TW200948908A - Anti-corrosive coating composition - Google Patents

Anti-corrosive coating composition Download PDF

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TW200948908A
TW200948908A TW98108521A TW98108521A TW200948908A TW 200948908 A TW200948908 A TW 200948908A TW 98108521 A TW98108521 A TW 98108521A TW 98108521 A TW98108521 A TW 98108521A TW 200948908 A TW200948908 A TW 200948908A
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Taiwan
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resin
coating composition
acid
group
epoxy resin
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TW98108521A
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Chinese (zh)
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TWI411653B (en
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Akihisa Sakamoto
Hideki Matsuda
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Kansai Paint Co Ltd
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  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

An anti-corrosive coating composition containing (A) a flexible organic moiety-modified bisphenol epoxy resin obtained by reacting 5 to 50% by weight of a flexible organic moiety with 95 to 50% by weight of a bisphenol epoxy resin, (B) a curing agent and (C) an anticorrosion pigment, the flexible organic moiety being at least one selected from the group consisting of an aliphatic polybasic acid having 4 to 36 carbon atoms, an acrylic resin having a glass transition temperature of -20 to 50 DEG C and a polyester resin having a glass transition temperature of -20 to 50 DEG C, wherein the anticorrosion pigment (C) is preferably a chrome-free anticorrosion pigment mixture containing a vanadium compound, silicon-containing compound such as a metal silicate and phosphate based metal salt.

Description

200948908 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種具有優異耐蝕性的塗布組成物以及 使用該塗布組成物所得之經塗布金屬片，更特別的是關於 一種耐蝕性的塗布組成物，其不只是可以有效改善經塗布 金屬片非製造之平坦部分的耐蝕性，同時也可以改善製造 部分及邊緣面的耐蝕性，即使是無鉻的塗布組成物；本發 明亦關於使用該塗布組成物所得之經塗布金靥片。 © 【先前技術】 以線圈塗布法塗布之預塗金屬片（如預塗鋼片）已被廣 泛用於住宅相關用品的領域，例如用於建築結構的建築材 料，如屋頂、牆壁、百葉窗、車庫等；各種家用電器；鑲 嵌板；冷凍櫃、鋼製傢倶；蔚具等。 住宅相關用品通常是由預塗金屬片來製備，例如，藉 由以下所述的方法，其包括切割預塗的鋼片，接著加以製 造，例如模壓成型和接合。因此，住宅相關用品通常會因 ^ 爲模壓成型而具有如切削表面的金屬曝露部分及和裂縫形 成部分。與其它部分相比，金屬曝露部分及和裂縫形成部 分的耐蝕性可能會被降低。爲了改善耐蝕性，在預塗鋼片 上的底漆（primer)塗布薄膜一般會含有鉻系的抗腐蝕顏料。 然而，鉻系抗腐蝕顔料可含有或產生具有優異耐蝕性 的六價鉻，但由人體健康及環境保護的觀點看來，其必需 被控制使用。 各種無鉻抗腐蝕顏料，如磷酸鋅、三聚磷酸鋁、鉬酸 鋅等已經有市售商品，並且已有人提出含有無鉻顏料組合 -4- 200948908 的各種底漆。例如，專利參考資料1揭露了 一種塗布組成 物，其係將矽酸鈣和釩酸磷之組合所構成的抗腐蝕顏料組 成物，或者是將碳酸鈣、矽酸鈣、磷酸鋁和釩酸磷之組合 所構成的抗腐蝕顏料組成物添加至由環氧樹脂和酚樹脂所 構成的載劑成分中而製得。此外，專利參考資料2揭露了 一種塗布組成物，其係將二元磷酸鎂和氧化錳•氧化釩的 煅燒產物之組合所構成的抗腐蝕顔料組成物，或者是將磷 酸鈣和氧化釩的煅燒產物所構成的抗腐蝕顏料組成物添加 〇 至聚酯樹脂中而製得。然而，由專利參考資料1和2揭露 之塗布組成物所形成的塗布薄膜呈現出不良的耐蝕性，特 別是與使用鉻系顏料所製得之塗布組成物相比，其在製造 部分及邊緣面部分的耐蝕性不能令人滿意，並且當使用大 量的抗腐鈾顏料混合物時，經常還會呈現出不良的耐化學 性，如耐鹼性和耐酸性及不良的耐水性。因此，在製備預 塗金屬片時，專利參考資料1和2中所揭露的抗腐蝕顔料 π 混合物不足以取代鉻系抗腐蝕顔料。 ❹ 專利參考資料3揭露了一種塗布組成物，其係藉由添 加具有30至200毫升/100克油吸收度及孔洞體積爲0.05 至1.2毫升/克的二氧化矽微粒來製備，並且形成了玻璃轉 移溫度在40至125 °C範圍內的硬化塗布薄膜。然而，由專 利參考資料3揭露之塗布組成物所形成的塗布薄膜雖然可 展現一些耐蝕性，但是與使用鉻系顔料所製得之塗布組成 物相比，其展現出不良的耐蝕性和不良的耐化學性，特別 是在邊緣面部分的耐蝕性不能令人滿意。 200948908 專利參考資料1:日本特許出願公開號6 1 001/99號。 專利參考資料2:日本特許出願公開號1 99078/00號。 專利參考資料3 :日本特許出願公開號1 29 1 63/00號。 【發明内容】 本發明的目的之一係提供一種塗布組成物’當其用於 經塗布金屬片時可形成一種塗布薄膜，其除了其它非製造 部分之外，也可在製造部分及邊緣面部分呈現出優異的耐 蝕性，即使是無鉻的塗布組成物；本發明的目的還包括提 供一種經塗布的金屬片，其係使用該種塗布組成物。 爲了解決舊有技術所面臨的上述問題，本發明人做了 密集的硏究而尋找出一種塗布組成物，其含有經脂肪族多 元酸改質之雙酚環氧樹脂和丙烯酸樹脂、硬化劑及抗腐蝕 顏料，當其用於經塗布金屬片時，除了可在其它非製造平 坦部分形成具優異耐蝕性的塗布薄膜之外，也可在製造部 分及邊緣面部分形成具優異耐蝕性的塗布薄膜。 也就是說，本發明係關於： “ 1.一種抗腐蝕塗布組成物，其含有（A)撓性有機基元 改質之雙酚環氧樹脂，其係將5至50重量％的撓性有機基 元與95至50重量％的雙酚環氧樹脂反應而得，（B)硬化劑 及（C)抗腐蝕顏料，此種撓性有機基元至少一種係選自由具 有4至36個碳原子的脂肪族多元酸、具有-20至50°C玻璃 轉移溫度的丙烯酸樹脂及具有-20至50 °C玻璃轉移溫度的 聚酯樹脂所構成之組群、 2.如第1.項之抗腐蝕塗布組成物，其中樹脂（A)爲雙酚 環氧樹脂’其係以具有4至36個碳原子的脂肪族多元酸及 200948908 具有-20至50 °C玻璃轉移溫度的丙烯酸樹脂改質。 3. 如第1.項之抗腐蝕塗布組成物，其中具有4至36個 碳原子的脂肪族多元酸爲二聚物酸。 4. 如第1.項之抗腐蝕塗布組成物，硬化劑（B)爲至少一 種交聯劑，其係選自胺基樹脂、酚樹脂和選用的阻斷聚異 氰酸酯化合物。 5. 如第1.項之抗腐鈾塗布組成物，其中抗腐蝕顏料（C) 爲無鉻抗腐蝕顏料。 ® 6.如第5.項之抗腐蝕塗布組成物，其中抗腐蝕顏料包 含（1)至少一種釩化合物，其係選自五氧化二釩、釩酸鈣和 偏釩酸銨，（2)至少一種含矽化合物，其係選自金屬矽酸鹽 和二氧化矽微粒，以及（3)磷酸鹽系金屬鹽。 7. 如第1.項之抗腐蝕塗布組成物，其中抗腐蝕塗布組 成物還進一步包含至少一種選自含二級或三級胺基的環氧 樹脂、含二級或三級胺基的丙烯酸樹脂及可溶酚醛樹脂。 8. —種經塗布的金屬片，在此金屬片表面的一側或兩 〇 側之上具有由第1.項之塗布組成物所形成的硬化塗布薄膜 ，該金屬表面被施以選用之金屬處理方法。 9. 一種經塗布的金屬片，其具有多層塗布薄膜，包括 在此金靥片表面的一側或兩側之上由第1.項之塗布組成物 形成的硬化塗布薄膜，該金屬表面被施以選用之金屬處理 方法，以及在此硬化塗布薄膜的至少一側形成之面漆塗布 薄膜。” 本發明之具體實施例可包括： “ A.如第6項之抗腐蝕塗布組成物，其中含矽化合物 200948908 (2)是一種金屬矽酸鹽，金屬係選自鈣、鎂和鋅。 B. 如第6項之抗腐蝕塗布組成物，其中抗腐蝕顔料（c) 含有（1)至少一種釩化合物，其係選自五氧化二釩、釩酸鈣 和偏釩酸銨，（2)至少一種含矽化合物，其係選自金屬矽酸 鹽和二氧化矽微粒，（3)磷酸鹽系金屬鹽；釩化合物（1)是在 3至50重量份數的範圍內，含矽化合物（2)是在3至50重 量份數的範圍內且磷酸鹽系金屬鹽（3)是在3至50重量份數 的範圍內，並且化合物（1)、化合物（2)及鹽（3)的總量是在 ® 10至150重量份數的範圍內，其係分別以每100重量份數 的樹脂（A)及硬化劑（B)總固體含量爲基準。 C. 如第1項之抗腐蝕塗布組成物，其中塗布組成物還 進一步包含至少一種顏料成分，其係選自二氧化鈦顔料及 塡充顏料。 D. 如第1項之抗腐蝕塗布組成物，此塗布組成物還進 —步包含至少一種選自紫外線吸收劑和紫外線安定劑。” 發明效果： 〇 本發明提供了如此特別的效果，即使是無鉻的抗腐蝕 顏料，當本發明之塗布組成物用於經塗布的金屬片時，除 了可在其它非製造平坦部分形成具優異耐蝕性的塗布薄膜 之外，也可在製造部分及邊緣面部分形成具優異耐蝕性的 塗布薄膜，雖然在此技術領域很難提供無鉻的抗腐蝕塗布 組成物。 被本發明之塗布組成物所形成之硬化塗布薄膜包覆的 經塗布金屬片在非製造的平坦部分、製造部分及邊緣面部 分皆展現出優異的耐蝕性，並且與使用鉻酸鹽系抗腐蝕顔 200948908 料（如鉻酸緦）之塗布組成物所形成之硬化塗布薄膜相比， 其具有相同或更佳的耐蝕性。 以本發明之塗布組成物所形成之硬化塗布薄膜包覆而 製得經塗布金屬片，接著再以形成於硬化塗布薄膜之上的 面漆薄膜予以包覆，其在非製造的平坦部分、製造部分及 邊緣面部分皆展現出優異的耐蝕性。在做爲塗布基板的金 屬片上塗布本發明之塗布組成物，除了可在其它非製造平 坦部分獲得優異的耐蝕性之外，也可在製造部分及邊緣面 〇 部分獲得優異的耐蝕性，而此種金屬片可爲例如，鍍鋅鋼 片或是鍍鋅合金的鋼片，如鍍鋁·鋅合金鋼片。 【實施方式】 本發明較佳實施實例： 本發明之塗布組成物包含撓性有機基元改質之雙酚環 氧樹脂（A)、硬化劑（B)及抗腐蝕顏料混合物（C)。 撓件有機某元改質之雙酚環氧樹脂（A) 在本發明塗布組成物中的這種撓性有機基元改質之雙 © 酚環氧樹脂（A)(下文中可能稱爲改質樹脂（A))是將撓性有 機基元與雙酚環氧樹脂反應所得之樹脂。 這種撓性有機基元是具有可與雙酚環氧樹脂反應之官 能基並且能將雙酚環氧樹脂塑化的有機基元，其至少一種 係選自具有4至36個碳原子的脂肪族多元酸、具有-20至 50°C玻璃轉移溫度的丙烯酸樹脂及具有-20至50°C玻璃轉 移溫度的聚酯樹脂。 這種聚酯樹脂可包括無油聚酯樹脂、油改質聚酯樹脂 及改質聚酯樹脂，如矽改質聚酯樹脂、胺基甲酸乙酯改質 200948908 聚酯樹脂等。 此種具有4至36個碳原子的脂肪族多元酸可包括 4至36個碳原子、較佳爲8至36個碳原子的飽和或不 脂環族多元酸，例如，脂環族二羧酸’如六氫異酞酸 氫對酞酸、六氫酞酸、甲基六氫酞酸、甲基六氫對酞酸 四氫酞酸、Δ2-四氫酞酸、Δ3·四氫酞酸、A4-四氫酞酸 四氫酞酸、A1-四氫異酞酸、A2-四氫異酞酸、Δ3-四氫 酸、A4-四氫異酞酸、Δ1-四氫對酞酸、A2-四氫對酞酸 © 基四氫酞酸、內亞甲四氫酞酸、甲基內亞甲四氫酞酸 氯內亞甲四氫酞酸等，及其酸酐；脂肪族二羧酸，丁 、戊二酸、己二酸、壬二酸、癸二酸、十二烷二酸、 烷二羧酸、辛二酸、庚二酸、順丁烯二酸、反丁烯二 伊康酸、十三烷二酸、檸康酸、氯順丁烯二酸、二聚 等，及其酸酐；三價或較高級的脂肪族多元酸，如六 苯三甲酸等；較低碳數的烷基酯，如這些酸的甲酯、 等等。 〇 在製備改質樹脂（A)中用來做爲撓性有機基元的 酸樹脂可包括具有可與雙酚環氧樹脂反應之反應性基 丙烯酸樹脂。此種丙烯酸樹脂可包括改質丙烯酸樹脂 胺基甲酸乙酯改質丙烯酸樹脂。此種反應性基團可包 基、胺基、羥基等。其中，以含羧基之丙烯酸樹脂爲 〇 此種含羧基之丙烯酸樹脂可包括將含有羧基之可 不飽和單體與其它可聚合之不飽和單體共聚合所得之 ’其係依照已知方法’如溶液聚合方法、懸浮聚合方 具有 飽和 、六 ' Δ1-、Δ1-異酞 、甲 、六 二酸 十二 酸、 物酸 氯偏 乙酯 丙烯 團的 ，如 括羧 較佳 聚合 樹脂 法、 -10- 200948908 總體聚合方法等，由控制聚合條件之容易性的觀點來看， 較佳係獲得溶液聚合方法。其它可聚合之不飽和單體可包 括（甲基）丙烯酸酯。（甲基）丙烯酸酯的使用量較佳是在30 至98重量％的範圍內，其係以構成改質樹脂（A)之單體的總 量爲基準。 含羧基之可聚.合不飽和單體可包括，例如，丙烯酸、 甲基丙烯酸、順丁烯二酸、順丁烯二酸酐、反丁烯二酸、 伊康酸等。 ® 其它可聚合之不飽和單體可包括，例如，含羥基之可 聚合不飽和單體’如（甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸 羥丙酯、（甲基）丙烯酸4-羥丁酯、（甲基）丙烯酸四氫呋喃酯 、ε-己內酯改質（甲基）丙烯酸四氫呋喃酯、ε-己內酯改質 (甲基）丙烯酸羥乙酯、聚乙二醇一（甲基）丙烯酸酯、聚丙二 醇一（甲基）丙烯酸酯、2-羥基-3-苯氧丙基（甲基）丙烯酸酯、 2-羥基-3-丁氧丙基（甲基）丙烯酸酯、（甲基）丙烯酸酞酸一羥 乙酯等；（甲基）丙烯酸烷酯，如（甲基）丙烯酸甲酯、（甲基） 〇丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸正丁酯、（ 甲基）丙烯酸異丁酯、（甲基）丙烯酸第三丁酯、（甲基）丙烯 酸2-乙基己酯、（甲基）丙烯酸十八酯、（甲基）丙烯酸十三酯 等；（甲基）丙烯酸環烷酯，如（甲基）丙烯酸環己酯等；（甲 基）丙烯酸苄酯；（甲基）丙烯酸苯酯；（甲基）丙烯酸二烷基 胺基烷酯，如（甲基）丙烯酸二甲基胺乙酯、（甲基）丙烯酸二 乙基胺乙酯等；含環氧基之可聚合不飽和單體，如（甲基） 丙烯酸環氧丙酯、（甲基）丙烯酸甲基環氧丙酯、烯丙基環 氧丙醚等；乙烯系芳香化合物，如苯乙烯、α-甲基苯乙烯 -11- 200948908 、乙烯甲苯等；丙烯腈、甲基丙烯腈、乙酸乙烯酯、 乙烯酯、丙烯醯胺、甲基丙烯醯胺、N-羥甲基丙烯醯 N-羥甲基甲基丙烯醯胺、二丙酮丙烯醯胺、丙烯醯基 琳、N-乙烯基-2-吡咯酮、7·-丙烯氧丙基三甲氧矽烷 甲基丙烯氧丙基三甲氧矽烷、氯乙烯、丙烯、乙 C'-C211- α-烯烴等。這些可以單獨使用或者是組合使用 在本專利申請書中，“（甲基）丙烯酸酯”係指" 酸酯或甲基丙烯酸酯”。 〇 由丙烯酸樹脂與雙酚環氧樹脂的相容性及反應性 點來看，當藉由溶液聚合法來合成丙烯酸樹脂時，其 的數目平均分子量是在2000至40000的範圍內，特別是 至30000之間。 在本專利申請書中，樹脂的數目平均分子量是藉 膠滲透層析法（HLC8120GPC，Tosoh公司銷售的商品4 所測得之層析圖並以標準聚苯乙烯的分子量爲基準計 得之數値。上述量測是在以下條件下進行，也就是， ❹管柱：TSK 凝膠 G-4000 HXL、TSK 凝膠 G-3000 HXL、 凝膠 G-2500 HXL 及 TSK 凝膠 G-2000 HXL(Tosoh 公司 的商品名稱）；移動相：四氫呋喃；量測溫度：40°C， :1毫升/分鐘，感測器：RI。 由丙烯酸樹脂與雙酚環氧樹脂的反應性及黏附性 観點來看，丙烯酸樹脂的酸値爲3至50毫克K0H/克 別是5至40毫克K0H/克；由塗布薄膜的硬化能力及 性的觀點來看，丙烯酸樹脂的羥値爲10至300毫克 克，特別是30至250毫克K0H/克；並且由製造性質 丙酸 胺、 嗎福 、r - 烯、 〇 丙烯 的観 具有 ^ 300 由凝 S稱） 算所 4個 TSK 銷售 流速 質的 ，特 耐水 K0H/ 和所 -12- 200948908 得塗布薄膜硬度之間平衡性的觀點來看，玻璃轉移溫度（Tg) 爲-20°C至50°C，較佳爲-20°C至40°C。在本專利申請書中 ，樹脂的玻璃轉移溫度（Tg)係由微差掃描熱量測定法（DSC) 來決定。 在製備改質樹脂（A)中用來做爲撓性有機基元的聚酯 樹脂可包括具有可與雙酚環氧樹脂反應之反應性基團的聚 酯樹脂。此種聚酯樹脂可包括無油聚酯樹脂、油改質聚酯 樹脂、矽改質聚酯樹脂及胺基甲酸乙酯改質聚酯樹脂。此 © 種反應性基團可包括，例如，羧基、胺基、羥基等。其中 ，以含羧基之聚酯樹脂爲較佳。 在這些聚酯樹脂中，無油聚酯樹脂依照已知的方法來 製備，例如直接酯化方法、酯化交換方法、開環方法等。 直接酯化方法的實例可包括將多元酸和多元醇進行聚縮合 反應之方法。做爲主要成分的這種多元酸可包括，例如， 至少一種選自酞酸酐、異酞酸、對酞酸、丁二酸、己二酸 、反丁烯二酸、順丁烯二酸酐、四氫酞酸酐及六氫酞酸酐 〇 的二 :元酸；三價或更高級的多元酸，如偏苯三甲酸酐、甲 基環己烯三羧酸、苯均四酸酐等，並且除了上述酸之外， 可選擇性地包括一元酸，如苯甲酸、巴豆酸、對三級丁基 苯甲酸等。做爲主要成分的這種多元醇可包括，例如，二 元醇，如乙二醇、二乙二醇、丙二醇、1，4-丁二醇、新戊二 醇、1,4-己二醇、1，6-己二醇等，並且除了上述醇類之外， 可選擇性地包括三元醇或更高級的多元醇，如丙 羥甲乙烷、三羥甲丙烷、季戊四醇等。 這種含竣基聚醋樹脂可依照已知的方法來製備，其包 -13- 200948908 含在酸基相對於羥基爲過量的情況下使多元酸和多元醇進 行反應，或者是將如偏苯三甲酸酐和酞酸酐之類的多元酸 與含羥基的聚酯樹脂的羥基進行後加成反應。 這種無油聚酯樹脂也可以藉由多元酸的低碳烷基酯與 多元醇之間的酯交換所造成的聚縮合反應來製備。此外， 這種無油聚酯樹脂也可以藉由內酯（如<5·戊內酯及 ε-己 內酯）的開環聚合反應來製備。 這種聚酯樹脂的油改質聚酯樹脂係藉由將無油聚酯樹 © 脂與油脂肪酸反應來製備。此種油脂肪酸可包括，例如， 椰子油脂肪酸、大豆油脂肪酸、亞麻仁油脂肪酸、紅花油 脂肪酸、松油脂肪酸、無水蓖麻油脂肪酸、桐油脂肪酸等 。聚酯樹脂和脂肪酸之間的反應可以依照已知的方法來進 行，並且其油長（oil length)通常爲30%或更少。 由聚酯樹脂與雙酚環氧樹脂的相容性及反應性的觀點 來看，此種聚酯樹脂具有的重量平均分子量係在1000至 30000的範圍內，特別是2000至20000。由聚酯樹脂與雙 〇 酚環氧樹脂的反應性及黏附性質的觀點來看，此種聚酯樹 脂的酸値爲3至100毫克KOH/克，特別是5至70毫克KOH/ 克。由製造性質和所得塗布薄膜硬度之間平衡性的觀點來 看，玻璃轉移溫度（Tg)爲-20°C至50°C，較佳爲-20°C至40°C 〇 在製備改質樹脂（A)中所用的雙酚型環氧樹脂可包括 ，例如，一種樹脂，其係將表氯醇和雙酚選擇性地在有觸 媒（如鹼金屬觸媒）存在的情況下進行縮合反應，而能夠具 有高分子量；以及一種樹脂，其係將表氯醇和雙酚選擇性 -14- 200948908 地在有觸媒（如鹼金屬觸媒）存在的情況下進行縮合反應以 形成低分子量環氧樹脂，接著再將低分子量環氧樹脂和雙 酚進行加成聚合反應。 此種雙酚環氧樹脂具有的數目平均分子量係在3 50至 5 000的範圍內，特別是400至4000，並且環氧基的含量爲 0.5至15.4毫莫耳/克，較佳爲0.8至10毫莫耳/克。 此種雙酚較佳可包括雙（4·羥苯基）甲烷[雙酚F]、l，l-雙（4-羥苯基）乙烷、2,2-雙（4-羥苯基）丙烷[雙酚A]、2,2-雙 © (4-羥苯基）丁烷[雙酚B]、雙（4-涇苯基）-l，l-異丁烷、雙（4- 羥基第三丁苯基）-2,2-丙烷、對-(4-羥苯基）苯酚、氧雙（4-羥苯基）、磺醯基雙（4-羥苯基）、4,4’-二羥基二苯基酮、雙 (2-羥萘基）甲烷等。其中以使用雙酚A和雙酚F爲較佳。 上述雙酚可單獨使用或者是組合使用。 