201109396 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種耐腐蝕性優異之非鉻系塗料組成物 及使用其之塗裝金屬板，更詳細而言係關於一種不僅可有 效提升塗裝金屬板之平面部的耐腐蝕性，亦可有效提升其 加工部或端面部的耐腐蝕性之塗料組成物（即使該塗膜於 屋外環境因光解或水解而開始劣化）及使用其之塗裝金屬 板。 【先前技術】 以往，藉由線圈塗覆處理等所塗裝的預塗覆鋼板等之 預塗覆金屬板，廣.泛使用作爲建築物之屋頂、牆壁、遮陽 板、車庫等之建築材料、各種家電製品、配電盤、冷凍展 示箱、鋼製家具及廚房器具等之住宅相關商品。 由該預塗覆金屬板製造此等之住宅相關商品時，通常 係切割該預塗覆鋼板予以壓製成型、接合。然而，此等之 住宅相關商品大多數存在有切割面之金屬露出部分或藉由 壓製加工處理之產生破裂部分。上述金屬露出部分或產生 破裂部分，與其他部分相比時，由於耐腐餓性容易降低， 一般而言爲提高耐腐蝕性時必須進行在預塗覆鋼板之底層 塗膜中含有鉻系防銹顏料。 然而’鉻系防銹顏料係爲含有防銹性優異的6價鉻所 生成，而該6價鉻對人體之健康、環境保護而言會有問題。 直至目前，非鉻系防銹顏料大多數使用市售的磷酸 鋅、三聚磷酸鋁、鉬酸鋅等，且組合非鉻系顏料之底漆已 201109396 有各種提案。例如，於專利文獻1中記載，在 苯酚樹脂之媒液成份中，摻混作爲防銹顏料之 與釩酸磷、或組合碳酸鈣與矽酸鈣與磷酸鋁與 銹顔料之塗料。此外，於專利文獻2中記載， 混作爲防銹顏料之組合亞磷酸鎂與氧化錳_ : 物' 或磷酸鈣與氧化釩之燒成物的塗料。然而 獻1及2記載的塗料所形成的塗膜，與使用鉻 料相比時，耐腐蝕性不佳，特別是於加工部及 腐蝕性不充分。而且，大多數耐腐蝕性或耐酸 品性不佳。另外，使用多量防銹顏料時，大多 佳’於製造預塗覆金屬板時仍無法達到可取代 料之效果。 另外，於專利文獻3中記載一種塗料組成 在含有羥基或環氧基之有機樹脂與硬化劑所成 中，含有吸油量爲 30〜200ml/100g、細孔容3 1 .2ml/g之二氧化矽微粒子的塗料，且該塗料所 塗膜之玻璃轉移溫度爲40〜125 °C範圍內。然 文獻3中記載的塗料所形成的塗膜，雖具有相 蝕性，惟與使用鉻系顏料之塗料相比時，仍爲 耐藥品性不佳者，特別是端面部之耐腐蝕性不 另外，於特許文獻4中記載一種耐腐蝕性 組成物，其係爲含有含有羥基之塗膜形成性樹 及防銹顏料混合物之塗料組成物，其中該防銹 係由特定的釩化合物、二氧化矽微粒子及磷酸: 環氧樹脂與 組合矽酸鈣 釩酸磷的防 在聚酯中摻 眞化釩燒成 ，由專利文 系顏料之塗 端面部之耐 性等之耐藥 數耐水性不 鉻系防銹顏 物，其係爲 的媒液成份 責爲 0.0 5〜 形成的硬化 而，由專利 當大的耐腐 耐腐蝕性及 充分。 優異之塗料 脂、交聯劑 顏料混合物 系金屬鹽（金 201109396 屬鹽爲鈣、鋅、鋁、鎂鹽等）所構成，其雖顯示有優異的耐 腐蝕性’但對於因暴露於屋外造成表層塗膜劣化後之腐蝕 反應的抵抗性，亦即在維持耐腐蝕性這方面仍被尋求更進 一步耐腐蝕性的提升、改良。 〔專利文獻1〕日本特開平11-61001號公報 〔專利文獻2〕日本特開2000-199078號公報 〔專利文獻3〕日本特開2000-129163號公報 〔專利文獻4〕日本特開2008-222833號公報 【發明内容】 發明所欲解決之課題 本發明之目的在於提供一種非鉻系塗料組成物，其不 僅可於塗裝金屬板等之一般部份形成具有耐腐蝕性優異之 塗膜，於其加工部或端面部亦可形成耐腐蝕性優異之塗膜 (即使該塗膜於屋外環境因光解或水解而開始劣化）；以及 提供一種使用其之塗裝金屬板。 用以解決課題之手段 因此，本發明人爲了解決習知之上述問題而經過努力 硏究’結果發現：藉由在含有羥基之塗膜形成性樹脂系中 配合有含磷酸基之樹脂及/或含磷酸鹽基之樹脂、特定的 釩化合物及離子交換二氧化矽之既定量的防銹顏料之塗料 組成物，可形成在屋外環境下不僅於平面部具有耐腐蝕性 優異之塗膜，且於塗裝金屬板等之加工部或端面部亦可具 有耐腐蝕性優異之塗膜，而完成本發明。 亦即本發明提供一種耐腐蝕性優異之塗料組成物，其 201109396 係含有：（A)不含磷酸基而含有羥基之塗膜形成性樹脂、（B) 交聯劑、（C)防銹顔料混合物及（D)含磷酸基之樹脂及/或 含磷酸鹽基之樹脂〔以下有時簡稱爲「含有磷酸（鹽）基之 樹脂（D)」〕’其特徵在於：該防銹顏料混合物（c)係由（1) 五氧化釩、釩酸鈣及甲基釩酸銨之中至少一種的釩化合物 及（2)離子交換二氧化矽所構成者；相對於該樹脂（A)及該 交聯劑（B)之合計固體成份1 〇 〇質量份，該釩化合.物（丨）之量 爲3〜50質量份，該離子交換二氧化矽（2)之量爲3〜5〇質 量份’及含有磷酸（鹽）基之樹脂（D)之合計量爲1〜30質量 份，且該防銹顏料混合物（C)之量爲6〜100質量份。 此外，本發明亦提供一種塗裝金屬板，係於表面可實 施化成處理（chemical conversion coating)的金屬板上藉由 上述塗料組成物而形成有硬化塗膜者。 此外，本發明亦提供一種具有複數層塗膜之塗裝金屬 板，係於表面可實施化成處理的金屬板上藉由上述塗料組 成物而形成有硬化塗膜，並於該硬化塗膜上形成有表層塗 膜者。 此外，本發明亦提供一種塗裝金屬板，係於表面可實 施化成處理的金屬板的雙面上藉由上述塗料組成物而形成 有硬化塗膜者。 此外，本發明亦提供一種具有複數層塗膜之塗裝金屬 板，係於表面可實施化成處理的金屬板的雙面上藉由上述 塗料組成物而形成有硬化塗膜’並於至少一面之硬化塗膜 上形成有表層塗膜者。 201109396 發明效果 本發明之塗料組成物，係爲不含鉻系防銹顏料、且對 環境衛生而言有利的塗料組成物，藉由本發明之塗料組成 物，可發揮形成平面部之耐腐蝕性優異、且直至目前非鉻 系防銹塗料所不易達成的塗裝金屬板等效果之加工部或端 面部之耐腐蝕性優異的塗膜效果。此外，本發明之塗料組 成物具有含有磷酸（鹽）基之樹脂（D)，於酸性氣體環境中扮 演著強力的附著賦予成分。其優異之附著賦予性被認爲會 與防銹顏料之特定的釩化合物及離子交換二氧化矽互相影 響而有助於大幅提升屋外環境之經時耐腐蝕性。 亦即，由釩化合物（1)及離子交換二氧化矽（2)所構成之 防銹顏料混合物（C)成分具有有效將素材露出面加以被覆 之作用，除此之外，含有磷酸（鹽）基之樹脂（D)成分於酸性 氛圍中扮演著強力的附著賦予成分，故具有抑制腐蝕進行 部份鄰近之陽極中之塗膜剝離的作用，是以根據本發明可 提供一種塗料組成物及使用其之塗裝金屬板，該塗料組成 物可形成即使塗膜於屋外環境因光解或水解而開始劣化， 但該塗膜不僅可有效提升塗裝金屬板之平面部的耐腐蝕 性，亦可有效提升加工部或端面部的耐腐蝕性。 藉由本發明之塗料組成物而形成有硬化塗膜之塗裝金 屬板，其於平面部、加工部或端面部具有優異之耐腐蝕性， 並具有藉由使用鉻酸緦等之習知的鉻酸鹽系防銹顏料之塗 料而形成有硬化塗膜之塗裝金屬板同等以上的耐腐蝕性。 藉由本發明之塗料組成物而形成有硬化塗膜，並於該 201109396 硬化塗膜上形成有表層塗膜之塗裝金屬板，其於平面部' 加工部或端面部具有優異之耐腐蝕性。使用鑛鋅鋼板、鋁· 辞合金電鍍鋼板來作爲被塗物之金屬板時，藉由塗覆本發 明之塗料組成物，可於平面部、端面部、加工部皆獲得優 異耐腐蝕性。 【實施方式】 本發明之塗料組成物係含有下述成分··含有羥基之塗 膜形成性樹脂（A)、交聯劑（B)、防銹顏料混合物（C)及含有 磷酸（鹽）基之樹脂（D)。 含羥基之塗膜形成性樹脂（A) 本發明塗料組成物中含羥基之塗膜形成樹脂，可使用 塗料領域中具有一般能使用的塗膜形成能力之含羥基樹脂 即可，沒有特別的限制，典型例如含羥基之聚酯樹脂、環 氧樹脂、丙烯酸樹脂、氟系樹脂、氯化乙烯基樹脂等之1 種或2種以上混合樹脂。塗膜形成性樹脂，其中可適當使 用至少1種選自含羥基之聚酯樹脂及環氧樹脂的有機樹 脂。 上述含羥基之聚酯樹脂，包含無油性聚酯樹脂、油改 性醇酸樹脂、及此等樹脂之改性物，其包括例如胺基甲酸 酯改性聚酯樹脂、胺基甲酸酯改性醇酸樹脂、環氧基改性 聚酯樹脂、丙烯酸改性聚酯樹脂等。上述含羥基之聚酯樹 脂’以具有數量平均分子量爲i，5〇〇〜35,000'較佳爲2,000 〜25,000，玻璃轉移溫度（Tg點）爲10〜1〇〇 °C、較佳爲20 〜80°C ’經基價爲2〜100mgKOH/g、較佳爲5〜80mgKOH/g 201109396 者爲宜。 於本發明中，樹脂之「數量平均分子量」係由以凝膠 滲透色層分析法（東曹（譯音）（股）公司製、「HLC8120GPC」） 所測定的色層分析圖、以標準聚苯乙烯之分子量爲基準所 求得之値。管柱係使用 4條之「TSKgel G-4000HXL」、 「TSKgel G-3000HXL」、「TSKgel G-2500HXL」、「TSKgel G2000HXL」（皆爲東曹（股）公司製、商品名），移動相：四 氫呋喃、測定溫度：40°C，流速：lcc/分，檢測器：RI之 條件進行者。另外，於本說明書中，樹脂之玻璃轉移溫度 (Tg)係爲藉由示差熱分析（DSC)者。 上述無油性聚酯樹脂係爲多元酸成份與多元醇成份之 酯化物。多元酸成份主要使用1種以上選自例如酞酸酐、 異酞酸、對酞酸、四氫酞酸酐、六氫駄酸酐、琥珀酸、富 馬酸、己二酸、癸二酸、馬來酸酐等之二元酸及此等酸之 低級烷酯化物，視其所需可倂用苯甲酸、丁烯酸、對-第三 丁基苯甲酸等之一元酸、偏苯三酸酐、甲基環己烯三羧酸、 均苯四甲酸酐等之3價以上多元酸等。多元醇成份主要使 用例如乙二醇、二甘醇、丙二醇、1，4-丁二醇、新戊醇' 3-甲基戊二醇、1，4-己二醇、1,6-己二醇等之二元醇，視其 所需可倂用丙三醇、三羥甲基乙烷、三羥甲基丙烷、季戊 四醇等之3價以上多元醇。此等之多元醇可單獨使用’或 2種以上混合使用。兩成份之酯化或酯交換反應’可藉由 其本身已知的方法進行。酸成份以異酞酸' 對酞酸 '及此 等酸之低級烷酯化物更佳。 -10- 201109396 醇酸樹脂係除上述無油性聚酯樹脂之酸成分及醇成分 外’亦可爲使油脂肪酸以其本身已知的方法進行反應者， 油脂肪酸例如椰子油脂肪酸、大豆油脂肪酸、蓖麻油脂肪 酸、葵花油脂肪酸、妥爾油脂肪酸、脫水蓖麻油脂肪酸、 桐油脂肪酸等。醇酸樹脂之油長度爲3 0%以下，特別是約 5〜2 0 %較佳。 胺基甲酸酯改性聚酯樹脂，例如上述無油性聚酯樹 脂、或使製造上述無油性聚酯樹脂時所使用的酸成份及醇 成份進行反應所得的低分子量無油性聚酯樹脂，與聚異氰 酸酯化合物以其本身已知的方法進行反應者。另外，胺基 甲酸酯改性醇酸樹脂包含使上述醇酸樹脂、或製造上述醇 酸樹脂時所使用的各成份進行反應所得的低分子量醇酸樹 脂、與聚異氰酸酯化合物以其本身已知的方法進行反應 者。胺基甲酸酯改性聚酯樹脂及製造胺基甲酸酯改性醇酸 樹脂時所使用的聚異氰酸酯化合物，例如六亞甲基二異氰 酸酯、異佛爾酮二異氰酸酯、苯二甲基二異氰酸酯、甲苯 基二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、4,4’-亞甲基 雙（環己基異氰酸酯）、2,4,6-三異氰酸酯甲苯等。上述之胺 基甲酸酯改性樹脂，一般而言以使用形成胺基甲酸酯樹脂 之聚異氰酸酯化合物的量相對於胺基甲酸酯改性樹脂而 言，以30重量％以下之量所成的改性程度者爲宜。 環氧基改性聚酯樹脂係可例如使用由製造上述聚酯樹 脂時所使用的各成份製造的聚酯樹脂，該樹脂的羧基與含 環氧基的樹脂之反應生成物、或使聚酯樹脂中之羥基與環 -11- 201109396 氧樹脂中之羥基經由聚異氰酸酯化合物鍵結的生成物等、 藉由聚酯樹脂與環氧樹脂之加成、縮合、接枝等反應的反 應生成物。該環氧基改性聚酯樹脂之改性程度，一般而言 環氧樹脂之量對環氧基改性聚酯樹脂而言，以0.1〜30重 量％爲宜。 丙烯酸改性聚酯樹脂係可例如使用由製造上述聚酯樹 脂時所使用的各成份所製造的聚酯樹脂，該樹脂之羧基或 羥基上含有與此等之基具有反應性的基（例如羧基、羥基或 •環氧基）之丙烯酸樹脂的反應生成物，或使聚酯樹脂與（甲 基）丙烯酸或（甲基）丙烯酸酯等使用過氧化物系聚合起始劑 進行接枝聚合所形成的反應生成物。該丙烯酸改性聚酯樹 脂之改性程度，一般而言丙烯酸樹脂之量相對於丙烯酸改 性聚酯樹脂而言，以0 · 1〜5 0重量％之量爲宜。 上述之聚酯樹脂中，就加工性、耐腐蝕性等之平衡性 而言’以無油性聚酯樹脂、環氧基改性聚酯樹脂爲宜。 作爲上述含羥基之塗膜形成樹脂的較佳環氧樹脂，例 如雙酚型環氧樹脂、酚醛清漆型環氧樹脂；此等環氧樹脂 中之環氧基或羥基與各種改性劑反應之改性環氧樹脂。於 製造改性環氧樹脂時，藉由該改性劑之改性時期，沒有特 別的限制’可以在製造環氧樹脂之途中階段進行改性，亦 可以在製造環氧樹脂之最終階段進行改性。 上述雙酚型環氧樹脂’例如使環氧氯丙烷與雙酚、視 其所需在鹼觸媒等之觸媒存在下縮合至高分子量所形成的 樹脂’使環氧氯丙烷與雙酚、視其所需在鹼觸媒等之觸媒 ί- -12- 201109396 存在下進行縮合，形成低分子量之環氧樹脂，且使 子量環氧樹脂與雙酚進行聚加成反應所得的樹脂。 上述之雙酚，例如雙（4-羥基苯基）甲烷[雙酚F 雙（4-羥基苯基）乙烷' 2,2-雙（4_羥基苯基）丙烷[雙g 2,2-雙（4-羥基苯基）丁烷[雙酚B]、雙（4-羥基苯基） 丁烷、雙（4-羥基-第三丁基-苯基）-2,2-丙烷、p-(4-基）苯酚、氧代雙（4-羥基苯基）、磺醯基雙（4-羥基3 4，4’-二羥基二苯甲酮、雙（2-羥基萘基）甲烷等，其 用雙酚A、雙酚F較佳。上述雙酚類可使用1種或 上之混合物。 雙酚型環氧樹脂之市售品，例如日本環氧樹月旨 Epoxy Resin Co.，Ltd.)製之 jER® 828、同 812、同 8 8 2 0、同 8 3 4、同 1 0 (Π、同 1 〇 0 4、同 1 0 0 7、同 1 0 0 9、同 旭千葉公司製之亞拉魯賴頓 AER6099;及三井化學 之耶伯米谷（譯音）R-309等。 而且，作爲含羥基之塗膜形成樹脂的較佳環氧 上述酚醛清漆型環氧樹脂，例如苯酚酚醛清漆型 脂、甲酚酚醛清漆型環氧樹脂、在分子內具有多數 之苯酚環氧乙烷型環氧樹脂等、各種酚醛清漆型環壽 上述改性環氧樹脂，係使上述雙酚型環氧樹脂 酚醛清漆型環氧樹脂、與例如乾性油脂肪酸進行反 氧酯樹脂；與含有丙烯酸或甲基丙烯酸等之聚合性 單體成分進行反應的環氧基丙烯酸酯樹脂；與異氰 合物進行反應的胺基甲酸酯改性環氧樹脂；使上述 該低分 ]' 1,1-J A ]、 -1,1 -異 羥基苯 疼基）、 中以使 2種以 ί (Japan 1 5、同 10 10； (股）製 樹脂之 環氧樹 環氧基 民樹脂。 或上述 應的環 不飽和 酸酯化 雙酚型 -13- 201109396 環氧樹脂、酚醛清漆型環氧樹脂或上述各種改性環氧樹脂 中之環氧基與胺基化合物進行反應，導入胺基或4級錢鹽 所形成的胺基改性環氧樹脂等。 交聯劑（B) 交聯劑（B)係爲與上述含羥基之塗膜形成樹脂（A)進行 反應 '形成硬化塗膜者，只要是可藉由加熱等、與上述含 徑基之塗膜形成樹脂（A)進行反應予以硬化者即可，沒有特 別的限制’其中以胺基樹脂、苯酚樹脂及可被嵌段化的聚 異氰酸酯化合物爲宜。此等之交聯劑可使用1種或2種以 上組合使用。 上述胺基樹脂，例如藉由使蜜胺、尿素、苯并胍胺、 乙醯基胍胺、類固醇胍胺、螺胍胺、二氰二醯胺等之胺成 分與醛進行反應所得的羥甲基化胺基樹脂。上述反應中所 使用的醛，例如甲醛、對甲醛、乙醛、苯甲醛等。此外， 使上述羥甲基化胺基樹脂藉由適當的醇予以醚化者亦可使 用作爲胺基樹脂。醚化時所使用的醇，例如甲醇、乙醇、 正丙醇 '異丙醇、正丁醇、異丁醇、2-乙基丁醇、2-乙基 己醇等。 可作爲上述交聯劑使用的苯酚樹脂，係爲與上述含羥 基之塗膜形成性樹脂（A)進行交聯反應者，使苯酚成分與甲 醛類在反應觸媒存在下進行加熱、縮合反應以導入羥甲 基’所得的羥甲基化苯酚樹脂部分或全部羥基，用醇予以 烷基醚化所形成的可溶酚醛型苯酚樹脂。 於製造可溶酚醛型苯酚樹脂時，作爲出發原料之上述 -14- 201109396 苯酚成份可使用2官能性苯酚化合物、3官能性苯酚化合 物、4官能性以上之苯酚化合物等。 上述苯酚化合物，例如以〇 -甲酚、P -甲酚、P -第三丁 基苯酚、P -乙基苯酚、2,3-二甲苯酚、2,5-二甲苯酚等作爲 2官能性苯酚化合物，以石碳酸、甲酚、乙基苯酚3,5-二甲苯酚、m -甲氧基苯酚等作爲3官能性苯酚化合物，以 雙酚A、雙酚F等作爲4官能性苯酚化合物。其中，爲提 高耐擦傷性時，以使用3官能性以上之苯酚化合物、特別 是石碳酸及/或m-甲酚較佳。此等之苯酚化合物可以1種或 2種以上混合使用。 於製造苯酚樹脂時所使用的甲醛類，例如甲醛、對甲 醛或三噁烷等，可以1種或2種以上混合使用。 使羥甲基化苯酚樹脂之部分羥甲基予以烷醚化時所使 用的醇，以使用碳原子數1〜8個、較佳者1〜4個之1元 醇爲宜。較佳的1元醇例如甲醇、乙醇、正丙醇、正丁醇、 異丁醇等。 苯酚樹脂就與含羥基之塗膜形成性樹脂（A)的反應性 等而言’每1核苯核中平均具有0.5個以上烷氧基甲基， 較佳者爲0.6〜3.0個。 亦可使用作爲上述交聯劑之嵌段化的聚異氰酸酯化合 物中沒有被嵌段化的聚異氰酸酯化合物，例如六亞甲基二 異氰酸酯或三甲基六亞甲基二異氰酸酯之脂肪族二異氰酸 酯類；如氫化苯二甲基二異氰酸酯或異佛爾酮二異氰酸酯 之環狀脂肪族二異氰酸酯類；如甲苯基二異氰酸酯、苯二 -15- 201109396 甲基二異氰酸酯或4,4’-二苯基甲烷二異氰酸酯、原mdi 之芳香族二異氰酸酯類的有機二異氰酸酯本身、或此等之 各有機二異氰酸酯與多元醇、低分子量聚酯樹脂或水等之 加成物、或如上述之各有機二異氰酸酯間的環化聚合物、 以及異氰酸酯·縮脲物等。 嵌段化聚異氰酸酯化合物，係爲使上述聚異氰酸酯化 合物中游離的異氰酸酯基藉由嵌段化劑予以嵌段化者。上 述嵌段化劑例如苯酚、甲酚、二甲酚等之苯酚系；ε -己內 醯胺；δ -戊內醯胺、γ -丁內醯胺等之內醯胺系；甲醇、乙 醇、正-、異·或第三丁醇、乙二醇單乙醚、乙二醇單丁醚、 二甘醇單乙醚、丙二醇單甲醚、苯甲醇等之醇系；甲醯胺 肟、乙醯胺肟、乙醯肟、甲基乙酮肟、二乙醯基單肟、二 苯甲酮肟、環己烷肟等之肟系；丙二酸二甲酯、丙二酸二 乙酯、乙醯基醋酸乙酯 '乙醯基丙酮等活性亞甲基系等之 嵌段化劑爲宜。藉由混合上述聚異氰酸酯化合物與上述嵌 段化劑，可容易使上述聚異氰酸酯化合物中游離的異氰酸 酯基予以嵌段化。 上述含羥基之塗膜形成性樹脂（Α)與上述交聯劑（Β)的 摻混比例，以100質量份（Α)及（Β)成分之合計固體成分爲 基準，含羥基之塗膜形成性樹脂（Α)爲5〜9 5重量份、較佳 者爲60〜95質量份，交聯劑（Β)爲5〜45質量份、較佳者 爲5〜40質量份之範圍內，就耐腐蝕性、耐沸騰水性、加 工性、硬化性等而言爲宜。 爲提高本發明塗料組成物之硬化性時，視其所需可摻 -16 - 201109396 混硬化觸媒。交聯劑（B)爲胺基樹脂、特別是含有低分子量 之甲醚化或甲醚與丁醚之混合醚化蜜胺樹脂時，以使用磺 酸化合物或磺酸化合物之胺中和物作爲硬化觸媒爲宜。磺 酸化合物之典型例’如p-甲苯磺酸' 十二烷苯磺酸、二壬 基萘磺酸、一壬基萘二磺酸等。擴酸化合物之胺中和物中 的胺’可以爲1級胺、2級胺、3級胺。於此等之中，就塗 料之安定性、反應促進效果 '所得塗膜之物性等而言，以 P -甲苯磺酸之胺中和物及/或十二烷苯磺酸的胺中和物爲 宜。 交聯劑（B)爲苯酚樹脂時，以使用上述磺酸化合物或磺 酸化合物之胺中和物作爲硬化觸媒。 交聯劑（B)爲嵌段化聚異氰酸酯化合物時，以促進交聯 劑之嵌段化聚異氰酸酯化合物的嵌段化劑解離之硬化觸媒 爲宜’較佳的硬化觸媒例如辛酸錫、二丁基錫二（2_乙基己 酸錫）、二辛基二（2 -乙基己酸錫）、二辛基二乙酸錫、二丁 基二月桂酸錫、二丁基氧化錫、二辛基氧化錫、2_乙基己 酸鉛等之有機金屬觸媒等。 交聯劑（B)爲2種以上之交聯劑組合時，各交聯劑可組 合有效的硬化觸媒使用。 防銹顔料混合物（C) 本發明塗料組成物中，防銹顏料混合物（c)係由下述（1) 釩化合物及（2)離子交換二氧化矽所構成。 釩化合物（1) 釩化合物（1)係五氧化釩、釩酸鈣及甲基釩酸銨之中至 C· -17- 201109396 少一種的釩化合物。五氧化釩、釩酸鈣及甲基釩酸銨爲5 價釩離子’對水的溶解性優異，同時釩化合物（1)所釋出之 5價釩離子會與原料金屬進行反應，並與來自其他之防銹 顏料混合物之離子進行反應，藉此有效提升耐腐飩性。 離子交換二氧化矽（2) 離子交換二氧化矽（2 )係細微之多孔質二氧化矽載體 透過離子交換而導入有鈣離子等陽離子之二氧化矽微粒 子。離子交換二氧化矽可列舉鈣離子交換二氧化矽、鎂離 子交換二氧化矽、鈷離子交換二氧化矽等。 離子交換二氧化矽（2)可較佳使用平均粒徑位於0.5〜 15μηι’較佳爲1〜ΐ〇μιη之二氧化矽微粉末，吸油量位於30 〜300ml/l〇0g，較佳爲30〜150ml/100g之範圍内者。 離子交換二氧化矽（2)其中又以鈣離子交換二氧化矽 較佳。鈣離子交換二氧化矽之市售品可列舉SHIELDEX(註 冊商標）C3 03、同 AC-3、同 C-5(以上均爲 W.R.Grace&Co. 公司製）等。 離子交換二氧化矽所釋出之鈣離子等陽離子係與電化 學作用、各種鹽的生成作用相關，並可有效提升耐腐蝕性。 此外，固定於塗膜中之二氧化矽可有效抑制於腐蝕氛圍下 塗膜的剝離等。 含有磷酸（鹽）基之樹脂（D) 含有磷酸（鹽）基之樹脂（D)之中，含有磷酸基之樹脂係 含磷酸基〔-OPCKOHKOR1)〕（此處之R1爲氫原子、苯基或 碳數1〜20之烷基，特佳爲氫原子、2〜10之烷基）者，在 -18 - 201109396 樹脂的種類方面，只要相溶於含有羥基之塗膜形成性樹脂 (A)及交聯劑（B)者則無特別限定，例如可列舉含磷酸基之 丙烯酸樹脂、含磷酸基之環氧樹脂、含磷酸基之聚酯樹脂 等。 上述含磷酸基之丙烯酸樹脂，可藉由例如將含磷酸基 之不飽和單體與其他聚合性不飽和單體進行共聚合而獲 得。 上述含磷酸基之不飽和單體，可列舉（2 -丙烯醯氧基乙 基）酸性磷酸酯、（2-甲基丙烯醯氧基乙基）酸性磷酸酯、（2-丙烯醯氧基丙基）酸性磷酸酯、（2-甲基丙烯醯氧基丙基）酸 性磷酸酯、10 -丙烯醯氧基癸基酸性磷酸酯、10 -甲基丙烯 醯氧基癸基酸性磷酸酯等（甲基）丙烯醯氧基烷基（碳數2〜 2〇)酸性磷酸酯；於正磷酸或酸性磷酸酯（碳數丨〜20)中等 莫耳加成有甲基丙烯酸環氧丙酯等含有環氧基之不飽和單 體者；KayamerPM-2、同PM-21(以上爲日本化藥公司製， 商品名）等。此處之酸性磷酸酯之例，可列舉甲基酸性磷酸 酯、丁基酸性磷酸酯、2-乙基己基酸性磷酸酯 '異癸基酸 性磷酸酯、月桂基酸性磷酸酯、異十三基酸性磷酸酯、油 烯基酸性磷酸酯及苯基酸性磷酸酯等。 與含磷酸基之不飽和單體進行共聚合而構成上述含磷 酸基之丙烯酸樹脂之其他聚合性不飽和單體，例如可列舉 (甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸2 -羥丙酯、（甲基） 丙烯酸4-羥丁酯、2-羥乙基乙烯醚、2_羥丙基乙烯酸、2_ 羥乙基丙烯醚等含有羥基之不飽和單體；丙烯酸、甲基丙 -19- 201109396 烯酸；苯乙烯、α -甲基苯乙烯、乙烯基甲苯、α -苯乙烯氯 等乙烯基芳香族化合物；（甲基）丙烯酸甲酯、（甲基）丙烯酸 乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（甲基） 丙烯酸（正、異、第三）丁酯、（甲基）丙烯酸己酯、（甲基）丙 烯酸環己酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸正辛 酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸月桂酯、（甲基）丙烯 酸硬脂酸酯、（甲基）丙烯酸異莰酯等丙烯酸或甲基丙烯酸 之碳數1〜24之烷基酯或環烷基酯；乙酸乙烯、氯乙烯' 乙烯醚、丙烯腈、甲基丙烯腈等。本發明中之「（甲基）丙 烯酸酯」意指「丙烯酸酯或甲基丙烯酸酯」。 此外，含磷酸基之丙烯酸樹脂，可藉由於具有甲基丙 烯酸環氧丙酯等環氧基之不飽和單體與上述其他聚合性不 飽和單體所構成之共聚合樹脂中加成磷酸系化合物之方法 獲得。加成之磷酸系化合物宜爲正磷酸、酸性磷酸酯等， 酸性磷酸酯之例可列舉上述作爲酸性磷酸酯所例示者。 上述含磷酸基之環氧樹脂，可藉由於環氧樹脂加成磷 酸系化合物而獲得。加成磷酸系化合物之環氧樹脂，例如 可列舉雙酚型環氧樹脂、酚醛型環氧樹脂、於該等環氧樹 脂中之環氧基或羥基與各種改性劑進行反應而成之改性環 氧樹脂等。加成之磷酸系化合物的種類，可同樣使用於上 述含磷酸基之丙烯酸樹脂之説明中作爲具有環氧基之不飽 和單體與其他聚合性不飽和單體所構成之共聚合樹脂中加 成之磷酸系化合物所列舉者。 上述含磷酸基之聚酯樹脂，可藉由例如將聚酯樹脂之 -20- 201109396 羥基與磷酸系化合物進行反應而獲得。反應之磷酸系化合 物的種類，可同樣使用於含磷酸基之丙烯酸樹脂之説明中 作爲磷酸系化合物所列舉者。 含有磷酸（鹽）基之樹脂（D)之中’含磷酸鹽基之樹脂， 可藉由將上述含磷酸基之樹脂中之磷酸基與金屬化合物進 行反應作爲磷酸鹽的方式獲得。與上述磷酸基進行反應之 金屬化合物，例如可列舉氧化鈣、氧化鎂、氧化鈷、氧化 鎳、氧化鋅、氧化铈、氧化鑭等。 含有磷酸（鹽）基之樹脂（D)之磷酸基或磷酸鹽基可有 效提升酸性氛圍中之附著賦予性或耐腐蝕性。 本發明塗料組成物中，相對於上述樹脂（A)及該交聯劑 (B)之合計固體成分100質量份，防銹顏料混合物（C)之上 述釩化合物（1)及離子交換二氧化矽（2)，以及含有磷酸（鹽） 基之樹脂（D)之量係位於下述範圍内，且由耐腐飽性的觀點 而言，防銹顏料混合物（C)之量較佳爲6〜1〇〇質量份，更 佳爲1 0〜6 0質量份。 釩化合物（1): 3〜50質量份，較佳爲5〜40質量份， 離子交換二氧化矽（2): 3〜50質量份，較佳爲3〜3〇 質量份， 含有磷酸（鹽）基之樹脂（D) : 1〜3〇質量份，較佳爲1 〜20質量份。 本發明塗料組成物中’可藉由將作爲防銹顏料混合物 (c)之該等釩化合物（1)及離子交換二氧化矽（2)，以及含有 磷酸（鹽）基之樹脂（D)以既定量組合，而相乘地提升耐腐倉虫 -21 - 201109396 性。 此外，由釩化合物（1)及離子交換二氧化矽（2)對水分之 溶解性及防銹顏料之溶解液與金屬板之間的反應性的觀點 而言，較佳爲：相對於上述樹脂（A)及交聯劑（B)之合計固 體成分100質量份所配合之構成防銹顏料混合物（C)之釩化 合物（1)及離子交換二氧化矽（2)當中各顏料之各質量份量 的混合物，其添加於2 5 °C之5質量％濃度的氯化鈉水溶液 1 0 0 0 0質量份進行攪拌6小時，再於2 5 °C靜置4 8小時後過 濾上層澄清液後所得之濾液之pH爲3〜8，較佳爲5〜8， 位於該範圍在耐腐蝕性方面較佳。 亦即，進行上述p Η測定之濾液，係添加溶解有以下者 之溶解液之濾液：相對於2 5 °C之5質量％濃度的氯化鈉水 溶液1 0000質量份，釩化合物（1)位於3〜50質量份之範圍 内之任意之量’離子交換二氧化矽（2)位於3〜50質量份之 範圍内之任意之量。 本發明塗料組成物中，除了上述含有羥基之塗膜形成 性樹脂（A)、交聯劑（B)、防銹顏料混合物（C)、含有磷酸（鹽） 基之樹脂（D)及視需要所配合之硬化觸媒以外，可視需要配 合於塗料領域可使用之著色顏料 '體質顏料 '紫外線吸收 劑、紫外線安定劑、有機溶劑；沈降防止劑、消泡劑、塗 面調整劑等添加劑等。 上述著色顏料，例如可列舉青藍（cyanine blue)、花青 綠 '偶氮系或喹吖啶系等有機紅顏料等有機著色顏料；鈦 白、鈦黃、鐵丹、碳黑、各種燒成顏料等之無機著色顔料， -22- 201109396 其中可較佳使用鈦白。 上述體質顏料，例如可列舉滑石、黏土、雲母、氧化 鋁、碳酸鈣、硫酸鋇等。 上述紫外線吸收劑，例如可列舉2 - (2 -羥基-3，5 -二-第 三戊基苯基）-2H-苯并三唑、異辛基_3_(3-(2H-苯并三唑·2-基）-5-第三丁基-4-羥基苯基丙酸酯、2-[2-羥基·3,5-二（1，1-二甲基石油醚）苯基]-2Η-苯并三唑、2-[2-羥基-3-二甲基苯 甲基-5-(1,1,3,3-四甲基丁基）苯基]-2Η-苯并三唑、甲基 -3-[3-第三丁基- 5-(2Η-苯并三唑-2-基）-4-羥基苯基]丙酸酯 /聚乙二醇300之縮合物等苯并三唑系衍生物；2-[4-(2 -羥 基-3-十二烷氧基丙基）氧基]-2-羥基苯基-4,6-雙（2，4-二甲 基苯基）-1,3,5-三阱等三阱系衍生物；乙烷二醯胺4-(2-乙 氧基苯基）-Ν’-(2-乙基苯基）-(乙二醯胺）' 乙烷二醯胺 -Ν-(2-乙氧基苯基）-Ν’-(4-異十二烷基苯基）-(乙二醯胺）等 草酸苯胺系衍生物等。 上述紫外線安定劑，例如可列舉受阻胺系化合物、受 阻苯酚系化合物；CHIMASORB944、TINUVIN1 44、 TINUVIN292、TINUVIN770、IRGANOX1010、IRGANOX1098 (以上該等商品名之製品皆爲Ciba Specialty Chemicals公 司之製品）等。 藉由在塗料中配合紫外線吸收劑或紫外線安定劑，可 抑制該塗膜表面之光所引起的劣化，即使在使用該塗料作 爲底漆時，由於能夠抑制通過表層塗膜而到達底漆塗膜表 面之光所引起的底漆表面之劣化，故可防止因底漆塗膜表 -23- 201109396 面劣化所導致的底漆塗膜與表層塗膜之層間剝離，並可維 持優異的耐腐蝕性。 本發明塗料組成物中可配合之上述有機溶劑，爲了改 善本發明組成物之塗覆性等可視需要予以配合，可使用可 使含有羥基之塗膜形成性樹脂（A)及交聯劑（B)溶解且分散 者’具體而言'例如可列舉甲苯、二甲苯、高沸點石油系烴 等之烴系溶劑 '甲基乙酮、甲基異丁酮、環己酮、異佛爾 酮等之酮系溶劑、乙酸乙酯、乙酸丁酯、乙二醇單乙醚乙 酸酯、二甘醇單乙醚乙酸酯等之酯系溶劑、甲醇、乙醇、 異丙醇、丁醇等之醇系溶劑、乙二醇單乙醚、乙二醇單丁 醚、二甘醇單丁醚等之醚醇系溶劑等，該等可單獨使用或 混合使用2種以上。 本發明塗料組成物，在塗膜之耐腐蝕性、耐酸性及加 工性等方面而言，較佳爲：由本發明組成物所獲得之硬化 塗膜之玻璃轉移溫度爲40〜1 15°C，較佳爲50〜105°C。塗 膜之玻璃轉移溫度係使用DINAMIC VISCOELASTOMETER MODEL VIBRON(動態黏彈性測定器型式 VIBRON) DDV-IIEA型（Toyo Baldwin公司製、自動動態黏彈性測定 機），藉由頻率1 10Hz之溫度分散測定的tan5變化，求取 的最大値之溫度。 本發明塗料組成物塗覆於金屬板上而形成之塗膜顯示 出優異的耐腐蝕性。本發明認爲其理由如下：第一理由在 於，腐蝕環境下因氯化物離子等造成之原料金屬溶解所生 成之金屬離子與5價釩離子（VOT或V043·之釩酸離子）未經 -24- 201109396 由氧化還原反應而直接生成之沉澱性鹽，以及藉由5價釩 離子與原料金屬間的氧化還原反應所生成之3價釩離子及 原料金屬離子與腐蝕環境中因離子交換二氧化矽的水解所 釋出之陽離子或矽酸離子有效地生成沉澱性的鹽或化合 物’而使原料露出面受到有效的被覆。 此外’第二理由在於，離子交換二氧化矽不僅具有腐 蝕氛圍中釋出陽離子所造成之功效，藉由其表面弱酸性官 能基的效果，而能有效發揮將其鄰近之濕潤氛圍的pH調整 成弱酸性之作用，而促進了 5價釩離子與原料金屬間的氧 化還原反應，再者，離子交換二氧化矽被固定於塗膜，故 即使長期處於腐蝕氛圍下進行腐蝕仍能維持pH調整能 力，甚至在較強的腐蝕進行氛圍下會自我犠牲進行水解， 而持續釋出矽酸離子。 進而，第三理由在於，塗裝鋼板中之表層塗膜被認爲 因劣化而親水化，使表層塗膜的平面部起透過著各種的腐 蝕促進因子，而含有磷酸（鹽）基之樹脂（D)於酸性氛圍中扮 演著強力的附著賦予成分，故可抑制腐蝕進行部份鄰近之 陽極中之塗膜的剝離，以及有效中和陰極中氧之還原反應 所產生之羥基，而將其pH保持於中性附近。 