearsal ring 4ΤΛαΧ部 〇〇 〇〇 ◎ ◎ 〇〇Ο 〇ο mmmm 犹〇〇〇 ◎ ◎ ο ο ο 〇〇 (must) 5UU1 〇〇〇〇〇〇 ◎ ◎ ◎ 〇mm SP-1 SP-2 SP-3 SP4 SP-5 SP-7 SPS SP-9 SP-10 m 〇Ο Ο 〇Ο 〇〇Ο 〇〇 Painting耐 _ _ 〇〇Ο Ο 〇 〇〇〇 〇〇〇 (SPC touch (Note 7) 〇Γ 〇〇〇〇Γ ο 〇 ο Ο ο ο m) 〇ο 〇〇〇〇Ο 〇ο 〇 salt water thanks (note 10) ο 〇〇〇ο Ο Ο 〇 ◎ ο [Table 8] tmn 11 Lion example 12 13 imn 14 Example 15 imm 16 1mm Ι7 18 pole paint ^^7 Noll No. 12 Νο.13 No. 14 Να 15 Ndl6 Νο.17 Ναΐ8 GUI GM2 GL-13 GW4 GM5 GL·^ GL-17 Cir】8 Miscellaneous (four) 〇〇〇〇Ο ◎ ◎ ◎ m 〇Ο 〇〇〇 ◎ ◎ (S) Wei Yao 41 (Note 7) Ο 〇 Ο 〇〇 ◎ ◎ (6) (GUSfe) 〇〇 〇 〇ο ◎ ◎ ◎ mm mmmm m 4TA〇x ο 〇〇Ο ο ◎ ◎ ◎ 槪 〇〇 〇 ◎ ◎ ◎ itXl'M- SP ο ◎ ◎ 〇ο ◎ ◎ GI-11 GI-12 GI-13 GI-14 GI-15 GH6 GH7 Q-18 娜附署 fi (>±5) Ο 〇〇〇Ο ◎ ◎ (S) (Foot ◎ ◎ ◎ Painting and <^ 11 (Note 7) 〇 "〇"〇〇Ο 〇〇〇(G峨脚Ο 〇〇〇〇 ◎ ◎ (5) 复^#环4ΤΛ〇Χ部Ο 〇Ο 〇 〇 (>i9)杂 〇〇Ο 〇Ο ◎ ^ ^ ^ 〇〇〇Ο SP . . Μ SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP SP ◎ ◎ ◎ Painting to shirt * r miscellaneous Ο 〇〇〇 ◎ ◎ ◎ (SPC outline (Note 7) 〇〇〇〇〇 ◎ ◎ β) (; i8) 〇ο ο 〇ο 〇〇〇m〇) 〇〇〇◎ ◎ 〇Ο ◎ 39 201012881 [Table 9] tbfe^J 1 Example 2 3 4 5 tfc^J 6 tbW 7 8 tb^-J 9 10 Water-based coating Να 19 No. 20 Νο.21 No. 22 Νο.23 No. 24 Να25 No. 26 Να 27 No. 28 Gir\9 GL-20 Gh-21 GL-72. 0^23 Ca^-24 GL-25 GL-26 GL*27 GL-28 Although >i5) ◎ X 〇Ο 〇〇〇〇〇X; ♦ Water-based feet ◎ X Ο 〇Ο Ο 〇〇〇X Painting requirements 1 (Gum (Note 7) 〇ο Δ 〇ο 〇X 〇〇〇m ) ο ο 〇A 〇X Δ 〇〇Δ Complex ring 4T processing part AX Λ X Δ 〇Δ Δ 〇 ◎ hiding part X 〇〇Δ Δ XX Δ 〇 ◎ (>i9) itxt X X 〇〇 Δ Λ Δ X Δ 〇 ◎ GH9 GI-20 GI-21 α-η α-23 ¢ 3-24 G1-25 GK26 GI-27 Q-28 Extraordinary l± (4) Ο X Δ A Δ 〇〇Ο 〇X 弗水 n (>i6) ο X Δ Δ Δ 〇〇〇〇X Wei wanti (>i7) ο Δ X Δ Δ Δ X ο 〇四mm. (4) ο Δ Δ X Δ X Δ ο Ο A mm. 4TA〇i part X Δ Δ X Δ XX Δ ο ◎ hiding part X Δ Ο X Δ XXX ο ◎ (4) Part X Λ 〇X Λ X Λ V 〇 〇SP-I9 SP-20 SP-21 SP-22 SP-23 SP-24 SP-25 SP-26 ^-27 SP-28 taw Miscellaneous (>i5) 〇XXX Δ 〇Ο 〇〇X Painting Clock (4) 〇XXX Δ 〇ο 〇〇X (SPC_ nn (Note 7) Δ XX Δ Λ Δ A Ο 〇〇 _ XXXX Λ X 〇〇〇X-like spray test (Note l〇) X 〇Δ 〇Ο Λ Δ Δ 〇〇 test method (Note 5) Coating adhesion: According to JIS K-5600-5-6 (1999) cross-cut method, the gap interval of the cut is set to 1 mm, and 丨00 grids are produced. Adhesive tape was applied to the surface to investigate the number of grids remaining on the coated surface after sharp peeling. ◎: There is no abnormality such as swelling or whitening of the coating film, and the number of remaining meshes is one, 〇: the coating film is not abnormal, such as swelling or whitening, and the number of remaining meshes is 91 to 99, △: slightly on the coating film It is confirmed that the number of abnormal residual grids such as swelling or whitening is 91 to 99, or the coating film is not abnormally expanded or whitened, but the number of remaining grids is 71 to 90, X: the coating film is considerably or Obviously confirm the occurrence of swelling, or 40 201012881 Remaining grid number is less than 70 (Note 6) Boiling water resistance: The coating plate will be cut into 5em chowder size, and immersed in about 10 (TC of Foshan water 2 After the hour, the appearance of the coating film on the side of the evaluation surface (front side) is evaluated. At the same time, the evaluation of the cross-hatch adhesion test is performed. The cross-hatch adhesion test is performed according to the method of Κ-5600_5-6(10)9), and the gap interval of the cut is set to! _, make a grid, stick a transparent belt on the surface, and investigate the number of grids remaining on the coated surface after sharp peeling. ◎: There is no abnormality such as swelling and whitening of the coating film, and the number of remaining grids is one, 〇: no swelling of the coating film, whitening, etc., and the number of remaining grids is 91 to 99, △. In the case of abnormality such as occurrence or whitening, the number of remaining grids is 91 to 99, or the coating film is free from impurities such as whitening and whitening, but the number of remaining grids is 71 to 9, X. Obviously, the expansion of the coating medium or the number of remaining grids is 70 or less. (Note 7) Testability: The back surface and the cut surface of each test coating board are cut to a size of 5 〇 by an anti-recording paint. And a scratch deep into the substrate is cut in the central portion of the surface side of the coated plate. After the coated plate was immersed in a 5% aqueous ammonia solution of a thief for 24 hours, the appearance of the coating film on the surface side of the coated plate which was washed and dried at room temperature was taken out, and the transparent tape was used at the cross-section. = Post evaluation 'evaluation of the width of peeling from the cut portion of the coating film after sharp peeling (single ◎. no expansion occurred, the width of the tape peeled off from the cut portion is below 15_ 41 201012881, 〇: no expansion, tape self-scratch The width of the partial peeling exceeds 1.5 mm, and is less than 3 mm. △: It is confirmed that some expansion occurs, but the width of the tape peeled off from the cut portion is 3 mm or less, or the expansion is not confirmed, but the width of the tape peeled off from the cut portion exceeds 3mm. X: The occurrence of expansion is confirmed, and the width of the vertical tape peeled off from the cut portion exceeds 3 mm.

(注8)耐酸性：用防銹塗料密封切斷成5cm><l〇cm之大小 的各試驗用塗裝板背面及切斷面，並在塗裝板的表面側中 央部切入深達基材的劃痕。評價將該塗裝板在2〇°c的5%硫 酸水溶液浸潰24小時後，取出洗淨，並於室溫乾燥過的塗 裳板表面側之塗料觀’㈣在_部収师帶黏貼， 評估急劇祕後，從塗朗切痕部分_的寬度(單側）。 ◎:未發生膨服’膠帶自切痕部分制離的寬度在L5mm 以下， 〇：未發生膨脹，膠帶自切箱(Note 8) Acid resistance: The back surface and the cut surface of each test coated sheet which were cut into 5 cm><l〇cm were sealed with a rust preventive paint, and cut deep in the center portion of the surface side of the coated sheet. Scratches on the substrate. After the coating plate was immersed in a 5% sulfuric acid aqueous solution at 2 ° C for 24 hours, the coating was taken out and washed at room temperature, and the surface of the coating surface of the coated slab was dried. , to assess the sharpness of the secret, from the width of the slashed portion _ (one side). ◎: No expansion occurred. The width of the tape from the cut portion is less than L5mm. 〇: no expansion, tape self-cutting

刀痕部分剝離的寬度超過 1.5mm，在3mm以下， △:確認有些膨脹的發生，轉帶自切痕部分剝離的 ^度在3随以下，或者未相的發生，惟膠帶自切 痕部分剝離的寬度超過3mm。 X:相發生_，且㈣自Μ部分卿的寬度超 Κ-5621 (1990)。將 G主9)複合循環腐姓試驗：準據jig 42 201012881 塗裝板切成6cmxl2cm的大小，使得在各試驗用塗裝板之長 邊的邊緣部分，朝向表面側塗膜面右側邊緣部，在正面侧 上存在毛邊’朝向表面側塗膜面左側邊緣部分，在背面側 上存在毛邊。在已經切斷的各試驗用塗裝板之表面側中央 部分’用切割刀的刀背，切入深達基材之窄角30度、線寬 〇_5mm的交又劃痕，用防銹塗料密封塗裝板上端邊緣部， 並在上端部設4T折彎加工部。此處，4T折彎加工部係指， 將塗裝板的表面側當做外側折彎，在其内側則夾著4片與塗 ® 裝板相同厚度的板，用老虎鉗將上述塗裝板折彎180度的加 工。對施行過上述加工的試驗用塗裝板，以（在30°C喷霧5% - 食鹽水0.5小時)-(在3(TC，RH95%以上之耐濕試驗器内試驗 、 L5小時)-(在50°C乾燥2小時)-(在30°C乾燥2小時）為一循 . 環，進行300循環(合計1800小時）的試驗。評估該試驗後的 塗裝板之邊緣部、交叉劃線部、4T加工部之狀態。 (4T加工部）評估4T加工部中生銹部分的合計長度。 ◎:未確認到生銹情形， ^ 〇：確認有白錄，惟未達2〇mm， △:白錢在20mm以上且未達40mm， X :白錢在40mm以上，或者確認有紅錄的出現。 (邊緣部）求取塗裝板左右長邊的邊緣潛變幅度之平均 值，根據以下的基準進行評估。 ◎:不滿5mm， 〇：5mm以上且不滿l〇mm， △ : 10mm以上且不滿20mm， 43 201012881 )K : 20mm以上。 (交叉劃線部）利用〇.5mm之切痕寬度的金屬露出部中 出現的白銹長度比例，以及切痕部分左右膨脹寬度（兩侧之 和）的平均值，採用以下的標準評估劃線部的腐蝕狀態。 ◎:金屬露出部中出現白銹的長度比例不滿5〇〇/0且膨 脹寬度不滿3mm， 〇：金屬露出部中出現白銹的長度比例在50%以上且 膨脹寬度不滿3mm，或者金屬露出部中出現白銹的長度比 例不滿50%且膨脹寬度在3mm以上而不滿5mm， _ △:金屬露出部中出現白銹的長度比例在50%以上且 膨脹寬度在5mm以上而不滿10mm， X :金屬露出部中出現白銹的長度比例在50%以上且 膨脹寬度在10mm以上。The width of the part of the knife mark peeled off exceeds 1.5 mm, and it is less than 3 mm. △: It is confirmed that some expansion occurs, and the degree of peeling of the belt from the cut portion is 3 or less, or the phase is not formed, but the tape is peeled off from the cut portion. The width is more than 3mm. X: phase occurs _, and (iv) the width of the self-sufficient part is higher than Κ-5621 (1990). G main 9) composite cycle rotten surname test: the standard jig 42 201012881 coated plate is cut into 6cmxl2cm size, so that the edge of the long side of each test coated plate, toward the surface side of the right side edge of the film surface, On the front side, there is a burr 'toward the left side edge portion of the surface side coating film side, and there is a burr on the back side. In the central portion of the surface side of each of the test coated sheets that have been cut, the back of the blade is cut into a narrow angle of 30 degrees, the line width is 〇5 mm, and the scratch is sealed with an anti-rust paint. The upper edge portion of the upper plate is applied, and a 4T bending portion is provided at the upper end portion. Here, the 4T bending portion means that the surface side of the coated sheet is bent as the outer side, and on the inner side, four sheets of the same thickness as the coated plate are sandwiched, and the coated plate is bent by a vise. 180 degree processing. For the test coated board subjected to the above processing, (spray 5% - brine for 0.5 hour at 30 ° C) - (in 3 (TC, RH 95% or more humidity tester, L5 hours) - (dried at 50 ° C for 2 hours) - (dried at 30 ° C for 2 hours) as a cycle. The test was carried out for 300 cycles (total 1800 hours). The edge of the coated plate after the test was evaluated and cross-drawn. (4T processing unit) The total length of the rusted part in the 4T processing part is evaluated. ◎: The rust is not confirmed, ^ 〇: It is confirmed that there is a white record, but it is less than 2 mm, △ : White money is 20mm or more and less than 40mm, X: White money is above 40mm, or it is confirmed that there is a red record. (Edge part) Find the average value of the edge creep width of the left and right long sides of the coated plate, according to the following The basis of the evaluation is ◎: less than 5mm, 〇: 5mm or more and less than l〇mm, △: 10mm or more and less than 20mm, 43 201012881) K: 20mm or more. (cross-dash line) The average length of the white rust appearing in the metal exposed portion of the cut width of 〇5 mm and the average value of the left and right expansion width (sum of both sides) of the cut portion are evaluated by the following standard The corrosion state of the part. ◎: The ratio of the length of white rust in the exposed portion of the metal is less than 5〇〇/0 and the expansion width is less than 3mm. 〇: The ratio of the length of white rust in the exposed portion of the metal is 50% or more and the expansion width is less than 3 mm, or the exposed portion of the metal The length ratio of white rust appears to be less than 50% and the expansion width is less than 3 mm and less than 5 mm. _ △: The ratio of the length of white rust in the exposed portion of the metal is 50% or more and the expansion width is 5 mm or more and less than 10 mm. X: Metal The ratio of the length of white rust in the exposed portion is 50% or more and the expansion width is 10 mm or more.