商用的雙酚型環氧樹脂之實例可包括jER 828、812、 815、 820' 834、 1001、 1004、 1007、 1009、 1010、 4004P、 4007P、4210(商品名稱，所有皆是由日本環氧樹脂公司銷 〇 售）；Araldite AER 6099(商品名稱，由Asahi-Ciba公司銷售 );Epomik R-309 (商品名稱，由三井化學股份有限公司銷 售）等。 使撓性有機基元與雙酚環氧樹脂進行反應來獲得改質 樹脂（A)的方法並沒有特別的限制。舉例來說，如果使用兩 種撓性有機基元，上述方法可包括使兩種撓性有機基元與 雙酚環氧樹脂同時進行反應的方法：以及使一種撓性有機 基元與雙酚環氧樹脂進行反應，接著再與剩下的撓性有機 基元進行反應的方法。 -15- 200948908 上述反應較佳是在，例如，100至15(TC的溫度下，於 能夠同時溶解兩種反應物的溶劑中進行1至5小時，胃_ 擇性地在有反應觸媒存在的情況下進行。 反應觸媒可包括，例如，四級鹽類觸媒，如溴化四乙 銨、溴化四丁銨、氯化四乙銨、溴化四丁鐵、氯化三苯基 苄銹等；胺類，如三乙胺、三丁胺等等。 在上述反應中，如果撓性有機基元的反應性基團是竣 基，（雙酚環氧樹脂中的環氧基）/(撓性有機基元中的竣基） © 之當量比係在10/1至1/1的範圍內，較佳爲5/1至2/1»如 果在改質樹脂（A)的合成反應中係具有反應性基團的丙稀 酸樹脂與異於羧基的環氧基進行反應，則除了在上式中將 “撓性有機基元中的羧基”取代爲“與異於羧基的環氧基 反應之反應性基團”之外，各別反應性基團的當量比仍在 上式範圍內。 在製備改質樹脂（A)時，撓性有機基團和雙酚環氧樹脂 的混合比爲：撓性有機基團是在5至50重量％的範圍內， 〇 較佳是10至40重量％，並且雙酚環氧樹脂是在50至95重 量％的範圍內，較佳是60至90重量％，其係分別以兩種反 應物的總重量爲基準。 如果脂肪族多元酸及由丙烯酸樹脂和/或聚酯樹脂所 構成之撓性樹脂的組合被用來做爲製備改質樹脂（A)中的 撓性有機基團時，在製備改質樹脂（A)的脂肪族多元酸、撓 性樹脂及雙酚環氧樹脂混合比爲：脂肪族多元酸是在1至 30重量份數的範圍內，較佳是3至20重量份數，可撓樹脂 是在1至49重量份數的範圍內，較佳是7至37重量份數 -16- 200948908 ，並且雙酚環氧樹脂是在50至95重量份數的範圍內，較 佳是60至90重量份數，其係分別以100重量份數的各別 反應物總重量爲基準。 如果在撓性有機基元和雙酚環氧樹脂之間的反應完全 之後仍殘留環氧基的話，爲了阻斷殘留的環氧基，可以使 改質樹脂（A)與例如苯甲酸、水楊酸、二級胺化合物等阻斷 劑反應。對這種情況而言，可以在撓性有機基元和雙酚環 氧樹脂之間的反應期間與阻斷劑進行反應。 © 改質樹脂（A)在分子結構中具有撓性基元，因此可在交 聯的塗布薄膜中參與應力鬆弛的發展、製造部分之製造和 黏附性質的改善、以及所得塗布薄膜高抗腐蝕能力的表現 硬化劑（B) 硬化劑（B)係與改質樹脂（A)反應以形成硬化的塗布薄 膜，並且可包括能夠藉由和改質樹脂（A)反應（例如，藉由 加熱，沒有特殊限制）而硬化的物質。其中較佳爲胺基樹 〇 脂、酚樹脂和選用的阻斷聚異氰酸酯化合物。這些硬化劑 可以單獨使用或者是組合使用。 胺基樹脂可包括由醛類與胺基成分（如三聚氰胺、脲、 苯胍胺、乙胍胺、硬脂胍胺、螺胍胺、二氰二胺等）反應所 獲得之羥甲基胺基樹脂。在上述反應中所使用的醛類可包 括甲醛、三聚甲醛、乙醛、苯甲醛等。胺基樹脂也可包括 以適當醇類將羥甲基胺基樹脂予以醚化所得之胺基樹脂。 用於醚化反應之醇類的實例可包括甲醇、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。 -17- 200948908 用來做爲硬化劑的酚樹脂係與改質樹脂（A)反應 聯’其可包括，例如，可溶酚醛樹脂，其係藉由加熱 酚成分和甲醛在反應觸媒存在的情況下進行縮合反應 入羥甲基，接著使所得羥甲基酚樹脂中至少一部分的 基與醇類進行烷基醚化反應而製得。 在製備可溶酚醛樹脂中用來做爲起始材料的酚成 包括雙官能酚化合物、三官能酚化合物及四-或更高官 酚化合物。 © 此種酚化合物可包括，例如，雙官能酚化合物，多 甲酚、對-甲酚、對-第三丁基酚、對-乙酚、2,3-茬酚、 茬酚等；三官能酚化合物，如酚、間-甲酚、間-乙酚、 茬酚、間-甲氧酚等；四官能酚化合物，如雙酚A、雙 等等。基於改善耐刮性的目的，其中以三官能或更高 化合物爲較佳，特別是酚和/或間-甲酚。這些酚化合 以單獨使用或者是組合使用。 可用於製備酚樹脂的甲醛類可包括甲醛、三聚甲 〇 三署烷等，並且其可以單獨使用或者是組合使用。 在羥甲基酚樹脂中之羥甲基的部分烷基醚化中所 的醇類以包括具有1至8個碳原子的一元醇爲較佳， 係具有1至4個碳原子，特別是甲醇、乙醇、正丙醇 丁醇、異丁醇等。 由與改質樹脂（A)之反應性的觀點來看，酚樹脂的 個苯環上所具有的平均烷氧甲基數爲0.5或更多，較 0.6 至 3.0。 在用於硬化劑中之選用阻斷聚異氰酸酯化合物中 及交 及使 以引 羥甲 分可 能的 13鄰- 2.5- 3.5-酚F 的酚 物可 醛、 使用 更佳 、正 每一 佳爲 的非 -18- 200948908 阻斷聚異氰酸酯化合物可包括有機二異氰酸酯，例如脂肪 族二異氰酸酯’如六亞甲二異氰酸酯、三甲基六亞甲二異 氰酸酯等；脂環族二異氰酸酯，如氫化之伸茬基二異氰酸 酯、異佛酮二異氰酸酯等；以及芳香二異氰酸酯，如甲苯 二異氰酸酯、伸茬基二異氰酸酯、4，4’-二苯基甲烷二異氰 酸酯、粗製MDI等；這些有機二異氰酸酯與多元醇、低分 子量聚酯樹脂、水等的加成物；上述有機二異氰酸酯之間 的環狀聚合物；異氰酸酯縮二脲等。 ® 可用來做爲交聯劑的阻斷聚異氰酸酯化合物爲藉由阻 斷劑來阻斷聚異氰酸酯化合物中的自由異氰酸基所製得之 化合物。用來阻斷異氰酸基之阻斷劑可包括，例如，酚類 ’如酚、甲酚、茬酚；內醯胺，如 ε-己內醯胺、5-戊內 酶胺、7-丁內醯胺等；醇類，如甲醇、乙醇、正-、異-或 第三丁基醇、乙二醇一甲醚、乙二醇一丁醚、二乙二醇一 乙醚、丙二醇一甲醚、苄醇等；肟類，如甲醯胺肟、乙醛 肟、丙酮肟、甲基乙酮肟、丁酮肟、二苯基酮肟、環己酮 Ο 聘等；以及活性亞甲基系的物質，如两二酸二甲醋、丙二 酸二乙酯、乙醯乙酸乙酯、丙酮乙醯等。將聚異氰酸酯化 合物與阻斷劑混合，可以輕易地阻斷聚異氰酸酯化合物中 的自由異氰酸基。 由耐餓性、耐沸水性、製造性質、硬化性質等觀點來 看’改質樹脂（Α)和硬化劑（Β)的混合數量應可使得改質樹 脂（Α)的量在55至95重量份數的範圍內，較佳是60至95 重量份數’並且硬化劑（Β)是在5至45重量份數的範圍內 ’較佳是5至40重量份數，其係以1〇〇重量份數的成分（Α) -19- 200948908 和（B)總固體含量爲基準。 爲了促進塗布組成物的硬化反應，可以選擇性地使用 硬化觸媒，並且可以任意挑選，並且視所使用硬化劑的種 類而定。 如果硬化劑（B)爲胺基樹脂，特別是甲基醚化或甲基醚 •丁基醚混合之醚化三聚氰胺樹脂時，硬化觸媒以包括磺酸 化合物及磺酸化合物的胺中和產物爲佳。磺酸化合物的典 型實例可包括對-甲苯磺酸、十二基苯磺酸、二壬基萘磺酸 © 、二壬基萘二磺酸等。在磺酸化合物之胺中和產物中所使 用的胺可包括一級胺、二級胺和三級胺。由塗布組成物的 穩定性和促進反應效果、所得塗布薄膜性質等觀點來看， 其中以對-甲苯磺酸的胺中和產物和/或十二基苯磺酸的 胺中和產物爲較佳。 如果硬化劑（B)是酚樹脂，則硬化觸媒可包括磺酸化合 物和磺酸化合物的胺中和產物。 如果硬化劑（B)是阻斷聚異氰酸酯化合物，較好是能有 〇 一種促進做爲硬化劑的阻斷聚異氰酸酯化合物之阻斷劑解 離之硬化觸媒。較佳硬化觸媒的實例可包括有機金屬觸媒 ，如鋅酸錫、二丁錫二（2-乙基己酸酯）、二辛錫二（2-乙基 己酸酯）、二辛錫二乙酸酯、二辛錫二月桂酸酯、氧化二丁 錫、氧化二辛錫、2·乙基己酸鉛等等。 如果硬化劑是兩種或更多種硬化劑的組合，則硬化觸 媒可包括可對各個硬化劑有效果之各個硬化觸媒的組合。 抗腐蝕顏料（ΓΛ 抗腐鈾顔料可包括鉻系顏料和無鉻顏料，此顏料須展 -20- 200948908 現出抗腐蝕的性質，由人體健康及環境保護的觀點來看’ 較佳爲無鉻的抗腐蝕顏料。 鉻系抗腐蝕顏料可包括，例如，鉻酸鋸、鉻酸鋅、鉻 酸鋅鉀、鉻酸鋇、鉻鉻酸鹽、鉻磷酸鹽等。 無鉻抗腐鈾顏料可包括，例如，磷酸鋅、三聚磷酸鋁 、鉬酸鋅、矽酸鈣、五氧化二釩、釩酸鈣、偏釩酸銨、釩 酸磷、磷酸鋁、磷酸鈣、磷酸氫鎂、氧化鈣與氧化釩的煅 燒產物、具有30至200毫升/100克的油吸收度及孔洞體積 r 〇 爲0.05至1.2毫升/克的二氧化矽微粒等。這些抗腐蝕顏料 可以單獨使用或者是組合使用。 在上述無鉻抗腐蝕顏料中，如下文中所述，以（1)釩化 合物，（2)含矽化合物和（3)磷酸鹽系之金屬鹽的組合特別適 合用於本發明之塗布組成物中。 釩化合物（Π 釩化合物（1)可包括至少一種選自五氧化二釩、釩酸鈣 及偏釩酸銨之釩化合物。這種五氧化二釩、釩酸鈣及偏釩 〇 酸銨在水中可展現出優異之五價釩離子的淘析性質，並且 由釩化合物（1)所放出的五價釩離子可有效改善耐蝕性，這 是因爲其與基板金屬的反應，或者是與來自其它抗腐蝕顔 料混合物放出離子的反應所造成。 含矽化合物（2) 含矽化合物（2)係至少一種選自金屬矽酸鹽和二氧化 矽微粒之含矽化合物。 金屬矽酸鹽係由二氧化矽和金屬氧化物所構成的鹽類 ’其可包括正矽酸鹽、聚矽酸鹽等。此種矽酸鹽可包括， -21 - 200948908 例如’矽酸鋅、矽酸鋁、正矽酸鋁、水合矽酸鋁、矽酸鈣 銘、砂酸鈉鋁、矽酸鈹鋁、矽酸鈉、正矽酸鈣、偏矽酸鈣 、政酸鈉鈣、矽酸鉻、正矽酸鎂、偏矽酸鎂、矽酸鈣鎂、 砍酸錳、矽酸鋇、貴橄欖石、石榴石、钪紇石、異極礦、 藍錐礦、柱星葉石、綠柱石、透輝石、矽灰石、薔薇輝石 、透閃石、硬矽鈣石、滑石、魚眼石、鋁矽酸鹽、硼矽酸 鹽、鈹矽酸鹽、長石、沸石等。 金屬矽酸鹽（2)較佳係包括正矽酸鈣和偏矽酸鈣。 €> 二氧化矽微粒可包括任何一種二氧化矽微粒，沒有特 別的限制，例如，未經表面處理之二氧化矽微粒、經有機 物質表面處理之二氧化矽微粒、鈣離子交換之二氧化矽微 粒、有機溶劑可分散之膠態二氧化矽等》 未經表面處理的二氧化矽微粒或經有機物質表面處理 的二氧化矽微粒可包括具有平均粒徑0.5至15微米之二氧 化矽微粒，較佳爲1至10微米，以及有機溶劑可分散之膠 態二氧化矽。此種二氧化矽微粒較佳係包括具有30至350 Ο 毫升/100克（更佳爲30至150毫升/100克）油吸收度的二氧 化矽微粒。其商品名稱可包括，例如，Sylysia 710、Sylysia 740 、Sylysia 550、Aerosil R972(商品名稱，如上分別係由 FujiSylysia 化學公司銷售）、MIZUKASIL(商品名稱，由水澤化學工業股 份有限公司銷售）、Gasil 200DF(商品名稱，由Crosfield化學 品公司銷售）等。鈣離子交換二氧化矽微粒是藉由離子交換 將鈣離子帶到微細的多孔二氧化矽載體上所獲得之二氧化 矽微粒。鈣離子交換二氧化矽的商品名稱，例如’ SHIELDEX( 商標）C303、SHIELDEX AC-3、SHIELDEX AC-5 (分别J 係由 W.R. -22- 200948908200948908 VI. Description of the Invention: [Technical Field] The present invention relates to a coating composition having excellent corrosion resistance and a coated metal sheet obtained by using the coating composition, and more particularly to a coating composition for corrosion resistance , which not only can effectively improve the corrosion resistance of the flat portion which is not manufactured by the coated metal sheet, but also can improve the corrosion resistance of the manufactured portion and the edge surface, even if it is a chromium-free coating composition; the present invention also relates to the use of the coating The coated gold crumb obtained from the composition. © [Prior Art] Precoated metal sheets (such as precoated steel sheets) coated by coil coating have been widely used in the field of residential related products, such as building materials for building structures such as roofs, walls, shutters, garages. Etc; various household appliances; inlaid panels; freezer cabinets, steel furniture; Residential related articles are typically prepared from pre-coated metal sheets, for example, by the methods described below, which include cutting pre-coated steel sheets, followed by fabrication, such as compression molding and joining. Therefore, the house related articles usually have a metal exposed portion such as a cutting surface and a crack forming portion due to press molding. The corrosion resistance of the metal exposed portion and the crack-forming portion may be lowered as compared with other portions. In order to improve corrosion resistance, a primer coated film on a precoated steel sheet generally contains a chromium-based anticorrosive pigment. However, the chromium-based anticorrosive pigment may contain or produce hexavalent chromium having excellent corrosion resistance, but it must be controlled for use in terms of human health and environmental protection. Various chromium-free anticorrosive pigments such as zinc phosphate, aluminum tripolyphosphate, and zinc molybdate have been commercially available, and various primers containing a chromium-free pigment combination -4-200948908 have been proposed. For example, Patent Reference 1 discloses a coating composition which is an anticorrosive pigment composition composed of a combination of calcium silicate and phosphorus vanadate, or a calcium carbonate, calcium silicate, aluminum phosphate, and phosphorus vanadate. The anticorrosive pigment composition composed of the combination is added to a carrier component composed of an epoxy resin and a phenol resin. Further, Patent Reference 2 discloses a coating composition which is an anticorrosive pigment composition composed of a combination of a magnesium dibasic magnesium phosphate and a calcined product of manganese oxide and vanadium oxide, or a calcination of calcium phosphate and vanadium oxide. The anticorrosive pigment composition composed of the product is obtained by adding hydrazine to the polyester resin. However, the coated film formed by the coating composition disclosed in Patent References 1 and 2 exhibits poor corrosion resistance, particularly in the production portion and the edge portion as compared with the coating composition prepared using the chromium-based pigment. Part of the corrosion resistance is unsatisfactory, and when a large amount of anti-corrosion uranium pigment mixture is used, it often exhibits poor chemical resistance such as alkali resistance and acid resistance and poor water resistance. Therefore, the anticorrosive pigment π mixture disclosed in Patent References 1 and 2 is not sufficient to replace the chromium-based anticorrosive pigment in the preparation of the precoated metal sheet.专利 Patent Reference 3 discloses a coating composition prepared by adding cerium oxide particles having a oil absorption of 30 to 200 ml/100 g and a pore volume of 0.05 to 1.2 ml/g, and forming a glass. A hardened coated film having a transfer temperature in the range of 40 to 125 °C. However, the coating film formed by the coating composition disclosed in Patent Reference 3 exhibits some corrosion resistance, but exhibits poor corrosion resistance and poor performance as compared with the coating composition prepared using the chromium-based pigment. Chemical resistance, particularly in the edge portion, is not satisfactory. 