此外，含有磷酸（鹽）基之樹脂（D)之磷酸基被認爲具有 將氛圍之pH保持於弱酸性之效果，而使釩酸離子或矽酸離 子於原料金屬面上可適當進行各種反應或生成鹽。一般認 爲藉由該等各種之機構之組合而達成了非常高度的耐腐蝕 性。 -25- 201109396 此外，藉由倂用構成防銹顔料混合物（c)之上述釩化合 物（1)、離子交換二氧化矽（2)及含有磷酸（鹽）基之樹脂 (D)，可有效抵消上述釩化合物（1)、離子交換二氧化矽（2) 及含有磷酸（鹽）基之樹脂（D )分別具有之耐酸性、耐鹼性及 耐水性的缺點。根據該等防绣顏料混合物（C)及含有憐酸 (鹽）基之樹脂（D)之作用可大幅發揮相乘效果，而達成優異 的耐腐蝕性。 亦即’由釩化合物（1)及離子交換二氧化矽（2)所構成之 防銹顏料混合物（C)成分具有有效將原料露出面加以被覆 之作用’除此之外，含有磷酸（鹽）基之樹脂（D)成分於酸性 氛圍中扮演著強力的附著賦予成分，故具有抑制腐蝕進行 部份鄰近之陽極中之塗膜剝離的作用，是以根據本發明可 提供一種塗料組成物及使用其之塗裝金屬板，該塗料組成 物不僅可有效提升塗裝金屬板之平面部的耐腐蝕性，亦可 有效提升加工部或端面部的耐腐蝕性，即使塗膜於屋外環 境因光解或水解而開始劣化。 塗裝金屬板 本發明之塗料組成物，可藉由在金屬板上進行塗覆、 硬化，製得塗裝金屬板。所塗裝的金屬板例如冷延鋼板、 溶融鍍鋅鋼板、電氣鍍鋅鋼板、鐵-鋅合金電鑛鋼板（電鍍 (galvanyl)鋼板）、鋁-鋅合金電鍍鋼板（合金中約含有55%鋁 之「鍍鋁鋅矽（galvalium)鋼板」、合金中約含有5%鋁之「稀 土合金鍍層（gal fan)」等）、鎳-鋅合金電鍍鋼板、不銹鋼鋼 板、鋁板、鋼板、鍍鋼鋼板、鍍錫鋼板等，此等之金屬板 -26- 201109396 表面亦可經過化成處理。化成處理例如可列舉磷酸鋅處理 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。 本發明組成物，可在上述金屬板上藉由輥塗覆法、簾 幕流動塗覆法、噴霧法、刷毛塗覆法、浸漬法等之習知方 法予以塗覆。由本發明組成物所得的塗膜之硬化膜厚並無 特別限制，通常爲位於2〜1 0 μιη，較佳爲位於3〜6 μιη之範 圍。塗膜之硬化處理，可視使用的樹脂種類予以適當設定， 使藉由線圏塗覆法等所塗覆者連續燒成時，通常在原料到 達最高溫度爲160〜250 °C、較佳爲180〜230 t之條件下進 行燒成1 5〜60秒。以分批式進行燒成時，亦可藉由在8〇 〜200 °C下進行燒成10〜30分鐘。另外，在使用沒有被嵌 段化的聚異氰酸酯作爲交聯劑（B)之情形時，或在如使用雙 酚型環氧樹脂作爲樹脂（A)、使用胺化合物作爲交聯劑（B ) 之情形’於塗膜形成過程中交聯反應不需特別與加熱組合 之情形下，可依照常法在常溫乾燥下予以硬化。 本發明之塗裝金屬板，係爲在可經化成處理的金屬板 上藉由上述本發明塗料組成物設置塗膜，提供給該藉由本 發明塗料組成物所形成的塗膜之塗裝金屬板使用，另外， 亦可在該塗膜上設置塗膜。表層塗膜之膜厚，通常爲8〜 3 〇 μηι > 較佳爲 10 〜25μιη。 形成上述表層塗膜之表層塗料，例如可列舉作爲預塗 覆鋼板用之習知聚酯樹脂系、醇酸樹脂系、砂改性聚醋樹 脂系、矽改性丙烯酸樹脂系、氟系樹脂系等之表層塗料。 -27- 201109396 特別重視加工性時，藉由使用高度加工用聚酯系表層塗 料，可製得加工性特別優異的塗裝鋼板。本發明之塗裝金 屬板’可具有耐腐蝕性優異的塗膜性能。 作爲被塗物之金屬板，當使用銨鋅鋼板、鋁-鋅合金電 镀鋼板時’可大幅提高平面部的耐腐蝕性，且目前爲止於 裁斷的端面部、成型加工後的加工部之耐腐蝕性仍不充 分，但藉由塗覆本發明塗料組成物，於端面部、加工部亦 可獲得優異的耐腐蝕性。 另外，亦可在被塗物雙面上設置本發明塗料組成物所 形成之塗膜，亦可視需要在本發明塗料組成物所形成之塗 膜上進一步形成上述表層塗膜。藉由將本發明塗料組成物 形成在雙面上，亦即在背面也形成，可獲得不含鉻系防銹 顏料、就環境衛生而言有利且耐腐蝕性優異的塗裝金屬板。 實施例 於下述中，藉由製造例、實施例更具體地說明本發明。 惟本發明不受下述實施例所限制。而且，於下述中「份」 及^ %」皆以質量爲基準。 製造例1 可溶酚醛型苯酚樹脂交聯劑溶液之製造 在反應容器中摻混100份雙酚A、178份3 7%之甲醛水 溶液及1份氫氧化鈉，且在60 °C下進行反應3小時後，在 減壓、50°C下進行脫水1小時。然後，加入1〇〇份正丁醇 與3份磷酸，在1 1 0〜1 2 0 °C下進行反應2小時。於反應完 成後，使所得的溶液過濾，使生成的磷酸鈉予以過濾分別’ 製得固體成分約 5 0 %之可溶酚醛型苯酚樹脂交聯劑溶液 -28- 201109396 B1。所得的樹脂，數量平均分子量880，每1當量苯核之 平均羥甲基數爲0.4個及平均烷氧基甲基數爲1.0個。 製造例2 背面用塗料之製造 在使 80 份 jER1009(Japan Epoxy Resins Co.，Ltd.製、 雙酚A型環氧樹脂、含羥基之樹脂）溶解於1 20份混合溶劑 1[環己酮/乙二醇單丁醚/ S〇lvessol50(Esso石油公司製、高 沸點芳香族烴系溶劑）= 3/1/1(質量比）]之200份環氧樹脂溶 液中，使 40份鈦白、40份氧化鋇及適量的混合溶劑 2[Solvessol50(Esso石油公司製、高沸點芳香族烴系溶劑）/ 環己酮=W1(質量比）]混合，進行顏料分散直至顆粒（顏料粗 粒子之粒徑）爲20微米以下爲止。其次，在該分散物中加 入 26.7 份（固體成分量爲 20 份）Desmodur BL-3175(Sumika Bayer Urethane公司製、以甲基乙酮蔣嵌段化的HDI異氰 酸酯型聚異氰酸酯化合物溶液、固體成分約 75%)、2份 ΤΑΚΕΝΑΤΕ ΤΚ-1 (武田藥品公司製、有機錫系嵌段劑解離 觸媒、固體成分約10%)予以均勻混合，然後，加入上述混 合溶劑2’調整成黏度約80秒（福特杯#4/2 5 °c )，製得背面 用塗料。 含有磷酸（鹽）基之樹脂之製造 製造例3 含磷酸基之丙烯酸樹脂1之製造 於反應容器準備好100份丁醇，一邊將反應容器内的 溫度維持在1 1 〇 °C ’同時花費3小時滴下預先混合單體原 料等之下述組成的混合物。 苯乙烯 50份 -29- 201109396 2-甲基丙烯酸乙基己酯 35份 甲基丙烯酸環氧丙酯 15份 2,2’-偶氮雙異丁腈 2.0份BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-chromium-based paint composition excellent in corrosion resistance and a coated metal sheet using the same, and more particularly to a coating which is not only effective for lifting Corrosion resistance of the flat portion of the metal plate, and the coating composition for effectively improving the corrosion resistance of the processed portion or the end portion (even if the coating film starts to deteriorate due to photolysis or hydrolysis in the outdoor environment) and using the same Painted metal plates. [Prior Art] Conventionally, a precoated steel sheet such as a precoated steel sheet coated by a coil coating treatment or the like is widely used. It is used as a house-related product such as building materials such as roofs, walls, sun visors, and garages of buildings, various home appliances, switchboards, frozen display boxes, steel furniture, and kitchen appliances. When such a house-related product is produced from the precoated metal sheet, the precoated steel sheet is usually cut and pressed and joined. However, most of these residential related products have a metal exposed portion of the cut surface or a cracked portion which is processed by press working. The exposed portion of the metal or the cracked portion is likely to be reduced in resistance to rot resistance when compared with other portions. Generally, in order to improve corrosion resistance, it is necessary to carry out chromium-based rust prevention in the undercoat film of the precoated steel sheet. pigment. However, the chromium-based rust-preventive pigment is produced by containing hexavalent chromium having excellent rust resistance, and the hexavalent chromium has problems in terms of human health and environmental protection. Until now, most of the non-chromium-based rust-preventive pigments have been commercially available, such as zinc phosphate, aluminum tripolyphosphate, zinc molybdate, etc., and a combination of non-chromium pigment primers has been proposed in 201109396. For example, Patent Document 1 discloses that a coating material of a phenol resin as a rust preventive pigment and phosphorus vanadate or a combination of calcium carbonate and calcium silicate and aluminum phosphate and rust pigment is blended. Further, Patent Document 2 discloses a coating material in which a combination of a rust preventive pigment and a sintered body of magnesium phosphite and manganese oxide _: a substance or a calcium phosphate and a vanadium oxide is mixed. However, when the coating film formed by the coating materials described in 1 and 2 is used as compared with the chrome-based material, the corrosion resistance is not good, and the processing portion and the corrosiveness are insufficient. Moreover, most of the corrosion resistance or acid resistance is not good. In addition, when a large amount of rust preventive pigment is used, it is often preferable that the effect of the replaceable material is not obtained when the precoated metal sheet is manufactured. Further, Patent Document 3 describes a coating composition comprising an organic resin containing a hydroxyl group or an epoxy group and a curing agent, and having an oil absorption of 30 to 200 ml/100 g and a pore volume of 3 1 . A coating of 2 ml/g of cerium oxide microparticles, and the glass transition temperature of the coating film of the coating is in the range of 40 to 125 °C. However, the coating film formed by the coating material described in Document 3 has phase corrosion resistance, but it is still inferior in chemical resistance when compared with a coating material using a chromium-based pigment, and in particular, the corrosion resistance of the end surface portion is not additionally Patent Document 4 describes a corrosion-resistant composition which is a coating composition containing a coating film-forming tree containing a hydroxyl group and a mixture of rust-preventive pigments, wherein the rust-preventing system is composed of a specific vanadium compound or cerium oxide. Micro-particles and phosphoric acid: Epoxy resin and combined calcium citrate vanadate anti-rust are mixed with vanadium-doped vanadium in polyester, resistant to surface resistance by patent-coated pigments, etc. Yan, the media component of the system is responsible for 0. 0 5~ Formed by hardening, by patent when large corrosion resistance and corrosion resistance are sufficient. Excellent coating grease, cross-linking pigment mixture is a metal salt (gold 201109396 is a salt of calcium, zinc, aluminum, magnesium salt, etc.), although it shows excellent corrosion resistance 'but for the surface layer caused by exposure to the outside The resistance of the corrosion reaction after the deterioration of the coating film, that is, the improvement of the corrosion resistance, is still sought to improve and improve the corrosion resistance. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-199078 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2000-129163 (Patent Document 4) JP-A-2008-222833 SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a non-chromium-based paint composition which can form a coating film having excellent corrosion resistance not only in a general portion such as a metal plate but also a coating film. The processed portion or the end surface portion can also form a coating film excellent in corrosion resistance (even if the coating film starts to deteriorate due to photolysis or hydrolysis in an outdoor environment); and a coated metal plate using the same. In order to solve the above-mentioned problems, the present inventors have made an effort to study the results of the present invention. It has been found that a resin containing a phosphate group and/or a compound are contained in a film-forming resin system containing a hydroxyl group. A coating composition of a phosphate-based resin, a specific vanadium compound, and an ion-exchanged cerium oxide, which is a quantitative anti-rust pigment, can form a coating film having excellent corrosion resistance not only in a flat portion in an outdoor environment, but also in coating The processed portion or the end surface portion on which a metal plate or the like is attached may also have a coating film excellent in corrosion resistance, and the present invention has been completed. That is, the present invention provides a coating composition excellent in corrosion resistance, wherein 201109396 contains: (A) a coating film-forming resin containing no hydroxyl group and having a hydroxyl group, (B) a crosslinking agent, and (C) an anti-rust pigment. The mixture and (D) a phosphate group-containing resin and/or a phosphate group-containing resin (hereinafter sometimes simply referred to as "phosphoric acid (salt) group-containing resin (D)") are characterized by: the rust preventive pigment mixture ( c) is composed of (1) a vanadium compound of at least one of vanadium pentoxide, calcium vanadate and ammonium methylvanadate, and (2) ion-exchanged ruthenium dioxide; relative to the resin (A) The total solid content of the crosslinking agent (B) is 1 part by mass, and the vanadium is combined. The amount of the substance (丨) is 3 to 50 parts by mass, and the total amount of the ion-exchanged cerium oxide (2) is 3 to 5 parts by mass 'and the total amount of the resin (D) containing the phosphate group is 1~ 30 parts by mass, and the amount of the rust preventive pigment mixture (C) is 6 to 100 parts by mass. Further, the present invention provides a coated metal sheet which is formed by forming a cured coating film on the metal sheet having a chemical conversion coating on the surface thereof. In addition, the present invention also provides a coated metal sheet having a plurality of coating films formed on a metal sheet having a chemical conversion treatment on the surface thereof, wherein a hard coating film is formed by the coating composition, and formed on the hard coating film. There are surface coatings. Further, the present invention provides a coated metal sheet obtained by forming a cured coating film on both sides of a metal sheet whose surface can be subjected to chemical treatment. In addition, the present invention also provides a coated metal sheet having a plurality of coating films formed on the both sides of a metal sheet on which a surface can be subjected to a chemical treatment to form a hardened coating film by the coating composition and on at least one side A surface coating film is formed on the hardened coating film. 201109396 EFFECT OF THE INVENTION The coating composition of the present invention is a coating composition which does not contain a chromium-based rust-preventive pigment and is environmentally-friendly, and the coating composition of the present invention can exhibit excellent corrosion resistance in forming a flat portion. Moreover, the coating film having an excellent effect of corrosion resistance of the processed portion or the end surface portion of the effect such as the coated metal sheet which is not easily achieved by the non-chromium-based rust-preventing paint has not been achieved. Further, the coating composition of the present invention has a phosphate (salt)-containing resin (D) and exhibits a strong adhesion-imparting component in an acid gas atmosphere. Its excellent adhesion imparting property is believed to affect the specific vanadium compound and ion-exchanged cerium oxide of the rust preventive pigment, and contributes to greatly improving the temporal and corrosion resistance of the outdoor environment. That is, the anti-rust pigment mixture (C) composed of the vanadium compound (1) and the ion-exchanged ceria (2) has an effect of effectively covering the exposed surface of the material, and contains phosphoric acid (salt). The base resin (D) component acts as a strong adhesion-imparting component in an acidic atmosphere, and thus has a function of suppressing corrosion and peeling off the coating film in a portion of the adjacent anode, and is capable of providing a coating composition and use according to the present invention. The coated metal plate can form a coating composition which can be degraded even if the coating film is photolyzed or hydrolyzed in the outdoor environment, but the coating film can not only effectively improve the corrosion resistance of the flat portion of the coated metal plate, but also Effectively improve the corrosion resistance of the processed part or the end face. A coated metal sheet having a cured coating film formed by the coating composition of the present invention, which has excellent corrosion resistance at a flat portion, a processed portion or an end portion, and has a conventional chromium by using strontium chromate or the like The coating of the anti-rust pigment of the acid salt forms a corrosion resistance equal to or higher than that of the coated metal sheet