(注10)鹽水喷霧試驗：用防銹塗料密封切斷成 5cmxl0cm大小的各試驗用塗裝板的背面及切斷面，並在塗 裝板的表面中央置入深達基材的交叉劃痕。對該塗裝板施 行在35°C用5%食鹽水的鹽水噴霧試驗(JIS Z-2371)500小 Q 時’評估試驗後塗面的紅銹出現狀態，同時在交又劃線部 黏貼透明膠帶，評估急劇剝離後，膠帶從塗膜的切痕部分 剝離的寬度(單側）。 ◎:無或僅有些微紅銹的發生，膠帶從切痕部分剝離 的寬度不滿5 mm， 〇：相當程度地確認到紅銹的出現，而且膠帶從切痕 部分剝離的寬度不滿5mm，或者無或僅有些微紅銹的發 44 201012881 生，惟膠帶從切痕部分剝離的寬度在5mm以上不滿10mm， △:在切痕部分全體確認到紅銹的發生，惟膠帶自切 痕部分剝離的寬度在5mm以上而不滿1 Omm，或者雖然不是 在切痕部分全體但卻相當程度地確認到紅銹的發生，而且 膠帶自切痕部分剝離的寬度在10mm以上， X :在切痕部分全體都確認到紅銹的發生，而且膠帶 自切痕部分剝離的寬度在l〇mm以上。 產業上之利用可能性 〇 本發明提供一種耐藥品性、平面部之耐蝕性、加工部 和端面部之对蚀性及附著性優良之塗裝金屬板及塗裝物 . 品。 t:圖式簡單說明3 4 [第1圖]示意連續線圈塗裝線之一例。 [第2圖]示意含有本發明之水性塗料組成物的塗膜之 塗膜構造之一例。 【主要元件符號說明】 ® 1...鋼板的一部分 4...底塗塗膜(本發明之水性塗 2.. .鍍層 料組成物） 3.. .依需要而施行的化學轉化 5...面漆塗膜 處理(前處理） 45 201012881 六、發明說明： 【發明戶斤屬之技術領域3 發明領域 本發明係關於一種可形成耐藥品性、金屬板之平面部 的而t触性、金屬板之加工部和端面部的财蚀性及附著性優 良的塗膜之水性塗料組成物及具有由該水性塗料組成物形 成的塗膜之塗裝金屬板。 φ 發明背景 過去以來，用線圈塗布(coil coating)等塗裝而成的預塗 鋼板等之預塗金屬板，被廣泛地當做建築物的屋頂、牆壁、 - 百葉窗、車庫等之建築材料，各種家電製品、配電盤、冷 凍展示櫃、鋼製傢具及廚房器具等之住宅相關商品使用。 在由預塗金屬板製成這些住宅相關商品上，通常是將 預塗金屬板切斷經加壓成型接合成。因此，在這些住宅相 關商品上，多數存在著切斷面的金屬露出部或因壓力加工 # 而產生的裂紋發生部。因為上述金屬露出部或裂紋發生 部，與其他部分相比耐蝕性容易降低，故一般是採行使預 塗金屬板的的底塗塗膜中含有鉻系防銹顏料以提昇耐蝕性 的作法。 然而，鉻系防銹顏料或含有防銹性優良的6價鉻，或者 會生成6價鉻。該6價鉻從對人體的健康面、環境保護的觀 點來看會構成問題。 截至目前為止，非鉻系防銹顏料已有磷酸鋅、三聚磷 3 201012881 酸銘、减鋅等為數眾多的產品出現在市場上作為組合 非鉻系顏料的底漆，财各種產品被提出。此外，從環境 問題出發，紐低揮發性有機化合物(實），水性塗料的開 發一直受到需求。 例如’專利文獻1中記栽’在環氧樹脂和祕樹脂的展 色劑成分中混合，㈣料㈣磷的組合之_顏料，或 碳酸妈和雜触魏銘及__組合之㈣顏料而成 的塗料。 另外’專利文獻2中記載，在聚酉旨中混合碗酸二鎮與氧 化猛.氧化飢燒結物作為p謂顏料的塗料和，混合碟酸妈與 氧化叙的塗料。 然而’將專利文獻丨及2中記載的防銹顏料應用於水性 塗料時，與使用鉻系顏料的塗料相比，耐蝕性差尤其在 金屬板之加工部及端面部的耐蝕性不足。另外，有耐鹼性 或耐酸性等之耐藥品性或耐水性差的情況。 另外，專利文獻3中記載—種塗料組成物，其係在含有 羥基或環氧基的有機樹脂和硬化劑形成的展色劑成分中， 3有吸油量30〜200ml/100g、細孔容積〇 〇5〜i 2ml/g之二 氧化矽微粒子的塗料，而且由該塗料形成的硬化塗膜之玻 螭轉移溫度在40〜125。(：的範圍内。然而，將專利文獻3中 。己栽之二氧化石夕微粒子應用於水性塗料而獲得的塗膜與 使用鉻系顏料的塗料相比，耐蝕性及耐藥品性差，尤其在 金屬板端面部的对姓性不足。 此外，專利文獻4中揭示一種耐蝕性優良的無鉻塗裝鋼 201012881 板，特徵在於其係將，混合了選自磷酸鎂、磷酸鋅、磷酸 氫鎮、三聚磷酸二氫紹、石夕酸約的一種或兩種以上之非絡 系防銹顏料的底塗塗膜和，混合了四烷氧矽烷的部分加水 分解縮合物(partial hydrolysis-condensation product of tetra- alkoxysilane)作為親水劑之面漆塗膜，依順積層於鑛層表 面。 另外，專利文獻5中揭示一種以含有平均粒徑0.4〜 0·6μιη的内部凝膠化硬質聚合物粒子(a)、水分散性二氧化矽 φ (b)、縮水甘油氧基烷基-三烷氧基矽烷（glycidoxyalkyl trialkoxysilanes)(c)、有機釩化合物(d)、水分散性氨酯樹脂 (urethane resin)(e)、锆化合物⑴及填酸氫二敍(g)的水性防 • 銹塗布劑組成物處理過之塗裝鍍鋅系鋼板。 但是，塗裝專利文獻4或專利文獻5中記載之含有防銹 顏料的塗料而獲得之塗膜，與塗裝含有鉻系顏料的塗料而 獲得之塗膜相比，耐蝕性及耐藥品性差，尤其在金屬板端 面部的耐姓性不足。 ® 專利文獻1 :特開平11-61001號公報 專利文獻2 :特開2000-199078號公報 專利文獻3 :特開2000-129163號公報 專利文獻4 :特開2007-260953號公報 專利文獻5 :特開2008-81785號公報 t 明内容】 發明概要 發明欲解決之課題 5 201012881 本發明之課題在於找出一種可以形成耐藥品性'金屬 板之平面部的耐蝕性、金屬板之加工部和端面部的耐蝕性 及附著性優良的塗膜之非鉻系水性塗料組成物，並提供— 種具有該塗膜性能優良之塗膜的塗裝金屬板。 用以欲解決課題之手段 因此’本發明人等為解決習知之上述問題，反復專心 研究，結果發現藉由在陽離子性樹脂(A)與多異氰酸酯硬化 劑(B)中’添加以預定量混合特定的釩化合物（cl)、矽化合 物（c2)及鱗酸系药鹽（C3)而成之防銹顏料混合物（c)做成水 性塗料組成物的方式，可以形成不僅耐藥品性、塗裝金屬 板之平面部的耐触性’在塗裝金屬板等的加工部和端面部 之耐姓性亦優良之塗膜，終而完成本發明。 亦即本發明係關於以下之水性塗料組成物。 1. 一種含有陽離子性樹脂(A)、多異氰酸酯硬化劑(B) 及下述防銹顏料混合物（C)的水性塗料組成物。 防銹顏料混合物(C)由：五氧化二釩、釩酸鈣及偏釩酸 銨之中的至少1種質釩化合物（cl)、矽化合物（C2)及磷酸系 鈣鹽(c3)組成，且相對於該樹脂(a)及該硬化劑（B)之合計固 體含量100質量份， 該飢化合物（cl)之量為1〜3〇質量份、石夕化合物（c2)之 量為1〜30質量份及該碟酸系鈣鹽（c3)之量為1〜30質量 份，並且該防銹顏料混合物(C)之量為3〜90質量份。 2·上述第1項記載之水性塗料組成物，其中陽離子性樹 脂(A)為含氨基環氧樹脂。 201012881 3. 上述第1項^己載之水性塗料組成物其中石夕化合物 (c=為，選自雜金屬鹽、二氧切微粒子及金屬離子交換 二氧化矽微粒子的至少1種。 4. 上述第1項記載之水性塗料組成物，其中磷酸系鈣鹽 (c3)為，磷酸鈣、磷酸一氫鈣、磷酸二氫鈣及三聚磷酸鈣之 中的至少1種。 5. 上述第1項記載之水性塗料組成物，其相對於陽離子 性樹脂(A)及多異氰酸酯（B)的固體含量合計，含有〇.ι〜10 φ 質量份的Resole型酚醛樹脂。 6. —種塗膜形成方法，特徵在於，其係在金屬板上， 形成用上述第1項記載之水性塗料組成物獲致的硬化塗 . 膜，並在該硬化塗膜上形成至少1種以上之面漆塗料的塗 膜。 7. —種塗裝金屬板’其具有用上述第6項記載之塗膜形 成方法獲得的塗膜。 8. —種塗裝物品’係藉加工上述第7項記載之塗裝金屬 Φ 板而獲得。 發明效果 本發明之含有特定的防銹顏料混合物之水性塗料组成^ 物，因不含鉻系防銹顏料且為水性塗料，故在環境衛生方 面是有利的。 以塗裝本發明之水性塗料組成物的方式獲得的塗膜， 耐藥品性優良，而且不僅塗裝金屬板之平面部的耐餘性優 良，在用含有習知之非鉻系防銹顏料的水性塗料難以達成 201012881 之塗裝金屬板的加工部和端面部的耐蝕性或附著性上，亦 可發揮優良的效果。 此外’在未施行化學轉化處理的熔融鍍鋅鋼板(GI鋼板) 上’用塗裝本發明之水性塗料組成物並經加熱乾燥而獲得 的硬化塗膜加以被覆之塗裝鋼板，與在施行過化學轉化處 理的熔融鍍鋅鋼板(GI鋼板)上，用含有鉻酸鹽系防銹顏料的 硬化塗膜予以被覆的塗裝鋼板，可以具有同等以上的耐勉 性。由此，亦可省略化學轉化處理程序（參見第丨圖），對塗 裝線的省程序化和省資源化是有利的。 圖式簡單說明 [第1圖]示意連續線圈塗裝線之一例。 [第2圖]示意含有本發明之水性塗料組成物的塗膜之 塗膜構造的一個例子。(Note 10) Salt spray test: The back surface and the cut surface of each test coated board of 5 cm x 10 cm size were sealed with an anti-rust paint, and a cross-draw of the substrate was placed in the center of the surface of the coated board. mark. The coated plate was subjected to a salt spray test (JIS Z-2371) at 500 ° C for 5 hours at 35 ° C. The red rust of the coated surface appeared after the evaluation test, and the paste was adhered to the cross section. The tape was evaluated for the width (one side) of the tape peeled off from the cut portion of the coating film after sharp peeling. ◎: No or only some reddish rust occurred. The width of the tape peeled off from the cut portion was less than 5 mm. 〇: The appearance of red rust was confirmed to a considerable extent, and the width of the tape peeled off from the cut portion was less than 5 mm, or none. Or only a little red rust hair 44 201012881, but the width of the tape peeled from the cut portion is less than 5mm and less than 10mm, △: the occurrence of red rust is confirmed in the whole part of the cut, but the width of the tape peeled off from the cut portion When it is less than 5 mm or less, it is not more than 1 Omm, or the occurrence of red rust is confirmed to a considerable extent, and the width of the tape peeled off from the cut portion is 10 mm or more. X : It is confirmed in the entire cut portion. The occurrence of red rust occurs, and the width of the tape peeled off from the cut portion is l〇mm or more. INDUSTRIAL APPLICABILITY The present invention provides a coated metal sheet and a coated article which are excellent in chemical resistance, corrosion resistance in a flat portion, and excellent in corrosion resistance and adhesion between a processed portion and an end portion. t: Simple description of the drawings 3 4 [Fig. 1] An example of a continuous coil coating line is illustrated. [Fig. 2] An example of a coating film structure of a coating film containing the aqueous coating composition of the present invention. [Description of main component symbols] ® 1... Part of the steel plate 4... Primer coating film (Water-based coating of the present invention 2. Composition of the coating material) 3. Chemical conversion performed as required. .. Topcoat Coating Treatment (Pretreatment) 45 201012881 VI. INSTRUCTIONS: [Technical Field of Invention] The present invention relates to a t-contact which can form a chemical resistant, flat portion of a metal plate. An aqueous coating composition of a coating film having excellent physical and chemical properties and adhesion to a processed portion of a metal sheet, and a coated metal sheet having a coating film formed of the aqueous coating composition. φ BACKGROUND OF THE INVENTION In the past, precoated metal sheets such as precoated steel sheets coated with coil coatings and the like have been widely used as building materials for roofs, walls, shutters, garages, etc. Use of home-related products such as home appliances, switchboards, refrigerated display cases, steel furniture, and kitchen appliances. In the case of these residential-related products made of pre-coated metal sheets, the pre-coated metal sheets are usually cut and joined by press molding. Therefore, in many of these residential related products, there are many metal exposed portions of the cut surface or crack generating portions due to the press working #. Since the metal exposed portion or the crack generating portion is more likely to have lower corrosion resistance than other portions, it is generally practiced to use a chromium-based rust-preventing pigment in the undercoat coating film which is used for the pre-coated metal sheet to improve corrosion resistance. However, chromium-based rust-preventive pigments or hexavalent chromium which is excellent in rust-preventing properties may generate hexavalent chromium. The hexavalent chromium poses a problem from the viewpoint of the health of the human body and environmental protection. Up to now, non-chromium-based anti-rust pigments have been produced in the market as a combination of non-chromium pigments, such as zinc phosphate and tripolyphosphate. In addition, from the environmental issues, the development of new low-VOC (real), water-based coatings has been demanded. For example, 'patent document 1 is written in a toner composition of an epoxy resin and a secret resin, (4) a combination of a material (four) phosphorus, or a mixture of a carbonated mother and a mixed contact Wei Ming and a __ Into the paint. Further, in Patent Document 2, it is described that a mixture of a bowl of acid and a oxidized smoldering sinter is used as a coating of a p-precipitated pigment, and a mixture of a dish of a sour mom and an oxidized coating is mixed. However, when the rust-preventive pigments described in Patent Documents 2 and 2 are applied to an aqueous coating material, the corrosion resistance is inferior to that of the processed portion and the end surface portion of the metal sheet as compared with the coating material using the chromium-based pigment. In addition, there is a case where the chemical resistance or the water resistance such as alkali resistance or acid resistance is poor. Further, Patent Document 3 describes a coating composition which is a toner component formed of an organic resin containing a hydroxyl group or an epoxy group and a curing agent, and has an oil absorption amount of 30 to 200 ml/100 g and a pore volume 〇. 〇5~i 2ml/g of the coating of cerium oxide microparticles, and the glass transition temperature of the hardened coating film formed by the coating is 40 to 125. However, in Patent Document 3, the coating film obtained by applying the coated cerium oxide particles to the aqueous coating has poor corrosion resistance and chemical resistance, especially in the coating material using the chromium-based pigment. In addition, Patent Document 4 discloses a chromium-free coated steel 201012881 plate excellent in corrosion resistance, characterized in that it is mixed with magnesium phosphate, zinc phosphate, hydrogen phosphate, A primer coating film of one or two or more kinds of non-stereoscopic rust-preventing pigments of dihydrogen-sodium dihydrogen phosphate, and a mixture of tetrahydrooxane and a partial hydrolysis-condensation product of Tetra- alkoxysilane as a topcoat coating film of a hydrophilic agent, which is laminated on the surface of the ore layer. Further, Patent Document 5 discloses an internally gelled hard polymer particle having an average particle diameter of 0.4 to 0.6 μm. ), water-dispersible cerium oxide φ (b), glycidoxyalkyl-trimethyl oxysilanes (c), organic vanadium compounds (d), water-dispersible urethane resin (urethane resi) n) (e), a zirconium compound (1), and a galvanized coating material having a water-borne anti-rust coating agent composition, which is treated with a hydrous sulphate (g), which is described in Patent Document 4 or Patent Document 5 The coating film obtained by the coating containing the rust-preventing pigment has poor corrosion resistance and chemical resistance as compared with the coating film obtained by coating the coating containing the chrome-based pigment, and particularly has insufficient resistance to the surname of the metal plate end face. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. 2000-129. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is to find a corrosion resistance of a flat portion of a metal sheet which can form a chemical resistance, a processed portion of a metal plate, and an end surface portion. A non-chromium-based aqueous coating composition of a coating film which is excellent in corrosion resistance and adhesion, and a coated metal sheet having a coating film having excellent coating film properties, and a means for solving the problem. To solve the conventional knowledge The problem was repeatedly studied intensively, and it was found that a specific vanadium compound (cl), a ruthenium compound (c2), and a scaly acid were mixed by a predetermined amount in the cationic resin (A) and the polyisocyanate hardener (B). The anti-rust pigment mixture (c) made of the medicinal salt (C3) is formed into a water-based paint composition, and can form not only chemical resistance but also the contact resistance of the flat portion of the coated metal sheet. The coated portion and the end surface portion are also excellent in coating resistance, and the present invention has been completed. That is, the present invention relates to the following aqueous coating compositions. An aqueous coating composition comprising a cationic resin (A), a polyisocyanate curing agent (B), and a rust preventive pigment mixture (C) described below. The rust preventive pigment mixture (C) is composed of at least one vanadium compound (cl), a cerium compound (C2), and a calcium phosphate salt (c3) among vanadium pentoxide, calcium vanadate and ammonium metavanadate. And the amount of the hunger compound (cl) is 1 to 3 parts by mass, and the amount of the stone compound (c2) is 1 to 1 part by mass based on the total solid content of the resin (a) and the curing agent (B). The amount of the 30 parts by mass of the disc acid calcium salt (c3) is 1 to 30 parts by mass, and the amount of the antirust pigment mixture (C) is 3 to 90 parts by mass. The aqueous coating composition according to the above item 1, wherein the cationic resin (A) is an amino group-containing epoxy resin. 201012881 3. The above-mentioned item 1 of the aqueous coating composition of the present invention, wherein the compound (c = is selected from the group consisting of a heterometal salt, a dioxo fine particle, and a metal ion-exchanged ceria microparticle. The aqueous coating composition according to the first aspect, wherein the phosphate-based calcium salt (c3) is at least one selected from the group consisting of calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, and calcium tripolyphosphate. The water-based paint composition described above contains a Resole type phenol resin in an amount of 0.1 to 10 parts by mass based on the total solid content of the cationic resin (A) and the polyisocyanate (B). Further, it is characterized in that it is formed on a metal plate to form a cured coating film obtained by the aqueous coating composition according to the above item 1, and a coating film of at least one of the top coat materials is formed on the cured coating film. 7. A coated metal plate having a coating film obtained by the method for forming a coating film according to the above item 6. 8. A coated article is processed by processing the coated metal Φ plate according to the above item 7. Obtained. Effect of the invention The aqueous coating composition of the pigment mixture is environmentally friendly because it does not contain the chromium-based rust-preventive pigment and is an aqueous coating. The coating film obtained by coating the aqueous coating composition of the present invention is resistant to the drug. It is excellent in the properties and is excellent in the durability of the flat portion of the coated metal sheet. It is difficult to achieve the corrosion resistance of the processed portion and the end portion of the coated metal sheet of 201012881 by using a water-based paint containing a conventional non-chromium-based anti-rust pigment. In addition, it is also excellent in adhesion. Further, 'on a hot-dip galvanized steel sheet (GI steel sheet) which is not subjected to chemical conversion treatment, 'hardened coating film obtained by coating the aqueous coating composition of the present invention and drying by heating The coated steel sheet to be coated and the coated steel sheet coated with the hardened coating film containing the chromate-based anti-rust pigment on the hot-dip galvanized steel sheet (GI steel sheet) subjected to the chemical conversion treatment may have the same or more. Resistance to entanglement. Therefore, the chemical conversion treatment procedure (see the figure) can be omitted, which is advantageous for the provincial programming and resource saving of the coating line. [Fig. 1] An example of a continuous coil coating line is shown. Fig. 2 is a view showing an example of a coating film structure of a coating film containing the aqueous coating composition of the present invention.

C實施方式J 用以實施發明之形態 本發明之水性塗料組成物係關於一種以含有特定量的 陽離子性樹脂(A)與多異氰酸酯硬化劑(B)及特定的防銹顏 料混合物(C)為特徵之水性塗料組成物。以下，將詳細敘述。 1·金屬板 作為被塗物的金屬板可舉例如，電氣鍍鋅鋼板、電氣 鑛鋅-鎳鋼板、熔融鍍辞鋼板、熔融鍍鋅_鋁鋼板等的鍍鋅 系鋼板，熱軋鋼板、冷軋鋼板、不鏽鋼鋼板、鍍銅鋼板、 銘板、熔融鍍錫-鋅（Sn-10%Zn)鋼板、熔融鍍鋁鋼板、Al-Mg 合金等。 201012881 2.陽離子性樹脂(A) 陽離子性樹脂(A)為’分子中有絲、雜、銕驗、鱗 驗等可陽離子化之基團的樹脂。樹脂種類為通常所使用 者，可舉例如，環氧_旨、丙烯_脂、訂讀樹脂、 醇酸樹脂、《樹脂等。特別是使含有胺基的化合物在環 氧樹脂中進行加成反應而獲得的含有胺基之環氧樹脂，不 僅耐藥如性優良’且金屬板之平面部的雜性優良，從提 高加工部和端面部的耐蝕性來看也是合適的。 上述含有胺*的環氧樹月旨，可舉例如， ⑴環氧樹脂與一級單、及多胺、二級單-及多胺或-、 -級此合多胺的加成物(例如，參見美國專利第3 984 299號 說明書）； (2) 環氧樹脂與含有經過酮亞胺化的—級胺基之二級 單-及多胺的加成物（例如，參見美國專利第4,〇17,438號說 明書）； (3) 環氧樹脂與含有經過_亞胺化的一級胺基之經基 化合物的經醚化而獲得的反應物（例如參見特開昭 59-43013號公報）等。 製造上述含有胺基的環氧樹脂時所使用的環氧樹脂 是，1分子中至少有1個環氧基，有2個以上為佳的化合物。 環氧樹脂的分子量一般適用的是有至少3〇()，以4〇〇〜4〇〇〇 為佳，更佳的是8〇〇〜2,500之範圍内的「數量平均分子量」 及至少160g/eq，以180〜2,5〇〇g/eq為佳，更佳的是4〇〇〜 l，500g/eq之範圍内的環氧當量者，尤以透過多酚化合物與 9 201012881 環氧鹵丙烧(epihalohydrin)之反應所得者為佳。 本說明書中’「數量平均分子量」係遵循JISK()124—83 中記載之方法’使用以下的4支分離管柱，用溶析液(Gpc 用四氫0夫味）在40°C及流速1.0ml/分鐘下，由利用折射計 得到的層析圖與標準聚苯乙烯的標準曲線求算。 分離管枉：「TSK GEL4000HXL」、「TSK G3000HXL」、 「TSK G2500HXL」、「TSK G2000HXL」（每一種都是東曹 (株)製）。 為形成該環氧樹脂所使用的多酚化合物可舉例如， 2,2-雙(4-羥苯基）丙烷[雙酚A]、雙(4-羥苯基）甲烷[雙酚 F]、雙(4-羥基環己基）甲烷[氫化雙酚F]、2,2-雙(4-羥基環 己基）丙烷[氫化雙酚A]、4,4’-二羥基二苯甲酮、1,1-雙(4-羥苯基）乙烷、1，卜雙(4-羥苯基）異丁烷、2,2-雙(4-羥基-3-叔丁基-苯基）丙院、雙（2-經基萘）曱烧 (bis(2-hydroxynaphthyl)methane)、1，1，2,2-四（4-經苯基）曱 烷、4,4’-二羥基二苯基砜、Novolac-type酚醛、甲酚醛(cresol novolac)等。 另外，利用多酚化合物與環氧氯丙烷的反應獲得的環 氧樹脂，其中尤以從雙酚A衍生而成的下述式之樹脂為合 適。 [化1]C. Embodiment J. Embodiment for carrying out the invention The aqueous coating composition of the present invention relates to a mixture containing a specific amount of a cationic resin (A) and a polyisocyanate curing agent (B) and a specific rust preventive pigment (C). A characteristic aqueous coating composition. Hereinafter, it will be described in detail. 1. Metal plate as a metal plate to be coated, for example, an galvanized steel plate, an electric ore zinc-nickel steel plate, a hot-dip steel plate, a galvanized steel plate such as a hot-dip galvanized steel plate, a hot-rolled steel plate, and a cold plate. Rolled steel plate, stainless steel plate, copper plated steel plate, name plate, hot-dip tin-zinc (Sn-10%Zn) steel plate, hot-dip aluminized steel plate, Al-Mg alloy, and the like. 201012881 2. Cationic resin (A) The cationic resin (A) is a resin having a cationizable group such as a filament, a hetero, a test, or a scale in the molecule. The type of the resin is usually used, and examples thereof include epoxy resin, propylene resin, finishing resin, alkyd resin, and resin. In particular, an amine group-containing epoxy resin obtained by subjecting an amine group-containing compound to an addition reaction in an epoxy resin is excellent in resistance, such as excellent resistance, and the surface portion of the metal sheet is excellent in impurities, and the processing portion is improved. It is also suitable for the corrosion resistance of the end face. The above-mentioned amine-containing epoxy resin may, for example, be an adduct of (1) an epoxy resin with a primary mono- and polyamine, a secondary mono- and polyamine or a -, - See U.S. Patent No. 3,984,299); (2) an epoxy resin with an adduct of a secondary mono- and polyamine containing a ketimine-based amine group (see, for example, U.S. Patent No. 4, 〇, No. 17, 438) (3) A reactant obtained by etherification of an epoxy resin and a transbasic compound containing an imidized primary amino group (for example, see JP-A-59-43013). The epoxy resin used in the production of the above-mentioned epoxy group-containing epoxy resin is one having at least one epoxy group in one molecule and preferably two or more. The molecular weight of the epoxy resin is generally applicable to at least 3 〇 (), preferably 4 〇〇 to 4 ,, more preferably in the range of 8 〇〇 to 2,500, and the number average molecular weight and at least 160 g / Eq, preferably 180~2,5〇〇g/eq, more preferably epoxy equivalents in the range of 4〇〇~l,500g/eq, especially through polyphenol compounds and 9 201012881 epoxy halide The result of the reaction of epihalohydrin is preferred. In the present specification, 'the number average molecular weight' is in accordance with the method described in JIS K() 124-83' using the following four separation columns, using a solution (Gpc with tetrahydrogen) at 40 ° C and flow rate. The chromatogram obtained by using a refractometer and the standard curve of standard polystyrene were calculated at 1.0 ml/min. Separation pipe: "TSK GEL4000HXL", "TSK G3000HXL", "TSK G2500HXL", "TSK G2000HXL" (each is manufactured by Tosoh Corporation). Examples of the polyphenol compound used for forming the epoxy resin include 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] and bis(4-hydroxyphenyl)methane [bisphenol F]. Bis(4-hydroxycyclohexyl)methane [hydrogenated bisphenol F], 2,2-bis(4-hydroxycyclohexyl)propane [hydrogenated bisphenol A], 4,4'-dihydroxybenzophenone, 1, 1-bis(4-hydroxyphenyl)ethane, 1, bis(4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxy-3-tert-butyl-phenyl)propene, Bis(2-hydroxynaphthyl)methane, 1,1,2,2-tetrakis(4-phenyl)decane, 4,4'-dihydroxydiphenyl sulfone , Novolac-type phenolic, cresol novolac, and the like. Further, an epoxy resin obtained by a reaction of a polyphenol compound with epichlorohydrin is used, and among them, a resin of the following formula derived from bisphenol A is particularly suitable. [Chemical 1]

上述式中，η以0〜8表示者為合適。 201012881 相關環氧樹脂的市售品可舉例如jER828EL、jER 1002、jER1004、jER1007 (Japan Epoxy Resins Co. Ltd，商 品名）、Araldite AER6099 (Asahi Ciba Co.’Ltd.製，商品名）、 EPOMIK R-309 (Mitsui Chemicals Inc.製，商品名）。In the above formula, η is preferably represented by 0 to 8. 201012881 A commercial product of the related epoxy resin may, for example, be jER828EL, jER 1002, jER1004, jER1007 (Japan Epoxy Resins Co. Ltd, trade name), Araldite AER6099 (manufactured by Asahi Ciba Co.' Ltd., trade name), EPOMIK R -309 (manufactured by Mitsui Chemicals Inc., trade name).