200948908 Patent Reference 1: Japanese Licensed Disclosure No. 6 1 001/99. Patent Reference 2: Japanese Licensed Publication No. 1 99078/00. Patent Reference 3: Japanese Licensed Disclosure No. 1 29 1 63/00. SUMMARY OF THE INVENTION One object of the present invention is to provide a coating composition 'when it is used for a coated metal sheet, a coating film can be formed which can be used in the manufacturing portion and the edge portion except for other non-manufactured portions. It exhibits excellent corrosion resistance, even a chromium-free coating composition; the object of the present invention also includes providing a coated metal sheet using the coating composition. In order to solve the above problems faced by the prior art, the inventors have conducted intensive research to find a coating composition containing a bisphenol epoxy resin modified with an aliphatic polybasic acid, an acrylic resin, a hardener, and Anti-corrosion pigment, when it is used for a coated metal sheet, in addition to forming a coating film having excellent corrosion resistance in other non-manufactured flat portions, it is also possible to form a coating film having excellent corrosion resistance at the manufacturing portion and the edge portion. . That is, the present invention relates to: "1. A corrosion-resistant coating composition comprising (A) a flexible organic element-modified bisphenol epoxy resin which is 5 to 50% by weight of a flexible organic The monomer is reacted with 95 to 50% by weight of a bisphenol epoxy resin, (B) a hardener and (C) a corrosion-resistant pigment, at least one selected from the group consisting of 4 to 36 carbon atoms. a group consisting of an aliphatic polybasic acid, an acrylic resin having a glass transition temperature of -20 to 50 ° C, and a polyester resin having a glass transition temperature of -20 to 50 ° C, 2. Corrosion resistance as in item 1. A coating composition in which the resin (A) is a bisphenol epoxy resin which is modified with an aliphatic polybasic acid having 4 to 36 carbon atoms and an acrylic resin having a glass transition temperature of -20 to 50 ° C in 200948908. An anti-corrosion coating composition according to item 1, wherein the aliphatic polybasic acid having 4 to 36 carbon atoms is a dimer acid. 4. The corrosion-resistant coating composition according to item 1. Hardener (B) Is at least one crosslinking agent selected from the group consisting of amine based resins, phenolic resins, and selected blocking polyisocyanates 5. The anti-corrosion uranium coating composition of item 1. The anti-corrosion pigment (C) is a chromium-free anti-corrosion pigment. ® 6. The corrosion-resistant coating composition of item 5. The pigment comprises (1) at least one vanadium compound selected from the group consisting of vanadium pentoxide, calcium vanadate and ammonium metavanadate, and (2) at least one cerium-containing compound selected from the group consisting of metal citrate and cerium oxide particles. And (3) a phosphate-based metal salt. 7. The corrosion-resistant coating composition according to Item 1, wherein the corrosion-resistant coating composition further comprises at least one epoxy resin selected from the group consisting of a secondary or tertiary amine group. An acrylic resin containing a secondary or tertiary amine group and a resol resin. 8. A coated metal sheet having a coating by the first item on one side or both sides of the surface of the metal sheet. a hardened coating film formed by the composition, the metal surface being subjected to a metal treatment method selected. 9. A coated metal sheet having a multilayer coating film comprising one or both sides of the surface of the gold sheet a hardened coating film formed from the coating composition of item 1. The metal surface is subjected to a metal treatment method selected, and a topcoat coating film formed on at least one side of the hardened coated film." Specific embodiments of the present invention may include: "A. Corrosion-resistant coating composition according to item 6. The cerium-containing compound 200948908 (2) is a metal cerate, the metal is selected from the group consisting of calcium, magnesium and zinc. B. The corrosion-resistant coating composition of item 6, wherein the anti-corrosive pigment (c) contains (1) At least one vanadium compound selected from the group consisting of vanadium pentoxide, calcium vanadate and ammonium metavanadate, and (2) at least one ruthenium-containing compound selected from the group consisting of metal ruthenate and ruthenium dioxide particles, (3) a phosphate-based metal salt; the vanadium compound (1) is in the range of 3 to 50 parts by weight, the cerium-containing compound (2) is in the range of 3 to 50 parts by weight, and the phosphate-based metal salt (3) is In the range of 3 to 50 parts by weight, and the total amount of the compound (1), the compound (2) and the salt (3) is in the range of from 10 to 150 parts by weight, respectively, per 100 parts by weight The total solid content of the resin (A) and the hardener (B) is based on the number. C. The corrosion-resistant coating composition of item 1, wherein the coating composition further comprises at least one pigment component selected from the group consisting of titanium dioxide pigments and anthraquinone pigments. D. The corrosion-resistant coating composition of item 1, the coating composition further comprising at least one member selected from the group consisting of ultraviolet absorbers and ultraviolet stabilizers. Effect of the Invention: The present invention provides such a special effect that even if it is a chromium-free anticorrosive pigment, when the coating composition of the present invention is used for a coated metal sheet, it is excellent in forming other non-manufactured flat portions. In addition to the corrosion-resistant coating film, a coating film having excellent corrosion resistance can be formed in the production portion and the edge portion, although it is difficult to provide a chromium-free corrosion-resistant coating composition in the technical field. The formed hard-coated film-coated coated metal sheet exhibits excellent corrosion resistance in the non-manufactured flat portion, the manufactured portion, and the edge portion, and is used with a chromate-based anti-corrosion film 200948908 (such as chromic acid). The cured coating film formed by the coating composition of the crucible has the same or better corrosion resistance. The hardened coating film formed by the coating composition of the present invention is coated to obtain a coated metal sheet, and then Covered with a topcoat film formed on the hardened coating film, in the non-manufactured flat portion, the manufactured portion, and the edge portion It exhibits excellent corrosion resistance. Coating the coating composition of the present invention on a metal sheet as a coated substrate, in addition to obtaining excellent corrosion resistance in other non-manufactured flat portions, can also be obtained in the manufacturing portion and the edge portion. Excellent corrosion resistance, and such a metal sheet may be, for example, a galvanized steel sheet or a galvanized steel sheet, such as an aluminized zinc alloy sheet. [Embodiment] Preferred Embodiments of the Invention: The Invention The coating composition comprises a flexible organic element modified bisphenol epoxy resin (A), a hardener (B) and a corrosion resistant pigment mixture (C). The flexible organic modified bisphenol epoxy resin (A) The flexible organic element-modified bis-phenol epoxy resin (A) (hereinafter may be referred to as a modified resin (A)) in the coating composition of the present invention is a flexible organic element and a double a resin obtained by reacting a phenol epoxy resin. The flexible organic element is an organic element having a functional group reactive with a bisphenol epoxy resin and capable of plasticizing a bisphenol epoxy resin, at least one selected from the group consisting of An aliphatic polybasic acid having 4 to 36 carbon atoms, An acrylic resin having a glass transition temperature of -20 to 50 ° C and a polyester resin having a glass transition temperature of -20 to 50 ° C. The polyester resin may include an oil-free polyester resin, an oil-modified polyester resin, and a modified Polyester resin, such as tamper-modified polyester resin, urethane modified 200948908 polyester resin, etc. Such an aliphatic polybasic acid having 4 to 36 carbon atoms may include 4 to 36 carbon atoms, a saturated or non-alicyclic polybasic acid of preferably 8 to 36 carbon atoms, for example, an alicyclic dicarboxylic acid such as hydrogen hexahydroisophthalic acid, hexahydrophthalic acid, methyl hexahydrofurfuric acid, Methyl hexahydro-p-tetrahydrofuric acid, Δ2-tetrahydrofurfuric acid, Δ3·tetrahydrofurfuric acid, A4-tetrahydrofurfuric acid tetrahydrofurfuric acid, A1-tetrahydroisodecanoic acid, A2-tetrahydroiso Citrate, Δ3-tetrahydro acid, A4-tetrahydroisodecanoic acid, Δ1-tetrahydropyridinic acid, A2-tetrahydroparaxamic acid, tetrahydrofurfuric acid, endo-tetrahydrofurfuric acid, methyl Methylenetetrahydrofurfuric acid, chlorotetramethyl phthalic acid, etc., and anhydrides thereof; aliphatic dicarboxylic acids, butyl, glutaric acid, adipic acid, sebacic acid, sebacic acid, dodecanedioic acid, Alkanedicarboxylic acid, suberic acid Pimelic acid, maleic acid, fubutane diconic acid, tridecanedioic acid, citraconic acid, chloro-maleic acid, dimerization, etc., and anhydrides thereof; trivalent