having the cured coating film. A coated metal sheet having a cured coating film formed thereon and having a surface coating film formed on the cured film of 201109396, which has excellent corrosion resistance at the processed portion or the end surface portion of the flat portion. When a mineral zinc plated steel or an aluminum alloy plated steel plate is used as the metal plate of the object to be coated, excellent coating corrosion resistance can be obtained in the flat portion, the end surface portion, and the processed portion by applying the coating composition of the present invention. [Embodiment] The coating composition of the present invention contains the following components: a coating film-forming resin (A) containing a hydroxyl group, a crosslinking agent (B), a rust-preventive pigment mixture (C), and a phosphate-containing group. Resin (D). Hydroxyl-containing coating film-forming resin (A) The coating film-forming resin containing a hydroxyl group in the coating composition of the present invention can be used, and a hydroxyl group-containing resin having a coating film forming ability which can be generally used in the field of coating can be used without particular limitation. Typically, for example, one or two or more kinds of mixed resins of a hydroxyl group-containing polyester resin, an epoxy resin, an acrylic resin, a fluorine resin, and a chlorinated vinyl resin are used. The film-forming resin may suitably use at least one organic resin selected from the group consisting of a hydroxyl group-containing polyester resin and an epoxy resin. The above hydroxyl group-containing polyester resin comprises an oil-free polyester resin, an oil-modified alkyd resin, and a modified product of the resins, which include, for example, a urethane-modified polyester resin, a urethane A modified alkyd resin, an epoxy-modified polyester resin, an acrylic modified polyester resin, or the like. The above hydroxyl group-containing polyester resin has a number average molecular weight of i, 5 〇〇 to 35,000', preferably 2,000 to 25,000, and a glass transition temperature (Tg point) of 10 to 1 〇〇 ° C, preferably 20 〜 It is preferred that the base price at 80 ° C '2 to 100 mg KOH / g, preferably 5 to 80 mg KOH / g 201109396. In the present invention, the "number average molecular weight" of the resin is determined by a gel permeation chromatography method ("HLC8120GPC", manufactured by Tosoh Corporation, "HLC8120GPC"), and the standard polystyrene is used. The molecular weight of ethylene is determined by the benchmark. For the column, four "TSKgel G-4000HXL", "TSKgel G-3000HXL", "TSKgel G-2500HXL", and "TSKgel G2000HXL" (both manufactured by Tosoh Corporation) are used. Tetrahydrofuran, measuring temperature: 40 ° C, flow rate: lcc / min, detector: RI conditions were carried out. Further, in the present specification, the glass transition temperature (Tg) of the resin is by means of differential thermal analysis (DSC). The above oil-free polyester resin is an esterified product of a polybasic acid component and a polyol component. The polybasic acid component is mainly used in one or more selected from, for example, phthalic anhydride, isophthalic acid, p-nonanoic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride. The dibasic acid and the lower alkyl ester of the acid, depending on the desired one, may be used as a monobasic acid such as benzoic acid, crotonic acid or p-tert-butylbenzoic acid, trimellitic anhydride, methylcyclohexene A trivalent or higher polybasic acid such as a carboxylic acid or a pyromellitic anhydride. The polyol component is mainly used, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl alcohol '3-methylpentanediol, 1,4-hexanediol, 1,6-hexane A diol such as an alcohol may be a trivalent or higher polyhydric alcohol such as glycerin, trimethylolethane, trimethylolpropane or pentaerythritol as needed. These polyols may be used singly or in combination of two or more. The esterification or transesterification of the two components can be carried out by a method known per se. The acid component is preferably isodecanoic acid 'p-citric acid' and lower alkyl esterified esters of such acids. -10- 201109396 Alkyd resin is not only the acid component and the alcohol component of the above oil-free polyester resin, but also the oil fatty acid such as coconut oil fatty acid or soybean oil fatty acid. Castor oil fatty acid, sunflower oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, tung oil fatty acid, and the like. The oil of the alkyd resin has a length of 30% or less, particularly preferably about 5 to 20%. a urethane-modified polyester resin, for example, the above-mentioned oil-free polyester resin or a low molecular weight oil-free polyester resin obtained by reacting an acid component and an alcohol component used in the production of the above oil-free polyester resin, and The polyisocyanate compound is reacted in a manner known per se. Further, the urethane-modified alkyd resin contains a low molecular weight alkyd resin obtained by reacting the above alkyd resin or each component used in the production of the above alkyd resin, and a polyisocyanate compound is known per se. The method of responding. a urethane-modified polyester resin and a polyisocyanate compound used in the manufacture of a urethane-modified alkyd resin, such as hexamethylene diisocyanate, isophorone diisocyanate, benzodimethyl di Isocyanate, tolyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 2,4,6-triisocyanate toluene, and the like. The above-mentioned urethane-modified resin is generally used in an amount of 30% by weight or less based on the amount of the polyisocyanate compound forming the urethane resin relative to the urethane-modified resin. The degree of modification is appropriate. The epoxy group-modified polyester resin can be, for example, a polyester resin produced from the respective components used in the production of the above polyester resin, a reaction product of a carboxyl group of the resin and an epoxy group-containing resin, or a polyester. A reaction product in which a hydroxyl group in a resin is a product obtained by a reaction of addition, condensation, grafting, or the like of a polyester resin and an epoxy resin, such as a product obtained by a polyisocyanate compound, such as a hydroxyl group in the epoxy resin. The degree of modification of the epoxy-modified polyester resin, generally, the amount of the epoxy resin to the epoxy-modified polyester resin, is 0. 1 to 30% by weight is preferred. The acrylic modified polyester resin can be, for example, a polyester resin produced by using each component used in the production of the above polyester resin, and the carboxyl group or the hydroxyl group of the resin contains a group reactive with such a group (for example, a carboxyl group). a reaction product of an acrylic resin of a hydroxyl group or an epoxy group, or a graft polymerization of a polyester resin with a (meth)acrylic acid or a (meth)acrylate or the like using a peroxide-based polymerization initiator. Reaction product. The degree of modification of the acrylic modified polyester resin is generally from 0 to 1 to 50% by weight based on the amount of the acrylic modified polyester resin. In the polyester resin described above, it is preferable to use an oil-free polyester resin or an epoxy-modified polyester resin in terms of balance between workability and corrosion resistance. A preferred epoxy resin for forming a resin containing the hydroxyl group-containing coating film, for example, a bisphenol type epoxy resin or a novolac type epoxy resin; and an epoxy group or a hydroxyl group in the epoxy resin reacts with various modifiers Modified epoxy resin. When the modified epoxy resin is produced, there is no particular limitation by the modification period of the modifier, which can be modified in the middle of the process of manufacturing the epoxy resin, or can be modified in the final stage of manufacturing the epoxy resin. Sex. The bisphenol type epoxy resin is condensed, for example, by epichlorohydrin and bisphenol, in the presence of a catalyst such as a base catalyst, to a resin having a high molecular weight, such that epichlorohydrin and bisphenol are used. It is required to carry out condensation in the presence of a catalyst such as a base catalyst, ί- -12-201109396, to form a low molecular weight epoxy resin, and to obtain a resin obtained by polyaddition reaction of a sub-quantity epoxy resin and bisphenol. The above bisphenols, such as bis(4-hydroxyphenyl)methane [bisphenol F bis(4-hydroxyphenyl)ethane ' 2,2-bis(4-hydroxyphenyl)propane [double g 2,2- Bis(4-hydroxyphenyl)butane [bisphenol B], bis(4-hydroxyphenyl)butane, bis(4-hydroxy-t-butyl-phenyl)-2,2-propane, p- (4-yl)phenol, oxobis(4-hydroxyphenyl), sulfonyl bis(4-hydroxy 3 4,4'-dihydroxybenzophenone, bis(2-hydroxynaphthyl)methane, etc. It is preferably bisphenol A or bisphenol F. One type or a mixture of the above bisphenols may be used. Commercially available bisphenol type epoxy resins, for example, Epoxy Resin Co., Japan Epoxy Resin Co. ,Ltd. )jER® 828, the same 812, the same 8 8 2 0, the same 8 3 4, the same 1 0 (Π, the same 1 〇 0 4, the same 1 0 0 7 , the same 1 0 0 9 , the same as Xu Chiye company Aaron Rurayton AER6099; and Mitsui Chemicals Jebami Valley (transliteration) R-309, etc. Moreover, as a hydroxyl-containing coating film forming resin, the preferred epoxy novolac type epoxy resin, such as phenol novolac A grease, a cresol novolac type epoxy resin, a phenol oxirane type epoxy resin having a plurality of molecules in the molecule, and various modified epoxies of the above-mentioned phenol varnish type ring-like epoxy resin a resin novolak type epoxy resin, a reverse oxy ester resin with, for example, a dry oil fatty acid; an epoxy acrylate resin which reacts with a polymerizable monomer component such as acrylic acid or methacrylic acid; and reacts with an isocyanide compound a urethane-modified epoxy resin; the above-mentioned low score]' 1,1-JA], -1,1-isohydroxybenzene oxime), to make 2 kinds of ί (Japan 1 5, The same as 10 10; (stock) resin epoxy resin epoxy resin or the above-mentioned ring unsaturated Esterified bisphenol type-13- 201109396 Epoxy resin, novolac type epoxy resin or epoxy group in the above various modified epoxy resins reacted with an amine compound to form an amine group or a 4-grade salt Amine-modified epoxy resin, etc. Cross-linking agent (B) The crosslinking agent (B) is reacted with the above-mentioned hydroxyl group-containing coating film-forming resin (A) to form a cured coating film, as long as it can be heated by heating The resin (A) having the above-described pore-containing coating film may be reacted and cured, and is not particularly limited. It is preferably an amine-based resin, a phenol resin or a polyisocyanate compound which can be blocked. The crosslinking agent may be used singly or in combination of two or more kinds. The above amine-based resin, for example, by using melamine, urea, benzoguanamine, acetyl decylamine, steroid decylamine, spiramide, a methylolated amine-based resin obtained by reacting an amine component such as cyanamide with an aldehyde, and an aldehyde used in the above reaction, for example, formaldehyde, p-formaldehyde, acetaldehyde, benzaldehyde, etc. Further, the above-mentioned methylol group is used. The amine-based resin is also etherified by a suitable alcohol. It can be used as an amine-based resin. The alcohol used in etherification, such as methanol, ethanol, n-propanol 'isopropanol, n-butanol, isobutanol, 2-ethylbutanol, 2-ethylhexanol, etc. The phenol resin which can be used as the crosslinking agent is a crosslinking reaction with the hydroxyl group-containing coating film-forming resin (A), and the phenol component and the formaldehyde are heated and condensed in the presence of a reaction catalyst. A resol type phenol resin formed by introducing a partial or total hydroxyl group of a methylolated phenol resin obtained by introducing a methylol group into an alkyl etherification reaction with an alcohol. When producing a novolac type phenol resin, it is used as a starting material. The above-mentioned -14 to 201109396 phenol component can be a bifunctional phenol compound, a trifunctional phenol compound, a tetrafunctional or higher phenol compound or the like. The above phenol compound is, for example, bismuth-cresol, P-cresol, P-tert-butylphenol, P-ethylphenol, 2,3-xylenol, 2,5-xylenol or the like as a bifunctional group. A phenolic compound, such as phenolic acid, cresol, ethyl phenol 3,5-xylenol, m-methoxyphenol or the like, is a trifunctional phenol compound, and bisphenol A, bisphenol F or the like is used as a tetrafunctional phenol compound. . Among them, in order to improve the scratch resistance, it is preferred to use a trifunctional or higher phenol compound, particularly, stone carbonate and/or m-cresol. These phenol compounds may be used singly or in combination of two or more kinds. The formaldehyde to be used in the production of the phenol resin, for example, formaldehyde, p-formaldehyde or trioxane, may be used singly or in combination of two or more kinds. The alcohol used for alkoxylation of a part of the methylol group of the methylolated phenol resin is preferably a monohydric alcohol having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Preferred monohydric alcohols are, for example, methanol, ethanol, n-propanol, n-butanol, isobutanol and the like. The phenol resin has an average of 0 per nuclear benzene nucleus in terms of reactivity with the hydroxyl group-containing coating film-forming resin (A). More than 5 alkoxymethyl groups, preferably 0. 