該環氧樹脂可以是和多元醇、聚醚多元醇、聚酯多元 醇、聚醯胺一胺(polyamidoamine)、多元酸、多異氰酸酯化 合物等之改質成分反應成的改質環氧樹脂，此外，也可以 是使ε-己内酯等的内酯類、丙烯酸單體等發生接枝聚合而 得的改質環氧樹脂。 再者，使上述改質成分與環氧樹脂發生反應以製造改 質環氧樹脂的方法並無特殊限定。改質成分與環氧樹脂的 反應可以透過，例如，在可溶解這些各別成分的溶劑中， 依需要在反應觸媒存在下，通常，在1〇〇〜15〇〇c使之反應丄 〜5小時的方式，適當地進行。 上述反應觸媒，可舉例如，四乙基溴化銨扣加_ ethylammonium bromide)、四丁基溴化銨、三苯基苄基氣化 膦（tdphenylbenzylphosphonium Chl0ride)等之四級鹽的觸 媒，三乙胺等的胺類。 製造上述(1)之含有胺基的環氧樹脂時所使用的一級單 -及多胺、二級單—及多胺，或一、二 級混合多胺，可舉例 如，單甲胺、 丙胺、一丁胺 甲胺、單乙胺、二乙胺、一異丙胺、二異 二丁胺等之單-或二-烷基胺；單乙醇胺、 二乙醇胺、單(2-經丙基)胺、-甲胺乙醇等之燒醇胺；乙二 胺、丙二胺、丁二胺、己二胺、二乙烯三胺、 乙烯四胺 11 201012881 等之亞烷基多胺等的胺化合物。 製泣上述(2)之含有胺基的環氧樹脂時所使用的具有經 過綱亞胺化之—級胺基的二級單—及多胺，可舉例如，在製 造^述(1)之環氧樹脂胺加成物時所使用的一、二級混合聚 胺田中命J如，二乙烯三胺等中使酮化合物發生反應而生 成之，胺化合物的酮亞胺化物。 製造上述(3)之含有胺基的環氧樹脂時所使用的具有經 過鋼亞胺化之-級胺基的經基化合物，可舉例如，在製造 上述⑴之環氧樹脂胺加成物時所使用的-級單-及乡胺、二 | 單及多胺或、一級混合多胺之中，含有一級胺基和羥 基的化合物’例如’單乙醇胺、單(2,丙基)胺等中使酮化 s物發生應而生成的，胺化合物之含經基_亞胺化物。 特別疋，在含胺基環氧樹脂之中，從提高預塗鋼板中 的加工部之耐祕的觀點來看，較佳的樹脂可以舉例如， ·The epoxy resin may be a modified epoxy resin which is reacted with a modified component such as a polyol, a polyether polyol, a polyester polyol, a polyamidoamine, a polybasic acid or a polyisocyanate compound. Further, it may be a modified epoxy resin obtained by graft-polymerizing a lactone such as ε-caprolactone or an acrylic monomer. Further, a method of reacting the above-mentioned modified component with an epoxy resin to produce a modified epoxy resin is not particularly limited. The reaction of the modified component with the epoxy resin can be transmitted, for example, in a solvent which can dissolve the respective components, and if necessary, in the presence of a reaction catalyst, usually, it is reacted at 1 〇〇 15 15 ° c. The 5-hour method is carried out as appropriate. The reaction catalyst may, for example, be a catalyst of a quaternary salt such as tetraethylammonium bromide or ethylammonium bromide, tetrabutylammonium bromide or tdphenylbenzylphosphonium Chlride. An amine such as triethylamine. The primary mono- and polyamines, the secondary mono- and polyamines, or the primary and secondary mixed polyamines used in the production of the amine group-containing epoxy resin of the above (1), for example, monomethylamine or propylamine Mono- or di-alkylamines such as monobutylamine, monoethylamine, diethylamine, monoisopropylamine, diisobutylamine, etc.; monoethanolamine, diethanolamine, mono(2-propyl)amine An amine compound such as an alkoxyamine such as methylaminoethanol or an alkylene polyamine such as ethylenediamine, propylenediamine, butanediamine, hexamethylenediamine, diethylenetriamine or ethylenetetraamine 11 201012881. A secondary mono- and polyamine having an amine group-substituted amine group used in the above-mentioned (2) amino group-containing epoxy resin, for example, in the production of (1) The first- and second-stage mixed polyamines used in the epoxy resin amine adducts, such as ketimine, which is formed by reacting a ketone compound in diethylenetriamine or the like, and an amine compound. The base compound having a metal imidized amine group used in the production of the amine group-containing epoxy resin of the above (3), for example, in the production of the epoxy resin amine adduct of the above (1) Among the mono- and mono- and poly- or poly-amines, the first-stage mixed polyamines, the compounds containing a primary amine group and a hydroxyl group, such as 'monoethanolamine, mono(2,propyl)amine, etc. The ketone s species is formed as a result of the formation of the amine compound containing a trans-imide. In particular, among the amine-containing epoxy resins, preferred resins are, for example, from the viewpoint of improving the resistance of the processed portion in the precoated steel sheet.

將胺化合物等加成到碳數4〜36的脂肪族多元酸與環氧樹 脂反應成之改質環氧樹脂而形成之，脂肪族多元酸改質之 含胺基環氧樹脂；其他，像是將胺化合物等加成到多異& Q 酸醋化合物與環氧樹脂反應成的改f環氧樹脂而形成之， 二異氰酸酯化合物改質之含胺基環氧樹脂。 上述碳數4〜36的脂肪族多元酸，以卜％的飽和或不 飽和脂肪族多元酸聽，可舉例如，六制苯二甲酸(ha. hydroisophthdk acid)、六氫對笨二甲酸（hexahydr〇_ terePhthalic acid)、六氫鄰苯二甲酸伽一—h偏^ ㈣、f基六氫鄰苯二甲酸、甲基六氫對苯二甲酸、卜四 12 201012881 氫鄰苯二曱酸、2-四氫鄰苯二曱酸' 3-四氫鄰苯二甲酸、 4-四氫鄰苯二甲酸、1-四氫間苯二甲酸、2-四氫間苯二甲 酸、3-四氫間苯二甲酸、4-四氫間苯二甲酸、1 —四氫對苯 二甲酸、2-四氫對苯二甲酸、甲基四氫鄰苯二甲酸、内亞 甲基四氫鄰苯二甲酸（endomethylene tetrahydrophthalic acid)、甲基内亞甲基四氫鄰苯二曱酸、六氯内亞甲基四氫 鄰苯二甲酸等之脂環式二羧酸基其酸酐；琥珀酸、戊二酸、 己二酸、壬二酸、癸二酸、十二烷二酸、十四烷二酸、辛 φ 二酸、庚二酸、順丁烯二酸(maleic acid)、反丁烯二酸 (fumaric acid)、亞甲基丁二酸(Itaconic acid)、十三烷二酸 (brassylic acid)、甲基順丁烯二酸(citraconic acid)、氣順丁 . 烯二酸(chloromaleic acid)、二聚酸等之脂肪族二叛酸及其 酸酐；六氫苯三甲酸(hexahydrotrimellitic acid)等之3價以上 的脂肪族多元酸；如這些酸的甲酯、乙酯之低級烷酯等。 上述的多異氰酸酯化合物，可舉例如，甲苯二異氰酸 酯（tolylene diisocyanate)、二苯甲二異氰酸酯（Xyiylene ❹ diisocyanate)、苯二異氰酸酯（phenylene diisocyanate)、二苯 甲烷-2,2’-二異氰酸酯、二苯甲烷-2,4’-二異氰酸酯、二苯 甲烷-4,4’-二異氰酸酯、粗MDI[多亞甲基多苯基異氰酸酯 (polymethylene polyphenyl isocyanate)]、二（異氰酸根合甲 基）環己烧(bis(isocyanatomethyl)-Cyclohexane)、四亞甲基二 異氰酸酯、六亞曱基二異氰酸酯、亞曱基二異氰酸酯 (methylene diisocyanate)、異佛爾酮二異氰酸酯等之芳香 族、脂肪族或脂環族多異氰酸酯化合物；這些多異氰酸酯 13 201012881 化合物的環化聚合物或縮二脲；或其等之故人 尤其，六亞甲基二異氣酸醋從提高加工部和端面部的 而十姓性方面來看是合適的。 〃再者，製造含絲魏樹脂時，•料_(改質環 乳樹flg) ’及含胺基化合物的加成反應，诵 通常可以在適當的An amine-based epoxy resin modified by adding an amine compound or the like to an aliphatic polybasic acid having a carbon number of 4 to 36 and an epoxy resin to be converted into an epoxy resin; It is an amine-containing epoxy resin modified by adding an amine compound or the like to an epoxy resin obtained by reacting a polyiso- and Q-acid vinegar compound with an epoxy resin. The above aliphatic polybasic acid having 4 to 36 carbon atoms is exemplified by a saturated or unsaturated aliphatic polybasic acid, for example, ha. hydroisophthdk acid, hexahydro-p-dicarboxylic acid (hexahydr). 〇 _ terePhthalic acid), hexahydrophthalic acid gamma-h partial ^ (four), f-based hexahydrophthalic acid, methyl hexahydroterephthalic acid, Bu four 12 201012881 hydrogen phthalic acid, 2 -tetrahydrophthalic acid ' 3-tetrahydrophthalic acid, 4-tetrahydrophthalic acid, 1-tetrahydroisophthalic acid, 2-tetrahydroisophthalic acid, 3-tetrahydrogen Phthalic acid, 4-tetrahydroisophthalic acid, 1-tetrahydroterephthalic acid, 2-tetrahydroterephthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid (endomethylene tetrahydrophthalic acid), methyl endomethylenetetrahydrophthalic acid, hexachloromethylenetetrahydrophthalic acid, etc., alicyclic dicarboxylic acid anhydride; succinic acid, glutaric acid , adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, octane dioic acid, pimelic acid, maleic acid, fumaric acid ( Fu Maric acid), itaconic acid, brassylic acid, citraconic acid, chloromaleic acid, two An aliphatic dibasic acid such as a polyacid or an acid anhydride thereof; a trivalent or higher aliphatic polybasic acid such as hexahydrotrimellitic acid; a methyl ester of these acids; a lower alkyl ester of an ethyl ester; and the like. Examples of the above polyisocyanate compound include tolylene diisocyanate, Xyiylene ❹ diisocyanate, phenylene diisocyanate, diphenylmethane-2,2'-diisocyanate, and Benzene-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, crude MDI [polymethylene polyphenyl isocyanate], bis(isocyanatomethyl) Aromatic, aliphatic or the like of bis(isocyanatomethyl)-cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate or the like An alicyclic polyisocyanate compound; a cyclized polymer or a biuret of these polyisocyanate 13 201012881 compounds; or the like, especially, hexamethylene diiso oleic acid vinegar from the processing part and the end face Sexually, it is appropriate. Further, when the silk-containing Wei resin is produced, the addition reaction of the material _(modified ring milk tree flg) and the amine-containing compound is usually appropriate.

溶劑中’宜在80〜n(TC(較佳為9G〜15η：)之溫度，進行】 〜6小時(較佳為1〜5小時）。上述溶劑可舉例如^甲苯#二 甲苯、環己烷、正己院等之煙系溶劑；醋酸甲酿、醋酸: 醋、醋酸丙醋等之酯系溶劑；丙酮、曱乙_、曱基異丁酮、 甲基戊基甲酮(methyl amylketone)等之㈣溶劑；二甲基甲 醯胺、二甲基乙醯胺等之醯胺系溶劑；甲醇、乙醇、二丙 醇、異丙醇等之醇系溶劑；或其等之混合物等。The solvent is preferably carried out at a temperature of 80 to n (TC (preferably 9 G to 15 η:) for ～6 hours (preferably 1 to 5 hours). For the above solvent, for example, toluene #xylene, cyclohexane Alcohol, Zhengjiyuan, etc.; solvent, acetic acid: acetic acid: vinegar, acetic acid, propyl vinegar, etc.; solvent, acetone, _, 曱, isobutyl ketone, methyl amylketone, etc. (4) a solvent; a guanamine solvent such as dimethylformamide or dimethylacetamide; an alcohol solvent such as methanol, ethanol, dipropanol or isopropanol; or a mixture thereof or the like.

上述加成反應中的各反應成分之使用比例，雖無嚴密 限制可適當改變’㈣環氧樹脂（改f環氧樹脂)與含胺基化 5物之&计固體含量質量做基準，環氧樹脂宜使用〜 質量％，較佳為70〜95質量。/。，更佳的是8〇〜95質量％ ;含 胺基化合物宜使用3〜30質量％，較佳為5〜3〇質量％，更佳 的是在5〜20質量％之範圍内。 另外’含胺基化合物之使用量從提高水分散性與塗膜 耐钮性的面來看’本發明之最終生成物的陽離子性樹脂之 胺價為10〜80mgKOH/g ’以落在2〇〜7〇mgKOH/g的範圍内 為佳。 3.多異氰酸酯硬化劑(B) 本發明的水性塗料組成物為，在陽離子性樹脂(A)中混 14 201012881 合多異氰酸酯硬化劑(B)而成的熱硬化性塗料。 在多異氰酸醋硬化劑(B)中所使用的多異氰酸酯化合 物，可以使用公知化合物，例如，甲苯二異氰酸酯、苯二 甲基二異氰酸酯、亞苯基二異氰酸酯、二苯甲烷_2,2’_二異 氰酸酯、二苯甲烷-2,4’-二異氰酸酯、二苯甲烷-4,4’-二異 氰酸酯、粗MDI[多亞甲基多苯基異氰酸酯]、二(異氰酸根 合曱基)環己烷、四亞曱基二異氰酸酯、六亞曱基二異氰酸 酯、亞甲基二異氰酸酯、異佛爾酮二異氰酸酯等之芳香族、 φ 脂肪族或脂環族多異氰酸酯化合物；此等多異氰酸酯化合 物的環化聚合物或縮二脲；或其等之組合。 尤其，曱苯二異氰酸酯、苯二甲基二異氰酸酯、亞苯 • 基二異氰酸酯、二苯甲烷-2,4’-二異氰酸酯、二苯甲烷-4,4’- 二異氰酸酯、粗MDI等的芳香族多異氰酸酯化合物，從金 屬板之平面部的耐蝕性觀點來看特別合適。 特別是，異氰酸酯的種類用六亞曱基二異氰酸酯時， 因為可以提高硬化性並賦予塗膜柔軟性，所以對提高預塗 © 鋼板的加工部和端面部之财蚀性是較佳的。 另外，本發明中，多異氰酸酯硬化劑(B)，可以適當地 使用使前述多異氰酸酯化合物與異氰酸酯封閉劑以接近化 學理論量進行加成反應而得到的封閉型多異氰酸酯化合 物。 前述異氰酸酯封閉劑係加成於多異氰酸酯化合物的異 氰酸酯基而將其封閉者。藉加成而生成之封閉型多異氰酸 酯化合物在常溫下是安定的，但是在加熱到塗膜的燒結溫 15 201012881 度(通常為100〜20(TC )時，希望異氰酸酯封閉劑可以解離再 生成游離的異氰酸醋基。The ratio of the use of each of the reaction components in the above-mentioned addition reaction may be appropriately changed, and the quality of the solid content of the (4) epoxy resin (modified epoxy resin) and the aminated compound may be appropriately changed. The oxygen resin is preferably used in an amount of -% by mass, preferably 70 to 95% by mass. /. More preferably, it is 8 Å to 95% by mass; and the amine group-containing compound is preferably used in an amount of 3 to 30% by mass, preferably 5 to 3% by mass, more preferably 5 to 20% by mass. Further, the amount of the amine-containing compound used is from the viewpoint of improving the water dispersibility and the resistance of the coating film. The amine resin of the final product of the present invention has an amine value of 10 to 80 mgKOH/g to fall at 2〇. It is preferably in the range of ~7 〇 mgKOH/g. 3. Polyisocyanate curing agent (B) The aqueous coating composition of the present invention is a thermosetting coating material obtained by mixing 14 201012881 polyisocyanate curing agent (B) with a cationic resin (A). As the polyisocyanate compound used in the polyisocyanate hardener (B), a known compound such as toluene diisocyanate, benzodimethylisocyanate, phenylene diisocyanate, diphenylmethane-2, 2 can be used. '_Diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, crude MDI [polymethylene polyphenyl isocyanate], bis(isocyanatoindolyl) An aromatic, φ aliphatic or alicyclic polyisocyanate compound such as cyclohexane, tetradecylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate or isophorone diisocyanate; A cyclized polymer or biuret of an isocyanate compound; or a combination thereof. In particular, aromatics such as toluene diisocyanate, benzodimethyl diisocyanate, phenylene diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, crude MDI, etc. The polyisocyanate compound is particularly suitable from the viewpoint of corrosion resistance of the flat portion of the metal plate. In particular, when hexamethylene diisocyanate is used as the type of isocyanate, since the curability is improved and the flexibility of the coating film is imparted, it is preferable to improve the economical property of the processed portion and the end surface portion of the precoated steel sheet. Further, in the present invention, as the polyisocyanate curing agent (B), a blocked polyisocyanate compound obtained by subjecting the polyisocyanate compound and the isocyanate blocking agent to an addition reaction amount close to a theoretical amount of the chemical can be suitably used. The above isocyanate blocking agent is added to the isocyanate group of the polyisocyanate compound to be blocked. The blocked polyisocyanate compound formed by addition is stable at normal temperature, but when heated to a sintering temperature of the coating film of 15 201012881 degrees (usually 100 to 20 (TC), it is desirable that the isocyanate blocking agent can be dissociated and regenerated. Isocyanate acrylate.

前述異氰酸酯封閉劑，可舉例如，甲乙酮肟（mdhy1-ethylketoxime)、曱戊銅將（methylamylketoxime)、環己酮肪 等之肟系化合物；苯酚、對叔丁基苯酚、甲酚等之酚系化 合物；正丁醇、2-乙基己醇等的脂肪族醇類；苯曱醇、甲 基苯甲醇等之芳香族烷醇類；乙二醇單丁醚、二乙二醇單 ***等之醚醇系化合物；ε-己内醯胺、γ-丁内酿胺等之内 醯胺系化合物等等。 前述陽離子性樹脂(Α)及多異氰酸酯硬化劑(Β)之混合 比例’以上述成分(Α)及成分(Β)的固體含量合計質量為基 準，且取成分(Α)為6〇〜95質ϊ%，較佳為〜9〇質量％ , 取成分(Β)為5〜40質量。/。為佳，較佳為1〇〜3〇質量％之範圍 内，從塗料安定性與硬化性的面看是合適的。 在製造本發明之水性塗料組成物時，除陽離子性樹月匕 (A)及多異氰酸酯硬化劑(B)外，在充分 曰 吒δ界面活性劑、 面調整劑和Resole型酚醛樹脂的等各種為 ^The isocyanate blocking agent may, for example, be an oxime compound such as mdhy1-ethylketoxime, methylamylketoxime or cyclohexanone; or a phenolic compound such as phenol, p-tert-butylphenol or cresol. An aliphatic alcohol such as n-butanol or 2-ethylhexanol; an aromatic alkanol such as benzoquinone or methyl benzyl alcohol; or an ether such as ethylene glycol monobutyl ether or diethylene glycol monoethyl ether An alcohol-based compound; an indoleamine compound such as ε-caprolactam or γ-butane amine; and the like. The mixing ratio of the cationic resin and the polyisocyanate curing agent is based on the total mass of the solid content of the above components (Α) and the component (Β), and the component (Α) is 6〇 to 95. ϊ%, preferably ～9% by mass, and the composition (Β) is 5 to 40 mass. /. Preferably, it is preferably in the range of 1 Å to 3 Å by mass, and is suitable from the viewpoint of coating stability and hardenability. In the production of the aqueous coating composition of the present invention, in addition to the cationic dendrimer (A) and the polyisocyanate curing agent (B), various δδ surfactants, surface conditioners, and Resole type phenol resins are sufficient. For ^

等以製成調合樹脂後，可以將上述調厶搞 機溶劑 σ埘月曰用醋酸、碰酿 甲酸、丙酸、乳酸等之有機缓酸；鹽駿、 、 等加以水溶化或水分散化而獲得乳液。酸等之無機酸 上述Resole型酚醛樹脂亦包含，Α + 應觸媒的存在下 使苯酚或雙酚Α等的酚類與曱醛等的駿類 &卜’ 入羥甲基而形成的酚醛樹脂，或以碳赵& 、、口反應’導 峡數6以下的醇使#邋入 的經曱基之一部分發生院基峻化而形成者 16 201012881After the blending resin is prepared, the above-mentioned sputum-making solvent can be used for the organic acid retardation of acetic acid, catalyzed formic acid, propionic acid, lactic acid, etc.; salt, sulphur, etc. are dissolved in water or water. Obtain an emulsion. Inorganic acid such as acid The above-mentioned Resole type phenol resin also contains a phenol which is formed by a phenol such as phenol or bisphenol oxime and a quinone such as furfural and a hydroxymethyl group in the presence of a catalyst. The resin, or the carbon ray &, the mouth reaction 'introduction number 6 or less of the alcohol to make the # 邋 的 之一 之一 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 发生 16 16 16 16 16 16 16