or higher fats A polybasic acid such as hexatricarboxylic acid or the like; a lower carbon number alkyl ester such as a methyl ester of these acids, and the like. The acid resin used as the flexible organic unit in the preparation of the modified resin (A) may include a reactive acrylic resin which is reactive with the bisphenol epoxy resin. Such an acrylic resin may include a modified acrylic resin urethane modified acrylic resin. Such a reactive group may be a group, an amine group, a hydroxyl group or the like. Wherein, the carboxyl group-containing acrylic resin may be such that the carboxyl group-containing acrylic resin may include a copolymerization of a carboxyl group-containing unsaturated monomer with another polymerizable unsaturated monomer, which is obtained according to a known method such as a solution. The polymerization method and suspension polymerization have a saturated, six' Δ1-, Δ1-isoindole, methyl hexaic acid, acid chloroprene propylene group, such as a carboxylate-preferred polymer resin method, -10- 200948908 The overall polymerization method and the like, from the viewpoint of easiness of controlling the polymerization conditions, it is preferred to obtain a solution polymerization method. Other polymerizable unsaturated monomers may include (meth) acrylate. The amount of the (meth) acrylate to be used is preferably in the range of from 30 to 98% by weight based on the total amount of the monomers constituting the modified resin (A). The carboxyl group-containing polymerizable unsaturated monomer may include, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like. ® Other polymerizable unsaturated monomers may include, for example, hydroxyl group-containing polymerizable unsaturated monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylic acid 4-hydroxybutyl ester, (meth)acrylic acid tetrahydrofuran ester, ε-caprolactone modified (meth)acrylic acid tetrahydrofuran ester, ε-caprolactone modified (meth)acrylic acid hydroxyethyl ester, polyethylene glycol one (Meth) acrylate, polypropylene glycol mono(meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate , (meth)acrylic acid monohydroxyethyl phthalate, etc.; alkyl (meth) acrylate, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (a Base) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octadecyl (meth)acrylate, (methyl) a tridecyl acrylate or the like; a cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate; Benzyl acrylate; phenyl (meth) acrylate; dialkylaminoalkyl (meth) acrylate, such as dimethylamine ethyl (meth) acrylate, diethylamine (meth) acrylate Ester or the like; an epoxy group-containing polymerizable unsaturated monomer such as (meth)acrylic acid propyl acrylate, methyl methacrylate methacrylate, allyl epoxidized ether, etc.; Compounds such as styrene, α-methylstyrene-11-200948908, vinyl toluene, etc.; acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ester, acrylamide, methacrylamide, N-hydroxyl Acryl hydrazine N-methylol methacrylamide, diacetone acrylamide, propylene hydrazino, N-vinyl-2-pyrrolidone, 7-propoxypropyltrimethoxy decyl methacrylate Trimethoxysilane, vinyl chloride, propylene, ethyl C'-C211-α-olefin, and the like. These may be used alone or in combination in the present patent application, "(meth)acrylate" means "ester or methacrylate"." Compatibility of acrylic resin with bisphenol epoxy resin And the reactivity point, when the acrylic resin is synthesized by solution polymerization, the number average molecular weight thereof is in the range of 2,000 to 40,000, particularly to 30,000. In the present patent application, the number of resins The average molecular weight is obtained by gel permeation chromatography (HLC8120GPC, a chromatogram measured by the product 4 of Tosoh Corporation and based on the molecular weight of standard polystyrene. The above measurement is carried out under the following conditions. , that is, the column: TSK gel G-4000 HXL, TSK gel G-3000 HXL, gel G-2500 HXL and TSK gel G-2000 HXL (trade name of Tosoh company); mobile phase: tetrahydrofuran Measuring temperature: 40 ° C, : 1 ml / min, sensor: RI. From the reactivity and adhesion of acrylic resin and bisphenol epoxy resin, the acidity of acrylic resin is 3 to 50 MGK0H/gram is 5 40 mg K0H / gram; from the viewpoint of the hardening ability and properties of the coated film, the hydroxyindole of the acrylic resin is 10 to 300 mg, especially 30 to 250 mg K0H / g; and the nature of the production of propionate,福, r - ene, 〇 観 観 観 ^ ^ ^ ^ ^ ^ ^ ^ ^ 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 The glass transition temperature (Tg) is -20 ° C to 50 ° C, preferably -20 ° C to 40 ° C. In the present patent application, the glass transition temperature (Tg) of the resin is differentially scanned by heat. Determined by the measurement method (DSC). The polyester resin used as the flexible organic element in the preparation of the modified resin (A) may include a polyester resin having a reactive group reactive with a bisphenol epoxy resin. Such a polyester resin may include an oil-free polyester resin, an oil-modified polyester resin, a tamper-modified polyester resin, and a urethane-modified polyester resin. Such a reactive group may include, for example, A carboxyl group, an amine group, a hydroxyl group, etc. Among them, a carboxyl group-containing polyester resin is preferred. Among these polyester resins, the oil-free polyester resin is prepared according to a known method, such as a direct esterification method, an esterification exchange method, a ring opening method, etc. Examples of the direct esterification method may include carrying out a polybasic acid and a polyhydric alcohol. A method of polycondensation reaction. The polybasic acid as a main component may include, for example, at least one selected from the group consisting of phthalic anhydride, isophthalic acid, citric acid, succinic acid, adipic acid, fumaric acid, cis. a di-acid of butenoic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride; a tribasic or higher polybasic acid such as trimellitic anhydride, methylcyclohexenetricarboxylic acid, pyromellitic anhydride, etc. And, in addition to the above acid, a monobasic acid such as benzoic acid, crotonic acid, p-tert-butylbenzoic acid or the like may be optionally included. The polyol as a main component may include, for example, a glycol such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,4-hexanediol. 1,6-hexanediol or the like, and in addition to the above alcohols, may optionally include a trihydric alcohol or a higher-order polyol such as propoxymethylethane, trimethylolpropane, pentaerythritol or the like. The fluorenyl-containing polyacetal resin can be prepared according to a known method, and the package 13-200948908 contains a polybasic acid and a polyhydric alcohol in an excess amount of an acid group relative to a hydroxyl group, or a benzene-based benzene. The polybasic acid such as tricarboxylic anhydride and phthalic anhydride is subjected to a post addition reaction with a hydroxyl group of the hydroxyl group-containing polyester resin. This oil-free polyester resin can also be produced by a polycondensation reaction caused by transesterification between a lower alkyl ester of a polybasic acid and a polyol. In addition, such oil-free polyester resins can also be obtained by lactones (eg <5·valerolactone and ε-caprolactone) were prepared by ring-opening polymerization. This oil-modified polyester resin of a polyester resin is prepared by reacting an oil-free polyester tree with a fatty acid. Such oil fatty acids may include, for example, coconut oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, safflower oil fatty acid, pine oil fatty acid, anhydrous castor oil fatty acid, tung oil fatty acid, and the like. The reaction between the polyester resin and the fatty acid can be carried out in accordance with a known method, and its oil length is usually 30% or less. From the viewpoint of compatibility and reactivity of the polyester resin with the bisphenol epoxy resin, the polyester resin has a weight average molecular weight of from 1,000 to 30,000, particularly from 2,000 to 20,000. The polyester resin has a acid hydrazone of from 3 to 100 mg KOH/g, particularly from 5 to 70 mg KOH/g, from the viewpoints of reactivity and adhesion properties of the polyester resin and the bisphenol epoxy resin. The glass transition temperature (Tg) is from -20 ° C to 50 ° C, preferably from -20 ° C to 40 ° C from the viewpoint of the balance between the properties of the production and the hardness of the resulting coated film. The bisphenol type epoxy resin used in (A) may include, for example, a resin which selectively condenses epichlorohydrin and bisphenol in the presence of a catalyst such as an alkali metal catalyst. And capable of having a high molecular weight; and a resin which is subjected to a condensation reaction of epichlorohydrin and bisphenol selective-14-200948908 in the presence of a catalyst such as an alkali metal catalyst to form a low molecular weight epoxy resin. Then, the low molecular weight epoxy resin and the bisphenol are subjected to addition polymerization. The bisphenol epoxy resin has a number average molecular weight in the range of 3 50 to 5,000, particularly 400 to 4000, and an epoxy group