6~3. 0. It is also possible to use a polyisocyanate compound which is not blocked in the block polyisocyanate compound as the above-mentioned crosslinking agent, for example, an aliphatic diisocyanate of hexamethylene diisocyanate or trimethylhexamethylene diisocyanate. a cyclic aliphatic diisocyanate such as hydrogenated dimethyl diisocyanate or isophorone diisocyanate; such as tolyl diisocyanate, benzene di-15-201109396 methyl diisocyanate or 4,4'-diphenyl An organic diisocyanate of methane diisocyanate, an original mdi aromatic diisocyanate, or an adduct of each of the organic diisocyanate and a polyhydric alcohol, a low molecular weight polyester resin or water, or the like A cyclized polymer between isocyanates, an isocyanate/urea, and the like. The blocked polyisocyanate compound is one in which the free isocyanate group in the above polyisocyanate compound is blocked by a blocking agent. The above-mentioned blocking agent is, for example, a phenol type such as phenol, cresol or xylenol; ε-caprolactam; a decylamine such as δ-valeroguanamine or γ-butylide; methanol, ethanol, An alcohol system of n-, iso- or tert-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, etc.; methotrexate, acetamide Anthraquinones such as hydrazine, ethyl hydrazine, methyl ethyl ketone oxime, diethyl hydrazine monoterpenes, benzophenone oxime, cyclohexane oxime, etc.; dimethyl malonate, diethyl malonate, acetamidine A blocking agent such as an active methylene group such as ethyl acetate ethyl acetonitrile or the like is preferred. By mixing the above polyisocyanate compound and the above-mentioned blocking agent, the free isocyanate group in the above polyisocyanate compound can be easily blocked. The mixing ratio of the hydroxyl group-containing coating film-forming resin (Α) and the crosslinking agent (Β) is based on 100 parts by mass of the total solid content of the components and the hydroxyl group-containing coating film is formed. The resin (Α) is 5 to 9 parts by weight, preferably 60 to 95 parts by mass, and the crosslinking agent is 5 to 45 parts by mass, preferably 5 to 40 parts by mass. Corresponding to corrosion resistance, boiling water resistance, workability, hardenability, and the like. In order to improve the hardenability of the coating composition of the present invention, it is possible to blend the -16 - 201109396 mixed hardening catalyst as needed. The crosslinking agent (B) is an amine-based resin, particularly a mixed etherified melamine resin containing a low molecular weight methyl etherification or methyl ether and dibutyl ether, and an amine neutralizing substance using a sulfonic acid compound or a sulfonic acid compound is used. Hardening catalyst is suitable. Typical examples of the sulfonic acid compound are, for example, p-toluenesulfonic acid 'dodecanebenzenesulfonic acid, dinonylnaphthalenesulfonic acid, monononylnaphthalene disulfonic acid and the like. The amine ' in the amine neutralizer of the acid-expanding compound may be a primary amine, a secondary amine, or a tertiary amine. Among these, the amine neutralizing substance of P-toluenesulfonic acid and/or the amine neutralizing substance of dodecylbenzenesulfonic acid are the properties of the coating film, the physical properties of the coating film obtained, etc. It is appropriate. When the crosslinking agent (B) is a phenol resin, an amine neutralizing product using the above sulfonic acid compound or sulfonic acid compound is used as a curing catalyst. When the crosslinking agent (B) is a blocked polyisocyanate compound, a hardening catalyst which promotes dissociation of a blocking agent of a blocked polyisocyanate compound of a crosslinking agent is preferably a preferred curing catalyst such as tin octylate. Dibutyltin bis(tin-ethyl 2-ethylhexanoate), dioctyl bis(2-ethylhexanoate), tin dioctyl diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctane An organic metal catalyst such as tin oxide or lead 2-ethylhexanoate. When the crosslinking agent (B) is a combination of two or more kinds of crosslinking agents, each crosslinking agent can be used in combination with an effective curing catalyst. Antirust pigment mixture (C) In the coating composition of the present invention, the antirust pigment mixture (c) is composed of the following (1) vanadium compound and (2) ion-exchanged hafnium oxide. Vanadium compound (1) Vanadium compound (1) is a vanadium compound such as vanadium pentoxide, calcium vanadate or ammonium methylvanadate to C· -17- 201109396. Vanadium pentoxide, calcium vanadate and ammonium methylvanadate are pentavalent vanadium ions' excellent solubility in water, and the vanadium ions released by the vanadium compound (1) react with the raw material metal and come from The ions of the other anti-rust pigment mixture are reacted, thereby effectively improving the corrosion resistance. Ion-exchanged cerium oxide (2) Ion-exchanged cerium oxide (2) is a fine porous cerium oxide carrier. The cerium oxide fine particles having a cation such as calcium ions are introduced by ion exchange. Examples of the ion-exchanged cerium oxide include calcium ion-exchanged cerium oxide, magnesium ion-exchanged cerium oxide, and cobalt ion-exchanged cerium oxide. The ion-exchanged cerium oxide (2) can preferably be used with an average particle diameter of 0. 5~15μηι' is preferably a cerium oxide micropowder of 1 to ΐ〇μιη, and the oil absorption is in the range of 30 to 300 ml/l 〇0 g, preferably 30 to 150 ml/100 g. It is preferred that the ion-exchanged cerium oxide (2) in turn exchanges cerium oxide with calcium ions. Commercially available products of calcium ion-exchanged cerium oxide include SHIELDEX (registered trademark) C3 03, AC-3, and C-5 (all of which are W. R. Grace&Co. Company system) and so on. The cations such as calcium ions released by the ion-exchanged cerium oxide are related to the electrochemical action and the formation of various salts, and can effectively improve the corrosion resistance. Further, the cerium oxide fixed in the coating film can effectively suppress peeling of the coating film under a corrosive atmosphere. Resin containing a phosphate (salt) group (D) Among the resins (D) containing a phosphoric acid (salt) group, the resin containing a phosphate group contains a phosphate group [-OPCKOHKOR1) (wherein R1 is a hydrogen atom or a phenyl group) Or an alkyl group having 1 to 20 carbon atoms, particularly preferably a hydrogen atom or an alkyl group of 2 to 10, in the case of the type of the resin of -18 - 201109396, as long as the phase is dissolved in the film-forming resin containing a hydroxyl group (A) The crosslinking agent (B) is not particularly limited, and examples thereof include an acrylic resin containing a phosphoric acid group, an epoxy resin containing a phosphoric acid group, and a polyester resin containing a phosphoric acid group. The above phosphoric acid group-containing acrylic resin can be obtained, for example, by copolymerizing a phosphoric acid group-containing unsaturated monomer with another polymerizable unsaturated monomer. Examples of the above-mentioned unsaturated group containing a phosphoric acid group include (2-propenyloxyethyl) acid phosphate, (2-methacryloxyethyl) acid phosphate, and (2-acryloxy) Acidic phosphate, (2-methacryloxypropyl) acid phosphate, 10-propenyloxy fluorenyl acid phosphate, 10-methyl propylene decyl hydroxy acid phosphate, etc. Acetyloxyalkyl group (carbon number 2 to 2 〇) acid phosphate; in the case of orthophosphoric acid or acid phosphate (carbon number 丨 ~ 20) medium molar addition of glycidyl methacrylate Oxygen-unsaturated monomer; Kayamer PM-2, same as PM-21 (above, manufactured by Nippon Kayaku Co., Ltd., trade name). Examples of the acidic phosphate ester herein include methyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate 'isodecyl acid phosphate, lauryl acid phosphate, and isotridecyl acid. Phosphate ester, oleyl acid phosphate, phenyl acid phosphate, and the like. Examples of the other polymerizable unsaturated monomer which is copolymerized with the phosphoric acid group-containing unsaturated monomer to form the phosphoric acid group-containing acrylic resin include, for example, 2-hydroxyethyl (meth)acrylate and (meth)acrylic acid 2. Hydroxypropyl ester, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl acid, 2-hydroxyethyl propylene ether and other hydroxyl-containing unsaturated monomers; acrylic acid, A基丙-19- 201109396 olefinic acid; vinyl aromatic compound such as styrene, α-methylstyrene, vinyl toluene, α-styrene chloride; methyl (meth) acrylate, ethyl (meth) acrylate , n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid (n-, iso-, third) butyl ester, (meth) hexyl acrylate, (meth) acrylate ring Ester, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearate (meth)acrylate, Acrylic acid or methacrylic acid having a carbon number of 1 to 24 such as isoamyl methacrylate Ester or cycloalkyl ester; vinyl acetate, vinyl chloride 'vinyl ether, acrylonitrile, methacrylonitrile and the like. The "(meth) acrylate" in the present invention means "acrylate or methacrylate". Further, the phosphoric acid group-containing acrylic resin may be a phosphate compound by a copolymerized resin comprising an epoxy group-containing unsaturated monomer such as glycidyl methacrylate and the above other polymerizable unsaturated monomer. The method is obtained. The phosphoric acid compound to be added is preferably orthophosphoric acid or acid phosphate, and examples of the acidic phosphate esters include those exemplified above as the acidic phosphate ester. The above-mentioned epoxy group-containing epoxy resin can be obtained by adding an epoxy resin to a phosphoric acid-based compound. Examples of the epoxy resin to which the phosphoric acid compound is added include a bisphenol epoxy resin and a novolac epoxy resin, and an epoxy group or a hydroxyl group in the epoxy resin is reacted with various modifiers. Epoxy resin, etc. The type of the phosphate compound to be added can be similarly used in the description of the above-mentioned phosphoric acid group-containing acrylic resin as a copolymerization resin composed of an epoxy group-containing unsaturated monomer and another polymerizable unsaturated monomer. The phosphate compounds are listed. The above-mentioned phosphoric acid group-containing polyester resin can be obtained, for example, by reacting a hydroxyl group of -20-201109396 with a phosphate compound. The type of the phosphate compound to be reacted can be similarly used in the description of the phosphoric acid group-containing acrylic resin as the phosphate compound. The phosphate group-containing resin in the phosphoric acid (salt) group-containing resin (D) can be obtained by reacting a phosphate group in the above phosphoric acid group-containing resin with a metal compound as a phosphate. Examples of the metal compound which reacts with the above phosphoric acid group include calcium oxide, magnesium oxide, cobalt oxide, nickel oxide, zinc oxide, cerium oxide, cerium oxide and the like. The phosphate group or the phosphate group of the phosphoric acid (salt)-based resin (D) can effectively enhance the adhesion imparting property or the corrosion resistance in an acidic atmosphere. In the coating composition of the present invention, the vanadium compound (1) and the ion-exchanged cerium oxide of the rust preventive pigment mixture (C) are compared with 100 parts by mass of the total solid content of the resin (A) and the crosslinking agent (B). (2), and the amount of the resin (D) containing a phosphoric acid (salt) group is within the following range, and the amount of the rust preventive pigment mixture (C) is preferably 6~ from the viewpoint of corrosion resistance. 