Resole型紛醒樹脂的數量平均分子量（注i)，以200〜 1,000為佳’較佳的是在3〇〇〜900之範圍内，而且每丨苯核 的羥曱基之平均數為0.3〜2.5個，以0.3〜2.0個的範圍内為 佳。藉使用上述Resole型酚醛樹脂，可形成密封性等之塗膜 性能優良的塗膜。 (注1)關於數量平均分子量，係如前述之「陽離子性樹 脂(A)」中所做的說明。 上述Resole型酚醛樹脂的市售產品，可舉例如，SumUite Φ Resin PR_55317(Sumitomo Bakelite製，商品名》、sh〇n〇1 BKS-316 等。 前述Resole型紛搭樹脂的混合量，以上述成分(a)及成 分(B)的固體含量合計質量為基準’從膜附著性與塗膜安定 • 性的點來看，以1〜20質量。/。為佳，2〜7質量❶/〇較佳。 4.防銹顏料混合物(C) 本發明之水性塗料組成物因含有一定量的特定防銹顏 料混合物(C)而可以獲得耐藥品性、平面部之耐钮性、加工 ® 部和端面部之耐蝕性及附著性優良的塗裝金屬板。防銹顏 料混合物(C)由，釩化合物(cl)、矽化合物卜2)及磷酸系鈣鹽 (c3)組成。另外，防銹顏料混合物亦可含有前述釩化合 物（cl)、矽化合物(c2)及磷酸系鈣鹽(C3)以外的化合物。 以下將做詳細記載。 4-1.飢化合物(cl) 釩化合物(cl)為五氧化二釩、釩酸鈣及偏釩酸銨中之至 少1種釩化合物。五氧化二釩、釩酸鈣及偏釩酸銨，利用5 17 201012881 價鈒粒子對容出性優異，從飢化合物⑷)釋出的5價飢 粒子或與材料金屬反應，或與來自其他_顏料混合物的 離子反應藉而發揮提高耐姓性的效果。其中特別是五氧 化二釩提高耐蝕性的效果明顯。 4-2.碎化合物(c2) 矽化合物(c2)含有選自矽酸金屬鹽、二氧化矽微粒子、 金屬離子交換二氧化秒微粒子之至少1種化合物。 矽酸金屬鹽係由二氧化矽與金屬氧化物形成的鹽，玎 為正石夕酸鹽、聚♦酸鹽等的任—種皆可。♦酸鹽可舉例如， 石夕酸鋅、赠IS、正㈣纟s、水合赠紹、㈣朗、石夕 酸鋁鈉、矽酸鋁鈹、矽酸鈉、正矽酸鈣偏矽酸鈣、矽酸 1弓納、石夕酸錘、正秒酸鎮、偏石夕酸鎖、石夕酸鎮辦、石夕酸锰、 夕酸鋇撖欖石、石權石、筑紀石（thortveitite)、異極礦、 藍錐礦(benitoite)、柱星葉石（neptunite)、綠柱石、透輝石、 矽灰石、薔薇輝石、透閃石、硬矽鈣石（x〇n〇tlite)、滑石、 魚眼石、鋁矽酸鹽、硼矽酸鹽、鈹矽酸鹽、長石、沸石等。 其等當中，作為矽酸金屬鹽尤以，正矽酸鈣、偏矽酸鈣、 偏矽酸鎂、矽酸鋁為佳，正矽酸鈣、偏矽酸鈣特別合適。 二氧化矽微粒子只要是二氧化矽微粒子即可以無特殊 限制地使用，可舉例如，表面無處理的二氧化矽微粉末、 表面用有機物處理過的二氧化矽微粉末、鈣離子交換二氧 化石夕微粒子、有機溶劑分散性膠體二氧化矽等。 表面無處理或以有機物處理過的二氧化矽微粒子可舉 例如，平均粒徑以〇.5〜15μιη為佳，較佳為1〜1〇μπι之二氧 18 201012881 化梦微粉末。 二氧化矽微粉末的吸油量為30〜350ml/100g、可以適 當地使用在30〜15〇ml/i〇0g之範圍内者。市售品可舉例The number average molecular weight of Resole type waking resin (Note i) is preferably from 200 to 1,000. Preferably, it is in the range of from 3 〇〇 to 900, and the average number of hydroxy fluorenyl groups per benzene nucleus is 0.3 〜 2.5, preferably in the range of 0.3 to 2.0. By using the above-mentioned Resole type phenol resin, it is possible to form a coating film having excellent coating properties such as sealing properties. (Note 1) The number average molecular weight is as described in the above-mentioned "cationic resin (A)". The commercially available product of the above-mentioned Resole-type phenol resin may, for example, be SumUite Φ Resin PR_55317 (manufactured by Sumitomo Bakelite, trade name), sh〇n〇1 BKS-316, etc. The amount of the Resole-type varnish resin mixed with the above components (a) and the total mass of the solid content of the component (B) are based on the viewpoint of the film adhesion property and the stability of the coating film, preferably 1 to 20 mass%, preferably 2 to 7 mass ❶/〇. 4. Antirust pigment mixture (C) The aqueous coating composition of the present invention can obtain chemical resistance, flatness resistance, processing of the portion and end face due to a certain amount of the specific antirust pigment mixture (C). A coated metal sheet having excellent corrosion resistance and adhesion. The rust preventive pigment mixture (C) is composed of a vanadium compound (cl), a bismuth compound 2), and a phosphate calcium salt (c3). Further, the rust preventive pigment mixture may contain a compound other than the vanadium compound (cl), the ruthenium compound (c2), and the phosphate calcium salt (C3). The details will be described below. 4-1. Hunger Compound (cl) The vanadium compound (cl) is at least one vanadium compound of vanadium pentoxide, calcium vanadate and ammonium metavanadate. Vanadium pentoxide, calcium vanadate and ammonium metavanadate, using 5 17 201012881 valence particles, excellent for containment, 5-valent starvation particles released from hunger compounds (4) or reacting with material metals, or with other _ The ionic reaction of the pigment mixture exerts an effect of improving the resistance to the surname. Among them, vanadium pentoxide has an obvious effect of improving corrosion resistance. 4-2. Fragmented Compound (c2) The ruthenium compound (c2) contains at least one compound selected from the group consisting of a metal ruthenate salt, a cerium oxide microparticle, and a metal ion-exchanged oxidized second particle. The metal citrate is a salt formed of cerium oxide and a metal oxide, and cerium is any one of a oxetane acid salt and a polyoxo acid salt. ♦ For example, zinc oxalate, donated IS, positive (four) 纟 s, hydrated gift, (four) lang, sodium alginate, aluminum bismuth citrate, sodium citrate, calcium orthosilicate , cinnamic acid 1 bowa, Shixi acid hammer, positive second acid town, partial stone acid lock, Shi Xi acid town office, Shishi acid manganese, yoghurt sapphire, stone right stone, Tsuki stone (thortveitite ), heteropolar ore, bentopite, neptunite, beryl, diopside, ash, rhodochite, tremolite, hard strontium (x〇n〇tlite), talc , fisheye stone, aluminosilicate, borosilicate, citrate, feldspar, zeolite, etc. Among them, as the metal citrate, calcium orthosilicate, calcium metasilicate, magnesium metasilicate, and aluminum citrate are preferred, and calcium orthosilicate and calcium metasilicate are particularly suitable. The cerium oxide microparticles can be used without any particular limitation as long as it is cerium oxide microparticles, and examples thereof include cerium oxide micropowder which has no surface treatment, cerium oxide micropowder which has been treated with an organic substance on the surface, and calcium ion-exchanged dioxide. Fine particles, organic solvent-dispersible colloidal cerium oxide, and the like. The cerium oxide microparticles having no surface treatment or organic treatment may, for example, preferably have an average particle diameter of 〇5 to 15 μm, preferably 1 to 1 〇μπι of dioxin 18 201012881. The cerium oxide fine powder has an oil absorption of 30 to 350 ml/100 g and can be suitably used in the range of 30 to 15 〇 ml/i 〇 0 g. Commercial products can be exemplified

如 Sylysia 710、Sylysia 74〇、Sylysia 55〇、Aerosil R 972(以 上’每一種都是Fuji Silysia chemicai Ltd·製）、MIZUKASIL P-73(水澤化學卫業（株）製）、―丨2〇〇呵㈤脇 Chemical Inc.製）等。 有機溶劑分散性谬體二氧化石夕亦稱為有機氧化石夕溶膠 (〇rgan〇smcaSol)，係在醇類、二醇類、醚類等之有機溶劑 中，安定地分散粒㈣W〜12Gnm左右的二氧切微粒子 而成，市售品可舉例如纟斯卡(OSCAL)系列(觸媒化成(株) 製）、有機溶膠（曰產化學(株)製）等。For example, Sylysia 710, Sylysia 74〇, Sylysia 55〇, Aerosil R 972 (all of which are manufactured by Fuji Silysia Chemicai Ltd.), MIZUKASIL P-73 (made by Mizusawa Chemical Industry Co., Ltd.), 丨2〇〇 (5) threat Chemical Inc.) and so on. The organic solvent-dispersible steroidal sulphur dioxide is also known as an organic oxidized oxide sol (〇rgan〇smcaSol), and is dispersed in an organic solvent such as an alcohol, a glycol, or an ether, and is stably dispersed (4) W~12Gnm or so. For the commercially available product, for example, the OSCAL series (manufactured by Catalyst Chemical Co., Ltd.) or the organosol (manufactured by Seiko Chemical Co., Ltd.) can be used.

金屬離子父換一氧化石夕微粒子，係透過離子交換將金 屬離子導人微細的多孔質二氧切載體之二氧切微粒 子。具體而言’係導人了_鎮的二氧化賴粒子。約離 子交換二氧化矽的市售產品可舉例如，shieldex (shidd，註冊商標）C303、職_χ ac—3、s職順 C-5 (以上每一種皆由W. R. Grace & c〇公司幻等。 由金屬離子交換二氧化石夕釋出的驗土類金屬離子，與 電化學作用或各種鹽的生成作用相關，可有效地提高雜 性。另外’被Μ在塗膜中的二氧切，在脑氛圍下有 效地抑制塗膜剝離。 4-3.磷酸系鈣鹽(C3) 鱗酸系弼鹽(C3)係含有約作為金屬元素的鱗酸鹽 ，可舉 19 201012881 例如，磷酸鈣、磷酸鈣銨、磷酸氫鈣、磷酸二氫鈣、氣氟 磷酸鈣、三聚磷酸鈣等。由磷酸系鈣鹽(£；3)釋出的磷酸離子 及鈣離子有效地提高耐蝕性。 本發明之水性塗料組成物中’相對於前述陽離子性樹 脂(A)及多異氰酸酯硬化劑(b)的合計固體含量1〇〇質量份， 防錢顏料混合物（C)的上述訊化合物（ci)與石夕化合物（C2)及 磷酸系鈣鹽(c3)在下述範圍内。 釩化合物（cl) : 1〜30質量份，以1〜20質量份為佳， 矽化合物(c2) : 1〜30質量份，以1〜20質量份為佳， 磷酸系鈣鹽(c3) : 1〜30質量份，以1〜20質量份為佳。 另外，釩化合物（cl)、矽化合物（C2)、磷酸系鈣鹽（c3) 之混合比率（質量基準），以3〜20/3〜20/5〜20為佳，較 佳為5〜15/5〜15/10〜20。在上述範圍内時，因不僅可 獲得耐藥品性、金屬板平面部的耐蝕性，還可獲得金屬板 之加工部和端面部的耐敍性及附著性優良的塗膜，故而合 適。 上述飢化合物（cl)與矽化合物（C2)及碟酸系鈣鹽（c3)之 添加量在上述範圍内時，不僅可獲得耐藥品性、金屬板平 面部的耐蝕性，還可獲得金屬板之加工部和端面部的耐蝕 性及附著性優良的塗膜，故而合適。 此外，本發明之水性塗料組成物中，相對於前述陽離 子性樹脂(A)及多異氰酸酯硬化劑(B)的合計固體含量100質 量份，防銹顏料混合物(C)之量為3〜90質量份，以9〜60質 量份為佳。防銹顏料混合物(C)之量在前述範圍内時，不僅 201012881 可獲得对藥品性、金屬板平面部的耐蝕性，還可獲得金屬 板之加工部和端面部的耐蝕性及附著性優良的塗膜，故而 合適。 本發明之水性塗料組成物，可透過將這些釩化合物 (cl)、石夕化合物(C2)及磷酸系鈣鹽（c3)按預定量組合的方式 形成防銹顏料混合物(C)，相乘地提高耐蝕性。防銹顏料混 合物(C)雖無特別限定，惟以含有五氧化二飢、偏石夕酸妈及 填酸飼的混合物為佳’從耐蝕性的觀點，五氧化二釩、偏 參 石夕酸妈及麟酸舞的組合特別合適。 再者’將相對於前述陽離子性樹脂及多異氰酸酯硬 化劑(B)之合計固體含量1〇〇質量份所混合的，構成防銹顏 • 料混合物(C)之釩化合物（c 1 )、矽化合物（c2)及該磷酸系鈣鹽 (c3)的混合物((cl)〜（c3)的混合量在前述範圍内），添加到 25°C之5質量％氣化鈉水溶液1〇 〇〇〇質量份中，攪拌6小時， 過滤在25°C靜置48小時後的上清液所得到的濾液，其pH以3 〜8為佳’較佳為4〜6。前述濾液之pH在前述範圍時，從釩 化合物（cl)、矽化合物(c2)及磷酸系鈣鹽（c3)對水的溶解性 及防錢顏料之溶解液與金屬板的反應性之觀點，或者耐蝕 性之觀點來看是適當的。 亦即’得到上述pH測定的濾液是，相對於25°C的5質量 〇/〇氯化納水溶液10,000質量份，添加釩化合物(cl)l〜30質量 份之範圍内的任意量，矽化合物(c2)l〜30質量份之範圍内 的任意量’以及磷酸系鈣鹽(c3)l〜30質量份之範圍内的任 意量，經溶解而得之溶解液的濾液。 21 201012881 春 製造本發明之水性塗料組成物時，係將前述之防銹顏 料混合物(c)和，依需要，顏料分散用樹脂、著色顏料、體 質顏料、有機錫化合物、紫外線吸收劑、紫外線安定劑、 有機溶劑、矽烷耦合劑、防沉劑、消泡劑、塗面調整劑等 自過去以來所公知的塗料用添加劑、中和劑（例如酸類，具 體而言’可舉例如醋酸、磷酸、乳酸，或其等之混合物等）、 鈒化合物(cl)、矽化合物(C2)、磷酸系鈣鹽(C3)以外的防銹 劑加以混合’並在球磨機、砂磨機、卵石磨機等之分散混 合機中施行分散處理以混合成所獲得之顏料分散漿。 另外，添加釩化合物(cl)、矽化合物(C2)、磷酸系鈣鹽 (c3)以外的防銹劑時，可以在不阻礙防銹顏料混合物之 添加效果的程度的量下做添加。 月1J述顏料分散用樹脂可以使用公知者，例如可以使用 含有羥基及陽離子性基的基體樹脂，或三級胺型環氧樹 脂、四級㈣型環氧樹脂、三⑽鹽型環氧樹料的樹脂。The metal ion parent is replaced by a oxidized oxidized fine particle, which is a metal ion that is guided by a microporous porous dioxygen carrier. Specifically, it has led to the oxidized particles of the town. Commercially available products of about ion-exchanged cerium oxide include, for example, shieldex (shidd, registered trademark) C303, _ _ ac _ 3, s shun C-5 (each of which is WR Grace & c〇 company illusion Etc. The soil-measuring metal ions released by the metal ion-exchanged dioxide are related to the electrochemical action or the formation of various salts, which can effectively improve the impurity. In addition, the 'dioxotomy' that is entangled in the coating film 4-3. Phosphate-based calcium salt (C3) The sulphate-based strontium salt (C3) contains a sulphate as a metal element, for example, 19 201012881 For example, calcium phosphate Calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium fluorophosphate, calcium tripolyphosphate, etc. Phosphate ions and calcium ions released by the phosphate calcium salt (£; 3) effectively improve corrosion resistance. In the aqueous coating composition of the invention, the total solid content of the cationic resin (A) and the polyisocyanate curing agent (b) is 1 part by mass, and the above-mentioned compound (ci) of the anti-money pigment mixture (C) The Shishi compound (C2) and the phosphate calcium salt (c3) are within the following ranges. Vanadium compound (cl): 1 to 30 parts by mass, preferably 1 to 20 parts by mass, hydrazine compound (c2): 1 to 30 parts by mass, preferably 1 to 20 parts by mass, and calcium phosphate salt (c3): 1 to 30 parts by mass, preferably 1 to 20 parts by mass. Further, the mixing ratio (mass basis) of the vanadium compound (cl), the cerium compound (C2), and the calcium phosphate salt (c3) is 3 to 20/3. 〜20/5~20 is preferably, preferably 5~15/5~15/10~20. In the above range, metal can be obtained not only by obtaining chemical resistance, corrosion resistance of the flat portion of the metal plate It is suitable for the coating of the processed portion and the end surface of the sheet, and the coating film having excellent adhesion. The addition amount of the above-mentioned hunger compound (cl), bismuth compound (C2) and disc acid calcium salt (c3) is within the above range. In addition, it is possible to obtain not only chemical resistance but also corrosion resistance of the flat portion of the metal sheet, and a coating film having excellent corrosion resistance and adhesion of the processed portion and the end surface portion of the metal sheet, and thus suitable for the aqueous coating composition of the present invention. The total solid content of the cationic resin (A) and the polyisocyanate curing agent (B) is 100 parts by mass, The amount of the rust pigment mixture (C) is from 3 to 90 parts by mass, preferably from 9 to 60 parts by mass. When the amount of the rust preventive pigment mixture (C) is within the above range, not only 201012881 can be obtained for the chemical property, the metal plate plane The corrosion resistance of the portion can also be obtained by obtaining a coating film having excellent corrosion resistance and adhesion to the processed portion and the end surface of the metal sheet. The aqueous coating composition of the present invention can transmit these vanadium compounds (cl) and Shi Xi The compound (C2) and the calcium phosphate salt (c3) are combined in a predetermined amount to form a rust preventive pigment mixture (C), and the corrosion resistance is multiplied. The rust preventive pigment mixture (C) is not particularly limited, but it is preferable to contain a mixture of pentoxide, bismuth, and acid feed. From the viewpoint of corrosion resistance, vanadium pentoxide and ginseng The combination of mom and sorrel dance is especially suitable. In addition, the vanadium compound (c 1 ) and ruthenium of the rust-preventing pigment mixture (C) are mixed with a total solid content of 1 〇〇 by mass of the cationic resin and the polyisocyanate curing agent (B). a mixture of the compound (c2) and the phosphate-based calcium salt (c3) (the amount of (cl) to (c3) is in the above range), and is added to a 5 mass% sodium carbonate aqueous solution at 25 ° C. The mixture obtained was stirred for 6 hours, and the filtrate obtained by filtering the supernatant after standing at 25 ° C for 48 hours had a pH of preferably 3 to 8 and preferably 4 to 6. When the pH of the filtrate is in the above range, from the viewpoints of the solubility of the vanadium compound (cl), the ruthenium compound (c2), and the calcium phosphate salt (c3) in water and the reactivity of the solution of the anti-money pigment with the metal plate, Or the viewpoint of corrosion resistance is appropriate. In other words, the filtrate obtained by the above pH measurement is an amount of the vanadium compound (cl) in an amount of from 1 to 30 parts by mass, based on 5% by mass of a 5 mass% ruthenium/niobium chloride aqueous solution at 25 ° C. (c2) a filtrate of a solution obtained by dissolving any amount within the range of 1 to 30 parts by mass and any amount in the range of 1 to 30 parts by mass of the phosphate-based calcium salt (c3). 21 201012881 When manufacturing the aqueous coating composition of the present invention in spring, the rust preventive pigment mixture (c) and, if necessary, the pigment dispersion resin, the coloring pigment, the extender pigment, the organotin compound, the ultraviolet absorber, and the ultraviolet stabilizer are used. A coating additive, a neutralizing agent (for example, an acid, such as acetic acid, phosphoric acid, etc.) which has been known from the past, such as an agent, an organic solvent, a decane coupling agent, an anti-settling agent, an antifoaming agent, a coating surface modifier, and the like. Lactic acid, or a mixture thereof, etc.), a rust inhibitor other than the cerium compound (cl), the cerium compound (C2), and the calcium phosphate salt (C3) are mixed, and are used in a ball mill, a sand mill, a pebble mill, or the like. Dispersion treatment is carried out in a dispersing mixer to mix into the obtained pigment dispersion slurry. Further, when a rust inhibitor other than the vanadium compound (cl), the ruthenium compound (C2), or the phosphate calcium salt (c3) is added, it can be added in an amount that does not inhibit the effect of the addition of the rust preventive pigment mixture. The resin for dispersing the pigment can be used by a known one. For example, a base resin containing a hydroxyl group and a cationic group, or a tertiary amine type epoxy resin, a fourth-grade (tetra) type epoxy resin, or a tris(10) salt type epoxy tree material can be used. Resin.

上述顏料分散騎㈣使帛量，對每刚質量份的顏料成分 為1〜150質量份，特別是1〇〜質量份為刀 上述著色顏料可舉例如，鳴、賦菁綠、偶\= 啥。丫㈣(qU1naerid_)系等之有機紅色顏料等的 顏料；鈦白、鈦黃、鐵丹山里. 者色 厌黑、各輯結顏料等的^ 著色顏料，射尤其可叫當地使祕白。 ‘、，、機 上述體質顏料可舉例如，滑石、枯土、二氧化石夕 母、氧化鋁、碳酸鈣、硫酸鋇等。 、 上述著色顏料及體質顏料的添加量並無特別限定， 22 201012881 例如’相對於前述陽離子性樹脂(A)及多異氰酸酯硬化劑(b) 之合計固體含量1〇〇質量份，分別為1〜1〇〇質量份左右。 上述有機錫化合物可以適當地使用二丁基二苯甲酸錫 (dibutyl tm dibenzoate)、二辛基氧化錫、二丁基氧化錫等。 前述有機溶劑係為改善本發明之水性塗料組成物的塗 裝性等而根據需要混合者’可以使用能夠溶解乃至於分散 陽離子性樹脂(A)及多氰酸酯硬化劑(B)的有機溶劑。具體而 言’可舉例如，甲笨、二甲苯、高沸點石油系烴等烴系溶 ® 劑、甲乙_、甲基異丁酮、環己酮、異佛酮等的酮系溶劑， 醋酸乙酯、醋酸丁酯、乙二醇單***醋酸酯、二乙二醇單 ***醋酸酯等的酯系溶劑，甲醇、乙醇、異丙醇、丁醇等 \ 的醇系溶劑，乙二醇單***、乙二醇單丁醚、二乙二醇單 丁醚等的醚醇系溶劑等，可以將它們單獨或混合2種以上使 用0 前述之矽烷偶合劑可舉例如，β-(3,4_環氧環己基）乙基 二甲氧基硬烧、γ-縮水甘油醚丙基三甲氧基秒燒 (γ-glycidoxypropyltrimethoxysilane)、γ-縮水甘油喊丙基甲 基二乙氧基矽烷、γ-縮水甘油醚丙基三乙氧基矽烷、Ν-β(胺 乙基)γ-胺丙基曱基二甲氧基矽烷、Ν—β(胺乙基)γ-胺丙基三 曱氧基矽烷、γ-胺丙基三甲氧基矽烷、β-胺丙基三乙氧基 石夕炫、Ν-苯基-γ-胺丙基三甲氧基石夕烧、Ν-(乙稀基苄胺)_β_ 胺乙基-γ-胺丙基三甲氧基矽烷等，可以將它們單獨或混合 2種以上使用。 可以利用將含有如上所述之防銹顏料混合物（C)的顏 23 201012881 料分散漿加弱述的乳液巾，並以 性塗料組成物。 正的方式來調整水 5.塗膜形成方法 ㈣Γ 料組成物，”透過塗裝在金屬板上 ^吏之,_法㈣得塗裝金屬板。被塗裝的金屬 舉例如刖狀金屬板。科，這些域板的表面亦可施 以化學轉化處理（前處理）。 第1圖為，用本發明之水性塗料組成物作為底 塗塗料時 之The pigment dispersion ride (four) is used to make the amount of the pigment, and the amount of the pigment component is from 1 to 150 parts by mass, particularly from 1 to 1 part by mass, per gram by mass of the pigment component. For example, the coloring pigment may be, for example, singular, cyanine green, or even\= 啥.丫(4)(qU1naerid_) is a pigment such as an organic red pigment; titanium white, titanium yellow, and iron danshan. Colors are black, and various pigments such as pigments are collected, especially for local secrets. ‘,,, and the above-mentioned extender pigments include, for example, talc, dry soil, silica dioxide, alumina, calcium carbonate, barium sulfate, and the like. The amount of the coloring pigment and the extender pigment to be added is not particularly limited, and 22 201012881 is, for example, 1% by mass of the total solid content of the cationic resin (A) and the polyisocyanate curing agent (b), respectively. 1 〇〇 mass part or so. As the above organotin compound, dibutyl tm dibenzoate, dioctyltin oxide, dibutyltin oxide or the like can be suitably used. The organic solvent is an organic solvent capable of dissolving or dispersing the cationic resin (A) and the polycyanate curing agent (B) in order to improve the coating property and the like of the aqueous coating composition of the present invention. . Specifically, for example, a hydrocarbon-based solvent such as methyl bromide, xylene or a high-boiling petroleum hydrocarbon, a ketone solvent such as methyl bromide, methyl isobutyl ketone, cyclohexanone or isophorone, and ethyl acetate B. Ester ester, butyl acetate, ethylene glycol monoethyl ether acetate, ester solvent such as diethylene glycol monoethyl ether acetate, alcohol solvent such as methanol, ethanol, isopropanol or butanol, ethylene glycol monoethyl ether An ether alcohol-based solvent such as ethylene glycol monobutyl ether or diethylene glycol monobutyl ether may be used alone or in combination of two or more. The above-described decane coupling agent may, for example, be β-(3, 4_ Epoxycyclohexyl)ethyldimethoxybenzoate, γ-glycidoxypropyltrimethoxysilane, γ-glycidyl propylmethyldiethoxy decane, γ-shrinkage Glycerol ether propyl triethoxy decane, Ν-β (aminoethyl) γ-aminopropyl decyl dimethoxy decane, Ν-β (aminoethyl) γ-aminopropyl trimethoxy decane, Γ-aminopropyltrimethoxydecane, β-aminopropyltriethoxyxanthene, fluorenyl-phenyl-γ-aminopropyltrimethoxycarbazide, Ν-(ethylenebenzylamine)_β_ Ethyl -γ- aminopropyl trimethoxy Silane, etc., can be used singly or as a mixture of two or more. It is possible to use an emulsion towel which contains the rust preventive pigment mixture (C) as described above and a weakly described emulsion towel, and an organic coating composition. A positive way to adjust the water 5. A method of forming a coating film (4) A composition of the coating material, "a metal plate is applied by coating on a metal plate, and the metal is coated, for example, a metal plate. The surface of these domain plates may also be subjected to chemical conversion treatment (pretreatment). Figure 1 is a diagram showing the use of the aqueous coating composition of the present invention as a primer coating.