content of 0.5 to 15.4 mmol/g, preferably 0.8 to 10 millimoles per gram. Such bisphenols may preferably include bis(4-hydroxyphenyl)methane [bisphenol F], l,l-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl). Propane [bisphenol A], 2,2-bis(4-hydroxyphenyl)butane [bisphenol B], bis(4-indolyl)-1,1-isobutane, bis(4-hydroxyl) Tert-butylphenyl)-2,2-propane, p-(4-hydroxyphenyl)phenol, bis(4-hydroxyphenyl)oxy, sulfonylbis(4-hydroxyphenyl), 4,4' - Dihydroxydiphenyl ketone, bis(2-hydroxynaphthyl)methane, and the like. Among them, bisphenol A and bisphenol F are preferably used. The above bisphenols may be used singly or in combination. Examples of commercially available bisphenol type epoxy resins may include jER 828, 812, 815, 820' 834, 801, 1004, 1007, 1009, 1010, 4004P, 4007P, 4210 (trade names, all of which are made of Japanese epoxy resin) The company sells and sells; Araldite AER 6099 (trade name, sold by Asahi-Ciba); Epomik R-309 (trade name, sold by Mitsui Chemicals Co., Ltd.). The method of obtaining the modified resin (A) by reacting the flexible organic element with the bisphenol epoxy resin is not particularly limited. For example, if two flexible organic motifs are used, the above method can include a method of simultaneously reacting two flexible organic motifs with a bisphenol epoxy: and a flexible organic motif with a bisphenol ring The method in which the oxy resin is reacted and then reacted with the remaining flexible organic unit. -15- 200948908 The above reaction is preferably carried out at a temperature of, for example, 100 to 15 (TC) for 1 to 5 hours in a solvent capable of simultaneously dissolving the two reactants, and the stomach is selectively present in a reaction catalyst. The reaction catalyst may include, for example, a quaternary salt catalyst such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, tetrabutylammonium bromide, triphenyl chloride Benzene rust, etc.; amines such as triethylamine, tributylamine, etc. In the above reaction, if the reactive group of the flexible organic unit is a mercapto group, (epoxy group in the bisphenol epoxy resin) / (the fluorenyl group in the flexible organic unit) The equivalence ratio of © is in the range of 10/1 to 1/1, preferably 5/1 to 2/1» if the synthesis of the modified resin (A) In the reaction, an acrylic resin having a reactive group is reacted with an epoxy group different from a carboxyl group, except that in the above formula, the "carboxyl group in the flexible organic moiety" is substituted with "a ring different from the carboxyl group". In addition to the reactive group of the oxy group, the equivalent ratio of the respective reactive groups is still in the range of the above formula. When preparing the modified resin (A), the flexible organic group The mixing ratio with the bisphenol epoxy resin is: the flexible organic group is in the range of 5 to 50% by weight, the hydrazine is preferably 10 to 40% by weight, and the bisphenol epoxy resin is 50 to 95% by weight. In the range of 60 to 90% by weight, based on the total weight of the two reactants, respectively, if a combination of an aliphatic polybasic acid and a flexible resin composed of an acrylic resin and/or a polyester resin When used as a flexible organic group in the preparation of the modified resin (A), the mixing ratio of the aliphatic polybasic acid, the flexible resin and the bisphenol epoxy resin in the preparation of the modified resin (A) is: aliphatic The polybasic acid is in the range of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and the flexible resin is in the range of 1 to 49 parts by weight, preferably 7 to 37 parts by weight - 16 - 200948908, and the bisphenol epoxy resin is in the range of 50 to 95 parts by weight, preferably 60 to 90 parts by weight, based on 100 parts by weight of the total weight of the respective reactants, respectively. If the epoxy group remains after the reaction between the flexible organic element and the bisphenol epoxy resin is completed, By blocking the residual epoxy group, the modified resin (A) can be reacted with a blocking agent such as benzoic acid, salicylic acid, or a secondary amine compound. In this case, it is possible to The reaction between the bisphenol epoxy resin reacts with the blocking agent. © The modified resin (A) has a flexible element in the molecular structure, so it can participate in the development and manufacture of stress relaxation in the crosslinked coating film. Partial improvement in manufacturing and adhesion properties, and high corrosion resistance of the resulting coated film. Hardener (B) Hardener (B) reacts with the modified resin (A) to form a hardened coating film, and may include A substance which is hardened by reaction with the modified resin (A) (for example, by heating without particular limitation). Among them, preferred are amino-based resin resins, phenol resins, and selected blocking polyisocyanate compounds. These hardeners may be used singly or in combination. The amine-based resin may include a methylolamine group obtained by reacting an aldehyde with an amine component such as melamine, urea, benzoguanamine, acetamide, stearylamine, spiramide, dicyandiamide or the like. Resin. The aldehyde used in the above reaction may include formaldehyde, trioxane, acetaldehyde, benzaldehyde or the like. The amine-based resin may also include an amine-based resin obtained by etherifying a methylolamine-based resin with a suitable alcohol. Examples of the alcohol used in the etherification reaction may include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylbutanol, 2-ethylhexanol, and the like. -17- 200948908 A phenol resin used as a hardener is reacted with a modified resin (A), which may include, for example, a resol resin which is present in a reaction catalyst by heating a phenol component and formaldehyde. In this case, a condensation reaction is carried out into a methylol group, and then at least a part of the group of the obtained methylol phenol resin is subjected to alkyl etherification reaction with an alcohol. The phenol used as a starting material in the preparation of the resol resin includes a bifunctional phenol compound, a trifunctional phenol compound, and a tetra- or higher phenol compound. © such a phenolic compound may include, for example, a bifunctional phenol compound, polycresol, p-cresol, p-tert-butylphenol, p-acetol, 2,3-indophenol, indophenol, etc.; Phenolic compounds such as phenol, m-cresol, m-ethylphenol, indophenol, m-methoxyphenol, etc.; tetrafunctional phenol compounds such as bisphenol A, bis, and the like. For the purpose of improving scratch resistance, a trifunctional or higher compound is preferred, particularly phenol and/or m-cresol. These phenol compounds are used singly or in combination. The formaldehyde which can be used for the preparation of the phenol resin may include formaldehyde, trimeric methyltriazine, and the like, and they may be used singly or in combination. The alcohol in the partial alkyl etherification of the methylol group in the methylol phenol resin is preferably a monohydric alcohol having 1 to 8 carbon atoms, and has 1 to 4 carbon atoms, particularly methanol. , ethanol, n-propanol butanol, isobutanol and the like. From the viewpoint of reactivity with the modified resin (A), the number of the average alkoxymethyl groups on the benzene rings of the phenol resin is 0.5 or more, more preferably from 0.6 to 3.0. The phenolic aldehyde which is used in the hardening agent to block the polyisocyanate compound and to make it possible to use 13 o-2.5-3.5-phenol F which is possible to induce hydroxyl groups, is better and more suitable. Non--18- 200948908 Blocking polyisocyanate compounds may include organic diisocyanates such as aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.; alicyclic diisocyanates such as hydrogenation Diisocyanate, isophorone diisocyanate, etc.; and aromatic diisocyanates such as toluene diisocyanate, decyl diisocyanate, 4,4'-diphenylmethane diisocyanate, crude MDI, etc.; these organic diisocyanates and polyols An adduct of a low molecular weight polyester resin or water; a cyclic polymer between the above organic diisocyanates; an isocyanate biuret or the like. The blocking polyisocyanate compound which can be used as a crosslinking agent is a compound obtained by blocking a free isocyanate group in a polyisocyanate compound by a blocking agent. The blocking agent for blocking the isocyanate group may include, for example, phenols such as phenol, cresol, indophenol; indoleamine such as ε-caprolactam, 5-pentalase, 7- Butanolamine, etc.; alcohols such as methanol, ethanol, n-, iso- or tert-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol mono Ether, benzyl alcohol, etc.; anthracene, such as methotrexate, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, butanone oxime, diphenyl ketone oxime, cyclohexanone oxime, etc.; and active methylene A substance such as dimethyl oxalate, diethyl malonate, ethyl acetate, acetone, and the like. By mixing the polyisocyanate compound with a blocking agent, the free isocyanate group in the polyisocyanate compound can be easily blocked. From the viewpoints of starvation resistance, boiling water resistance, manufacturing properties, hardening properties, etc., the amount of the modified resin (Α) and the hardener (Β) should be such that the amount of the modified resin (Α) is 55 to 95 by weight. In the range of parts, preferably 60 to 95 parts by weight 'and the hardener (Β) is in the range of 5 to 45 parts by weight 'preferably 5 to 40 parts by weight, which is 1 〇〇. The parts by weight of the ingredients (Α) -19- 200948908 and (B) the total solids content is the basis. In order to promote the hardening reaction of the coating composition, a hardening catalyst may be selectively used, and may be arbitrarily selected, depending on the kind of the hardener to be used. If the hardener (B) is an amine-based resin, in particular an etherified melamine resin mixed with methyl etherification or methyl ether butyl ether, the hardening catalyst is an amine neutralized product comprising a sulfonic acid compound and a sulfonic acid compound. It is better. Typical examples of the sulfonic acid compound may include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid © , dinonylnaphthalene disulfonic acid, and the like. The amine used in the amine neutralizing product of the sulfonic acid compound may include a primary amine, a secondary amine, and a tertiary amine. From the viewpoints of stability of the coating composition, promotion of the reaction effect, properties of the obtained coating film, and the like, among them, an amine neutralized product of p-toluenesulfonic acid and/or an amine neutralized product of dodecylbenzenesulfonic acid is preferred. . If the hardener (B) is a phenol resin, the hardening catalyst may include an amine neutralized product of a sulfonic acid compound and a sulfonic acid compound. If the hardener (B) is a blocking polyisocyanate compound, it is preferred to have a hardening catalyst which acts as a hardener to block the blocking of the polyisocyanate compound. Examples of preferred hardening catalysts may include organometallic catalysts such as tin zincate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin. Diacetate, dioctyltin dilaurate, dibutyltin oxide, dioctyl tin oxide, lead diethyl hexanoate, and the like. If the hardener is a combination of two or more hardeners, the hardening catalyst may comprise a combination of individual hardening catalysts which may be effective for the individual hardeners. Anti-corrosion pigments (ΓΛ Anti-corrosion uranium pigments may include chrome-based pigments and chrome-free pigments. This pigment has to be exhibited -20- 200948908. It has anti-corrosion properties. From the viewpoint of human health and environmental protection, it is preferably chrome-free. Corrosion-resistant pigments. Chromium-based anti-corrosion pigments may include, for example, chromic acid saws, zinc chromate, potassium zinc chromate, strontium chromate, chromic chromates, chromium phosphates, etc. Chromium-free anti-corrosive uranium pigments may include For example, zinc phosphate, aluminum tripolyphosphate, zinc molybdate, calcium citrate, vanadium pentoxide, calcium vanadate, ammonium metavanadate, phosphorus vanadate, aluminum phosphate, calcium phosphate, magnesium hydrogen phosphate, calcium oxide and A calcined product of vanadium oxide, having an oil absorbance of 30 to 200 ml/100 g and a ceria particle having a pore volume r 〇 of 0.05 to 1.2 ml/g, etc. These anticorrosive pigments may be used singly or in combination. Among the above chromium-free anticorrosive pigments, as described below, a combination of (1) a vanadium compound, (2) a ruthenium-containing compound, and (3) a phosphate-based metal salt is particularly suitable for use in the coating composition of the present invention. Vanadium compound (ΠVanadium compound (1) can be packaged At least one vanadium compound selected from the group consisting of vanadium pentoxide, calcium vanadate and ammonium metavanadate. The vanadium pentoxide, calcium vanadate and ammonium metavanadate can exhibit excellent pentavalent vanadium ions in water. The properties of the pentavalent vanadium ion released from the vanadium compound (1) are effective in improving the corrosion resistance due to the reaction with the substrate metal or the reaction with ions from other anticorrosive pigment mixtures. Ruthenium compound (2) The ruthenium-containing compound (2) is at least one ruthenium-containing compound selected from the group consisting of metal ruthenate and ruthenium dioxide particles. Metal ruthenate is a salt composed of ruthenium dioxide and a metal oxide. It may include n-decanoate, polysilicate, etc. Such a bismuth may include, -21 - 200948908, for example, 'zinc citrate, aluminum citrate, aluminum orthosilicate, aluminum citrate, calcium citrate, Sodium aluminum silicate, strontium aluminum citrate, sodium citrate, calcium orthosilicate, calcium metasilicate, calcium citrate, chromium citrate, magnesium orthosilicate, magnesium metasilicate, calcium magnesium citrate, acid Manganese, bismuth ruthenate, olivine, garnet, vermiculite, heteropolar ore, blue cone Column star boulder, beryl, diopside, ash, rhodochrosite, tremolite, hard strontite, talc, fisheye, aluminosilicate, borosilicate, strontium, feldspar, zeolite The metal ruthenate (2) preferably comprises calcium orthosilicate and calcium metasilicate. The above-mentioned cerium oxide particles may include any of the cerium oxide particles, and are not particularly limited, for example, without surface treatment. Cerium sulphide particles, cerium oxide particles surface treated with organic substances, calcium ion exchanged cerium oxide particles, organic solvent dispersible colloidal cerium oxide, etc. Surface-treated cerium oxide particles or organic The material-surface-treated cerium oxide microparticles may include cerium oxide microparticles having an average particle diameter of 0.5 to 15 μm, preferably 1 to 10 μm, and an organic solvent-dispersible colloidal cerium oxide. Such cerium oxide microparticles preferably include cerium oxide microparticles having an oil absorbance of 30 to 350 cc / 100 gram (more preferably 30 to 150 ml / 100 gram). The trade name may include, for example, Sylysia 710, Sylysia 740, Sylysia 550, Aerosil R972 (trade name, sold by Fuji Sylysia Chemical Co., Ltd., respectively), MIZUKASIL (trade name, sold by Mizusawa Chemical Industry Co., Ltd.), Gasil 200DF (trade name, sold by Crosfield Chemicals Inc.), etc. The calcium ion-exchanged cerium oxide microparticles are cerium oxide microparticles obtained by ion exchange of calcium ions onto a fine porous cerium oxide carrier. The trade name for calcium ion exchange of ruthenium dioxide, such as ' SHIELDEX (trademark) C303, SHIELDEX AC-3, SHIELDEX AC-5 (J, respectively, by W.R. -22- 200948908

Grace公司銷售）等。由鈣離子交換二氧化矽放出的鈣離子可 參與電化學作用及各種成鹽作用，並且可有效改善耐蝕性 。固定於塗布薄膜中的二氧化矽可有效控制塗布薄膜在腐 蝕性環境中的剝離。這種有機溶劑可分散之膠態二氧化矽 可以是有機二氧化矽溶膠，並且係穩定分散於有機溶劑中 ，如醇類、二醇類、醚類等，成爲粒徑約爲5至120奈米 之二氧化矽微粒。其商品名稱可包括，例如，0SCAL系列（ 商品名稱，由日揮觸媒化成股份有限公司銷售）、ORGANO © SOL(商品名稱，由日產化學工業股份有限公司銷售）等。其 中以鈣離子交換·二氧化矽微粒爲較佳。 各種做爲含矽化合物（2)之金屬矽酸鹽類和二氧化矽 微粒可以單獨使用或者是組合使用。 磷酸鹽系金靨鹽η) 磷酸鹽系金屬鹽（3)可包括至少一種選自磷酸金屬鹽 、磷酸氫金屬鹽和三聚磷酸金屬鹽之磷酸鹽系金靥鹽，並 且在各別金靥鹽中的金屬爲鈣、鋅、鋁或鎂》 〇 磷酸鹽系金屬鹽可包括，例如，磷酸鈣、磷酸銨鈣、 磷酸一氫鈣、磷酸二氫鈣、磷酸氟氯鈣、磷酸鋅、磷酸鋁 、磷酸鎂、磷酸氫鋅、磷酸鋁、磷酸鎂、磷酸氫鋁、磷酸 氫鎂、磷酸銨鎂、三聚磷酸二氫鋁等。由耐蝕性的觀點來 看，其中以磷酸鈣、磷酸一氫鈣和磷酸二氫鈣爲較佳。 由磷酸鹽系金屬鹽（3)分別放出的磷酸鹽離子和金屬 離子（如鈣離子、鋅離子、鋁離子和鎂離子等）可有效改善 耐蝕性。 在本發明之塗布組成物中，抗腐蝕顔料（C)含有（1)至少 -23- 200948908 一種釩化合物，其係選自五氧化二釩、釩酸鈣和偏釩酸銨 ，（2)至少一種含矽化合物，其係選自金屬矽酸鹽和二氧化 矽微粒，（3)磷酸鹽系金屬鹽；並且釩化合物（1)是在3至50 重量份數的範圍內，含矽化合物（2)是在3至50重量份數的 範圍內且磷酸鹽系金屬鹽（3)是在3至50重量份數的範圍內 ，並且化合物（1)、化合物（2)及鹽（3)的總量是在10至150 重量份數的範圍內，較佳爲15至90重量份數，其係分別 以每100重量份數的樹脂（A)及硬化劑（B)總固體含量爲基 ©準。 在本發明之塗布組成物中，化合物（1)、化合物（2)及金 屬鹽（3)以各別指定的數量組合而成的抗腐蝕顏料組成物 可協力增強耐蝕性的改善。 本發明之塗布組成物除了改質樹脂（A)、硬化劑（B)、 抗腐蝕顏料（C)及選擇性使用的硬化觸媒之外，可選擇性地 含有已知可用於塗布組成物領域的賦黏劑、彩色顏料、塡 充顏料、紫外線吸收劑、紫外線安定劑、有機溶劑；添加 〇 劑，如防沈劑、消泡劑、塗布表面控制劑等。 這種賦黏劑可包括含二級或三級胺基的環氧樹脂及含 二級或三級胺基的丙烯酸樹脂。如同在硬化劑（B)中所說明 ，可溶酚醛樹脂也可以做爲賦黏劑。 含二級或三級胺基之樹脂是具有環氧樹脂骨幹及二級 或三級胺基的樹脂，並且環氧樹脂骨幹可包括雙酚環氧樹 脂骨幹、酚醛環氧樹脂骨幹等。 含二級或三級胺基之環氧樹脂可藉由（例如）將胺化合 物添加至環氧基（如環氧丙基）以引入二級或三級胺基而獲 -24- 200948908 得。由環氧樹脂與胺化合物之反應性的觀點來看，這種環 氧樹脂以具有200至1000環氧當量爲佳，並且較佳係包括 雙酚環氧樹脂和酚醛環氧樹脂。 如果使用的是雙酚環氧樹脂，在樹脂骨幹或在端基具 有二級或三級胺基的環氧樹脂可藉由將具有400至1000環 氧當量的雙酚環氧樹脂與一級或三級胺化合物反應而得。 如果是使用酚醛環氧樹脂，由於通常是使用具有200至500 環氧當量的酚醛環氧樹脂，並且其與一級胺化合物的反應 〇 可導致在製備時很容易發生膠凝，所以酚醛環氧樹脂較佳 係與二級胺化合物反應，如N-甲基乙醇胺、二乙醇胺等， 以獲得具有高二級或三級胺基含量的酚醛環氧樹脂。 含胺基的丙烯酸樹脂可包括，例如，將含環氧基之丙 烯酸單體（如甲基丙烯酸環氧丙酯）共聚合作用所產生的丙 烯酸樹脂與一級或二級胺化合物反應所獲得之丙烯酸樹脂 ，以及含三級胺基之丙烯酸酯或甲基丙烯酸酯單體（如Ν,Ν-二甲基胺乙基（甲基）丙烯酸酯和Ν,Ν-二甲基胺丙基（甲基） 〇 丙烯酸酯）共聚合作用所形成的丙烯酸樹脂。 在上述賦黏劑（D)之中，由塗布薄膜因抗刮性質而需要 韌度的觀點來看，以環氧樹脂爲較佳，但若由耐水性和耐 化學性的觀點來看，則以丙烯酸樹脂爲較佳。可以將兩或 以上種類的賦黏劑選擇性地組合使用。 彩色顏料可包括，例如，有機彩色顏料，如花青藍、 花青綠；有機紅色顏料，如偶氮顏料和喹吖啶酮顔料等； 無機彩色顏料鈦白、鈦黃、赤鐵氧化物、碳黑、各種煅燒 顔料，其中以鈦白爲較佳。 -25- 200948908 塡充顏料可包括，例如，滑石、黏土、雲母、氧化鋁 、碳酸鈣、硫酸鋇等。 紫外線吸收劑可包括，例如，苯并三唑衍生物，如2-(2-羥基-3,5-二-第三戊苯基）-2H-苯并三唑、異辛基-3-(3-(2H-苯并三唑-2-基）-5-第三丁基-4-羥苯基）丙酸酯、2-[2-羥基 -3,5-二（1,1-二甲基石油醚）苯基]-2H-苯并三唑、2-[2·羥基 -3-二甲基苄基- 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-羥苯基]丙 © 酸酯與聚乙二醇300的縮合產物等；三嗪衍生物，如2-[4-(2-羥基-3-十二氧丙基）氧基]-2-羥苯基-4,6-雙（2，4-二甲基苯 基）-1，3,5-1，3,5-三嗪等；草酸苯胺衍生物，如乙二醯胺 -1(2-乙氧苯基）卞’-(2-乙基苯基）-(草醯胺）、乙二醯胺 ->1-(2-乙氧苯基）-1^’-(4-異十二基苯基）-(草醯胺）等。 紫外線安定劑可包括，例如，受阻胺系化合物、受阻 酚系化合物；CHIMASORB 944、TINUVIN 144、TINUVIN 292、 TINUVIN 770、IRGANOX 1010、IRGANOX 1098(商品名稱，分別 Ο 係由Ciba特化品股份有限公司銷售），等等。 將紫外線吸收劑和紫外線安定劑添加至塗料組成物中 ，可使得它能夠控制塗布薄膜表面被光線降解，並且，當 此種塗布組成物被用來做爲底漆塗布組成物時，可使得它 能夠控制底漆塗布薄膜表面被經由面漆到達底漆塗布薄膜 表面之光線降解，而可避免底漆塗布薄膜和面漆薄膜之間 的層間漆因爲底漆塗布薄膜表面降解而剝離，並且可以維 持優異的耐蝕性。 