1 part by mass, more preferably 1 0 to 60 parts by mass. Vanadium compound (1): 3 to 50 parts by mass, preferably 5 to 40 parts by mass, ion-exchanged cerium oxide (2): 3 to 50 parts by mass, preferably 3 to 3 parts by mass, containing phosphoric acid (salt) The base resin (D): 1 to 3 parts by mass, preferably 1 to 20 parts by mass. The coating composition of the present invention can be obtained by using the vanadium compound (1) as the rust preventive pigment mixture (c) and the ion-exchanged cerium oxide (2), and the resin (D) containing the phosphoric acid (salt) group. Both quantitative combination, and multiplying the anti-corrosion worms - 21, 201109396 sex. Further, from the viewpoints of the solubility of water and the reactivity between the dissolved solution of the vanadium compound (1) and the ion-exchanged cerium oxide (2) and the rust-preventing pigment and the metal plate, it is preferred to: relative to the above resin (A) and a total of 100 parts by mass of the solid content of the crosslinking agent (B), the mass fraction of each of the pigments of the vanadium compound (1) and the ion-exchanged cerium oxide (2) constituting the rust preventive pigment mixture (C) a mixture obtained by adding 5% by mass of a 5% by mass aqueous sodium chloride solution at 25 ° C for 6 hours, and then standing at 25 ° C for 48 hours, and then filtering the supernatant liquid. The pH of the filtrate is from 3 to 8, preferably from 5 to 8, and is preferably in the range of corrosion resistance. In other words, the filtrate subjected to the measurement of p Η is added with a filtrate in which a solution of the following is dissolved: 1,000,000 parts by mass of a sodium chloride aqueous solution having a concentration of 5 mass% at 25 ° C, and the vanadium compound (1) is located. Any amount in the range of 3 to 50 parts by mass 'ion exchanged cerium oxide (2) is in any amount within the range of 3 to 50 parts by mass. The coating composition of the present invention contains, in addition to the above-mentioned hydroxyl group-containing coating film-forming resin (A), crosslinking agent (B), rust-preventive pigment mixture (C), phosphoric acid (salt)-containing resin (D), and optionally In addition to the hardening catalyst to be blended, it is possible to use a coloring pigment 'physical pigment' ultraviolet absorber, an ultraviolet stabilizer, an organic solvent, a sedimentation preventive agent, an antifoaming agent, a coating surface adjusting agent, and the like, which can be used in the coating field. Examples of the coloring pigment include organic coloring pigments such as cyanine blue, cyanine-azo or quinacridyl organic red pigments; titanium white, titanium yellow, iron oxide, carbon black, and various calcined pigments. Inorganic coloring pigments, etc., -22- 201109396 Among them, titanium white can be preferably used. Examples of the above-mentioned extender pigments include talc, clay, mica, alumina, calcium carbonate, barium sulfate, and the like. Examples of the above ultraviolet absorber include 2-(2-hydroxy-3,5-di-third-pentylphenyl)-2H-benzotriazole, isooctyl_3_(3-(2H-benzotriazole). Azole-2-yl)-5-tert-butyl-4-hydroxyphenylpropionate, 2-[2-hydroxy-3,5-di(1,1-dimethyl petroleum ether)phenyl]- 2Η-benzotriazole, 2-[2-hydroxy-3-dimethylbenzyl-5-(1,1,3,3-tetramethylbutyl)phenyl]-2Η-benzotriazole And benzoic acid such as methyl-3-[3-tert-butyl-5-(2Η-benzotriazol-2-yl)-4-hydroxyphenyl]propionate/polyethylene glycol 300 condensate Triazole derivative; 2-[4-(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl-4,6-bis(2,4-dimethylbenzene a triple-trap derivative such as a -1,3,5-tritrap; ethanediamine 0.4-(2-ethoxyphenyl)-anthracene-(2-ethylphenyl)-(ethylene) Hydrazine phthalamide derivatives such as ethanediamine-indole-(2-ethoxyphenyl)-fluorene-(4-isododecylphenyl)-(ethylenediamine) Examples of the ultraviolet stabilizer include a hindered amine compound and a hindered phenol compound; CHIMASORB944, TINUVIN1 44, TINUVIN292, TINUVIN770, and IRGA. NOX1010, IRGANOX1098 (all of the above-mentioned products are products of Ciba Specialty Chemicals), etc. By incorporating an ultraviolet absorber or an ultraviolet stabilizer in the paint, deterioration caused by light on the surface of the film can be suppressed, even if When the paint is used as a primer, since deterioration of the surface of the primer caused by light reaching the surface of the primer coating film by the surface coating film can be suppressed, it is possible to prevent deterioration of the surface of the primer coating film -23-201109396 The resulting primer coating film and the surface coating film are peeled off between layers, and excellent corrosion resistance can be maintained. The above organic solvent which can be blended in the coating composition of the present invention can be visually improved in order to improve the coating property of the composition of the present invention. In the case where the coating film-forming resin (A) and the crosslinking agent (B) having a hydroxyl group are dissolved, and the dispersion is carried out, specifically, a hydrocarbon system such as toluene, xylene, or a high-boiling petroleum hydrocarbon can be used. Ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or isophorone, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol An ester solvent such as ether acetate, an alcohol solvent such as methanol, ethanol, isopropanol or butanol; an ether alcohol such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or diethylene glycol monobutyl ether; These may be used singly or in combination of two or more kinds. The coating composition of the present invention is preferably obtained from the composition of the present invention in terms of corrosion resistance, acid resistance and processability of the coating film. The glass transition temperature of the cured coating film is 40 to 15 ° C, preferably 50 to 105 ° C. The glass transition temperature of the coating film was measured using a DINAMIC VISCOELASTOMETER MODEL VIBRON (Dynamic Viscoelasticity Type VIBRON) DDV-IIEA type (manufactured by Toyo Baldwin Co., Ltd., automatic dynamic viscoelasticity measuring machine), tan5 measured by a temperature dispersion of 1 10 Hz. Change, the maximum temperature to be determined. The coating film formed by coating the coating composition of the present invention on a metal plate exhibits excellent corrosion resistance. The reason for the present invention is as follows: The first reason is that metal ions generated by dissolution of a raw material metal due to chloride ions or the like in a corrosive environment and pentavalent vanadium ions (VOT or V043·vanadate ions) are not-24. - 201109396 Precipitating salt directly formed by redox reaction, and trivalent vanadium ion and raw material metal ion generated by redox reaction between pentavalent vanadium ion and raw material metal and ion exchanged cerium oxide in corrosive environment The cation or citric acid ion released by the hydrolysis effectively forms a precipitated salt or compound', and the exposed surface of the raw material is effectively coated. In addition, the second reason is that the ion-exchanged cerium oxide not only has the effect of releasing cations in the corrosive atmosphere, but also effectively adjusts the pH of the adjacent wet atmosphere to the effect of the weakly acidic functional groups on the surface. The weak acidity promotes the redox reaction between the pentavalent vanadium ion and the raw material metal. Furthermore, the ion-exchanged ceria is fixed to the coating film, so the pH adjustment ability can be maintained even if it is corroded for a long time. Even in a strong corrosive atmosphere, it will self-fertilize and hydrolyze, and continuously release citrate ions. Further, the third reason is that the surface coating film in the coated steel sheet is considered to be hydrophilized by deterioration, and the surface of the surface coating film is permeable to various corrosion promoting factors and contains a phosphate (salt)-based resin ( D) plays a strong adhesion-imparting component in an acidic atmosphere, so that corrosion can be inhibited from peeling off the coating film in the adjacent anode, and the hydroxyl group generated by the reduction reaction of oxygen in the cathode can be effectively neutralized, and the pH thereof is adjusted. Stay near neutral. Further, the phosphoric acid group of the phosphoric acid (salt)-based resin (D) is considered to have an effect of keeping the pH of the atmosphere weakly acidic, and various reactions can be suitably carried out by using vanadate ions or ruthenic acid ions on the raw material metal surface. Or produce salt. It is generally believed that a very high degree of corrosion resistance is achieved by a combination of these various mechanisms. -25- 201109396 In addition, by using the above-mentioned vanadium compound (1) constituting the rust preventive pigment mixture (c), ion-exchanged cerium oxide (2), and a resin (D) containing a phosphoric acid (salt) group, it can effectively cancel The vanadium compound (1), the ion-exchanged cerium oxide (2), and the phosphoric acid (salt)-based resin (D) each have the disadvantages of acid resistance, alkali resistance, and water resistance. According to the action of the anti-embroidery pigment mixture (C) and the resin (D) containing the pity acid (salt), the synergistic effect can be greatly exerted, and excellent corrosion resistance can be achieved. That is, the anti-rust pigment mixture (C) composed of the vanadium compound (1) and the ion-exchanged ceria (2) has an effect of effectively covering the exposed surface of the raw material, and contains phosphoric acid (salt). The base resin (D) component acts as a strong adhesion-imparting component in an acidic atmosphere, and thus has a function of suppressing corrosion and peeling off the coating film in a portion of the adjacent anode, and is capable of providing a coating composition and use according to the present invention. The coated metal plate can not only effectively improve the corrosion resistance of the flat portion of the coated metal plate, but also effectively improve the corrosion resistance of the processed portion or the end portion, even if the coating film is in the outdoor environment due to photolysis Or hydrolyzed and began to deteriorate. Coated Metal Sheet The coating composition of the present invention can be coated and cured by coating on a metal plate to obtain a coated metal sheet. The coated metal plate is, for example, a cold-rolled steel plate, a molten galvanized steel plate, an electrogalvanized steel plate, an iron-zinc alloy electric ore plate (galvanyl steel plate), an aluminum-zinc alloy plated steel plate (the alloy contains about 55% aluminum). "Aluminum-plated galvalium steel plate", alloy containing approximately 5% aluminum "galvanium alloy" (galvanium), nickel-zinc alloy plated steel plate, stainless steel plate, aluminum plate, steel plate, plated steel plate, Tin plate steel, etc., these metal plates -26- 201109396 surface can also be chemically processed. Examples of the chemical conversion treatment include phosphate treatment such as zinc phosphate treatment or iron phosphate treatment, composite oxide treatment, chromium phosphate treatment, and chromate treatment. The composition of the present invention can be applied to the above-mentioned metal plate by a conventional method such as a roll coating method, a curtain flow coating method, a spray method, a brush coating method, or a dipping method. The thickness of the cured film of the coating film obtained from the composition of the present invention is not particularly limited, and is usually in the range of 2 to 10 μm, preferably 3 to 6 μm. The hardening treatment of the coating film is appropriately set depending on the kind of the resin to be used, and when the coating is carried out by a coating method such as a wire coating method, the raw material reaches a maximum temperature of 160 to 250 ° C, preferably 180. Sintering is carried out for 1 to 5 seconds under conditions of ~230 t. When the baking is carried out in a batch mode, it may be calcined at 8 Torr to 200 ° C for 10 to 30 minutes. Further, when a polyisocyanate which is not blocked is used as the crosslinking agent (B), or if a bisphenol type epoxy resin is used as the resin (A), an amine compound is used as the crosslinking agent (B) In the case where the crosslinking reaction does not need to be specifically combined with heating in the formation of the coating film, it can be hardened under normal temperature drying in accordance with a conventional method. The coated metal sheet of the present invention is a coated metal sheet provided on the metal sheet which can be chemically treated by the coating composition of the present invention described above, and provided to the coating film formed by the coating composition of the present invention. In addition, a coating film may be provided on the coating film. The film thickness of the surface coating film is usually 8 to 3 〇 μηι > preferably 10 to 25 μm. The surface coating material for forming the surface coating film may, for example, be a conventional polyester resin, an alkyd resin, a sand modified polyester resin, a fluorene modified acrylic resin, or a fluorine resin which is used for a precoated steel sheet. Surface coating. -27- 201109396 When the workability is taken into consideration, a coated steel sheet which is particularly excellent in workability can be obtained by using a polyester-based surface layer coating for high processing. The coated metal plate of the present invention can have a coating film property excellent in corrosion resistance. When a metal plate for a coated object is used, an aluminum-zinc steel plate or an aluminum-zinc alloy plated steel plate can greatly improve the corrosion resistance of the flat portion, and the end portion of the cut surface and the processed portion after the forming process are resistant to the present. Corrosion is still insufficient, but by coating the coating composition of the present invention, excellent corrosion resistance can be obtained also in the end surface portion and the processed portion. Further, a coating film formed by the coating composition of the present invention may be provided on both sides of the object to be coated, and the above surface layer coating film may be further formed on the coating film formed by the coating composition of the present invention as needed. By forming the coating composition of the present invention on both sides, that is, on the back surface, a coated metal sheet which does not contain a chromium-based rust-preventive pigment, is advantageous in terms of environmental hygiene, and is excellent in corrosion resistance can be obtained. EXAMPLES Hereinafter, the present invention will be specifically described by way of Production Examples and Examples. However, the invention is not limited by the following examples. Moreover, in the following, "parts" and "%" are based on mass. Production Example 1 Production of Resole Phenolic Phenol Resin Crosslinking Solution 100 parts of bisphenol A, 178 parts of 3 7% aqueous formaldehyde solution and 1 part of sodium hydroxide were blended in a reaction vessel, and the reaction was carried out at 60 ° C. After 3 hours, dehydration was carried out under reduced pressure at 50 ° C for 1 hour. Then, 1 part of n-butanol and 3 parts of phosphoric acid were added, and the reaction was carried out at 1 to 10 °C for 2 hours. After completion of the reaction, the resulting solution was filtered, and the resulting sodium phosphate was filtered to obtain a resol-type phenol resin cross-linking agent solution having a solid content of about 50% -28-201109396 B1. The obtained resin has a number average molecular weight of 880 and an average number of methylol groups per one equivalent of the benzene nucleus of 0. 