塗裝線的模式圖此處，因為於溶融鑛鋅鋼板上塗裝本 發明之水性塗料組成物而獲得的塗膜，即使不施行化學轉 化處理（前處理），也可獲得耐蝕性優良之塗膜，故在塗裝線 中亦可省略化學轉化處理（前處理）的程序，對於省工程和省 資源化也可有所貢獻。 另外’可依需要而施行的化學轉化處理（前處理），可以 舉例如’磷酸鋅處理或磷酸鐵處理等之磷酸鹽處理、複合 氧化膜處理、磷酸鉻處理、鉻酸鹽處理等。Pattern diagram of the coating line Here, since the coating film obtained by coating the aqueous coating composition of the present invention on the molten zinc-zinc steel sheet can be obtained, even if the chemical conversion treatment (pretreatment) is not performed, the coating having excellent corrosion resistance can be obtained. Since the film is used, the process of chemical conversion treatment (pretreatment) can be omitted in the coating line, and it can contribute to provincial engineering and resource saving. Further, the chemical conversion treatment (pretreatment) which can be carried out as needed can be exemplified by phosphate treatment such as 'zinc phosphate treatment or iron phosphate treatment, composite oxide film treatment, chromium phosphate treatment, chromate treatment and the like.

使用本發明之水性塗料組成物的塗裝’可在上述金屬 板上，利用滾筒式塗布法、淋幕式塗布法（curtain flow coating)、喷塗法、毛刷塗布法、浸潰法等公知的方法來進 行塗裝。 由水性塗料組成物獲得之塗膜的硬化膜厚度並無特殊 限定，通常在0.5〜ΙΟμηι、宜在2〜7μπι之範圍使用。 塗膜的硬化，只要依據使用的樹脂之種類等做適當設 定即可，在連續燒結利用線圏塗布法等塗裝成的塗膜時， 24 201012881 是在材料到達的最高溫度為100〜250°c，以達到180〜 230C為佳之條件下，燒結15〜60秒。批次式燒結的情形， 則亦可在80〜20(TC燒結10〜30分鐘。 本發明之水性塗料組成物塗裝於金屬板上，所形成的 塗膜，不僅在金屬板之平面部，在金屬板之加工部和端面 部也表現出優良的耐蝕性。 其理由考慮有以下3點。 L在腐蝕環境下’因氣化物離子等造成素材金屬的溶 ® 解而生成之金屬離子，與5價的釩離子(VCV或V043—的釩酸 離子）不經歷氧化還原反應而直接生成沉澱性的鹽，5價釩 離子與素材金屬之因氧化還原反應而生成的3價釩離子及 素材金屬離子’和石夕酸離子有效地生成沉殺性的鹽或化合 . 物’藉而有效地被覆素材露出面。此外，認為是因為同時 溶出的碟酸離子，使得腐姓進行部位及其周邊被調整成特 別適合於5價釩離子與素材金屬進行氧化還原反應的pH範 圍。 2.本水性塗料組成物中防銹劑有一部分溶解而以金屬 離子狀態存在。將本水性塗料組成物塗裝於金屬素材並加 熱乾燥形成塗膜時，該溶解成分在素材金屬的界面上有效 地發生反應，於前述塗膜之下’形成發揮如化學轉化處理 皮膜的作用之氧化皮膜。而且’即使該皮膜上之塗膜受損， 依然可以從塗膜中，因防錢顏料混合物(C)的金屬離子溶出 而形成具有保護該損傷之作用（自我修復性）的塗膜。上述的 「皮膜與塗膜」之形成，可通過1次塗裝與加熱乾燥獲得， 25 201012881 &點推測對於獲得耐紐優良之塗裝物品大有幫助。 藉併用構成防錢顏料混合物的前述釩化合物(cl)、 石夕化合物(e2)及該碟酸系㉝鹽⑹，可以有效地節制前述 ()(c2)及(C3)各自具有的耐酸性或耐驗性及财水性的薄 弱部分。此外’因為鈣離子在超過pH 1〇之素材金屬易於溶 解的強驗乳圍下’具有抑制素材金屬溶解的作用，故可同 時實現優良的耐藥品性和耐水性。以這些防錢顏料混合物 為基礎的作用之相乘效果發揮了很大功能 ，推斷這也對本 水性塗料之優良耐姓性大有幫助。 麵 再者’由本發明之水性塗料組成物獲得的硬化塗膜之 玻璃轉移溫度為40〜115。(：，從塗膜之耐姓性、耐酸性及加 工性等的點來看，以50〜i〇5t為佳。 . 而’塗膜的玻璃轉移溫度是使用DINAMIC VISC〇_ ELASTO METER MODEL VIBRON (振動子型動態粘彈譜 儀）DDV-IIEA型（ToyoBaldwinCo·製，自動動態粘彈性測 定儀），根據在頻率110Hz中之溫度分散測定所得到的tan5 之變化所求得的極大值溫度。 @ 在燒結乾燥水性塗料組成物所得的塗膜之上，依需要 亦可配設面漆塗膜（參見第2圖）。面漆塗膜之膜厚為5〜 ΙΟμιη，以 1〇〜5〇μπι為佳。 上述之面漆塗料可舉例如，作為預塗鋼板之公知的聚 酯樹脂系、醇酸樹脂系、矽酮改質聚酯（silicone modified polyester)樹脂系、石夕酮改質丙烯酸樹脂系、氟樹脂系等的 面漆塗料。面漆塗料之種類並不限於上述種類。此外，在 26 201012881 特別重視加工性之情形中，可使用高度加工用的聚醋系面 漆塗料，藉以獲得加工性特別優良的塗裝金屬板。 此外，使用鍍辞鋼板、鍍鋁—辞合金鋼板作為被塗物的 金屬板時，金屬板平面部的耐钱性大為提高，不過，截至 月j的技術，在切斷的端面部和經過成型加工的加工部， 耐钱性卻都是不足的。然而，藉塗裝本發明之水性塗料組 成可以獲得具有耐藥品性，而且無論是在金屬板之平面 ^端面郤、加工部，均可以體現優良耐餘性的塗膜。 實施例 以下’將藉製造例、實施例及比較例更詳細地說明本 發明，但本發明不限於此。各例中之「份」表示質量份、「％」 表示質量％。 陽離子性樹脂(A)的製造 製造例1陽離子性環氧樹脂Ν ο · 1之製造例(環氧樹脂系） 用裝有攪拌器、溫度計、氮氣導入管及回流冷卻器的 燒瓶，將jERl〇〇4(雙酚A型環氧樹脂，環氧值〇.108 • mol/10〇g’ 數量平均分子量 1，650, Japan Epoxy Resins Co.，The coating of the aqueous coating composition of the present invention can be applied to the above-mentioned metal plate by a drum coating method, a curtain flow coating method, a spray coating method, a brush coating method, a dipping method, and the like. The method to paint. The thickness of the cured film of the coating film obtained from the aqueous coating composition is not particularly limited, and is usually used in the range of 0.5 to ΙΟμηι, preferably 2 to 7 μm. The curing of the coating film may be appropriately set depending on the type of the resin to be used, and when the coating film coated by the wire coating method or the like is continuously sintered, 24 201012881 is the highest temperature at which the material reaches 100 to 250°. c, to achieve 180~230C, preferably sintered for 15~60 seconds. In the case of batch sintering, it can also be sintered at 80 to 20 (TC for 10 to 30 minutes. The aqueous coating composition of the present invention is coated on a metal plate, and the formed coating film is formed not only on the flat portion of the metal plate, It also exhibits excellent corrosion resistance in the processed portion and the end surface of the metal sheet. The reason is as follows: L. In the corrosive environment, the metal ions generated by the dissolution of the material metal due to vapor ions or the like, and The pentavalent vanadium ion (vanadium ion of VCV or V043) does not undergo a redox reaction and directly forms a precipitated salt, and the trivalent vanadium ion and the material metal formed by the redox reaction of the pentavalent vanadium ion and the material metal Ion's and oxalic acid ions effectively form a stagnation salt or a compound. The material 'is effectively coated with the material to expose the surface. In addition, it is thought that it is because the acid ions of the dish are simultaneously dissolved, so that the site of the rot and its surroundings are It is adjusted to a pH range which is particularly suitable for the redox reaction of the pentavalent vanadium ion and the material metal. 2. The rust preventive agent in the aqueous coating composition is partially dissolved and exists in a metal ion state. When the material composition is applied to a metal material and dried by heating to form a coating film, the dissolved component is effectively reacted at the interface of the material metal, and an oxide film that functions as a chemical conversion treatment film is formed under the coating film. Further, even if the coating film on the film is damaged, it is possible to form a coating film having a function of protecting the damage (self-healing property) by eluting the metal ions of the anti-money pigment mixture (C) from the coating film. The formation of "film and coating film" can be obtained by one coating and heat drying, 25 201012881 & point speculation is very helpful for obtaining the excellent coated articles of Nike. By using the above-mentioned vanadium compound which constitutes a mixture of anti-money pigments (cl), Shishi compound (e2) and the disc acid salt 33 (6) can effectively control the weak portions of the acid resistance or the testability and the water property of each of the above () (c2) and (C3). 'Because calcium ions are more effective than the strong test medium in which the metal of the material exceeds pH 1 易于, it has the effect of inhibiting the dissolution of the metal, so it can achieve excellent chemical resistance and water resistance at the same time. The synergistic effects of the anti-money pigment mixture-based effects play a large role, and it is inferred that this is also helpful for the excellent resistance of the water-based paint. Further, the hardened coating film obtained from the aqueous paint composition of the present invention is further improved. The glass transition temperature is 40 to 115. (:, from the point of resistance of the coating film, acid resistance, and processability, 50 to i 〇 5t is preferable. The glass transition temperature of the coating film is Using DINAMIC VISC〇_ ELASTO METER MODEL VIBRON (Vibrator-type dynamic viscoelastic spectrometer) DDV-IIEA type (manufactured by ToyoBaldwin Co., automatic dynamic viscoelasticity meter), tan5 obtained by temperature dispersion measurement at a frequency of 110 Hz The maximum temperature obtained by the change. @ On top of the coating film obtained by sintering and drying the aqueous coating composition, a top coat film may be provided as needed (see Fig. 2). The film thickness of the topcoat film is 5~ ΙΟμιη, preferably 1〇~5〇μπι. The above-mentioned top coat paint may, for example, be a known polyester resin type, an alkyd resin type, a silicone modified polyester resin, a linalool modified acrylic resin type, or a fluorine as a precoated steel sheet. A top coat such as a resin. The type of the top coat is not limited to the above types. In addition, in the case of 26 201012881, when processing is particularly important, a highly processed urethane-based topcoat can be used to obtain a coated metal sheet having particularly excellent workability. In addition, when a plated steel plate or an aluminum-plated alloy steel plate is used as the metal plate of the object to be coated, the durability of the flat portion of the metal plate is greatly improved, but as of the technique of the month j, the cut end face and the passage are The processing department of the molding process is not enough for the money. However, by coating the water-based paint composition of the present invention, it is possible to obtain a coating film which is chemically resistant and which exhibits excellent durability irrespective of the flat surface of the metal plate and the processed portion. EXAMPLES Hereinafter, the present invention will be described in more detail by way of Production Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In each example, "parts" means parts by mass and "%" means mass%. Production of the cationic resin (A) Production example 1 cationic epoxy resin 制造 1 Production example (epoxy resin) Using a stirrer, a thermometer, a nitrogen gas introduction tube, and a reflux condenser, jERl〇 〇4 (bisphenol A type epoxy resin, epoxy value 〇.108 • mol/10〇g' number average molecular weight 1,650, Japan Epoxy Resins Co.,

Ltd.製）100份與 ’ 3-甲氧基乙酸丁醋（3-methoxybutyl acetate) 25份在l〇〇°C加溫混合。 確認已均勻溶解後，添加單乙醇胺2.75份，就這樣反 應2小時。確認環氧值達到0.018 mol/100g後，添加二乙醇 胺1.89份，再繼續反應2小時。如果環氧值降到0.005 mol/100g以下，就用預先混合成甲乙酮肟/二甲笨/丁醇 = 1/1/1的混合溶劑稀釋，獲得固體含量65%的陽離子性環 27 201012881 氧樹脂No. 1。而，獲得的陽離子性環氧樹脂N〇. 1的胺價 為35.1 mgKOH/g。 製造例2陽離子性環氡樹脂No. 2之製造例（二異氰酸唣 化合物改質系） 用裝有攪拌器、溫度計、氮氣導入管及回流冷卻器的 燒瓶’將jER1004 (雙酚A型環氧樹脂，環氧值〇.1〇8 mol/l〇〇g ’ 數董平均分子量 i，65〇，japan Epoxy Resins C〇 Ltd.製）和’ 3-甲氧基乙酸丁酯25份在i〇〇°c加溫混合。 確認已均勻溶解後’添加n-曱基乙醇胺6 75份，就這 樣反應2小時。確認環氧值達到〇 〇18 mol/100g後，添加預 先混合成甲乙酮肟/二曱笨的混合溶劑lhl份，並將反 應溫度冷卻至40°C為止。 確認均勻溶解後，添加六亞甲基二異氰酸酯7 56份， 就這樣反應1小時。之後，再度將反應溫度加溫至100°c， 添加二乙醇胺1.89份，再繼續反應丨小時。如果環氧值降到 0.005 mol/100g以下’就用預先混合成曱乙酮肟/二曱笨/丁 醇= 1/1/1的混合溶劑稀釋，獲得固體含量65%的二異氰酸 酯化合物改質的陽離子性環氧樹脂N〇 2。而，所獲得的陽 離子性環氧樹脂No. 2的胺價為53.〇 mgKOH/g。 製造例3陽離子性環氧樹脂ν〇· 3之製造例（二元酸改質 系） 用裝有授拌器、溫度計、氮氣導入管及回流冷卻器的 燒瓶，將jER1004(雙酚a型環氧樹脂、環氧值〇.1〇8 mol/100g ’ 數量平均分子量 i，65〇，japan Ep〇xy Resins Co” 28 201012881100 parts of "3-methoxybutyl acetate" made by Ltd. was mixed and heated at 10 °C. After confirming that it was uniformly dissolved, 2.75 parts of monoethanolamine was added, and the reaction was carried out for 2 hours. After confirming that the epoxy value reached 0.018 mol/100 g, 1.89 parts of diethanolamine was added, and the reaction was further continued for 2 hours. If the epoxy value falls below 0.005 mol/100g, it is diluted with a mixed solvent premixed with methyl ethyl ketone oxime / dimethyl benzene / butanol = 1 / 1 / 1 to obtain a cationic ring of 65% solids. 201012881 Oxygen resin No. 1. Further, the obtained cationic epoxy resin N〇.1 had an amine value of 35.1 mgKOH/g. Production Example 2 Production Example of Cationic Cyclic Resin No. 2 (Modification of Bismuthocyanate Compound) JER1004 (bisphenol A type) was used in a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser. Epoxy resin, epoxy value 〇.1〇8 mol/l〇〇g 'number average molecular weight i, 65 〇, made by japan Epoxy Resins C〇Ltd.) and '3-methoxy butyl acetate 25 parts I〇〇°c warms and mixes. After confirming that it had been uniformly dissolved, 6 75 parts of n-mercaptoethanolamine was added, and the reaction was carried out for 2 hours. After confirming that the epoxy value reached 〇 18 mol/100 g, a lhl portion of a mixed solvent previously mixed with methyl ethyl ketone oxime / dioxane was added, and the reaction temperature was cooled to 40 ° C. After confirming uniform dissolution, 7 56 parts of hexamethylene diisocyanate was added, and the reaction was carried out for 1 hour. Thereafter, the reaction temperature was again raised to 100 ° C, 1.89 parts of diethanolamine was added, and the reaction was continued for another hour. If the epoxy value falls below 0.005 mol/100g, it is diluted with a mixed solvent pre-mixed with acetophenone oxime/dioxadol/butanol = 1/1/1 to obtain a diisocyanate compound with a solid content of 65%. Cationic epoxy resin N〇2. Further, the obtained ionic epoxy resin No. 2 had an amine value of 53. 〇 mgKOH/g. Production Example 3 Production Example of Cationic Epoxy Resin ν〇·3 (Dibasic Acid Modification System) jER1004 (bisphenol a type ring) was used in a flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a reflux condenser. Oxygen resin, epoxy value 〇.1〇8 mol/100g 'Quantitative average molecular weight i, 65〇, japan Ep〇xy Resins Co” 28 201012881

Ltd.製）1〇〇份，與3-甲氧基乙酸丁酷2S份在1〇〇t：加溫混合。 確認已均勻溶解後，添加Tsunodime 205 (二聚酸、築野 食品工業社(TSUNO CO·，LTD.)製）1〇份，就這樣反應2小 時。確認酸價達到0·5 mgKOH/g以下之後，添加單乙醇胺 2.36份’再繼續保持這樣地反應2小時。確認環氧值達到 0.018 mol/l〇〇g後，添加二乙醇胺丨89份，再反應1小時。 環氧值如果降到0.005mol/100g以下，就用預先混合成曱乙 酮將/二曱苯/丁醇= 1/1/1的混合溶劑稀釋，獲得固體含量 ® 65%的二聚酸改質的陽離子性環氧樹脂No. 3。而，所得陽 離子性環氧樹脂No. 3的胺價為28.9 mgKOH/g。 水性塗料用乳液的製造 ·. 製造例4 乳膠No. 1之製造例 ， 將在製造例1製得的陽離子性環氧樹脂No. 1 (固體含 量 80份）123.1 份、Desmodur BL-3175 (Sumitomo Bayer Urethane Co., Ltd.製，用甲乙酮肟封閉的六亞甲基二異氰酸 酯型多異氰酸酯化合物溶液，固體含量約75%) 26.7份（固體 ® 含量20份）、乙二醇單丁醚20份加以混合，再混合10%醋酸 30.3份並攪拌混勻後，將去離子水133·2份邊強烈攪拌邊以 大約30分鐘滴下，獲得樹脂固體含量30%的乳液No. 1。 製造例5〜1〇乳膠N〇. 2〜No. 7之製造例 除表1的混合内容以外，與製造例4同樣地處理，獲得 乳液No. 2〜No. 7。 29 201012881 [表1] 製造例 4 5 6 7 δ 9 10 乳液 No.l No.2 No.3 No.4 Ν〇.5 Νο.6 Νο.7 混 合 物 質 陽離子性環氧樹脂No.l 固體含量65% 123.1 _ 123.1 (80) 123.1 (80) 123.1 (80) 153.8 (1〇〇) 陽離子性環氧樹脂No2 固體含量65% 123.1 (80) 陽離子性環氧樹脂No.3 固體含量65% 123.1 (80) 乙二酵單丁醚 20 20 20 20 20 20 20 Desmodur BL-3175 固體含量75% (註2) 26.7 (20) 26.7 (20) 26.7 (20) 26.7 (20) Duranate MF-K60X 固體含量60% (註3) 33.3 (20) 33.3 (20) 10%醋酸 〈當量&gt; 30.3 &lt;!.0&gt; 34.7 &lt;0.67&gt; 27.2 &lt;1.0&gt; 30.3 &lt;!.0&gt; 15.1 &lt;0.5&gt; 15.1 &lt;0.5&gt; 30.3 &lt;1.0&gt; 10°/4 酼 &lt;當量&gt; 24.8 &lt;0.5&gt; 24.8 &lt;0.5&gt; 去離子水 133.2 128.8 136.3 126.6 123.6 117 129.2 30%乳液的合計量 333.3 0〇〇) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) ❿ 混合中0内之數字表示固體含量。 (注2) Desmodur BL-3175 : Sumitomo Bayer Urethane Co.，Ltd.) 1 part, and 3-methoxyacetic acid 2S parts in 1 〇〇 t: warm mixed. After confirming that it was uniformly dissolved, one part of Tsunodime 205 (dimer acid, manufactured by TSUNO CO., LTD.) was added, and the reaction was carried out for 2 hours. After confirming that the acid value reached 0.5 mgKOH/g or less, 2.36 parts of monoethanolamine was added, and the reaction was further continued for 2 hours. After confirming that the epoxy value reached 0.018 mol/l 〇〇g, 89 parts of diethanolamine hydrazine was added, and the reaction was further carried out for 1 hour. If the epoxy value is reduced to 0.005 mol/100 g or less, it is diluted with a mixed solvent pre-mixed with acetophenone/diphenylbenzene/butanol = 1/1/1 to obtain a solid content of 65% dimer acid. A cationic epoxy resin No. 3. Further, the amine value of the obtained cationic epoxy resin No. 3 was 28.9 mgKOH/g. Production Example of Emulsion Paint for Water-Based Coatings. Production Example 4 Production Example of Latex No. 1 The cationic epoxy resin No. 1 (solid content: 80 parts) obtained in Production Example 1 was 123.1 parts, and Desmodur BL-3175 (Sumitomo) Bayer Urethane Co., Ltd., a solution of hexamethylene diisocyanate type polyisocyanate compound blocked with methyl ethyl ketone oxime, solid content: about 75%) 26.7 parts (solid content: 20 parts), ethylene glycol monobutyl ether 20 parts After mixing and mixing 30.3 parts of 10% acetic acid and stirring and stirring, 133. 2 parts of deionized water was added dropwise with vigorous stirring for about 30 minutes to obtain an emulsion No. 1 having a resin solid content of 30%. Production Example 5 to 1 〇 Latex No. 2 to No. 7 Production Example The emulsion No. 2 to No. 7 were obtained in the same manner as in Production Example 4 except for the contents of the mixing in Table 1. 29 201012881 [Table 1] Production Example 4 5 6 7 δ 9 10 Emulsion No. 1 No. 2 No. 3 No. 4 Ν〇.5 Νο.6 Νο.7 Mixed substance cationic epoxy resin No.1 Solid content 65% 123.1 _ 123.1 (80) 123.1 (80) 123.1 (80) 153.8 (1〇〇) Cationic epoxy resin No2 Solid content 65% 123.1 (80) Cationic epoxy resin No.3 Solid content 65% 123.1 ( 80) Ethylenediacetate monobutyl ether 20 20 20 20 20 20 20 Desmodur BL-3175 Solids content 75% (Note 2) 26.7 (20) 26.7 (20) 26.7 (20) 26.7 (20) Duranate MF-K60X Solids content 60 % (Note 3) 33.3 (20) 33.3 (20) 10% acetic acid <equivalent> 30.3 &lt;!.0&gt; 34.7 &lt;0.67&gt; 27.2 &lt;1.0&gt; 30.3 &lt;!.0&gt; 15.1 &lt;0.5 &gt; 15.1 &lt;0.5&gt; 30.3 &lt;1.0&gt; 10°/4 酼&lt;Equivalent&gt; 24.8 &lt;0.5&gt; 24.8 &lt;0.5&gt; Deionized water 133.2 128.8 136.3 126.6 123.6 117 129.2 30% emulsion Total 333.3 0〇〇) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 数字 The number in 0 in the mixture indicates the solid content. (Note 2) Desmodur BL-3175 : Sumitomo Bayer Urethane Co.,