用於本發明之塗布組成物的有機溶劑可包括爲了改善 -26- 200948908 本發明塗布組成物之塗布性質而選擇性添加的有機溶劑； 能夠溶解或分散含羥基之成膜樹脂（A)及交聯劑（B)的有機 溶劑，特別是（例如）烴類溶劑，如甲苯、二甲苯、高沸點 石油系的烴類等；酮類溶劑，如甲基乙酮、甲基異丁酮、 環己酮、異佛酮等；酯類溶劑，如乙酸乙酯、乙酸丁酯、 乙二醇一乙醚乙酸酯、二乙二醇一乙醚乙酸酯等；醇類溶 劑，如甲醇、乙醇、異丙醇、丁醇等；醚醇溶劑，如乙二 醇一乙醚、乙二醇一丁醚、二乙二醇一丁醚等等。這些溶 〇 劑可單獨使用或者是組合使用。 由耐蝕性、耐酸性、製造性質等觀點來看，本發明之 塗布組成物可使得由本發明之組成物所獲得硬化塗布薄膜 的玻璃轉移溫度在40至115 °C的範圍內，較佳爲50至105 °C 。在本發明中，塗布薄膜的玻璃轉移溫度爲因溫度分散而 造成tan 5改變所測得的最大溫度，其係使用型號爲Vibron DDV-II EA的動態黏彈量測儀（自動黏彈性量測儀器，由 TOYO BALDWIN公司銷售）在頻率1 10 Hz的條件下進行量測 ❹ 。 本發明之塗布組成物係塗布在金屬片之上，並且所得 之塗布薄膜可呈現出優異的耐蝕性，這是因爲本發明之塗 布組成物中的樹脂基元具有優異的應力鬆弛性質，並且可 以使它形成一種塗布薄膜，其在彈性模數和拉伸模數之間 具有優異的平衡性。 經塗布的金靥片 本發明之經塗布的金屬片具有一層塗布薄膜，其係藉 由將本發明之塗布組成物塗布在做爲基板的金屬片之上， -27- 200948908 接著予以硬化而形成。 這種做爲基板的金屬片可包括冷軋鋼片、熱浸鍍鋅片 、電鍍鍍鋅片、鍍鐵-鋅合金鋼片（鍍鋅退火鋼片）、鍍鋁-鋅合金鋼片（“ galvalume鋼片”，在合金中含有約55 %的鋁 ，“ galfan” ，在合金中含有約5%的鋁等）、鍍鎳-鋅合金鋼 片、不銹鋼片、鋁片、銅片、鍍銅鋼片、鍍錫鋼片等。這 些金屬片可以選擇性地施以傳統的金靥表面處理方法，例 如，磷酸鹽處理方法，如磷酸鋅處理方法、磷酸鐵處理方 © 法等、複合氧化物薄膜處理方法、鉻磷酸鹽處理方法、鉻 酸鹽處理方法等。 本發明之塗布組成物可以藉由傳統的塗布方法塗布於 金屬片之上，如輥塗法、淋幕塗布法、噴塗法、刷塗法、 浸塗法等。由本發明之塗布組成物所形成之塗布薄膜的膜 厚並沒有特別的限制，但是通常是在2至1 0微米的範圍內 ，較佳爲3至6微米。塗布薄膜的乾燥可以在適當條件下 進行，但是如果藉由線圈塗布法形成之塗布薄膜被連續熱 〇 硬化，則通常可以在160至250°C，較佳爲180至230°C， 的基板最大溫度下進行熱硬化15至60秒。在批次方法中 ，通常可以在80至200°C的周圍溫度下進行熱硬化10至 30秒。 如果在形成塗布薄膜的交聯反應中不需要加熱，例如 ，如果用來做爲硬化劑（B)的是非阻斷聚異氰酸酯化合物， 可以依照傳統方法，在被硬化的室溫下進行乾燥。 本發明之經塗布金屬片可以包括只由本發明塗布組成 物在選用之經表面處理金屬片上形成塗布薄膜的金屬片， -28- 200948908 也可以包括在上述塗布薄膜之上具有面漆薄膜的金屬片。 這種面漆薄膜的膜厚是在8至30微米的範圍內，較佳爲10 至25微米。 形成面漆薄膜的面漆組成物可包括傳統上用於預塗金 屬片的面漆組成物，例如，聚酯樹脂系、醇酸樹脂系、矽 改質聚酯樹脂系、矽改質丙烯酸樹脂系、氟碳樹脂系面漆 組成物。如果製造性質相當重要，使用具有良好製造性質 的面漆組成物可以獲得具有特別良好製造性質之經塗布金 ❹ 屬板，如聚酯樹脂系面漆組成物。在本發明中具有上述面 漆薄膜之經塗布金屬片可在耐蝕性方面展現出良好的薄膜 功能。 在此技術領域中，對於鍍鋅鋼片及鍍鋁-鋅合金鋼片而 言，其在非製造平坦部分的耐蝕性已有某種程度的改善， 但是在切削邊緣表面部分及製造部分的耐蝕性卻不令人滿 意。相反地，塗上本發明之塗布組成物可在邊緣表面部分 及製造部分得到優異的耐蝕性。 〇 來自本發明之塗布組成物的塗布薄膜可以在基板的兩 側同時形成，並且面漆薄膜可以選擇性地在來自本發明之 塗布組成物的塗布薄膜上形成。如果使用無鉻抗腐蝕顏料 做爲本發明之塗布組成物中的抗腐蝕顏料時，由本發明之 塗布組成物所形成的塗布薄膜可獲得不含鉻系抗腐蝕顏料 的經塗布金屬片，同時亦有利於環境保護及健康，並且能 夠展現出優異的耐鈾性。 實施例 本發明將參考以下的製備實施例及實施例做更詳盡的 -29- 200948908 解釋。本發明不應侷限於以下的實施例。在下文中，“份 數”及“ ％ ”係分別代表“重量份數”及“重量％ ” 。 合成實施例1 撓性丙烯酸樹脂AC1溶液的製備 在裝配了攪拌器、冷凝器、溫度計、氮氣入口及滴料 裝置的反應器中裝入65.0份的SWA SOL 1000(商品名稱， 由Maruzen石化公司銷售，高沸點的芳香石油溶劑），接著 在攪拌的同時，將反應器內的溫度提升至11 0°C之間，並且 〇 將包含單體的下列起始材料之混合物以超過3小時的時間 滴入，同時亦將溫度維持在110°C。 苯乙烯 1 8.4份 甲基丙烯酸甲酯 31.2份 丙烯酸正丁酯 37.5份 丙烯酸2-羥乙酯 11.0份 丙烯酸 1.9份 2,2’-偶氮雙異丁腈 1.7份 Ο 在完全滴入之後，加入0.5份的2,2’-偶氮雙異丁腈， 接著在該溫度下反應2小時，並且加入3 5.0份的環己酮， 以獲得固體含量爲50%的撓性丙烯酸樹脂AC1溶液。丙烯 酸樹脂AC1溶液的酸値爲15毫克K0H/克，羥値爲53毫克 K0H/克，玻璃轉移溫度爲5eC且數目平均分子量約爲10000 〇 合成實施例2-10 除了使用表1中配方所示的單體組成物之外，重覆製 備實施例1之程序，以分別獲得具有50%固體含量之撓性 -30- 200948908 丙烯酸樹脂AC2至AC10。 合成實施例1 1 在裝配了攪拌器、加熱器、溫度計、分離器及蒸餾液 儲存容器的反應器中裝入下列起始材料之混合物，接著予 以加熱。 新戊二醇 105份 1,6-己二醇 354份 六氫酞酸酐 564份 己二酸 123份 在開始加熱之後而可以進行攪拌時，於排放冷凝液的 同時開始進行攪拌，並且使溫度上升至240°C，接著在該溫 度下進一步進行反應，在水停止流出1.5小時之後，裝入 40份的二甲苯以促進反應，並且進一步進行脫氫縮合，直 到酸値變成52，使之冷卻並且加入417份稀釋用的環己酮 ，以獲得固體含量爲70%的聚酯樹脂PE1溶液。聚酯樹脂 PE1的數目平均分子量爲2100。 φ 合成實施例1 2 -1 5 除了使用表1中所示的配方之外，重覆製備實施例11 之程序，以獲得撓性聚酯樹脂PE2至PE5。表1中所示的 配方係代表重量。 -31- 200948908 ο ο Ο) ρGrace sales) and so on. Calcium ions released by calcium ion exchange of ceria can participate in electrochemical action and various salt formation effects, and can effectively improve corrosion resistance. The cerium oxide fixed in the coated film can effectively control the peeling of the coated film in a corrosive environment. The organic solvent dispersible colloidal cerium oxide may be an organic cerium oxide sol, and is stably dispersed in an organic solvent such as an alcohol, a glycol, an ether or the like to have a particle diameter of about 5 to 120 Å. Rice cerium oxide particles. The trade name may include, for example, the 0SCAL series (trade name, sold by Nisko Touch Chemical Co., Ltd.), ORGANO © SOL (trade name, sold by Nissan Chemical Industries Co., Ltd.), and the like. Among them, calcium ion-exchanged cerium oxide particles are preferred. The various metal silicates and cerium oxide particles as the cerium-containing compound (2) may be used singly or in combination. Phosphate-based metal ruthenium salt η) The phosphate-based metal salt (3) may include at least one phosphate-based metal ruthenium salt selected from the group consisting of a metal phosphate, a metal hydrogen phosphate, and a metal phosphate, and is in each case. The metal in the salt is calcium, zinc, aluminum or magnesium. The phosphonium phosphate metal salt may include, for example, calcium phosphate, calcium ammonium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium chlorophosphate, zinc phosphate, phosphoric acid. Aluminum, magnesium phosphate, zinc hydrogen phosphate, aluminum phosphate, magnesium phosphate, aluminum hydrogen phosphate, magnesium hydrogen phosphate, magnesium ammonium phosphate, aluminum dihydrogen phosphate, and the like. From the viewpoint of corrosion resistance, calcium phosphate, calcium monohydrogen phosphate and calcium dihydrogen phosphate are preferred. Phosphate ions and metal ions (e.g., calcium ions, zinc ions, aluminum ions, and magnesium ions) which are respectively released from the phosphate metal salt (3) can effectively improve corrosion resistance. In the coating composition of the present invention, the anticorrosive pigment (C) contains (1) at least -23-200948908 a vanadium compound selected from the group consisting of vanadium pentoxide, calcium vanadate and ammonium metavanadate, and (2) at least An antimony-containing compound selected from the group consisting of metal citrate and cerium oxide microparticles, (3) a phosphate metal salt; and the vanadium compound (1) is in the range of 3 to 50 parts by weight, containing a cerium compound ( 2) is in the range of 3 to 50 parts by weight and the phosphate metal salt (3) is in the range of 3 to 50 parts by weight, and the compound (1), the compound (2) and the salt (3) The total amount is in the range of 10 to 150 parts by weight, preferably 15 to 90 parts by weight, based on the total solid content per 100 parts by weight of the resin (A) and the hardener (B), respectively. quasi. In the coating composition of the present invention, the anticorrosive pigment composition in which the compound (1), the compound (2) and the metal salt (3) are combined in each of the specified amounts can synergistically enhance the improvement of the corrosion resistance. The coating composition of the present invention may optionally contain, in addition to the modified resin (A), the hardener (B), the anti-corrosive pigment (C), and the selectively used hardening catalyst, a field known to be useful for coating compositions. Adhesives, color pigments, enamel pigments, UV absorbers, UV stabilizers, organic solvents; addition of tinctures, such as anti-settling agents, defoamers, coating surface control agents. Such a binder may include an epoxy resin containing a secondary or tertiary amine group and an acrylic resin containing a secondary or tertiary amine group. As explained in the hardener (B), the resol resin can also be used as a tackifier. The resin containing a secondary or tertiary amine group is a resin having an epoxy resin backbone and a secondary or tertiary amine group, and the epoxy resin backbone may include a bisphenol epoxy resin backbone, a phenolic epoxy backbone, and the like. The epoxy resin containing a secondary or tertiary amine group can be obtained, for example, by adding an amine compound to an epoxy group such as a glycidyl group to introduce a secondary or tertiary amine group, which is obtained from -24 to 200948908. The epoxy resin is preferably from 200 to 1,000 epoxy equivalents from the viewpoint of reactivity of the epoxy resin with the amine compound, and preferably includes a bisphenol epoxy resin and a novolac epoxy resin. If a bisphenol epoxy resin is used, an epoxy resin having a secondary or tertiary amine group at the resin backbone or at the terminal group can be made of a bisphenol epoxy resin having 400 to 1000 epoxy equivalents with one or three The amine compound is obtained by reaction. If a phenolic epoxy resin is used, since a phenolic epoxy resin having 200 to 500 epoxy equivalents is usually used, and its reaction with the primary amine compound can cause gelation easily during preparation, the novolac epoxy resin It is preferred to react with a secondary amine compound such as N-methylethanolamine, diethanolamine or the like to obtain a novolac epoxy resin having a high secondary or tertiary amine group content. The amino group-containing acrylic resin may include, for example, acrylic acid obtained by reacting an acrylic resin produced by copolymerization of an epoxy group-containing acrylic monomer such as glycidyl methacrylate with a primary or secondary amine compound. Resins, as well as acrylate or methacrylate monomers containing tertiary amine groups (eg hydrazine, hydrazine-dimethylamine ethyl (meth) acrylate and hydrazine, hydrazine-dimethylaminopropyl (methyl) An acrylic resin formed by copolymerization of hydrazine acrylate). Among the above-mentioned tackifiers (D), an epoxy resin is preferred from the viewpoint that the coating film requires toughness due to scratch resistance, but from the viewpoint of water resistance and chemical resistance, Acrylic resin is preferred. Two or more types of adhesives may be selectively used in combination. The color pigments may include, for example, organic color pigments such as cyanine blue, cyanine green; organic red pigments such as azo pigments and quinacridone pigments; inorganic color pigments titanium white, titanium yellow, erythritol oxide, carbon black And various