4 and the average alkoxymethyl number is 1. 0. Production Example 2 Production of paint for back surface 80 parts of jER1009 (Japan Epoxy Resins Co.) ,Ltd. , bisphenol A type epoxy resin, hydroxyl group-containing resin) dissolved in 1 20 parts of mixed solvent 1 [cyclohexanone / ethylene glycol monobutyl ether / S〇lvessol50 (Esso Petroleum Co., Ltd., high boiling point aromatic hydrocarbon system) Solvent) = 3/1/1 (mass ratio) of 200 parts of epoxy resin solution, 40 parts of titanium dioxide, 40 parts of cerium oxide and an appropriate amount of mixed solvent 2 [Solvessol50 (Esso Petroleum Co., Ltd., high boiling point aromatics) The hydrocarbon solvent) / cyclohexanone = W1 (mass ratio) is mixed, and the pigment is dispersed until the particles (particle diameter of the pigment coarse particles) are 20 μm or less. Second, add 26. to the dispersion. 7 parts (solid content: 20 parts) Desmodur BL-3175 (manufactured by Sumika Bayer Urethane Co., Ltd., HDI isocyanate type polyisocyanate compound solution blocked with methyl ethyl ketone, about 75% solid content), 2 parts ΤΑΚΕΝΑΤΕ ΤΚ -1 (made by Takeda Pharmaceutical Co., Ltd., organotin blocker dissociation catalyst, solid content of about 10%), uniformly mixed, and then added to the above mixed solvent 2' to adjust the viscosity to about 80 seconds (Ford Cup #4/2 5 °c), made a coating for the back side. Production Example 3 of Resin Containing Phosphate (Salt) Group The acrylic resin 1 containing a phosphate group is prepared by preparing 100 parts of butanol in a reaction vessel while maintaining the temperature in the reaction vessel at 1 1 〇 ° C ' while taking 3 A mixture of the following components, such as a monomer raw material, is preliminarily mixed in an hour. Styrene 50 parts -29- 201109396 2-ethylhexyl methacrylate 35 parts Glycidyl methacrylate 15 parts 2,2'-azobisisobutyronitrile 2. 0 copies
之後，進一步添加0.5份2,2’ -偶氮雙異丁腈’在1 l〇°C 之下進行反應2小時。其次，將反應容器内溫度設爲80 °C， 慢慢地添加12.2份濃度85%之正磷酸與1 0.4份丁醇，進 行反應1小時直到反應容器内之混濁消失爲止，得到固體 成分50%之含磷酸基之丙烯酸樹脂1溶液。固體成分之含 磷酸基之丙烯酸樹脂1，其樹脂酸價爲54(磷酸基濃度爲 0.096當量/ 100g樹脂）。 製造例4 含磷酸基之丙烯酸樹脂2之製造 於反應容器準備好100份丁醇，一邊將反應容器内的 溫度維持在1 1 〇 °C，同時花費3小時滴下預先混合單體原 料等之下述組成的混合物。 苯乙烯 5 3部 2-甲基丙烯酸乙基己酯 40部 甲基丙烯酸環氧丙酯 7部 2,2’ ·偶氮雙異丁腈 2.0部 之後，進一步添加0.5份2,2’ -偶氮雙異丁腈，在！ 10。(： 之下進行反應2小時。其次’將反應容器内溫度設爲8〇°c， 慢慢地添加5.7份濃度85%之正磷酸與4.9份丁醇，進行 反應1小時直到反應容器内之混濁消失爲止，得到固體成 分50%之含磷酸基之丙烯酸樹脂2溶液。固體成分之含磷 酸基之丙烯酸樹脂2’其樹脂酸價爲26(磷酸基濃度爲〇.047 -30- 201109396 當量/ 1 0 0 g樹脂）。 製造例5 含磷酸基之丙烯酸樹脂3之製造 於反應容器準備好100份丁醇，一邊將反應容器内的 溫度維持在1 1 〇°C，同時花費3小時滴下預先混合單體原 料等之下述組成的混合物。 苯乙烯 40份 2-甲基丙烯酸乙基己酯 30份 甲基丙烯酸環氧丙酯 30份 2,2’ ·偶氮雙異丁腈 2.0份Thereafter, 0.5 part of 2,2'-azobisisobutyronitrile was further added and the reaction was carried out at 1 l ° C for 2 hours. Next, the temperature in the reaction vessel was set to 80 ° C, and 12.2 parts of 85% orthophosphoric acid and 10.4 parts of butanol were gradually added, and the reaction was carried out for 1 hour until the turbidity in the reaction vessel disappeared, thereby obtaining a solid content of 50%. A solution of a phosphate group-containing acrylic resin 1. The solid content phosphate-containing acrylic resin 1 has a resin acid value of 54 (phosphoric acid group concentration: 0.096 equivalent / 100 g of resin). Production Example 4 Production of Phosphate-Based Acrylic Resin 2 In the reaction vessel, 100 parts of butanol was prepared while maintaining the temperature in the reaction vessel at 1 1 〇 ° C, and it took 3 hours to drip the pre-mixed monomer raw material or the like. a mixture of the compositions. Styrene 5 3 2-ethylhexyl methacrylate 40 parts of glycidyl methacrylate 7 parts 2, 2' · azobisisobutyronitrile 2.0 parts, further added 0.5 parts 2,2'-even Nitrogen bisisobutyronitrile, in! 10. (: The reaction was carried out for 2 hours. Next, the temperature in the reaction vessel was set to 8 ° C, and 5.7 parts of orthophosphoric acid having a concentration of 85% and 4.9 parts of butanol were slowly added, and the reaction was carried out for 1 hour until the reaction vessel was When the turbidity disappeared, a solution of a phosphoric acid group-containing acrylic resin 2 having a solid content of 50% was obtained. The solid content of the phosphate group-containing acrylic resin 2' had a resin acid value of 26 (the phosphoric acid group concentration was 〇.047 -30 - 201109396 equivalent / 100 g of resin). Production Example 5 Production of Phosphate-Based Acrylic Resin 3 In the reaction vessel, 100 parts of butanol was prepared while maintaining the temperature in the reaction vessel at 1 1 〇 ° C, and it took 3 hours to drip in advance. A mixture of the following components, such as a monomer raw material, is mixed. 40 parts of styrene 2-ethylhexyl methacrylate 30 parts of glycidyl methacrylate 30 parts 2,2' · azobisisobutyronitrile 2.0 parts
之後，進一步添加0.5份2,2’ -偶氮雙異丁腈，在ll〇°C 之下進行反應2小時。其次，將反應容器内溫度設爲80°C， 慢慢地添加2 5份濃度8 5 %之正磷酸與1 7份丁醇，進行反 應1小時直到反應容器内之混濁消失爲止，得到固體成分 50%之含磷酸基之丙烯酸樹脂3溶液。固體成分之含磷酸 基之丙烯酸樹脂3，其樹脂酸價爲98 (磷酸基濃度爲0.17 當量/ 100g樹脂）。 製造例6 含磷酸基之環氧樹脂之製造 於反應容器準備100份環己酮與100份jER1007(Japan Epoxy Resins Co., Ltd.製、雙酚A型環氧樹脂、含羥基之 樹脂），攪拌並力卩溫至70°C使樹脂溶解。然後，添加5.76 份85%正磷酸，以70 °C進行反應2小時，接著添加4份環 己酮，製得50%之含磷酸基之環氧樹脂溶液。固體成分之Thereafter, 0.5 part of 2,2'-azobisisobutyronitrile was further added, and the reaction was carried out at ll ° C for 2 hours. Next, the temperature in the reaction vessel was set to 80 ° C, and 25 parts of orthophosphoric acid having a concentration of 85 % and 17 parts of butanol were slowly added, and the reaction was carried out for 1 hour until the turbidity in the reaction vessel disappeared to obtain a solid component. 50% solution of phosphoric acid-containing acrylic resin 3. The solid content phosphate-containing acrylic resin 3 has a resin acid value of 98 (phosphate group concentration of 0.17 equivalent / 100 g of resin). Production Example 6 Production of Phosphoric Acid Group-Containing Epoxy Resin 100 parts of cyclohexanone and 100 parts of jER1007 (made by Japan Epoxy Resins Co., Ltd., bisphenol A type epoxy resin, hydroxyl group-containing resin) were prepared in a reaction container. Stir and heat to 70 ° C to dissolve the resin. Then, 5.76 parts of 85% orthophosphoric acid was added, and the reaction was carried out at 70 ° C for 2 hours, followed by the addition of 4 parts of cyclohexanone to obtain a 50% phosphoric acid group-containing epoxy resin solution. Solid component
I 含磷酸基之環氧樹脂，其樹脂酸價爲2 8 (磷酸基濃度爲0.05 當量/ l〇〇g之樹脂）。 -31 - 201109396 製造例7 含磷酸鹽基之丙烯酸樹脂之製造 於堅固之玻璃容器內，混合100份（固體成分量爲50 份）於製造例3所得之固體成分50%之丙烯酸樹脂溶液1 與5份以乳鉢搗碎之氧化鈣，充塡玻璃珠，以 Skandex (Mitsuwa-Tech Ltd.公司製、商品名、攪拌機）進行分散直 到樹脂溶液變成透明爲止。其次於室溫下放置4 8小時。之 後，除去玻璃珠，得到作爲目的之含磷酸鹽基之丙烯酸樹 脂溶液。 離子交換二氧化矽之製造 製造例8 Mg離子交換二氧化矽之製造 於濃度5質量％之氯化鎂水溶液1 0000質量份中，將 10 質量份之 Sylysia，710(Fuji Silysia Chemical Ltd.製、 商品名、二氧化矽微粒子、吸油量約105ml/ lOOg)攪拌 混合5小時之後，過濾取出固體成分，將固體成分仔細洗 淨乾燥得到Mg離子交換二氧化矽。 製造例9 Co離子交換二氧化矽之製造 於濃度5質量％之氯化鈷水溶液1 0 000質量份中，將 10 質量份之 Sylysia710(Fuji Silysia Chemical Ltd.製、商 品名、二氧化矽微粒子、吸油量約l〇5ml/100g)攪拌混 合5小時之後，過濾取出固體成分，將固體成分仔細洗淨 乾燥得到Co離子交換二氧化矽。 防銹塗料組成物之製造 實施例1 在使 85 份 jER1009 (Japan Epoxy Resins Co·, Ltd.製、 -32- 201109396 雙酚A型環氧樹脂、含羥基之樹脂）溶解於1 3 5份混合溶劑 1[環己酮/乙二醇單丁醚/ Solvessol50(Esso石油公司製、高 沸點芳香族烴系溶劑）= 3/1/1 (質量比）]之2 2 5份環氧樹脂溶 液中，使5份五氧化釩、3份Shieldex AC-3(W.R.Grace & C〇.公司製、商品名、鈣離子交換二氧化矽）、20份鈦白、 2〇份氧化鋇及適量的混合溶劑2[Solvessol50(Esso石油公 司製、高沸點芳香族烴系溶劑）/環己酮==1/1(質量比）]混 合’進行顏料分散直至顆粒（顏料粗粒子之粒徑）爲2 0微米 以下爲止。其次，在該分散物中加入20份（固體成分量爲 15 份）Desmodur BL-3175(Sumika Bayer Urethane 公司製、 以甲基乙酮肟嵌段化的HD I異氰酸酯型聚異氰酸酯化合物 溶液、固體成分約75%)、4份（固體成分爲2份）於製造例3 所得之含磷酸基之丙烯酸樹脂1溶液、2份ΤΑΚΕΝΑΤΕ ΤΚ-1(武田藥品公司製、有機錫系嵌段劑解離觸媒、固體成 分約1 0 %)予以均勻混合’然後，加入上述混合溶劑2，調 整成黏度約80秒（福特杯#4/2 5°C )，製得防銹塗料組成物。 實施例2〜2 0、比較例1〜1 〇以及參考例1及2 除了將實施例1中所使用之含有羥基之樹脂、交聯 劑、防銹顏料、其他顔料更改爲如下述表1所示之外，與 實施例1進行相同實驗，得到各防銹塗料組成物。參考例 1及2’爲既有之含有鉻酸鹽系防銹顏料之防銹塗料組成 物。表1中含有羥基之樹脂、交聯劑、含有磷酸（鹽）基之 樹脂及顏料成分之量’皆以固體成分質量表示。惟於實施 例1 5中，沒有混合ΤΑΚΕΝΑΤΕ TK-1，又，於實施例丨6 ~ -33- 201109396 19中，取代2份之ΤΑΚΕΝΑΤΕ ΤΚ-1，分SU混合了 1份 NACURE 5225(美國 King Industries Inc.製、十二院基苯磺 酸之胺中和溶液）。 對樹脂成分（含有羥基之樹脂與交聯劑之合計固體成 分之質量爲100質量份）而言所摻混的各防銹顏料（C)之量 與鉻酸緦之量，添加於1 0000質量份' 25°C之5質量％濃 度的氯化鈉水溶液中，進行攪拌6小時，且使在25 °C下靜 置48小時之上層澄清液進行過濾的濾液之pH値（防銹顏料 溶解液之p Η)亦記載於表1 。例如，實施例1之防銹顏料 溶解液之pH値，係於1 0000質量部、25°C之5質量％濃度 的氯化鈉水溶液中，添加5質量份五氧化釩及3質量份 Shieldex AC-3，以上述條件使其溶解之上層澄清液進行過 濾的濾液之pH値。 -34- 201109396 § 〇 〇 ι«-Η 〇 〇 1〇 o 〇 〇 〇 寸 〇 〇 〇 〇 CO g o 〇. 〇 〇 <N iTi oo 〇 〇\ 00 〇 〇 〇 o in 00 〇 〇 in Os 00 ΐΤϊ 〇 〇 00 4^5 n 〇〇 ^T) 00 »rj 〇 〇 ο 卜 oo in 〇 〇 ο IT) U-ϊ 00 i〇 〇 〇 ο 们 00 们 〇 〇 ο uS 寸 oo in 〇 <Ν CO 00 〇 S ο CN oo W"» m (N 00 Ο) 寸· to 00 i〇 CN 00 σ\ — jER1009 Epokey 837(注 1) Vylon 296(注 2) Desmodur BL3175 rn 埋 〇" m m 2 u -§ • *—( S 5 製造例1製得之可溶酚醛型苯酚樹脂溶液 B-1 Cymel 303(注 4) 五氧化釩 釩酸鈣 ShieldexAC-3 Shieldex C-303(注 5) Mg離子交換二氧化矽(製造例8) Co離子交換二氧化矽(製造例9) 磷酸鈣 含磷酸基之丙烯酸樹J5旨1(製造例3) 含磷酸基之丙烯酸樹脂2(製造例4) 含磷酸基之丙烯酸樹脂3(製造例5) 含磷酸基之環氧樹脂(製造例6) 含磷酸鹽基之丙烯酸樹脂(製造例7) 鈦白 氧化鋇 sandvor 3058(注 7) 防銹顏料C成分與鉻酸緦的合計 防銹顏料c成分(含鉻酸緦)溶解液的pH 含羥基 之樹脂 (A成分） 硬化劑 (B成分） 防銹顏料 (c成分） 含有磷酸 (鹽)基 之樹脂 (D成分） 其他 顏料 cnI. A phosphate group-containing epoxy resin having a resin acid value of 28 (resin having a phosphate group concentration of 0.05 equivalent/l〇〇g). -31 - 201109396 Production Example 7 A phosphate-based acrylic resin was prepared in a sturdy glass container, and 100 parts (solid content: 50 parts) of the acrylic resin solution 1 obtained in the production example 3 was 50%. Five parts of granulated calcium oxide were filled with glass beads, and dispersed by Skandex (manufactured by Mitsuwa-Tech Ltd., trade name, stirrer) until the resin solution became transparent. Next, it was allowed to stand at room temperature for 48 hours. Thereafter, the glass beads were removed to obtain a target phosphate-containing acrylic resin solution. Production of the ion-exchanged cerium oxide Manufacture of Mg ion-exchanged cerium oxide In a mass ratio of 5% by mass of a magnesium chloride aqueous solution of 5% by mass, 10 parts by mass of Sylysia, 710 (manufactured by Fuji Silysia Chemical Ltd., trade name) After the mixture was stirred and mixed for 5 hours, the solid component was removed by filtration, and the solid component was carefully washed and dried to obtain Mg ion-exchanged cerium oxide. Production Example 9 Co ion-exchanged ruthenium dioxide is produced in 10 parts by mass of a cobalt chloride aqueous solution having a concentration of 5 mass%, and 10 parts by mass of Sylysia 710 (manufactured by Fuji Silysia Chemical Ltd., trade name, cerium oxide microparticles, The oil absorption amount was about 10 ml/100 g. After stirring and mixing for 5 hours, the solid component was taken out by filtration, and the solid component was carefully washed and dried to obtain Co ion-exchanged cerium oxide. Production Example 1 of the rust-preventing paint composition 85 parts of jER1009 (manufactured by Japan Epoxy Resins Co., Ltd., -32-201109396 bisphenol A type epoxy resin, hydroxyl group-containing resin) were dissolved in 135 parts of a mixture. Solvent 1 [cyclohexanone / ethylene glycol monobutyl ether / Solvessol 50 (manufactured by Esso Petroleum Co., Ltd., high-boiling aromatic hydrocarbon solvent) = 3/1/1 (mass ratio)] 2 2 5 parts of epoxy resin solution 5 parts of vanadium pentoxide, 3 parts of Shieldex AC-3 (WRGrace & C〇. company, trade name, calcium ion exchange of cerium oxide), 20 parts of titanium dioxide, 2 parts of cerium oxide and appropriate amount of mixing Solvent 2 [Solvessol 50 (manufactured by Esso Petroleum Co., Ltd., high-boiling aromatic hydrocarbon solvent) / cyclohexanone = 1 / 1 (mass ratio)] mixed 'pigmented pigment dispersion until the particles (particle diameter of the pigment coarse particles) is 2 0 Below the micron. Next, 20 parts (15 parts solid content) of Desmodur BL-3175 (Sumika Bayer Urethane Co., Ltd., HD I isocyanate type polyisocyanate compound solution blocked by methyl ethyl ketone oxime, solid content) was added to the dispersion. About 75%), 4 parts (2 parts of solid content) of the phosphoric acid group-containing acrylic resin 1 solution obtained in Production Example 3, and 2 parts of hydrazine-1 (made by Takeda Pharmaceutical Co., Ltd., organotin block dissociation catalyst) The solid content was about 10%) and uniformly mixed. Then, the above mixed solvent 2 was added to adjust the viscosity to about 80 seconds (Ford Cup #4/2 5 ° C) to prepare a rust preventive paint composition. Examples 2 to 20, Comparative Examples 1 to 1 and Reference Examples 1 and 2 except that the hydroxyl group-containing resin, the crosslinking agent, the rust preventive pigment, and other pigments used in Example 1 were changed to the following Table 1. In the same manner as in Example 1, except for the above, each rust-preventive coating composition was obtained. Reference Examples 1 and 2' are rust-preventive coating compositions containing a chromate-based rust-preventive pigment. The amount of the resin containing a hydroxyl group, the crosslinking agent, the resin containing a phosphate group, and the pigment component in Table 1 are represented by the mass of the solid component. However, in Example 15, there was no mixing of ΤΑΚΕΝΑΤΕTK-1, and in Example ~6 ~ -33-201109396 19, instead of 2 parts of ΤΑΚΕΝΑΤΕ ΤΚ-1, the sub-SU was mixed with 1 part of NACURE 5225 (US King) A neutralization solution of a 12-yard benzenesulfonic acid amine manufactured by Industries Inc.). The amount of each rust preventive pigment (C) and the amount of strontium chromate blended in the resin component (the mass of the solid component of the hydroxyl group-containing resin and the crosslinking agent is 100 parts by mass) is added to 100,000 mass. The pH of the filtrate (the rust preventive pigment solution) was stirred for 6 hours in a 5% by mass aqueous sodium chloride solution at 25 ° C and allowed to stand at 25 ° C for 48 hours. p) is also shown in Table 1. For example, the pH 値 of the rust preventive pigment solution of Example 1 is added to 5 parts by mass of a sodium chloride aqueous solution having a concentration of 5 mass% at 25 ° C, and 5 parts by mass of vanadium pentoxide and 3 parts by mass of Shieldex AC are added. -3, the pH of the filtrate in which the supernatant liquid was filtered by the above conditions was dissolved under the above conditions. -34- 201109396 § 〇〇ι«-Η 〇〇1〇o 〇〇〇 inch〇〇〇〇CO go 〇. 