Ltd.製，用甲乙酮肟封閉的六亞甲基二異氰酸酯型多異氰酸 酯化合物溶液，固體含量約75% (注 3) Duranate MF-K60X : Asahi Kasei Chemicals Corp. 製，活性亞甲基封閉的六亞甲基二異氰酸酯之樹脂溶液， ❹ 固體含量60% 製造例11 顏料分散用樹脂之製造例 將390份的雙酚A，240份的Plaxel 212 (聚己醯内酯二 醇，Daicel Chemical Industries Ltd.，商品名，重量平均分 子量約 1，250)及 0.2份的二甲基苄胺（dimethylbenzylamine) 加到1010份的jER828EL(注4)，在130°C反應直至環氧當量 成為約1,090 g/eq為止。 30 201012881 接著，加入134份的二甲基乙醇胺及150份之90%乳酸 水溶液，在120°C反應4小時。接著，加入曱基異丁基酮調 整固體含量，獲得固體含量60%的銨鹽型樹脂之顏料分散 用樹脂。上述分散用樹脂的銨鹽濃度為0.78 mmol/g。 (注4) jER828EL:商品名，環氧樹脂，Japan Epoxy Resins Co.， Ltd.製 製造例12顏料分散漿No. 1之製造例 加入在製造例11中獲得之固體含量60%的顏料分散用 &amp; 樹脂8.3份（固體含量5份）、五氧化二釩2份、偏矽酸鈣1份、 磷酸鈣2份、鈦白20份、氧化鋇(硫酸鋇)20份及去離子水37.6 份，用球磨機分散20小時，施行顏料分散直至粒子（顏料粗 粒子的粒徑）成為20μιη以下，獲得固體含量55%的顏料分散 衆 Ν〇· 1。 • 對25°C的5質量％氯化鈉水溶液ι〇,〇〇〇份，添加構成防 銹顏料混合物(C)的五氧化二飢2份、偏梦酸妈1份、麟酸約 2份的混合物並攪拌6小時，測定過濾在25。(：靜置了 48小時 φ 的上清液而得到之濾液的pH。濾液的pH為5.5。 製造例13〜21 除表2的混合内容以外，與製造例12同樣地處理，製得 顏料分散漿No· 2〜No. 1〇。另外，以和製造例12同樣的方 法’將測定化合物（cl)〜(c3)混合物的氣化鈉水溶液濾液之 pH的結果示於表2。 31 201012881 [表2] 製造例 12 13 14 15 16 17 18 19 20 21 顏料分散漿 No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 No. 10 顏料分散用樹脂 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 釩化合物 (cl) 五氧化二釩 2 10 20 30 20 20 20 20 偏叙酸敍 20 釩酸飼 20 混 偏矽酸妈 1 5 5 20 10 10 矽化合物 (c2) 偏矽酸錢 5 矽酸鋁 5 shieldex C303 20 20 20 20 20 20 sylysia710 10 20 合 磷酸系鈣鹽 (c3) 磷酸詞 2 10 20 30 20 20 磷酸一氫鈣 20 20 20 三聚磷酸#5 20 著色顏料 鈦白 20 20 20 20 20 20 20 20 20 20 體質顏料 氧化鋇 20 20 20 20 20 20 20 20 20 20 去離子水 37.6 54 86.7 107.2 86.7 86.7 90.8 90.8 82.6 82.6 顏料分散漿 90.9 127.3 200 245.5 200 200 209.1 209.1 190.9 190.9 固體含量55% (5〇) (70) (110) (135) (110) (110) (115) (115) (105) (105) 防銹顏料混合物(C)的合計量 5 25 65 90 65 65 70 70 60 60 濾液的pH 5.5 5.5 6.0 7.0 5.5 5.5 5.8 6.0 7.8 7.7 數值表示混合質量份，（)表示固體含量。Co., Ltd., a solution of hexamethylene diisocyanate type polyisocyanate compound blocked with methyl ethyl ketone oxime, solid content of about 75% (Note 3) Duranate MF-K60X: Asahi Kasei Chemicals Corp., active methylene-closed six Resin solution of methyl diisocyanate, ❹ Solid content 60% Production Example 11 Production example of pigment dispersion resin 390 parts of bisphenol A, 240 parts of Plaxel 212 (polycaprolactone diol, Daicel Chemical Industries Ltd. , trade name, weight average molecular weight about 1,250) and 0.2 parts of dimethylbenzylamine were added to 1010 parts of jER828EL (Note 4), and reacted at 130 ° C until the epoxy equivalent became about 1,090 g / eq. until. 30 201012881 Next, 134 parts of dimethylethanolamine and 150 parts of a 90% aqueous lactic acid solution were added, and the mixture was reacted at 120 ° C for 4 hours. Next, decyl isobutyl ketone was added to adjust the solid content to obtain a pigment dispersion resin of an ammonium salt type resin having a solid content of 60%. The ammonium salt concentration of the above dispersion resin was 0.78 mmol/g. (Note 4) jER828EL: Trade name, epoxy resin, manufactured by Japan Epoxy Resins Co., Ltd.. Production Example 12 Pigment Dispersion Pulp No. 1 Production Example The pigment dispersion having a solid content of 60% obtained in Production Example 11 was added. &amp; 8.3 parts of resin (5 parts solids), 2 parts of vanadium pentoxide, 1 part of calcium metasilicate, 2 parts of calcium phosphate, 20 parts of titanium dioxide, 20 parts of cerium oxide (barium sulphate) and 37.6 parts of deionized water After dispersing for 20 hours in a ball mill, pigment dispersion was carried out until the particles (particle diameter of the pigment coarse particles) became 20 μm or less, and a pigment dispersion of 15% solid content was obtained. • For 5 mass% sodium chloride aqueous solution at 25 ° C, 〇〇〇, add 2 parts of bismuth pentoxide, 1 part of ecstasy, and 2 parts of linonic acid, which constitute the rust preventive pigment mixture (C) The mixture was stirred for 6 hours and the assay was filtered at 25. (The pH of the filtrate obtained by allowing the supernatant of 48 hours of φ to stand. The pH of the filtrate was 5.5. Production Examples 13 to 21 In the same manner as in Production Example 12 except for the mixing contents of Table 2, pigment dispersion was obtained. In the same manner as in Production Example 12, the results of measuring the pH of the filtrate of the sodium carbonate aqueous solution of the mixture of the compounds (cl) to (c3) are shown in Table 2. 31 201012881 [ Table 2] Production Example 12 13 14 15 16 17 18 19 20 21 Pigment Dispersion No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 6 No. Resin 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) Vanadium compound (cl) pentoxide Vanadium 2 10 20 30 20 20 20 20 偏 酸 酸 20 Vanadium acid 20 mixed 矽 矽 1 1 5 5 20 10 10 矽 compound (c2) 矽 矽 5 5 20 sylysia710 10 20 Phosphate-based calcium salt (c3) Phosphoric acid word 2 10 20 30 20 20 Monocalcium phosphate 20 20 20 Tripolyphosphate #5 20 Coloring Pigment Titanium White 20 20 20 20 20 20 20 20 20 20 Body Pigment Cerium Oxide 20 20 20 20 20 20 20 20 20 20 Deionized Water 37.6 54 86.7 107.2 86.7 86.7 90.8 90.8 82.6 82.6 Pigment Dispersion 90.9 127.3 200 245.5 200 200 209.1 209.1 190.9 190.9 Solids content 55% (5〇) (70) (110) (135) (110) (110) (115) (115) (105) (105) Total amount of anti-rust pigment mixture (C) 5 25 65 90 65 65 70 70 60 60 pH of the filtrate 5.5 5.5 6.0 7.0 5.5 5.5 5.8 6.0 7.8 7.7 The values indicate the mixed mass parts and () indicates the solid content.

表2中之 rsylysia710」、「shieldexC303」如下。 sylysia 710 :二氧化石夕微粉末，平均粒徑2.8μπι，吸油量190 ml/100g、BET比表面積700 m2/g，Fuji Silysia Chemical Ltd.製 shieldex C303 :好離子交換二氧化石夕，W.R. Grace &amp; Co. 社製 比較製造例1〜10 除表3的混合内容以外，與製造例12同樣地處理，製得 顏料分散漿No. 11〜No. 20。另外，以和製造例12同樣的 方法，將測定化合物(cl)〜（c3)混合物的氣化納水溶液渡液 之pH的結果示於表3。 32 201012881 [表3] 比較-製造例 1 2 3 4 5 6 「7 8 9 10 &quot; 顔料分散漿 No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 No. 19 iNo. 20 顏料分散用樹脂 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 i5) 叙化合物(cl) 五氧化二釩 0 40 50 20 20 0 20 20 偏釩酸鍵 釩酸约 混 石夕化合物(c2) 偏矽酸約 0 40 20 50 20 20 0 20 偏矽酸鎮 矽酸鋁 磷酸系鈣鹽(c3) 磷蘭 0 40 20 20 50 20 20 0 合 磷酸一氛妈 三聚磷酸朽 著色染料 鈦白 20 20 20 20 20 20 20 20 20^ 20 體質染料 氧化鋇 20 20 20 20 20 20 20 20 2〇Ί 20 鉻賴 50 90 去離子水 33.5 131.7 107.2 107.2 107.2 66.2 66.2 662 74.4 107.2 顏料分散漿 固體含量55% 81.S (45) 300 (165) 245.5 (135) 245.5 (135) 245.5 (135) 154.51 (85) 154.5 (85) 154.5 (85) 172.7 (95) 245.5 (135) 防鎊顏料C成分之合計 0 120 90 90 90 40 40 40 0 0 濾液的pH - 8.2 4.8 9.1 8.0 112 4.3 8.3 7.7 8.1 數值表示混合質量份，（)表示固體含量。The rsylysia 710" and "shieldex C303" in Table 2 are as follows. Sylysia 710 : SiO2 powder, average particle size 2.8μπι, oil absorption 190 ml/100g, BET specific surface area 700 m2/g, shieldex C303 manufactured by Fuji Silysia Chemical Ltd.: good ion exchange dioxide, WR Grace Comparative Production Examples 1 to 10 In the same manner as in Production Example 12 except that the contents of the mixing in Table 3 were used, pigment dispersions No. 11 to No. 20 were obtained. Further, the results of measuring the pH of the vaporized aqueous solution of the mixture of the compounds (cl) to (c3) in the same manner as in Production Example 12 are shown in Table 3. 32 201012881 [Table 3] Comparison - Manufacturing Example 1 2 3 4 5 6 "7 8 9 10 &quot; Pigment Dispersion Pulp No. 11 No. 12 No. 13 No. 14 No. 14 No. 15 No. 16 No. No. 19 iNo. 20 Resin for pigment dispersion 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 (5) 8.3 i5) Compound (cl) Vanadium pentoxide 0 40 50 20 20 0 20 20 Metavanadic acid bond vanadic acid about mixed stone compound (c2) Heteroic acid about 0 40 20 50 20 20 0 20 Bismuthic acid strontium aluminate phosphate Calcium salt (c3) Phosphorus 0 40 20 20 50 20 20 0 Phosphoric acid one atmosphere mother tripolyphosphate coloring dye titanium white 20 20 20 20 20 20 20 20 20^ 20 Body dye yttrium oxide 20 20 20 20 20 20 20 20 2〇Ί 20 chrome lye 50 90 deionized water 33.5 131.7 107.2 107.2 107.2 66.2 66.2 662 74.4 107.2 pigment dispersion solids content 55% 81.S (45) 300 (165) 245.5 (135) 245.5 (135) 245.5 ( 135) 154.51 (85) 154.5 (85) 154.5 (85) 172.7 (95) 245.5 (135) Total anti-pound pigment C composition 0 120 90 90 90 40 40 40 0 0 liquid pH - 8.2 4.8 9.1 8.0 112 4.3 8.3 7.7 8.1 Values represent the mixing parts by mass, () represents a solid content.

製造例22 Resole型紛搭樹脂交聯劑溶液之製造 於反應容器中，混合100份的雙酚A、178份的37%甲醛 水溶液及1份的氫氧化鈉，在60°C使其反應3小時後，在減 壓下，5〇°C脫水1小時。接著，加入正丁醇1〇〇份和磷酸3份， φ 在110〜120°C反應2小時。反應結束後，過濾所得溶液並濾 掉生成的磷酸鈉，獲得固體含量約50%的Resole型酚醛樹脂 交聯劑溶液。所得樹脂之數量平均分子量為880，每1苯核 的平均羥甲基數為0.4個以及平均烷氧曱基數為1.0個。 實施例1 水性塗料組成物No. 1之製造 混合333.3份（固體含量1〇〇份)在製造例4製得的乳膠No. 1，90.9份（固體含量50份)在製造例12製得的顏料分散漿及 75.8份的去離子水，製得固體含量30%的水性塗料組成物 33 201012881Production Example 22 A Resole-type resin cross-linking agent solution was prepared in a reaction vessel, and 100 parts of bisphenol A, 178 parts of a 37% aqueous formaldehyde solution, and 1 part of sodium hydroxide were mixed and reacted at 60 ° C. After the hour, it was dehydrated at 5 ° C for 1 hour under reduced pressure. Next, 1 part of n-butanol and 3 parts of phosphoric acid were added, and φ was reacted at 110 to 120 ° C for 2 hours. After completion of the reaction, the resulting solution was filtered and the resulting sodium phosphate was filtered off to obtain a Resole type phenol resin crosslinker solution having a solid content of about 50%. The obtained resin had a number average molecular weight of 880, an average number of methylol groups per benzene nucleus of 0.4, and an average alkoxy fluorenyl group of 1.0. Example 1 Preparation of Aqueous Coating Composition No. 1 333.3 parts (solid content: 1 part) Latex No. 1, 90.9 parts (solid content: 50 parts) obtained in Production Example 4, obtained in Production Example 12. A pigment dispersion slurry and 75.8 parts of deionized water to prepare an aqueous coating composition having a solid content of 30% 33 201012881

No. 1。 實施例2〜18 水性塗料組成物No. 2〜No. 18之製造 除下述表4及表5所示的混合以外，與實施例1同樣地處 理，獲得水性塗料組成物No. 2〜No. 18。 [表4] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例ό 實施例7 實施例8 實施例9 實施例10 雜塗料組成物 No.l No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 No. 10 混 合 物 質 祕 No. 1 333.3 _ 3333 _ 333.3 _ 猶 No. 2 333.3 (100) ㈣ No. 3 333.3 (100) «No. 4 333J (100) ㈣ No. 5 333.3 0〇〇) 獅 No. 6 3333 (100) 舰 No. 7 1 90.9 (50) 嫩;mtNo.2 127.3 (70) 200 (110) 200 (110) 200 (110) 200 (110) 200 (Π〇) 200 (110) 245.5 (135) 赚^ttNo.5 200 (110) 去離子水 75.8 106.1 166.7 166.7 166.7 166.7 166.7 166.7 204.5 166.7 撒塗料減物 固想含量30% 500 (150) 566.7 (170) 700 (210) 700 (210) 700 (210) 700 (210) 700 (210) 700 (210) 783.3 (235) 700 (210) 數值表示混合質量份，（)表示固體含量。 34 201012881 [表5] 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 實施例17 實施例18 水性塗料組成物 No. 11 No. 12 No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 混 合 物 質 瓣 No. 1 3333 (100) 3333 000) 333.3 (100) 3333 _ 3333 (100) 3333 (1〇〇) 333.3 (1〇〇) 3333 (100) 顏#漿 No. 3 200 (110) 200 (Π0) 200 010) 顏奸诚漿No_6 200 010) 顏价綠漿No.7 209.1 015) 顏#漿 No.8 209.1 (115) 顏料綠漿No.9 190.9 (105) 顏料分散漿No. 10 190.9 (105) Resole型酌齡樹脂交 聯齊臟固想^*50% (製ΦΗ22) 10 (5) 10 (5) 10 (5) 去離子水 166.7 174.3 174.3 159.1 159.1 173.4 173.4 173.4 水性塗料組成物 固體含量30% 700 (210) 716.7 (215) 716.7 (215) 6833 (205) 683.3 (205) 716.7 (215) 716.7 (215) 716.7 (215) 數值表示混合質量份，0表示固體含量。 - 比較例1〜10 除做成示於下述表6的混合外，與實施例1同樣地處 理，製得水性塗料組成物No. 19〜No. 28。 35 201012881 [表6] 味例1 tbfeW2 tbft例5蛾体J6 t着J7 罐项 比較例10 水性塗料組物 No. 19 No. 20 No. 21 No. 22 No. 23 No. 24 No. 25 No. 26 No. 27 No. 28 混 合 内 容 t^o.l 3333 (100) 3333 (100) 3333 (100) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 3333 0〇〇) 333.3 (100) ίΙ^Νο.7 顏外讀紙3 顏#^_· 11 81.8 (45) 12 300 (165) 顏#^狐13 245.5 (135) 顏料分散_· 14 245.5 (135) 顏15 245*5 035) 顏料分散槳No. 16 154.5 (85) 顏#^狐17 154.5 (85) 顏料分散衆No. 18 1545 (85) 顏料分散《Νο· 19 172.7 (95) 顏料分散聚No. 20 245.5 (135) 去離子水 77.9 250 204.5 2045 204.5 128.9 128.9 128.9 144 204.5 水性塗料緘物 — 固雄含量30% 493 (145) 8833 (265) 7833 (235) 783J (235) 7833 (235) 616.7 (185) 616.7 (185) 616.7 (185) 650 (195) 7833 (235)No. 1. Example 2 to 18 Aqueous coating composition No. 2 to No. 18 was produced in the same manner as in Example 1 except that the mixing shown in Tables 4 and 5 below was carried out to obtain an aqueous coating composition No. 2 to No. 18. [Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 实施 Example 7 Example 8 Example 9 Example 10 Miscellaneous coating composition No. 1 No. 2 No. 3 No. 4 No. 5 No. 5 No. 6 No. 5 No. 4 No. 4 No. 4 No. 4 No. 4 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 3 No. 333J (100) (4) No. 5 333.3 0〇〇) Lion No. 6 3333 (100) Ship No. 7 1 90.9 (50) tender; mtNo.2 127.3 (70) 200 (110) 200 (110) 200 (110 200 (110) 200 (Π〇) 200 (110) 245.5 (135) Earn ^ttNo.5 200 (110) Deionized water 75.8 106.1 166.7 166.7 166.7 166.7 166.7 166.7 204.5 166.7 Sprinkle paint reduction material 30% 500 (150) 566.7 (170) 700 (210) 700 (210) 700 (210) 700 (210) 700 (210) 700 (210) 783.3 (235) 700 (210) Values indicate the mass fraction, () indicates the solids content . 34 201012881 [Table 5] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Aqueous coating composition No. 11 No. 12 No. 13 No. 14 No. 15 No 16 No. 17 No. 18 Mixed material flap No. 1 3333 (100) 3333 000) 333.3 (100) 3333 _ 3333 (100) 3333 (1〇〇) 333.3 (1〇〇) 3333 (100) 颜#浆No. 3 200 (110) 200 (Π0) 200 010) Yan Yucheng Pulp No_6 200 010) Yan price green pulp No.7 209.1 015) Yan #浆No.8 209.1 (115) Pigment green pulp No.9 190.9 ( 105) Pigment Dispersion Pulp No. 10 190.9 (105) Resole type resin of age cross-linking solidification ^*50% (manufacturing ΦΗ22) 10 (5) 10 (5) 10 (5) Deionized water 166.7 174.3 174.3 159.1 159.1 173.4 173.4 173.4 Aqueous coating composition Solids content 30% 700 (210) 716.7 (215) 716.7 (215) 6833 (205) 683.3 (205) 716.7 (215) 716.7 (215) 716.7 (215) Numerical values indicate the mass parts, 0 represents the solid content. - Comparative Examples 1 to 10 The aqueous coating compositions No. 19 to No. 28 were obtained in the same manner as in Example 1 except that they were mixed as shown in the following Table 6. 35 201012881 [Table 6] Taste Example 1 tbfeW2 tbft Example 5 Moth J6 t with J7 Canister Comparative Example 10 Water-based paint composition No. 19 No. 20 No. 21 No. 22 No. 23 No. 24 No. 26 No. 27 No. 28 Mixed content t^ol 3333 (100) 3333 (100) 3333 (100) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 333.3 (100) 3333 0〇〇) 333.3 (100) ίΙ^Νο.7 颜外读纸3 颜#^_· 11 81.8 (45) 12 300 (165) 颜#^狐13 245.5 (135) Pigment dispersion _· 14 245.5 (135) 颜15 245 *5 035) Pigment Dispersion Paddle No. 16 154.5 (85) Yan #^狐17 154.5 (85) Pigment Dispersion No. 18 1545 (85) Pigment Dispersion "Νο· 19 172.7 (95) Pigment Dispersion Poly No. 20 245.5 (135) Deionized water 77.9 250 204.5 2045 204.5 128.9 128.9 128.9 144 204.5 Waterborne coatings - 30% solids 493 (145) 8833 (265) 7833 (235) 783J (235) 7833 (235) 616.7 (185) 616.7 (185) 616.7 (185) 650 (195) 7833 (235)

數值表示混合質量份，（)表示固體含量。 [試驗用塗裝板的製作]The numerical value indicates the mixed mass portion, and () indicates the solid content. [Production of test coated board]

利用上述實施例1〜18、比較例1〜1〇中製得的各水性 塗料組成物No. 1〜No. 28及面漆塗料，以下述的塗裝要求 1、塗裝要求2及塗裝要求3，塗裝各素材並進行燒結，製得 各試驗用塗裝板。 塗裝要求1 在施行過無鉻系化學轉化處理（前處理）的鑛鋁辞鋼板 (Galvalume Steel)(板厚〇.35mm，鍍層被覆量為 150 g/m2， 表中表示為「GL鋼板」。）上，將由實施例及比較例製得的 36 201012881 各水性塗料組成物，用刮棒塗布機塗裴成乾燥膜厚3μιη， 在140°C(素材到達的最高溫度）用鏈條式平爐（c〇nvey〇r oven)加熱乾燥20秒鐘。 接著，於剛才的塗裝面（正面）之相反面，塗裝和正面同 樣的水性塗料組成物形成乾燥膜厚度3μηι，在21〇ΐ(素材到 達的最咼溫度）用鏈條式平爐加熱乾燥4〇秒鐘，製得各底漆 塗裝板。 冷卻後，在這些底漆塗裝板上(正面），用刮棒塗布機將 ❹ KP C〇1〇r 1580B40(Kansai paint Co·，Ltd.製，商品名，聚酯 系面漆塗料，藍色，硬化塗膜的玻螭轉移溫度約為7〇〇c)塗 裝成乾燥膜厚度約15μπι，以素材到達的最高溫度 - 結40秒鐘，製知各試驗用板GL-1〜GL-28(以正面供作試 驗）。 塗裝要求2 在未施行化學轉化處理的熔融鍍鋅鋼板（板厚 0.35mm ’鍍鋅鍍層被覆量為25〇g/m2、表中略稱為「GI鋼 ® 板」）上，將由實施例及比較例製得的各水性塗料組成物， 用刮棒塗布機塗裝成乾燥膜厚3μηι，在140。(：（素材到達的最 高溫度）用鏈條式平爐加熱乾燥15秒鐘。 接著，於剛才的塗裝面（正面）之相反面，將和正面同樣 的水性塗料組成物，用刮棒塗布機塗裝成乾燥膜厚度 3μιη ’在140C(素材到達的最高溫度）用鏈條式平爐加熱乾 燥15秒鐘，製得各底漆塗裝板。 冷卻後，在這些底漆塗裝板上(正面），用刮棒塗布機將 37 201012881 KPcolorl510(KansaiPaintCo.，Ltd.製，商品名，高分子聚 醋系面漆塗料’茶色，硬化塗膜的玻璃轉移溫度約為4〇°c ) 塗裝成乾燥膜厚度約15μιη，用鏈條式平爐在220°C (素材至,j 達的最高溫度）燒結40秒鐘，製得各試驗用板GI4〜 GI-28(以正面供作試驗）。 塗裝要求3 在施行過磷酸鋅化學轉化處理的冷軋鋼板（板厚〇 8 mm、表中表不為「SPC鋼板」）上’將由實施例及比較例製 得的各水性塗料組成物，用刮棒塗布機塗裝成乾燥膜厚 0 8μιη，在180°C(素材到達的最高溫度）用鏈條式平爐乾燥30 秒鐘。 接著，於剛才的塗裝面（正面）之相反面，將和正面同樣 的水性塗料組成物，用刮棒塗布機塗裝成乾燥膜厚度 20μιη’在180°C (素材到達的最高溫度）用鏈條式平爐加熱乾 燥30分鐘’獲得各試驗用塗裝板SP-1〜SP-28(以正面供作 試驗）。 塗膜性能試驗 @ 針對使用上述實施例1〜18、比較例1〜1〇中製得之各 水性塗料組成物塗裝過的各試驗用塗裝板GL-i〜GL-28、 GI-1〜GI-28、SP-1〜SP-28，依據下述試驗方法，進行塗 膜性能試驗。試驗結果示於表7〜表9。 38 201012881 [表7] imn 1 ifife例 2 3 1mm 4 魏例 5 倾例 6 tm 7 imm 8 tmi 9 ttm ΙΟ 水性物 Ναΐ Νο.2 Να3 No. 4 Νο.5 Ναό Νο.7 Νο.8 No. 9 Να 10 GI^l Gb*2 GL3 GL4 GL6 Gh7 GM GW GW0 塗裝要求1 (Gwm ^««紐脚 ◎ ◎ ◎ Ο 〇 ◎ 〇 Ο Ο 〇 •ϋ _ ◎ ◎ ◎ 〇 〇 ◎ 〇 〇 〇 Ο (注7) 〇 ◎ 〇 ο 〇 Ο 〇 Ο 〇 〇 礙H (·;瑪 〇 〇 〇 〇 Ο 〇 ◎ 〇 ο ο 複^#環 雜嫩 ㈣ 4T加工部 〇 Ο Ο ◎ ◎ 〇 〇 〇 ◎ ο 魏部 Ο 〇 〇 ◎ ◎ 〇 ◎ ◎ ◎ ο 5txl_ 〇 f〇 Ο 〇 Ο 〇 ◎ ◎ ◎ 〇 GI-l GI-2 GI-3 GI4 GI-5 GI-6 GI-7 GI-8 GI-9 GI-10 塗裝要和 (G崎 (ίΐ5) 〇 h Ο 〇 〇 〇 〇 〇 Ο Ο ο 邮紙 （ίΐβ) 〇 「〇 〇 〇 Ο 〇 〇 〇 〇 ο 礙1± (注7) Ο 〇 〇 〇 ο 〇 〇 〇 〇 ο (&gt;iS) Ο 〇 〇 〇 ο 〇 〇 〇 〇 ό ^m. 腐姓嫩 _ 4T加工部 〇 〇 〇 ◎ ◎ 〇 0 〇 〇 ο _部 〇 〇 〇 ◎ ◎ 〇 〇 〇 〇 〇 ^Χί丨嫩Ρ ο 〇 〇 Ο ο 〇 ◎ ◎ ◎ ο tiSStfe SM SP-2 SP-3 SP4 SP-5 SP4 SP-7 SP-« SP4 SP-10 塗裝要勒 (SPC觸 紐 （as) Ο Ο 〇 〇 〇 〇 〇 〇 〇 〇 时雜 （哗 〇 Ο 〇 〇 ο 〇 〇 〇 〇 ο (注7) 〇 〇 〇 〇 〇 〇 〇 〇 〇 ο _ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 鹽水喷霧試除（注10) 〇 〇 Ο 〇 〇 〇 〇 Ο ◎ οEach of the aqueous coating compositions No. 1 to No. 28 and the top coats prepared in the above Examples 1 to 18 and Comparative Examples 1 to 1 were coated with the following coating requirements, coating requirements 2, and coating. Requirement 3, coating each material and sintering it, and preparing each test coated board. Coating Requirements 1 Galvalume Steel (plate thickness 〇.35mm, coating thickness 150g/m2, expressed as “GL steel plate” in the chromium-free chemical conversion treatment (pre-treatment) 36) The water-based coating compositions prepared by the examples and the comparative examples were coated with a bar coater to a dry film thickness of 3 μm, and a chain type open hearth was used at 140 ° C (the highest temperature at which the material reached). C〇nvey〇r oven) Heat and dry for 20 seconds. Next, on the opposite side of the painted surface (front side), the same aqueous coating composition as the front surface is applied to form a dry film thickness of 3 μm, and dried in a chain type open hearth at 21 〇ΐ (the most enthalpy temperature at which the material reaches). In each second, each primer coating plate was prepared. After cooling, on these primer coating plates (front side), ❹ KP C〇1〇r 1580B40 (manufactured by Kansai paint Co., Ltd., trade name, polyester-based topcoat paint, blue) was applied by a bar coater. Color, hardened coating film transfer temperature is about 7 〇〇 c) coated into a dry film thickness of about 15 μπι, with the highest temperature reached by the material - knot 40 seconds, to know the test plates GL-1 ~ GL- 28 (for positive test). Coating requirements 2 On the case of a hot-dip galvanized steel sheet (plate thickness 0.35 mm 'coated with a galvanized coating of 25 μg/m 2 , abbreviated as “GI steel plate” in the table), which has not been subjected to chemical conversion treatment, Each of the aqueous coating compositions prepared in the comparative examples was coated with a dry film thickness of 3 μm by a bar coater at 140. (: (the highest temperature at which the material arrives) is dried by heating in a chain type open hearth for 15 seconds. Next, on the opposite side of the painted surface (front side), the same aqueous coating composition as the front surface is coated with a bar coater. Filled with a dry film thickness of 3 μm η 'at 140 C (the highest temperature reached by the material) was dried by heating in a chain type open hearth for 15 seconds to prepare each primer coating plate. After cooling, on these primer coating plates (front side), 37 201012881 KPcolorl 510 (manufactured by Kansai Paint Co., Ltd., trade name, high-molecular vinegar topcoat paint - brown, glass transition temperature of hardened coating film of about 4 ° C) was applied as a dry film by a bar coater. The thickness of about 15 μm was sintered in a chain type open hearth at 220 ° C (material to the highest temperature reached by j) for 40 seconds to prepare test plates GI4 to GI-28 (for test on the front side). On the cold-rolled steel sheet subjected to the chemical conversion treatment of zinc phosphate (thickness 〇 8 mm, not shown as "SPC steel sheet" in the table), each of the aqueous coating compositions prepared in the examples and the comparative examples was coated with a doctor bar. The machine is painted to a dry film thickness of 0 8μιη, at 180 ° C (the highest temperature at which the material arrives) is dried in a chain-type open hearth for 30 seconds. Next, on the opposite side of the painted surface (front side), the same aqueous coating composition as the front surface is coated with a bar coater. The dry film thickness of 20 μm was set to 180 ° C (the highest temperature at which the material reached) and dried by heating in a chain type open hearth for 30 minutes to obtain test plates SP-1 to SP-28 for each test (tested on the front side). Membrane performance test @ Each of the test coated sheets GL-i to GL-28, GI-1 which were coated with each of the aqueous coating compositions prepared in the above Examples 1 to 18 and Comparative Examples 1 to 1 was used. GI-28, SP-1 to SP-28 were tested for film properties according to the following test methods. The test results are shown in Table 7 to Table 9. 38 201012881 [Table 7] imn 1 ifife Example 2 3 1mm 4 Wei Example 5 Pour the case 6 tm 7 imm 8 tmi 9 ttm 水性 Water-based substance Ναΐ Νο.2 Να3 No. 4 Νο.5 Ναό Νο.7 Νο.8 No. 9 Να 10 GI^l Gb*2 GL3 GL4 GL6 Gh7 GM GW GW0 Painting requirements 1 (Gwm ^««纽脚◎ ◎ ◎ Ο 〇 ◎ 〇Ο Ο 〇•ϋ _ ◎ ◎ ◎ 〇〇 ◎ 〇〇〇Ο (Note 7) 〇 〇ο 〇Ο 〇Ο 〇〇 H H (·; 玛〇〇〇〇Ο 〇 ◎ 〇ο ο 复^#环杂嫩(4) 4T processing department Ο ◎ ◎ 〇〇〇 ◎ ο Wei Ο 〇〇 ◎ ◎ 〇 ◎ ◎ ◎ ο 5txl_ 〇f〇Ο 〇Ο 〇 ◎ ◎ ◎ 〇 GI-l GI-2 GI-3 GI4 GI-5 GI-6 GI-7 GI-8 GI-9 GI-10 Painting and (G崎(ΐ5) 〇h Ο 〇〇〇〇〇Ο Ο ο 邮纸(ίΐβ) 〇“〇〇〇Ο 〇〇〇〇ο 11± (Note 7) Ο 〇〇〇ο 〇〇〇〇ο (&gt;iS) Ο 〇〇〇ο 〇〇〇〇ό ^m. 腐姓嫩_ 4T processing department 〇〇〇 ◎ ◎ 〇0 〇〇ο _ 〇〇〇 ◎ ◎ 〇〇〇〇〇 ^Χί丨Ρ ο 〇〇Ο ο 〇 ◎ ◎ ◎ ο tiSStfe SM SP-2 SP-3 SP4 SP-5 SP4 SP-7 SP-« SP4 SP-10 Painting to Le (SPC Touch (as) Ο Ο 〇〇 〇〇〇〇〇〇 杂 哗〇Ο (哗〇Ο 〇〇ο 〇〇〇〇ο (Note 7) 〇〇〇〇〇〇〇〇〇ο _ 〇〇〇〇〇〇〇〇〇〇 salt spray test (Note 10) 〇〇Ο 〇 〇 〇 〇 Ο ◎ ο