〇〇<N iTi oo 〇〇\ 00 〇〇〇o in 00 〇〇in Os 00 ΐΤϊ 〇〇00 4^5 n 〇〇^T) 00 »rj 〇〇ο oo in 〇〇ο IT) U-ϊ 00 i〇〇〇ο 00 〇〇ο uS inch oo in 〇<Ν CO 00 〇S ο CN oo W"» m (N 00 Ο) inch · to 00 i〇CN 00 σ\ — jER1009 Epokey 837 (Note 1) Vylon 296 (Note 2) Desmodur BL3175 rn Buried " mm 2 u -§ • *—( S 5 Resole type phenol resin solution B-1 Cymel 303 prepared in Production Example 1 (Note 4) Vanadium pentoxide vanadate Shieldex AC-3 Shieldex C-303 (Note 5) Mg ion exchange Cerium oxide (manufacturing example 8) Co ion二 二 矽 矽 制造 制造 制造 制造 矽 矽 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Phosphoric acid-based epoxy resin (Production Example 6) Phosphate-based acrylic resin (Production Example 7) Titanium white cerium oxide sandvor 3058 (Note 7) Anti-rust pigment C component of anti-rust pigment C component and strontium chromate ( pH of bismuth chromate-containing solution Hydroxyl-containing resin (component A) Hardener (component B) Anti-rust pigment (c component) Resin containing phosphate (salt) (D component) Other pigments
S 201109396 參考例 <N u-i 00 卜 卜·’ 00 泛 卜 比較例 Ο Ό 00 *T) Τ—Η 〇〇 〇\ *Τ) 00 Ό 〇 〇 CN οο οο 〇 宕 m rsi 卜 00 U-j 〇 〇 〇\ νο 00 V) 〇 〇 宕 g VO »〇 00 〇 〇 寸 οο 〇 Ο o ΓΛ «η 00 Ό Ο o fN ΙΛ> 00 g § 〇 宕 (N … 00 trj 1—Η 〇 (Ν \D 寸 g 〇 Ο On g 〇 ΓΛ Ο 〇 IH 00 g 〇 ο o wS 卜 Ο r—Η 〇 ο o *rl jER1009 Epokey 837(注 1) Vylon 296(注 2) Desmodur BL3175 Sumidur N3300(注 3) 1雛之可溶酹_賴樹麟液B-l Cymel 303(注 4) 五氧化釩 釩酸鈣 Shieldex AC-3 Shieldex C-303(注 5) Mg離子交換二氧化矽(製造例8) Co離子交換二氧化矽(製造例9) 磷酸鈣 含磷酸基之丙烯酸樹脂1(製造例3) 含磷酸基之丙烯酸樹脂2(製造例4) 含磷酸基之丙烯酸樹脂3(製造例5) 含磷酸基之環氧樹脂(製造例6) Ϊ 棚 m sg m 氍 Ν m 翻 氍 箨 4¾ Aerosil 200(注 6) 鉻酸緦 m 氧化鋇 sandvor 3058(注 7) 防銹顏料c成分與鉻酸緦的合計 防銹顏料C成分(含鉻酸緦)溶解液的pH 含羥基 之樹脂 (A成分） 硬化劑 (B成分） _1 1 1 防銹顏料 (C成分） 含有磷酸 (鹽)基 之樹脂 (D成分） κ i cnS 201109396 Reference example <N ui 00 Bu Bu · ' 00 泛 卜 比较 00 00 *T) Τ Η 〇〇〇 Τ Τ Τ Τ Τ 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 〇\ νο 00 V) 〇〇宕g VO »〇00 〇〇 inch οο 〇Ο o ΓΛ «η 00 Ό Ο o fN ΙΛ> 00 g § 〇宕(N ... 00 trj 1—Η 〇(Ν \D inch g 〇Ο On g 〇ΓΛ Ο 〇IH 00 g 〇ο o wS Ο rΟΗ 〇ο o *rl jER1009 Epokey 837 (Note 1) Vylon 296 (Note 2) Desmodur BL3175 Sumidur N3300 (Note 3) 1 Soluble 酹_赖树麟液 Bl Cymel 303 (Note 4) Vanadium pentoxide vanadate Shieldex AC-3 Shieldex C-303 (Note 5) Mg ion exchange cerium oxide (Production Example 8) Co Sub-exchanged cerium oxide (Production Example 9) Calcium phosphate-containing acrylic acid resin 1 (Production Example 3) Phosphoric acid group-containing acrylic resin 2 (Production Example 4) Phosphoric acid group-containing acrylic resin 3 (Production Example 5) Phosphoric acid Base epoxy resin (manufacturing example 6) Ϊ shed m sg m 氍Ν m 氍箨 43⁄4 Aerosil 200 (Note 6) strontium chromate m 钡 钡 sandvor 3058 (Note 7) anti-rust pigment c component with strontium chromate Total anti-rust pigment C component (containing strontium chromate) solution pH Hydroxyl-containing resin (component A) Hardener (component B) _1 1 1 Anti-rust pigment (component C) Resin containing phosphate (salt) Ingredients) κ i cn
201109396 於上述表1中，表中之（注）各具有下述意義。 (注l)Ep〇key 837 :三井化學（股）公司製，商品名，胺基甲酸酯 改性環氧樹脂，含羥基之樹脂，一級羥基價約35、酸價約0。 (注2)Vylon 296 :東洋紡績（股）公司製，商品名，環氧改性聚 酯樹脂，含有羥基之樹脂、羥基價7、酸價6。 (注 3)Sumidur N3300+: Sumika Bayer Urethane(股）公司製，異 氰酸酯型聚異氰酸酯化合物，固體成分100%。 (注 4)Cym el 303: Nihon Cytec Indus tries(股）公司製，商品名， 甲基醚化三聚氰胺樹脂。 (注 5)Shieldex C303 : W.R.Grace & CO.公司製，商品名，銘 離子交換二氧化矽。 (注6)Aerosil 200 : Nippon Aerosil公司製，商品名，二氧化砂 微粒子，吸油量約280ml/100g。 (注7)Sandvor 3 05 8 : Clariant公司製，商品名，受阻胺系紫外 線安定劑。 試驗用塗裝板之作成 使用上述實施例1〜20、比較例1〜10及參考例1及2 所得的各防銹塗料組成物及表層塗料，以下.述之塗覆處理 塗覆各原料，且進行燒成，製得各試驗用塗裝板。 塗裝處理1 : 在實施有化成處理的鑛鋁鋅矽鋼板（板厚〇.35mm、鋁-鋅合金電鍍鋼板、合金中含有約55 %鋁、合金電鍍單位面 積重量爲150g/m2、表2中以「GL鋼板」表示）上，使上述 製造例2所得的背面用塗料以乾燥膜厚8μιη下以棒塗覆器 -37- 201109396 予以塗覆，且使原料到達最高溫度爲1 8 0 °C下進行燒成3 〇 秒，形成背面塗膜。在與該形成有背面塗膜之塗裝板的背 面塗膜之相反側鋼板面上，使上述各例所得的各防銹塗料 組成物以乾燥膜厚爲5μιη下、以棒塗覆器予以塗覆，且使 原料到達最高溫度爲2 2 0 °C下進行燒成4 0秒，各形成主要 塗膜。於冷卻後，在此等之主要塗膜上使 KP顏色 1 5 8 0B40(KansaiPaintCo.，Ltd.製、商品名、聚酯系表層塗 料、藍色、硬化塗膜之玻璃轉移溫度約70°C )以棒塗覆器、 乾燥膜厚約爲1 5 μ m下予以塗覆，使原料到達最高溫度爲 220 °C下進行燒成40秒，製得各試驗用塗裝板。 塗裝處理2: 在實施有化成處理的熔融鍍鋅鋼板（板厚0.35mm、鋅 電鍍單位面積重量爲250g/m2、表2中以「GI鋼板」表示） 上，使上述製造例2所得的背面用塗料以乾燥膜厚8 μηι下 以棒塗覆器予以塗覆，且使原料到達最高溫度爲1 8 0 °C下 進行燒成3 0秒’形成背面塗膜。在與該形成有背面塗膜之 塗裝板的背面塗膜之相反側鋼板面上，使上述各例所得的 各防銹塗料組成物以乾燥膜厚爲5μιη下、以棒塗覆器予以 塗覆，且使原料到達最高溫度爲22(TC下進行燒成40秒， 製得各底漆塗裝板。於冷卻後，在此等之底漆塗裝板上使 KP 顏色 1 5 8 0B40(Kansai Paint Co.，Ltd.製' 商品名、聚酯 系表層塗料、藍色 '硬化塗膜之玻璃轉移溫度約701)，以 棒塗覆器、乾燥膜厚約爲1 5 μιη下予以塗覆，使原料到達 最高溫度爲22〇°C下進行燒成40秒，製得各試驗用塗裝板。 -38- 201109396 塗裝處理3 : 在與用於塗裝處理1相同之鍍鋁鋅矽鋼板上，使實施 例3所得的防銹塗料組成物以乾燥膜厚8 μηι下以棒塗覆器 予以塗覆’且使原料到達最高溫度爲1801下進行燒成30 秒’形成背面塗膜。在與該形成有背面塗膜之塗裝板的背 面塗膜之相反側鋼板面上，使上述各例所得的各防銹塗料 組成物以乾燥膜厚爲5 μιη下、以棒塗覆器予以塗覆，且使 原料到達最高溫度爲22(TC下進行燒成40秒，製得各底漆 塗膜。於冷卻後，在此等之底漆塗膜上使KP顏色1580B40 (Kansai ?&!^<：〇.，1^(1.製、商品名、聚酯系表層塗料、藍色、 硬化塗膜之玻璃轉移溫度約7 0 °C )，以棒塗覆器、乾燥膜厚 約爲15 μιη下予以塗覆，使原料到達最高溫度爲220。(：下進 行燒成40秒，製得各試驗用塗裝板。 塗膜性能試驗 有關上述實施例1〜2 0及比較例1〜1 〇以及參考例1 及2所得的各試驗用塗裝板，以下述試驗方法進行塗膜性 能試驗。試驗結果如下述表2所示。 試驗方法 耐沸騰水性：使裁成5 cm X 1 0 cm大小之各試驗用塗裝 板浸漬於約1 〇 〇 °C之沸騰水中5小時後，取出且評估表面 側之塗膜外觀，並進行評估棋盤格膠帶附著試驗。棋盤格 膠帶附著試驗係以JIS K-5400 8.5.2( 1 990)棋盤格膠帶法爲 基準，使切傷的間隙間隔爲1 m m，製作1 0 0個棋盤格，在 其表面上使黏著膠帶密接，觀察激烈剝離後殘存於塗面之 -39- 201109396 棋盤格數。 ◎:在塗膜上沒有產生碎片、白化等之異常情形，殘 存棋盤格數爲100個 〇：在塗膜上沒有產生碎片、白化等之異常情形，殘 存棋盤格數爲91〜99個 △:在塗膜上有稍微產生碎片、白化等之異常情形， 殘存棋盤格數爲91個以上，或在塗膜上沒有產生碎片、白 化等之異常情形，惟殘存棋盤格數爲7 1〜90個 X:在塗膜上產生相當顯著的碎片情形，或殘存棋盤格 數爲7 0個以下。 耐鹼性：使裁成5cmxl0cm大小之各試驗用塗裝板背 面及切割面以防銹塗料予以密封，於塗裝板的表面側中央 部分切割出到達質地之十字形。使該塗裝板在4(TC之5% 氫氧化鈉水溶液浸漬4 8小時後，取出且洗淨，評估在室溫 下乾燥的塗裝板表面側之塗膜外觀，且在十字切割部分以 黏著膠帶予以密接，評估激烈剝離後塗膜自切割部之剝離 寬度（單面）。 ◎:沒有產生碎片情形，自切割部之膠帶剝離寬度爲 1 . 5mm以下 〇：沒有產生碎片情形，自切割部之膠帶剝離寬度大 於1.5mm、3mm以下 △:有稍微產生碎片情形，自切割部之膠帶剝離寬度 爲3mm以下，或沒有產生碎片情形，惟自切割部之膠帶剝 離寬度大於3mm -40- 201109396 χ :有碎片情形產生，且自切割部之膠 3 m m 〇 耐酸性：使裁成5 c m χ 1 0 c m大小之各 面及切割面以防銹塗料予以密封，於塗裝 部分切割出到達質地之十字形。使該塗裝 氫氧化鈉水溶液浸漬4 8小時後，取出且沒 下乾燥的塗裝板表面側之塗膜外觀，且在 黏著膠帶予以密接，評.估激烈剝離後塗膜 寬度（單面）。 ◎:沒有產生碎片情形，自切割部之 1 . 5 m m以下 〇：沒有產生碎片情形，自切割部之 於1.5mm、3mm以下 △:有稍微產生碎片情形，自切割部 爲3mm以下，或沒有產生碎片情形，惟自 離寬度大於3mm X:有碎片情形產生，且自切割部之膠 3 m m 〇 耐擦傷性：在20°C之室溫下，使用線 化技硏工業公司製），在各試驗用塗裝板之 使10圓銅幣之邊緣保持45度之角度，施 以押附，且使10圓銅幣以l〇mm/秒之速ί 使塗面擦傷時之擦傷程度以下述基準進行 ◎:在擦傷部分沒有金屬原料存在 帶剝離寬度大於 試驗用塗裝板背 板的表面側中央 板在40°C之 5% i淨，評估在室溫 十字切割部分以 自切割部之剝離 膠帶剝離寬度爲 膠帶剝離寬度大 之膠帶剝離寬度 切割部之膠帶剝 帶剝離寬度大於 圈擦傷試驗（自動 .表面側的塗面上 加3 k g之荷重予 蒙拉伸約3 0 m m， 評估。 -41 - 201109396 〇 :在擦傷部分梢有金屬原料存在 △:在擦傷部分有顯著的金屬原料存在 x:在擦傷部分幾乎完全沒有塗膜存在，完全爲金屬 原料。 複合耐腐蝕性試驗：供複合耐腐蝕性試驗使用之試驗 片係依下述方式製作。將預先裁成7cm Μ 5cm大小之各試 驗用塗裝板，於使用氙弧燈式促進耐候性試驗機進行促進 耐候性試驗5 00小時之後，分別從長邊兩側邊緣部5mm處 以剪機（shearing machine)剪切，使毛邊朝向表面側塗膜 面’右側朝向表面側，左側朝向背面側。該試驗片之表側 中央部分到達質地之狹角30度、線寬度〇.5mm之十字切 割部使用切刀之背後切入，使塗裝板上端邊緣部份以防銹 塗料密封，且在上端部分 '設置3T彎曲加工部分（以塗裝 板之表面側爲外側予以彎曲，在其內側夾住3張與塗裝板 相同厚度的板，以上述塗裝板以老虎鉗進行1 8 0度彎曲加 工處理）以製作試驗片。對於所得之各試驗片，進行依據J IS K-5621(1990)之複合循環腐蝕試驗。複合循環腐蝕試驗之 條件爲，以（3〇°C之5%食鹽水噴霧0.5小時）—（3(TC之 RH95%以上耐濕試驗器內進f了試驗1.5小時）一（50 °C下進 行乾燥2小時）-（3 0 °C進行乾燥2小時）爲1次循環，進行 200次循環（合計1200小時）試驗。評估該試驗後試驗片之 3 T彎曲加工部、邊緣部、十字切割部、平面部之狀態。 (3 T彎曲加工部）根據3 T彎曲加工部中銹部的合計長 度及有無赤銹產生情形’以下述基準予以評估。 -42- 201109396 ◎:沒有白銹產生情形’或白銹產生部分低於5mm 〇：白銹產生部分爲5mm以上且低於20mm △:白銹產生部份爲2〇mm以上且低於40mm X :白銹產生部份爲4 〇 m m以上，或有紅銹產生情形。 (邊緣部）根據試驗片左右之長邊的有效邊緣寬度之 平均値及有無赤銹產生情形，以下述基準予以評估。 ◎:沒有赤銹產生情形，有效邊緣寬度之平均値低於 5mm 〇：沒有赤銹產生情形，有效邊緣寬度之平均値爲5mm 以上且低於1 〇 m m △:沒有赤銹產生情形’有效邊緣寬度之平均値爲 10mm以上且低於20mm x:有效邊緣寬度之平均値20mm爲以上，或有赤銹 產生情形。 (十字切割部）使十字切割部之腐蝕狀態，藉由〇.5 mm 之切割寬度的鏟金露出部分上白銹產生的比例，及切割部 分左右之碎片寬度（兩側之和）的平均値，以及有無赤銹產 生情形，以下述基準予以評估。 ◎:鍍金露出部分上白銹產生的比例低於50%且碎片 寬度低於3 m m 〇：鍍金露出部分上白銹產生比例爲5 0 %以上且碎片 寬度低於3mm ’或鍍金露出部分上白銹產生比例低於5〇 % 且碎片寬度爲3mm以上、低於5mm △:鍍金露出部分上白銹產生比例爲50 %以上且碎片 -43- 201109396 寬度爲5mm以上、低於10mm x:鍍金露出部分上白銹產生比例爲50%以上且碎片寬 度爲1 0 m m以上，或沒有赤銹產生情形。 (平面部）非處於連續邊緣的腐蝕部位，而位於平面部 之非連續且偶發之碎片，以下述基準予以評估。 ◎:沒有碎片產生情形 〇：碎片直徑約低於2 m m，個數亦低於1 〇個 △:碎片直徑約爲2mm以上且個數低於10個，或碎 片直徑低於2 m m且個數爲1 〇個以上 X:碎片直徑約爲2mm以上，且個数爲10個以上。 -44- 201109396 ◎ ◎ 〇 ◎ 〇 〇 〇 〇 ◎ ◎ 〇 〇 〇 〇 〇 〇 ◎ ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 〇 ◎ ◎ 〇 ◎ ◎ 〇 〇 〇 ◎ 〇 〇 ◎ 〇 〇 〇 〇 ◎ ◎ 〇 ◎ ◎ ◎ 寸 ◎ ◎ ◎ 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ ◎ 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ ◎ 〇 〇 ◎ 〇 ◎ CN 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ Η 〇 〇 〇 〇 ◎ 〇 ◎ ◎ 〇 〇 〇 〇 ◎ 〇 〇 〇 〇 〇 〇 〇 ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇 〇 〇 ◎ ◎ 〇 〇 〇 〇 ◎ 〇 〇 〇 〇 〇 〇 〇 〇 ◎ ◎ ◎ On 〇 〇 〇 〇 ◎ 〇 ◎ ◎ 〇 〇 〇 〇 ◎ 〇 〇 〇 〇 〇 〇 〇 ◎ ◎ ◎ ◎ IK 00 ◎ ◎ ◎ ◎ 〇 〇 ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ 卜 ◎ ◎ ◎ ◎ 〇 〇 ◎ 〇 ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ 〇 〇 ◎ ◎ 〇 ◎ ◎ 〇 〇 〇 ◎ 〇 〇 ◎ 〇 〇 〇 〇 ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 ◎ 〇 ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ ◎ 〇 〇 ◎ ◎ ◎ 寸 〇 〇 〇 〇 〇 ◎ ◎ 〇 〇 〇 〇 〇 〇 ◎ 〇 〇 〇 〇 〇 〇 〇 ◎ ◎ ◎ m 〇 〇 ◎ ◎ 〇 ◎ ◎ ◎ 〇 〇 ◎ 〇 〇 ◎ 〇 〇 〇 〇 ◎ ◎ 〇 ◎ ◎ ◎ (N ◎ 〇 〇 〇 〇 〇 〇 ◎ ◎ 〇 〇 〇 〇 〇 〇 〇 ◎ 〇 〇 〇 〇 ◎ 〇 ◎ ◎ 〇 〇 〇 〇 〇 〇 〇 ◎ 〇 〇 〇 〇 〇 〇 〇 ◎ 〇 〇 〇 〇 ◎ 〇 ◎ 耐沸騰水性 耐鹼性 耐酸性 3T加工部 邊緣部 十字切割部 平面部 ώ 耐鹼性 耐酸性 3T加工部 邊緣部 十字切割部 平面部 V/ 耐鹼性 耐酸性 3T加工部 邊緣部 十字切割部 平面部 耐擦傷七 複合耐 腐蝕性 試驗 Ν' m 辑 耐擦傷屯 複合耐 腐蝕性 試驗 耐沸騰 耐擦傷t 複合耐 腐蝕性 試驗 1 塗覆加工1 (GL鋼板） 塗覆加工2 (G I鋼板） - 剡亡· Sis 201109396 8Ϊ 參考例 CN < < ◎ ◎ ◎ ◎ ◎ X X < ◎ 〇 ◎ ◎ 〇 < < < 〇 ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ 〇 〇 〇 〇 〇 〇 ◎ ◎ 〇 〇 〇 〇 〇 〇 ◎ ◎ ◎ 比較例 〇 〇 〇 〇 〇 〇 <1 < <3 〇 〇 〇 〇 < < < <] 〇 〇 〇 〇 < 〇 < 〇\ 〇 < 〇 X X X X X 〇 〇 X X X X X 〇 <] 〇 X X 〇 X < 00 〇 < 〇 < X X X X 〇 < 〇 < X X X X 〇 < 〇 < X 〇 X < 卜 〇 〇 0 < X X X X 〇 〇 < X X X X X 〇 〇 < < X 〇 X < 〇 < 〇 < < < 〇 < 〇 < 〇 X < <1 < <] 〇 < 〇 < <3 〇 〇 〇 < X 〇 〇 <3 < 〇 〇 < X 〇 〇 < < < <3 < X 〇 〇 < 〇 〇 ◎ 寸 < <1 〇 〇 < 〇 〇 <] <] <] 〇 <] 〇 <] X <] <3 〇 〇 ◎ 〇 〇 〇 〇 〇 〇 < X < < 〇 〇 〇 < < X X < 〇 〇 〇 〇 < 〇 < 〇 <N X < < 〇 <] 〇 < X <3 < <] < 〇 <1 < X < < 〇 < ◎ <] < r-H ◎ ◎ ◎ < X X X X ◎ ◎ ◎ X X X X X ◎ ◎ ◎ < X 〇 X < ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 ◎ 〇 〇 ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ a\ ◎ 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 ◎ ◎ 〇 〇 ◎ 〇 〇 〇 ◎ ◎ ◎ ◎ 4^5 00 ◎ 〇 ◎ 〇 〇 ◎ 〇 〇 ◎ 〇 ◎ 〇 〇 ◎ 〇 〇 ◎ 〇 ◎ 〇 〇 ◎ 〇 〇 ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ ◎ 〇 〇 〇 〇 〇 ◎ ◎ ◎ 〇 〇 ◎ 〇 ◎ 耐沸騰水性 耐鹼性 耐酸性 耐擦傷性 3T加工部 邊緣部 十字切割部 平面部 耐鹼性 耐酸性 耐擦傷性 3Τ加工部 邊緣部 十字切割部 平面部 耐沸騰水性 耐鹼性 耐酸性 耐擦傷性 3T加工部 邊緣部 十字切割部 平面部 a <ίπ遨盤 耐沸騰水 m 4□溫盤 鹅越跽 S a <!□ S 盤 鹧輕Μ fi 塗覆加工1 (GL鋼板） 塗覆加工2 (G I鋼板） § iSr? 鹧靈!ϋ ‘ ,9寸. 201109396 【圊式簡單說明】 •M、\ 【主要元件符號說明】201109396 In the above Table 1, the (note) in the table has the following meanings. (Note l) Ep〇key 837: manufactured by Mitsui Chemicals Co., Ltd., trade name, urethane-modified epoxy resin, hydroxyl-containing resin, a primary hydroxyl group value of about 35, and an acid value of about 0. (Note 2) Vylon 296: manufactured by Toyobo Co., Ltd., trade name, epoxy-modified polyester resin, resin containing hydroxyl group, hydroxyl group price 7, acid value 6. (Note 3) Sumidur N3300+: manufactured by Sumika Bayer Urethane Co., Ltd., isocyanate type polyisocyanate compound, 100% solid content. (Note 4) Cym el 303: Nihon Cytec Indus tries, trade name, methyl etherified melamine resin. (Note 5) Shieldex C303: manufactured by W.R.Grace & CO., trade name, Ion exchange cerium oxide. (Note 6) Aerosil 200: manufactured by Nippon Aerosil Co., Ltd., trade name, silica sand microparticles, oil absorption of about 280 ml / 100 g. (Note 7) Sandvor 3 05 8: manufactured by Clariant, trade name, hindered amine-based UV stabilizer. Each of the rust-preventive paint compositions and the surface coatings obtained in the above-mentioned Examples 1 to 20, Comparative Examples 1 to 10, and Reference Examples 1 and 2 was used as a test-coated plate, and the respective materials were coated by the coating treatment described below. Further, firing was carried out to obtain coating sheets for each test. Coating treatment 1: In the implementation of the chemical processing of the aluminum-zinc-bismuth steel plate (plate thickness 〇.35mm, aluminum-zinc alloy plated steel, alloy contains about 55 % aluminum, alloy plating unit area weight is 150g / m2, Table 2 The back surface coating material obtained in the above Production Example 2 was coated with a dry coat thickness of 8 μm as a bar coater-37-201109396, and the raw material reached a maximum temperature of 1 80 °. The film was fired at C for 3 sec seconds to form a back coating film. On the steel sheet surface opposite to the back surface coating film of the coating sheet on which the back coating film was formed, each of the rust-preventive coating compositions obtained in the above respective examples was coated with a bar coater at a dry film thickness of 5 μm. The coating was applied, and the raw materials were brought to a maximum temperature of 2 2 ° C for 40 seconds to form a main coating film. After cooling, the KP color of the main coating film was set to 1 508 0 B40 (manufactured by Kansai Paint Co., Ltd., trade name, polyester-based surface coating, blue, hardened coating film, glass transition temperature