[表8] II 柄例 12 ΙίΜΗ 13 tmn 14 料例 15 热例 16 料例 17 料例 18 ΝαΠ No. 12 Να 13 No. 14 No. 15 No. 16 No. 17 No. 18 Gl^ll GW2 GU3 Gh-H GM5 GU6 GLr\l GH8 塗裝要和 魏附著I4 脚 〇 〇 〇 〇 Ο ◎ ◎ ◎ 对(测 Ο Ο 〇 〇 〇 ◎ ◎ ◎ (注7) 〇 〇 〇 〇 〇 ◎ ◎ ◎ Mm± 脚 「〇 ο 〇 〇 〇 ◎ ◎ ◎ 複純環 腐 ㈣ 4T加工部 〇 〇 〇 〇 〇 ◎ ◎ ◎ 遶缘部 〇 〇 〇 〇 〇 ◎ ◎ ◎ 餘部 〇 ◎ ◎ Ο 〇 ◎ ◎ ◎ GI-ll GH2 GI-13 GH4 CH-15 GH6 CH-17 GM8 塗裝要拉 (G麵 «雜 (35) 〇 Ο 〇 〇 〇 ◎ ◎ ◎ 对并It (蝴 〇 〇 〇 〇 〇 ◎ ◎ ◎ 礙险 （注7) 〇 〇 〇 〇 〇 〇 〇^ 〇 mm _ 〇 〇 〇 Ο 〇 ◎ ◎ ◎ 複 (m 4T加工部 〇 〇 〇 〇 Ο 〇 〇 o 雜部 〇 〇 〇 ο 〇 〇 〇 ◎ 交X*_J線部 〇 〇 〇 〇 ο 〇 o ◎ SP-ll SM2 SP-13 SP-14 SP-15 SP-16 SP-17 SP-18 塗裝要彩 雜 ㈣ ο 〇 〇 ο 〇 ◎ ◎ ◎ 球嫩 （赖 〇 〇 Ο 〇 〇 ◎ ◎ ◎ (注7) 〇 Ο 〇 〇 〇 ◎ ◎ ◎ ^m± (ιίβ) 〇 〇 〇 〇 〇 〇 〇 o 逢水嘖霧試險 _) ο 〇 〇 ◎ ◎ 〇 〇 ◎ 39 201012881 [表9] t削 1 2 tbfe例 3 4 t讓 5 6 tkMm 7 tb^J 8 峨例 9 itmj 10 水性餅 No. 19 No. 20 No. 21 No. 22 No. 23 No. 24 No. 25 No. 26 No. 27 No. 28 GW9 GL-20 GU21 GL-22 GLrH GL*24 GL*25 GL·^ GL-27 GL-28 塗裝要拟 {GLm〇 (ίί5) ◎ y o 〇 〇 〇 〇 〇 〇 X 耐·弗水ft _ ◎ y o 〇 〇 〇 〇 〇 〇 X 猶改 （注7) 〇 〇 Λ o 〇 〇 X 〇 o 〇 〇 o o Δ 〇 X △ o 〇 Δ 複傾環 m 4T加工部 Δ X Δ X Δ 〇 Δ △ 〇 ◎ 錄部 X 〇 〇 Δ Δ X X Δ 〇 ◎ X 〇 〇 △ △ Δ X Δ 〇 ◎ GM9 Gt20 Gi-21 0-22 G9-23 Gm GI-25 GK26 a-27 GI-28 塗裝要粘 {Gism 雜 脚 Ο X A Δ Δ 〇 〇 〇 〇 X 时桃性 （蝴 ο X △ Λ Δ 〇 〇 〇 〇 X ο △ X A Δ Δ X 〇 〇 〇 (&gt;i8) 〇 Δ △ X △ X Δ o 〇 Δ 複合循環 腐姓嫩 (&gt;ί9) 4T加工部 X Δ △ X Δ X X Δ 〇 ◎ 絲部 X △ 〇 X Δ X X X o ◎ 線部 X Δ 〇 X △ X Λ V o 〇 SP-19 SP-20 SF-21 SP-22 SP-23 SP-24 SP-25 SP-26 SP-27 SP-28 塗裝要β (SPC觸 (ii5) 〇 X X X △ o o 0 〇 X 对^K性 （剛 〇 X X X △ o Γ) 〇 〇 X (注7) Λ X X Δ △ Δ Δ 〇 〇 0 (&gt;ig) X X X x △ X 〇 〇 〇 X (注i〇) X o △ 〇 〇 △ A Δ 〇 〇 試驗方法 (/主5)塗膜附著性：遵循JIS K-5600-5-6 (1999)割格 法，切痕的間隙間隔設為1mm，製作100個網格，在其表面 黏貼透明膠帶，調查在急劇剝離後塗面上所殘存的網格數。 ◎ •塗膜無發生膨脹、白化等的異常，殘存網格數1〇〇 個， 〇·塗膜無發生膨脹、白化等的異常，殘存網格數91 〜99個， △ ··塗膜上稍微確認到發生膨脹或白化等的異常，殘 存網格數91〜99個，或者塗膜雖無發生膨脹、白化等的異 常’惟殘存網格數為71〜90個， X :塗膜上相當程度或明顯確認到膨脹的發生，或者 40 201012881 殘存網格數在70個以下 (注6)耐沸水性：將切斷成5cmxl0cm之大小的各試驗用 塗裝板，在約l〇〇°C的沸水中浸潰2小時後取出，評估表面 (正面）侧的塗膜外觀’同時進行劃格附著試驗的評估。劃格 附著試驗係遵循HS K-5600-5-6 (1999)劃格法，將切痕的間 隙間隔設為1mm，製作1〇〇個網格，在其表面黏貼透明膠 帶，調查在急劇剝離後塗面上所殘存的網格數。 ◎:塗膜無發生膨脹、白化等的異常，殘存網格數1〇〇 φ 個， 〇：塗膜無發生膨脹、白化等的異常，殘存網格數91 〜99個， ·· △:塗膜上稍微確認到膨脹的發生或白化等的異常， ， 殘存網格數91〜99個，或者塗膜雖無膨脹的發生、白化等 的異常，惟殘存網格數為71〜9〇個， X :相當程度或明顯確認到塗膜上發生膨脹，或者殘 存網格數在70個以下 • (/主7)耐驗性.用防鱗塗料密封切斷成之大小 的^試驗用塗裝板背面及切斷面，並在塗裝板的表面側中 央部切入深達基材的劃痕。評價將該塗裝板在贼的5%氫 氧化納水冷液/文潰24小時後，取出洗淨，並於室溫乾燥過 的塗裝板之表面側的塗膜外觀，同時在劃格部用透明膠帶 黏貼’ s平估急劇剝離後，從塗膜的切痕部分剝離的寬度(單 側）。 ◎.未發生膨脹，谬帶自切痕部分剝離的寬度在15類 41 201012881 以下， 〇：未發生膨脹，膠帶自切痕部分剝離的寬度超過 1.5mm，在3mm以下， △:確認有些膨脹的發生，惟膠帶自切痕部分剝離的 寬度在3mm以下，或者未確認到膨脹的發生’惟膠帶自切 痕部分剝離的寬度超過3min。 X:確認膨脹的發生，而且膠帶自切痕部分剝離的寬 度超過3mm。 (注8)耐酸性：用防銹塗料密封切斷成5cmxl0cm之大小 參 的各試驗用塗裝板背面及切斷面，並在塗裝板的表面側中 央部切入深達基材的劃痕。評價將該塗裝板在20°C的5%硫 酸水溶液浸潰24小時後，取出洗淨，並於室溫乾燥過的塗 . φ 裝板表面側之塗膜外觀，同時在劃格部用透明膠帶黏貼， 會 評估急劇剝離後’從塗膜的切痕部分剝離的寬度(單側）。 — ◎:未發生膨脹，膠帶自切痕部分剝離的寬度在1.5mm 以下， 〇：未發生膨脹’膠帶自切痕部分剝離的寬度超過 ❹ 1.5mm，在3mm以下， △:確認有些膨脹的發生，惟穋帶自切痕部分剝離的 寬度在3mm以下，或者未確認到膨脹的發生，惟膠帶自切 痕部分剝離的寬度超過3mm。 X ··確認發生膨脹’且膠帶自切痕部分剝離的寬度超 %3mm ° (注9)複合循環腐蝕試驗：準據JIS κ-5621 (1990)。將 42 201012881 塗裝板切成6cmxl2cm的大小，使得在各試驗用塗裝板之長 邊的邊緣部分，朝向表面側塗膜面右側邊緣部，在正面側 上存在毛邊，朝向表面侧塗膜面左側邊緣部分，在背面側 上存在毛邊。在已經切斷的各試驗用塗裝板之表面侧中央 部分，用切割刀的刀背，切入深達基材之窄角30度、線寬 〇.5mm的交又劃痕，用防銹塗料密封塗裝板上端邊緣部， 並在上端部設4T折彎加工部。此處，4T折彎加工部係指， 將塗裝板的表面側當做外側折彎，在其内側則夾著4片與塗 裝板相同厚度的板，用老虎鉗將上述塗裝板折彎180度的加 工。對施行過上述加工的試驗用塗裝板，以（在^。(^喷霧巧％ 食鹽水0.5小時)-(在30°C ’RH95%以上之耐濕試驗器内試驗 1_5小時)-(在50°C乾燥2小時)-(在3〇。(：乾燥2小時）為一循 環，進行300循環(合計1800小時）的試驗。評估該試驗後的 塗裝板之邊緣部、交叉劃線部、4T加工部之狀態。 (4T加工部）評估4T加工部中生銹部分的合計長度。 ◎ ··未確認到生銹情形， 〇：確認有白銹，惟未達2〇mm， △ ’白錢在20mni以上且未達4〇mm， X :白銹在4〇mm以上，或者確認有紅銹的出現。 (邊緣部）求取塗裝板左右長邊的邊緣潛變幅度之平均 值，根據以下的基準進行評估。 ◎:不滿5mm， Ο · 5nun以上且不滿1 ， △ : 10mm以上且不滿2〇mm， 43 201012881 X : 20mm以上。 (交叉劃線部）利用0.5mm之切痕寬度的金屬露出部中 出現的白銹長度比例，以及切痕部分左右膨脹寬度（兩側之 和）的平均值，採用以下的標準評估劃線部的腐姓狀態。 ◎:金屬露出部中出現白銹的長度比例不滿5〇%且膨 脹寬度不滿3mm， 〇：金屬露出部中出現白銹的長度比例在50%以上且 膨脹寬度不滿3mm，或者金屬露出部中出現白銹的長度比 例不滿50%且膨脹寬度在3mm以上而不滿5mm， _ △:金屬露出部中出現白銹的長度比例在50%以上且 膨脹寬度在5mm以上而不滿i〇mm， X :金屬露出部中出現白銹的長度比例在50%以上且 · 膨脹寬度在l〇mm以上。 · (注10)鹽水噴霧試驗··用防銹塗料密封切斷成 · 5cmxl0cm大小的各試驗用塗裝板的背面及切斷面，並在塗 裝板的表面中央置入深達基材的交叉劃痕。對該塗裝板施 行在35°C用5%食鹽水的鹽水噴霧試驗(JIS Z—2371)500小 時，評估試驗後塗面的紅銹出現狀態，同時在交又劃線部 黏貼透明膠帶’評估急劇剝離後，膠帶從塗膜的切痕部分 剝離的寬度（單側）。 ◎:無或僅有些微紅銹的發生，膠帶從切痕部分剝離 的寬度不滿5mm， 〇.相當程度地確認到紅錢的出現，而且膠帶從切痕 部分剝離的寬度不滿5mm ’或者無或僅有些微紅錄的發 44 201012881 生，惟膠帶從切痕部分剝離的寬度在5mm以上不滿10mm， △:在切痕部分全體確認到紅銹的發生，惟膠帶自切 痕部分剝離的寬度在5mm以上而不滿1 Omm，或者雖然不是 在切痕部分全體但卻相當程度地確認到紅銹的發生，而且 膠帶自切痕部分剝離的寬度在l〇mm以上， X :在切痕部分全體都確認到紅銹的發生，而且膠帶 自切痕部分剝離的寬度在1 Omm以上。 產業上之利用可能性 參 本發明提供一種财藥品性、平面部之财姓性、加工部 和端面部之对独性及附著性優良之塗裝金屬板及塗裝物 品。 . 【圖式簡單說明】 龜 [第1圖]示意連續線圈塗裝線之一例。 蠓 [第2圖]示意含有本發明之水性塗料組成物的塗膜之 塗膜構造之一例。 【主要元件符號說明】 Ο 1...鋼板的一部分 4...底塗塗膜(本發明之水性塗 2.. .鍍層 料組成物） 3.. .依需要而施行的化學轉化 5...面漆塗膜 處理(前處理） 45[Table 8] II Handle Example 12 ΙίΜΗ 13 tmn 14 Material Example 15 Thermal Example 16 Material Example 17 Material Example 18 ΝαΠ No. 12 Να 13 No. 14 No. 15 No. 16 No. 17 No. 18 No. 18 No. 18 No. 1 GW2 GU3 Gh-H GM5 GU6 GLr\l GH8 Painting and Wei attaching I4 ankle ◎ ◎ ◎ Pair (measured Ο 〇〇〇 ◎ ◎ ◎ (Note 7) 〇〇〇〇〇 ◎ ◎ ◎ Mm ± Feet "〇ο 〇〇〇◎ ◎ ◎ Fu pure ring rot (4) 4T processing part 〇〇〇〇〇 ◎ ◎ ◎ Around the edge 〇〇〇〇〇 ◎ ◎ ◎ 〇 〇 ◎ ◎ Ο 〇 ◎ ◎ ◎ GI-ll GH2 GI-13 GH4 CH-15 GH6 CH-17 GM8 Painting to pull (G-face «Miscellaneous (35) 〇Ο 〇〇〇 ◎ ◎ ◎ Right and It (Butterfly ◎ ◎ ◎ 碍 ( (Note 7 〇〇〇〇〇〇〇^ 〇mm _ 〇〇〇Ο 〇 ◎ ◎ ◎ complex (m 4T processing department 〇〇〇〇Ο 〇〇o miscellaneous 〇〇〇ο 〇〇〇 ◎ cross X*_J line 〇〇〇〇ο 〇o ◎ SP-ll SM2 SP-13 SP-14 SP-15 SP-16 SP-17 SP-18 Painting to be mixed (4) ο 〇〇ο 〇◎ ◎ ◎ Ball tender (Lai Wei Ο 〇〇 ◎ ◎ ◎ (Note 7) 〇Ο 〇〇〇 ◎ ◎ ◎ ^m± (ιίβ) 〇〇〇〇〇〇〇o 逢 啧 试 _ _ _ ◎ ◎ ◎ ◎ ◎ 39 201012881 [Table 9] t-cut 1 2 tbfe Example 3 4 t let 5 6 tkMm 7 tb^J 8 9 Example 9 itmj 10 Water-based cake No. 19 No. 20 No. 21 No. 22 No. 23 No. 24 No. No. 26 No. 27 No. 28 GW9 GL-20 GU21 GL-22 GLrH GL*24 GL*25 GL·^ GL-27 GL-28 Painting to be {GLm〇(ίί5) ◎ yo 〇〇〇〇〇 〇X 耐·弗水 ft _ ◎ yo 〇〇〇〇〇〇X 犹 ( (Note 7) 〇〇Λ o 〇〇X 〇o 〇〇oo Δ 〇X △ o 〇Δ Complex tilting ring m 4T processing part Δ X Δ X Δ 〇 Δ Δ 〇 ◎ Recording part X 〇〇 Δ Δ XX Δ 〇 ◎ X 〇〇 △ △ Δ X Δ 〇 ◎ GM9 Gt20 Gi-21 0-22 G9-23 Gm GI-25 GK26 a-27 GI -28 Painting to be sticky {Gism Ο Ο XA Δ Δ 〇〇〇〇 X when peach ((ο X △ Λ Δ 〇〇〇〇X ο △ XA Δ Δ X 〇〇〇 (&gt; i8) 〇 Δ △ X △ X Δ o 〇 Δ compound cycle rot (&gt; ί9) 4T processing part X Δ △ X Δ XX Δ 〇 ◎ Silk X △ 〇X Δ XXX o ◎ Line X Δ 〇X △ X Λ V o 〇SP-19 SP-20 SF-21 SP-22 SP-23 SP-24 SP-25 SP-26 SP-27 SP-28 Applying β (SPC touch (ii5) 〇 XXX △ oo 0 〇X to ^K (just 〇 XXX △ o Γ) 〇〇X (Note 7) Λ XX Δ △ Δ Δ 〇〇0 (&gt;ig) XXX x △ X 〇〇〇X (Note i〇) X o △ 〇〇△ A Δ 〇〇 Test method (/Main 5) Coating adhesion: Follow JIS K-5600- 5-6 (1999) Cutting method, the gap interval of the cuts was set to 1 mm, 100 meshes were produced, and a transparent tape was stuck on the surface, and the number of meshes remaining on the coated surface after the sharp peeling was investigated. ◎ • There is no abnormality such as swelling or whitening of the coating film, and the number of remaining grids is one, and there is no abnormality such as swelling or whitening of the coating film, and the number of remaining grids is 91 to 99, △ ·· on the coating film A slight abnormality such as swelling or whitening was observed, and the number of remaining grids was 91 to 99, or the coating film was not abnormally expanded or whitened, but the number of remaining grids was 71 to 90, and X was equivalent to the coating film. Degree or obvious confirmation of the occurrence of swelling, or 40 201012881 Remaining grid number is less than 70 (Note 6) Boiling water resistance: Each test coating plate will be cut into a size of 5cm x 10cm, at about l ° ° C After boiling for 2 hours in boiling water, the appearance of the coating film on the surface (front side) was evaluated, and the evaluation of the cross-hatch adhesion test was performed. The cross-hatch adhesion test follows the HS K-5600-5-6 (1999) cross-cut method, and the gap interval between the cuts is set to 1 mm, and one grid is made, and a transparent tape is adhered to the surface to investigate the sharp peeling. The number of grids remaining on the back surface. ◎: There is no abnormality such as swelling or whitening of the coating film, and the number of remaining grids is 1〇〇φ. 〇: There is no abnormality such as swelling or whitening of the coating film, and the number of remaining grids is 91 to 99, ··· △: Coating An abnormality such as occurrence of swelling or whitening was slightly observed on the film, and the number of remaining meshes was 91 to 99, or the coating film did not have an abnormality such as swelling or whitening, but the number of remaining meshes was 71 to 9 inches. X: A considerable degree or obvious confirmation of expansion on the coating film, or the number of remaining grids is less than 70. (/Main 7) Testability. Sealed into a size with a scale coating. The back surface and the cut surface are cut into a scratch deep into the substrate at the center portion of the surface side of the coated sheet. After evaluating the coated plate in a thief's 5% sodium hydroxide water/cooling solution for 24 hours, the coating film was taken out and washed, and the appearance of the coating film on the surface side of the coated plate dried at room temperature was simultaneously in the cross-section portion. Paste with scotch tape 's flattened width (one side) peeled off from the cut portion of the coating film after sharp peeling. ◎. No expansion occurred, and the width of the tape peeled off from the cut portion was 15 class 41 201012881 or less, 〇: no expansion occurred, and the width of the tape peeled off from the cut portion exceeded 1.5 mm, below 3 mm, △: confirmed some expansion Occurs, but the width of the tape peeled off from the cut portion is less than 3 mm, or the occurrence of expansion is not confirmed. However, the width of the tape peeled off from the cut portion exceeds 3 minutes. X: The occurrence of swelling was confirmed, and the width of the tape peeled off from the cut portion exceeded 3 mm. (Note 8) Acid resistance: The back surface and the cut surface of each test coated sheet cut into 5 cm x 10 cm size were sealed with a rust preventive paint, and a scratch deep into the substrate was cut in the center portion of the surface side of the coated sheet. . After the coated plate was immersed in a 5% sulfuric acid aqueous solution at 20 ° C for 24 hours, the appearance of the coating film on the surface side of the φ plate was dried and washed at room temperature, and used in the cross-cut portion. The scotch tape is adhered and the width (one side) of the peeling from the cut portion of the coating film after the sharp peeling is evaluated. — ◎: No expansion occurred, the width of the tape peeled off from the cut portion was 1.5 mm or less, 〇: no expansion occurred. The width of the tape peeled off from the cut portion exceeded ❹ 1.5 mm, and was less than 3 mm. △: Confirmed that some expansion occurred. However, the width of the tape peeled off from the cut portion was 3 mm or less, or the expansion was not confirmed, but the width of the tape peeled off from the cut portion exceeded 3 mm. X ·· Confirmation of expansion&apos; and the width of the tape peeled off from the cut portion exceeds %3 mm ° (Note 9) Composite cycle corrosion test: JIS κ-5621 (1990). The 42 201012881 coated plate was cut into a size of 6 cm x 12 cm so that the edge portion of the long side of each test coated sheet was directed toward the right side edge portion of the surface side of the coating surface, and there was a burr on the front side and a film side facing the surface side. On the left side edge portion, there is a burr on the back side. In the central portion of the surface side of each of the test coated sheets that have been cut, the back of the substrate is cut into a narrow angle of 30 degrees and the line width is 55 mm, and the surface is scratched with a rustproof paint. The upper edge portion of the upper plate is applied, and a 4T bending portion is provided at the upper end portion. Here, the 4T bending process means that the surface side of the coated sheet is bent as the outer side, and four sheets of the same thickness as the coated sheet are sandwiched inside, and the coated sheet is bent by a vise 180. Degree of processing. For the test coated board subjected to the above processing, (in ^^.(^ spray 巧% saline for 0.5 hours) - (tested in the humidity tester at 30 ° C 'RH 95% or more for 1 _ 5 hours) - ( Drying at 50 ° C for 2 hours) - (at 3 〇. (: drying for 2 hours) for one cycle, 300 cycles (total 1800 hours) of the test. Evaluation of the edge of the coated plate after the test, cross-dash (4T processing unit) The total length of the rusted part in the 4T processing part is evaluated. ◎ ··The rust is not confirmed, 〇: It is confirmed that there is white rust, but it is less than 2〇mm, △ ' White money is above 20mni and less than 4〇mm, X: white rust is above 4〇mm, or red rust is confirmed. (Edge part) to obtain the average value of edge creep of the left and right long sides of the coated plate It is evaluated according to the following criteria: ◎: less than 5mm, Ο · 5nun or more and less than 1 , △ : 10mm or more and less than 2〇mm, 43 201012881 X : 20mm or more. (cross-dash line) using 0.5mm cut The ratio of the length of the white rust appearing in the exposed portion of the metal of the width, and the width of the left and right expansion of the incision portion (the sum of the two sides) For the average value, the rot state of the scribe line is evaluated by the following criteria: ◎: The ratio of the length of white rust in the exposed portion of the metal is less than 5% and the expansion width is less than 3 mm, 〇: the ratio of the length of white rust in the exposed portion of the metal 50% or more and the expansion width is less than 3 mm, or the length of the white rust in the exposed portion of the metal is less than 50% and the expansion width is less than 3 mm and less than 5 mm, _ Δ: the ratio of the length of white rust in the exposed portion of the metal is 50%. Above, the expansion width is 5 mm or more and less than i〇mm, X: the ratio of the length of white rust in the exposed portion of the metal is 50% or more and the expansion width is l〇mm or more. · (Note 10) Salt spray test·· The rustproof paint is sealed and cut into the back surface and the cut surface of each test coated sheet having a size of 5 cm x 10 cm, and a cross-scratch deep to the substrate is placed in the center of the surface of the coated sheet. The salt spray test (JIS Z-2371) of 5% saline solution was used at 35 ° C for 500 hours to evaluate the appearance of red rust on the coated surface after the test, and the scotch tape was adhered in the cross-hatched portion to evaluate the sharp peeling. Peeling of the cut portion of the coating film Width (one side) ◎: No or only some reddish rust occurs, the width of the tape peeled off from the cut portion is less than 5 mm, 〇. The occurrence of red money is confirmed to a considerable extent, and the width of the tape peeled off from the cut portion Less than 5mm 'or no or only a little reddish hair 44 201012881 raw, but the width of the tape peeled from the cut portion is less than 5mm above 5mm, △: the occurrence of red rust is confirmed in the whole part of the cut, but the tape is self-cut The width of the peeling of the mark portion is less than 5 mm and less than 1 Omm, or the occurrence of red rust is confirmed to a considerable extent although not in the entire portion of the cut portion, and the width of the peeling of the tape from the cut portion is l〇mm or more, X: The occurrence of red rust was confirmed in all of the cut portions, and the width of the tape peeled off from the cut portion was 1 Omm or more. INDUSTRIAL APPLICABILITY The present invention provides a coated metal sheet and a coated article which are excellent in the chemical property, the wealth of the flat portion, the uniqueness of the processed portion and the end portion, and the adhesion. [Simplified illustration] Turtle [Fig. 1] shows an example of a continuous coil coating line.第 [Fig. 2] An example of a coating film structure of a coating film containing the aqueous coating composition of the present invention. [Explanation of main component symbols] Ο 1... Part of the steel plate 4... Primer coating film (Water-based coating of the present invention 2. Composition of the coating material) 3. Chemical conversion performed as needed 5. .. Topcoat film treatment (pretreatment) 45

Claims (1)

201012881 七、申請專利範圍： 1· 一種水性塗料組成物，其中含有陽離子性樹脂(A)、多 異氰酸酯硬化劑(B)及下述之防銹顏料混合物(c); 防銹顏料混合物（C)係由：五氧化二釩、釩酸鈣及 偏鈒酸錄中之至少1種鈒化合物(cl)、石夕化合物(c2)及鱗 酸系鈣鹽(c3)組成者，且相對於該樹脂(A)及該硬化劑 之合計固體含量100質量份， 該飢化合物（cl)之量為1〜30質量份、矽酸化合物 (c2)之量為1〜3〇質量份及該磷酸系鈣鹽（c3)之量為丄〜 參 3〇質量份，而且該防銹顏料混合物(c)之量為3~9〇質量 份。 2. 如申請專利範圍第1項記載之水性塗料組成物，其中陽 ¥ 離子性樹脂(A)為，含有胺基的環氧樹脂。 3. 如申請專利範圍第1項記載之水性塗料組成物，其中矽 化合物(c2)係選自矽酸金屬鹽、二氧化矽微粒子及金屬 離子交換二氧化矽微粒子的至少1種。 4·如申請專利範圍第1項記載之水性塗料組成物，其中磷 © 酸系鈣鹽(c3)為磷酸鈣、磷酸一氫鈣、磷酸二氫鈣及三 聚麟酸#5中之至少1種。 5.如申請專利範圍第1項記載之水性塗料組成物，其相對 於陽離子性樹脂（A)及多異氰酸酯硬化劑（B)的固體含 量，含有〇.1〜10質量份的Resole型酚醛樹脂。 6· —種塗膜形成方法，特徵在於，其係在金屬板上形成由 申請專利範圍第丨項記載之水性塗料組成物造成的硬化 46 201012881 塗膜，且該硬化塗膜上形成至少1種以上的面漆塗料之 塗膜。 7. —種塗裝金屬板，其具有以申請專利範圍第6項記載之 塗膜形成方法獲得的塗膜。 8. —種塗裝物品，係透過加工申請專利範圍第7項記載之 塗裝金屬板的作法獲得。201012881 VII. Patent application scope: 1. An aqueous coating composition containing a cationic resin (A), a polyisocyanate hardener (B) and a rust preventive pigment mixture (c) described below; a rust preventive pigment mixture (C) And consisting of at least one bismuth compound (cl), shixi compound (c2) and tartaric acid calcium salt (c3) of vanadium pentoxide, calcium vanadate and bismuth acid, and relative to the resin (A) and the total solid content of the hardener are 100 parts by mass, the amount of the hunger compound (cl) is 1 to 30 parts by mass, the amount of the citric acid compound (c2) is 1 to 3 parts by mass, and the calcium phosphate is used. The amount of the salt (c3) is 丄~3 parts by mass, and the amount of the rust-preventing pigment mixture (c) is 3 to 9 parts by mass. 2. The aqueous coating composition according to claim 1, wherein the cation resin (A) is an epoxy resin containing an amine group. 3. The aqueous coating composition according to claim 1, wherein the cerium compound (c2) is at least one selected from the group consisting of a metal ruthenate salt, a cerium oxide microparticle, and a metal ion-exchanged cerium oxide microparticle. 4. The aqueous coating composition according to claim 1, wherein the phosphorus acid salt (c3) is at least one of calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, and trimeric acid #5. Kind. 5. The aqueous coating composition according to claim 1, which contains 0.1 to 10 parts by mass of Resole type phenol resin with respect to the solid content of the cationic resin (A) and the polyisocyanate curing agent (B). . 6. A method for forming a coating film, characterized in that it is formed on a metal plate by a coating film of a curing coating of 2010-12881 caused by an aqueous coating composition described in the scope of the patent application, and at least one of the hardening coating film is formed. The above coating film for the top coat. A coated metal sheet having a coating film obtained by the coating film forming method described in claim 6 of the patent application. 8. A coated article obtained by processing a coated metal sheet as described in item 7 of the patent application. 47 201012881 第98126755號專利申請案申請專利範圍替換本 98年12月 七、申請專利範圍： 1. 一種水性塗料組成物，其中含有陽離子性樹脂(A)、多 異氰酸酯硬化劑(B)及下述之防銹顏料混合物(C); 防銹顏料混合物（C)係由：五氧化二釩、釩酸舞及 偏釩酸銨令之至少1種釩化合物(cl)、矽化合物(c2)及磷 酸系鈣鹽(c3)組成者，且相對於該樹脂（A)及該硬化劑(B) 之合叶固體含量100質量份， 該釩化合物(Cl)之量為1〜30質量份、矽化合物(c2) 之量為1〜30質量份及該磷酸系鈣鹽(6)之量為丨〜3〇質 讀 量份，而且該防銹顏料混合物(C)之量為3〜9〇質量份。 2·如申請專利範圍第1項記載之水性塗料組成物，其中陽 離子性樹脂(A)為，含有胺基的環氧樹脂。 ， 3·如申請專利範圍第丨項記載之水性塗料組成物，其㈣ * 化合物（C2)係選自石夕酸金屬鹽、二氧化石夕微粒子及金丨 .· 離子交換二氧化矽微粒子的至少1種。 4· ^申請專利範圍…項記載之水性塗料組成物，其中磷 酸系每鹽㈣為碟酸㉟、鱗酸一氫舞、磷酸二氫妈及三 ❹ 聚磷酸鈣中之至少丨種。 5·如申請專利範圍第1項記載之水性塗料組成物，其相對 於陽離子性樹脂⑷及多異氰_硬化劑⑻的固體含 量’含有0.1〜10質量份的Resole型紛酸樹脂。 種塗膜幵V成方法’特徵在於’其係在金屬板上形成由 申請專利範圍第丨項記載之水性塗料組成物造成的硬化 、且該硬化塗膜上形成至少J種以上的面漆塗料之 46 20101288147 201012881 Patent Application No. 98126755 Patent Application Renewal Patent Application No. December 7, 1998, Patent Application Range: 1. A water-based paint composition containing a cationic resin (A), a polyisocyanate hardener (B) and the following Anti-rust pigment mixture (C); anti-rust pigment mixture (C) consists of: vanadium pentoxide, vanadic acid dance and ammonium metavanadate at least one vanadium compound (cl), antimony compound (c2) and phosphoric acid The composition of the calcium salt (c3), and the amount of the vanadium compound (Cl) is 1 to 30 parts by mass, based on 100 parts by mass of the solid content of the resin (A) and the hardener (B). The amount of (c2) is 1 to 30 parts by mass and the amount of the calcium phosphate salt (6) is 丨3 to 3 〇, and the amount of the rust-preventing pigment mixture (C) is 3 to 9 parts by mass. . 2. The aqueous coating composition according to claim 1, wherein the cationic resin (A) is an epoxy group containing an amine group. 3. The aqueous coating composition as described in the scope of the patent application, (4) * The compound (C2) is selected from the group consisting of metal salts of oxalic acid, cerium dioxide, and cerium. · ion-exchanged cerium oxide microparticles At least one. 4. The application of the water-borne paint composition described in the scope of the patent application, wherein the phosphate-based salt (four) is at least one of the disc acid 35, the scaly monohydrogen dance, the dihydrogen phosphate, and the tri-polyphosphate. 5. The aqueous coating composition according to the first aspect of the invention, wherein the solid content of the cationic resin (4) and the polyisocyanuric curing agent (8) is 0.1 to 10 parts by mass of a Resole-type acid resin. The method for forming a coating film 'V is characterized in that it is formed on a metal plate by hardening caused by the aqueous coating composition described in the scope of the patent application, and at least J or more of the top coating is formed on the cured coating film. Of 46 201012881 塗膜。 7. —種塗裝金屬板，其具有以申請專利範圍第6項記載之 塗膜形成方法獲得的塗膜。 8. —種塗裝物品，係透過加工申請專利範圍第7項記載之 塗裝金屬板的作法獲得。 47Coating film. A coated metal sheet having a coating film obtained by the coating film forming method described in claim 6 of the patent application. 8. A coated article obtained by processing a coated metal sheet as described in item 7 of the patent application. 47
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