of about 70 ° C). The test coating sheets were prepared by coating with a bar coater and a dry film thickness of about 15 μm, and baking the raw materials to a maximum temperature of 220 ° C for 40 seconds. Coating treatment 2: The hot-dip galvanized steel sheet having a chemical conversion treatment (thickness: 0.35 mm, zinc plating unit weight: 250 g/m2, and "GI steel plate" in Table 2) was used to obtain the above-mentioned production example 2. The back coating was applied as a dry coat at a thickness of 8 μηη with a bar coater, and the raw material was allowed to reach a maximum temperature of 180 ° C for 30 seconds to form a back coat film. On the steel sheet surface opposite to the back surface coating film of the coating sheet on which the back coating film was formed, each of the rust-preventive coating compositions obtained in the above respective examples was coated with a bar coater at a dry film thickness of 5 μm. Covering, and letting the raw material reach the maximum temperature of 22 (40 degree firing at TC, each primer coating plate is obtained. After cooling, the KP color is 1 5 8 0B40 on the primer coating plate ( Kansai Paint Co., Ltd. manufactured by 'product name, polyester-based surface coating, blue 'hardened coating film glass transfer temperature about 701'), coated with a bar coater and a dry film thickness of about 15 μm The raw materials reached the maximum temperature of 22 ° C for 40 seconds to obtain the test plates for each test. -38- 201109396 Coating treatment 3 : The same aluminum-zinc-coated bismuth as used for the coating treatment 1 On the steel sheet, the rust-preventive coating composition obtained in Example 3 was coated with a bar coater at a dry film thickness of 8 μm and the raw material reached a maximum temperature of 1801 and baked for 30 seconds to form a back coating film. The above-mentioned each surface is formed on the side of the steel sheet opposite to the back coating film of the coated sheet on which the back coating film is formed Each of the obtained rust-preventive coating compositions was coated with a bar coater at a dry film thickness of 5 μm, and the raw materials were brought to a maximum temperature of 22 (40 sec under TC to prepare each primer coating film). After cooling, the KP color is 1580B40 (Kansai?&!^<:〇.,1^(1., product name, polyester surface coating, blue, etc.) on the primer coating film. The glass transition temperature of the hardened coating film is about 70 ° C), and the coating is applied at a bar coater and a dry film thickness of about 15 μm to bring the raw material to a maximum temperature of 220. (: firing for 40 seconds) A coating plate for each test was obtained. Coating film performance test Each of the test coated sheets obtained in the above Examples 1 to 20 and Comparative Examples 1 to 1 and Reference Examples 1 and 2 was subjected to coating film performance by the following test method. The test results are shown in the following Table 2. The test method is resistant to boiling water: the test coated sheets cut to a size of 5 cm X 10 cm are immersed in boiling water of about 1 ° C for 5 hours, and then taken out. And evaluate the appearance of the coating on the surface side, and evaluate the checkerboard tape adhesion test. Checkerboard tape adhesion test Based on the JIS K-5400 8.5.2 (1 990) checkerboard tape method, the gap between the cuts was 1 mm, and 100 checkerboards were made. The adhesive tape was adhered to the surface to observe the residual after the strong peeling. -39- 201109396 The number of checkerboards. ◎: There are no abnormalities such as debris and whitening on the coating film. The number of remaining checkerboards is 100: There are no abnormalities such as debris and whitening on the coating film. The number of remaining checkerboards is 91 to 99. △: There are abnormalities such as fragmentation and whitening on the coating film. The number of remaining checkerboards is 91 or more, or there is no abnormality such as debris or whitening on the coating film. However, the number of remaining checkerboards is 7 1 to 90 X: a fairly significant fragmentation occurs on the coating film, or the number of remaining checkerboards is 70 or less. Alkali resistance: The back surface and the cut surface of each test coated sheet which were cut to a size of 5 cm x 10 cm were sealed with an anti-rust paint, and a cross shape reaching the texture was cut at the center portion of the surface side of the coated sheet. After the coated plate was immersed in 4 (TC of 5% aqueous sodium hydroxide solution for 48 hours, it 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 evaluated, and in the cross-cut portion The adhesive tape was adhered to each other to evaluate the peeling width (single side) of the coating film from the cutting portion after the strong peeling. ◎: No chipping occurred, and the tape peeling width from the cutting portion was 1. 5 mm or less 〇: no chipping occurred, self-cutting The stripping width of the tape is greater than 1.5 mm and less than 3 mm. △: There is a slight fragmentation. The tape peeling width from the cutting portion is 3 mm or less, or no chipping occurs, but the tape peeling width from the cutting portion is greater than 3 mm -40- 201109396 χ : There is a fragmentation situation, and the glue from the cutting part is 3 mm 〇 Acid resistance: the surface and the cut surface which are cut into 5 cm χ 10 cm size are sealed with anti-rust paint, and the texture is cut out to reach the texture. After the immersion of the sodium hydroxide aqueous solution for 48 hours, the appearance of the coating film on the surface side of the dried coated plate is taken out, and the adhesive tape is closely adhered to the evaluation. After coating film width (single side) ◎: No chipping occurred, less than 1.5 mm from the cutting part 〇: no chipping occurred, the self-cutting part was 1.5 mm or less, △: There was a slight fragmentation. The self-cutting part is 3mm or less, or there is no fragmentation, but the self-distribution width is more than 3mm. X: There is fragmentation, and the glue from the cutting part is 3 mm. 〇 Scratch resistance: at room temperature of 20 ° C, use the line. Chemical Technology Co., Ltd.), at the angle of the 10 round copper coins of each test coating plate, at an angle of 45 degrees, and attached, and make the 10 round copper coins at a speed of l〇mm/sec. The degree of scratching at the time of scratching was performed on the following basis: ◎: There was no metal raw material in the scratched portion, and the peeling width was larger than the surface side central plate of the test coated back sheet at 5% at 40 ° C, and the cross cut at room temperature was evaluated. In some cases, the stripping width of the stripping width of the stripping width of the self-cutting portion is the stripping width of the tape, and the peeling width of the stripping strip is larger than the strip scratching test (automatically. The surface of the coated side is added with a load of 3 kg to be stretched about 3 0 mm Evaluation -41 - 201109396 〇: There is a metal material in the scratched part. △: There is a significant metal material in the scratched part. x: There is almost no coating film in the scratched part. It is completely a metal material. Composite corrosion resistance test: The test piece used for the composite corrosion resistance test was produced in the following manner. Each of the test coated sheets having a size of 7 cm Μ 5 cm was preliminarily cut, and the weather resistance test was carried out using a xenon arc lamp type accelerated weather resistance tester. After 00 hours, the shearing machine was cut from the edge portions of both sides of the long side by 5 mm, so that the burrs were directed toward the surface side of the coating film surface, the right side toward the surface side, and the left side toward the back side. The center portion of the front side of the test piece reaches a narrow angle of 30 degrees of the texture, and the cross-cut portion of the line width 〇.5 mm is cut by the back of the cutter so that the end edge portion of the coating plate is sealed with the rust-proof paint, and the upper end portion is ' The 3T bending portion is provided (the surface side of the coating plate is bent to the outside, and three sheets of the same thickness as the coating plate are sandwiched inside, and the above-mentioned coated plate is subjected to a 180-degree bending process with a vise) To make a test piece. For each of the obtained test pieces, a composite cyclic corrosion test according to J IS K-5621 (1990) was carried out. The conditions of the composite cyclic corrosion test are: (0.5 hr sprayed with 5% saline solution at 0.5 ° C) - (3 (RH 95% or more of the TC RH 95% test) for 1.5 hours) (at 50 °C) Drying for 2 hours) - (drying at 30 ° C for 2 hours) was 1 cycle, and 200 cycles (total 1200 hours) were performed. The 3 T bending portion, edge portion, and cross cut of the test piece after the test were evaluated. (3 T bending part) The evaluation is based on the following criteria based on the total length of the rust part in the 3 T bending part and the presence or absence of red rust. -42- 201109396 ◎: No white rust is generated. 'The white rust is less than 5mm. 白: The white rust is 5mm or more and less than 20mm. △: The white rust is 2mm or more and less than 40mm. X: The white rust is 4 〇mm or more. (The edge portion) is evaluated based on the average 値 of the effective edge width of the long side of the test piece and the presence or absence of red rust. The ◎: no red rust is generated, the effective edge width The average 値 is less than 5mm 〇: no red In the case of occurrence, the average edge width of the effective edge width is 5 mm or more and less than 1 〇mm △: no red rust is generated. The average edge width of the effective edge width is 10 mm or more and less than 20 mm x: the average edge width of the effective edge width is 20 mm or more. , or the occurrence of red rust. (Cross cut) The corrosion state of the cross-cut portion, the proportion of white rust on the exposed portion of the shovel with a cutting width of 〇5 mm, and the width of the shards on the left and right sides of the cut portion ( The average enthalpy of the sum of the two sides, and the presence or absence of red rust, were evaluated on the basis of the following criteria: ◎: The ratio of white rust on the exposed part of the gold plating is less than 50% and the shard width is less than 3 mm 〇: the exposed part of the gold plating The ratio of white rust is more than 50% and the width of the shard is less than 3mm' or the ratio of white rust on the exposed portion of gold plating is less than 5% and the width of the shard is more than 3mm and less than 5mm. △: the proportion of white rust on the exposed portion of gold plating 50% or more and debris -43-201109396 Width is 5mm or more and less than 10mm x: The ratio of white rust on the gold-plated exposed portion is 50% or more and the fragment width is more than 10 mm, or there is no red rust. Case (planar portion) is not a corroded portion of a continuous edge, and discontinuous and sporadic fragments located at the plane portion are evaluated on the basis of the following criteria: ◎: no debris is generated 〇: the fragment diameter is less than 2 mm, the number Also less than 1 △ △: the fragment diameter is about 2mm or more and the number is less than 10, or the fragment diameter is less than 2 mm and the number is more than 1 X X: the fragment diameter is about 2mm or more, and the number is 10 -44- 201109396 ◎ ◎ 〇 ◎ 〇〇〇〇 ◎ ◎ 〇〇〇〇〇〇 ◎ ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇〇 ◎ ◎ 〇 ◎ ◎ 〇〇〇 ◎ 〇〇 ◎ 〇〇〇〇 ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇◎ 〇◎ CN 〇〇〇◎ ◎ ◎ ◎ ◎ 〇〇〇 ◎ ◎ ◎ 〇〇〇〇〇 ◎ ◎ ◎ ◎ ◎ Η 〇〇〇〇 ◎ 〇 ◎ ◎ 〇〇〇〇 ◎ 〇〇〇〇〇〇〇 ◎ ◎ ◎ ◎ 〇〇〇〇〇〇〇 ◎ ◎ 〇〇〇〇 ◎ 〇〇〇〇〇〇〇〇 ◎ ◎ ◎ On 〇〇〇〇 ◎ 〇 ◎ ◎ 〇〇〇〇 ◎ 〇〇〇〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇〇〇〇 〇〇〇〇〇 ◎ ◎ 〇〇〇〇〇〇 ◎ 〇〇〇〇〇〇〇 ◎ ◎ ◎ m 〇〇 ◎ ◎ 〇 ◎ ◎ ◎ 〇〇 ◎ 〇〇 ◎ 〇〇〇〇 ◎ ◎ 〇 ◎ ◎ ◎ (N ◎ 〇〇〇〇〇〇 ◎ ◎ 〇〇〇〇〇〇〇 ◎ 〇〇〇〇 ◎ 〇 ◎ ◎ 〇〇〇〇〇〇〇 ◎ 〇〇〇〇〇〇〇 ◎ 〇〇〇〇 ◎ 〇 ◎ 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐Partial surface scratch resistance seven composite corrosion resistance test Ν' m series scratch resistance 屯 composite corrosion resistance test resistance to boiling and scratch resistance t composite corrosion resistance test 1 coating processing 1 (GL steel plate) coating processing 2 (GI steel plate) - 剡死· Sis 201109396 8Ϊ Reference example CN << ◎ ◎ ◎ ◎ ◎ XX < ◎ 〇 ◎ ◎ 〇 <<<<<<<<< 〇 ◎ ◎ ◎ ◎ 〇〇〇〇〇 ◎ ◎ 〇〇〇〇〇 〇 ◎ ◎ 〇〇〇〇〇〇 ◎ ◎ ◎ Comparative example <1 <<3〇〇〇〇<<<<>〇〇〇〇<〇<〇\〇< 〇XXXXX 〇〇XXXXX 〇<] 〇XX 〇X < 00 〇<〇< XXXX 〇<〇< XXXX 〇<〇< X 〇X < 〇〇0 < XXXX 〇〇< X XXXX 〇〇<< X 〇X <〇<〇<<<〇<〇< 〇X <<1<<]〇<〇<<3 〇 〇〇< X 〇〇<3 <〇〇< X 〇〇<<<<3< X 〇〇< 〇〇◎ inch<<1〇〇< 〇〇 <] <] <] 〇<] 〇<] X <] <3 〇〇◎ 〇〇〇〇〇〇< X <<〇〇〇<< XX <〇〇〇〇<〇<〇<NX<<〇<]〇< X <3 <<>〇<1< X <<〇< ◎ <] < rH ◎ ◎ ◎ < XXXX ◎ ◎ ◎ XXXXX ◎ ◎ ◎ < X 〇 X < ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ a ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 〇〇 〇 〇〇 〇〇 〇〇 〇〇 〇 〇 〇 〇 〇 〇◎ 〇〇◎ ◎ ◎ 〇〇〇〇〇 ◎ ◎ 〇〇〇〇〇 ◎ ◎ ◎ 〇〇 ◎ 〇 ◎ 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐Cutting plane, boiling resistance, alkali resistance, acid resistance, scratch resistance, 3T processing part, edge portion, cross cutting portion, plane part a <ίπ遨盘, boiling water, m 4□, warm plate, goose, 跽S a <!□ S plate鹧 Μ Μ fi coating processing 1 (GL steel plate) coating processing 2 (GI steel plate) § iSr? 鹧灵!ϋ ', 9 inch. 201109396 [圊 simple description] • M, \ [Main component symbol description]