calcined pigments, of which titanium white is preferred. -25- 200948908 The extender pigment may include, for example, talc, clay, mica, alumina, calcium carbonate, barium sulfate, and the like. The ultraviolet absorber may include, for example, a benzotriazole derivative such as 2-(2-hydroxy-3,5-di-p-pentylphenyl)-2H-benzotriazole, isooctyl-3-( 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate, 2-[2-hydroxy-3,5-di(1,1-di) Methyl petroleum ether) phenyl]-2H-benzotriazole, 2-[2.hydroxy-3-dimethylbenzyl-5-(1,1,3,3-tetramethylbutyl)phenyl ]·2Η-benzotriazole, methyl 3-[3-t-butyl-5-(2Η-benzotriazol-2-yl)-4-hydroxyphenyl]propanoate and polyethyl b a condensation product of diol 300, etc.; a triazine derivative such as 2-[4-(2-hydroxy-3-dodeoxypropyl)oxy]-2-hydroxyphenyl-4,6-bis (2, 4-dimethylphenyl)-1,3,5-1,3,5-triazine, etc.; aniline oxalic acid derivatives such as ethanediamine-1 (2-ethoxyphenyl) 卞'-(2 -ethylphenyl)-(prasamine), ethylenediamine-> 1-(2-ethoxyphenyl)-1^'-(4-isododecylphenyl)-(oxalin )Wait. The UV stabilizer may include, for example, a hindered amine compound, a hindered phenol compound; CHIMASORB 944, TINUVIN 144, TINUVIN 292, TINUVIN 770, IRGANOX 1010, IRGANOX 1098 (trade name, respectively, by Ciba Specialty Chemicals Co., Ltd. Sales), and so on. The addition of the ultraviolet absorber and the ultraviolet stabilizer to the coating composition allows it to control the surface degradation of the coated film, and when such a coating composition is used as a primer coating composition, it can be made The surface of the primer coating film can be controlled to be degraded by the light reaching the surface of the primer coating film through the topcoat, and the interlayer paint between the primer coating film and the topcoat film can be prevented from being peeled off due to surface degradation of the primer coating film, and can be maintained. Excellent corrosion resistance. The organic solvent used for the coating composition of the present invention may include an organic solvent which is selectively added to improve the coating property of the coating composition of the present invention from -26 to 200948908; capable of dissolving or dispersing the hydroxyl group-containing film-forming resin (A) and The organic solvent of the crosslinking agent (B), in particular, for example, a hydrocarbon solvent such as toluene, xylene, a hydrocarbon having a high boiling point petroleum, etc.; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, or a ring Ethyl ketone, isophorone, etc.; ester solvents, such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.; alcohol solvents, such as methanol, ethanol, Isopropanol, butanol, etc.; ether alcohol solvent, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and the like. These solvants may be used singly or in combination. The coating composition of the present invention can make the glass transition temperature of the cured coating film obtained from the composition of the present invention in the range of 40 to 115 ° C, preferably 50, from the viewpoints of corrosion resistance, acid resistance, manufacturing properties and the like. Up to 105 °C. In the present invention, the glass transition temperature of the coated film is the maximum temperature measured by the temperature dispersion, and the dynamic viscoelasticity meter (automatic viscoelasticity measurement) using the model Vibron DDV-II EA is used. The instrument, sold by TOYO BALDWIN, was measured at a frequency of 10 Hz. The coating composition of the present invention is coated on a metal sheet, and the resulting coated film can exhibit excellent corrosion resistance because the resin element in the coating composition of the present invention has excellent stress relaxation properties and can It is formed into a coated film which has an excellent balance between the elastic modulus and the tensile modulus. Coated Metal Sheet The coated metal sheet of the present invention has a coated film formed by coating the coating composition of the present invention on a metal sheet as a substrate, -27-200948908, followed by hardening. . Such a metal sheet as a substrate may include cold rolled steel sheets, hot dip galvanized sheets, electrogalvanized sheets, iron-zinc alloy steel sheets (galvanized annealed steel sheets), and aluminized-zinc alloy steel sheets ("galvalume" Steel sheet", containing about 55 % aluminum in the alloy, "galfan", containing about 5% aluminum in the alloy, etc.), nickel-zinc alloy steel sheet, stainless steel sheet, aluminum sheet, copper sheet, copper plated steel Sheet, tin plated steel sheet, etc. These metal sheets can be selectively subjected to a conventional metal ruthenium surface treatment method, for example, a phosphate treatment method such as a zinc phosphate treatment method, an iron phosphate treatment method, a composite oxide film treatment method, and a chromium phosphate treatment method. , chromate treatment methods, etc. The coating composition of the present invention can be applied to a metal sheet by a conventional coating method such as a roll coating method, a curtain coating method, a spray coating method, a brush coating method, a dip coating method, or the like. The film thickness of the coating film formed by the coating composition of the present invention is not particularly limited, but is usually in the range of 2 to 10 μm, preferably 3 to 6 μm. The drying of the coated film can be carried out under appropriate conditions, but if the coated film formed by the coil coating method is continuously heat-cured, it can usually be at a maximum of 160 to 250 ° C, preferably 180 to 230 ° C. Thermal hardening is carried out at a temperature for 15 to 60 seconds. In the batch process, heat hardening can usually be carried out at an ambient temperature of 80 to 200 ° C for 10 to 30 seconds. If heating is not required in the crosslinking reaction for forming the coating film, for example, if it is used as the hardener (B) as a non-blocking polyisocyanate compound, drying can be carried out at room temperature under hardening according to a conventional method. The coated metal sheet of the present invention may comprise a metal sheet which is formed from a coating composition of the present invention on a selected surface treated metal sheet, and -28-200948908 may also include a metal sheet having a top coat film on the above coated film. . The film thickness of such a topcoat film is in the range of 8 to 30 μm, preferably 10 to 25 μm. The topcoat composition forming the topcoat film may include a topcoat composition conventionally used for precoating a metal sheet, for example, a polyester resin type, an alkyd resin type, a tamper type polyester resin type, a tamper type acrylic resin A fluorocarbon resin topcoat composition. If the manufacturing properties are quite important, a coated metal enamel sheet having particularly good manufacturing properties, such as a polyester resin topcoat composition, can be obtained by using a topcoat composition having good manufacturing properties. The coated metal sheet having the above-mentioned topcoat film in the present invention exhibits a good film function in terms of corrosion resistance. In this technical field, for galvanized steel sheets and aluminized-zinc alloy steel sheets, the corrosion resistance in the non-manufactured flat portion has been improved to some extent, but the corrosion resistance at the surface portion of the cutting edge and the manufacturing portion is improved. Sex is not satisfactory. On the contrary, application of the coating composition of the present invention provides excellent corrosion resistance at the edge surface portion and the manufactured portion.涂 A coated film from the coating composition of the present invention may be simultaneously formed on both sides of the substrate, and a top coat film may be selectively formed on the coated film from the coating composition of the present invention. If a chromium-free anticorrosive pigment is used as the anticorrosive pigment in the coating composition of the present invention, the coated film formed from the coating composition of the present invention can obtain a coated metal sheet containing no chromium-based anticorrosive pigment, and also Conducive to environmental protection and health, and can show excellent uranium resistance. EXAMPLES The present invention will be explained in more detail with reference to the following Preparation Examples and Examples -29-200948908. The invention should not be limited to the following examples. In the following, "parts" and "%" represent "parts by weight" and "% by weight", respectively. Synthesis Example 1 Preparation of Flexible Acrylic Resin AC1 Solution In a reactor equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet, and a dropping device, 65.0 parts of SWA SOL 1000 (trade name, sold by Maruzen Petrochemical Company) was charged. , a high-boiling aromatic petroleum solvent), and then, while stirring, the temperature in the reactor is raised to between 110 ° C, and the mixture of the following starting materials containing the monomer is dropped over a period of more than 3 hours. Into, while maintaining the temperature at 110 ° C. Styrene 1 8.4 parts methyl methacrylate 31.2 parts n-butyl acrylate 37.5 parts 2-hydroxyethyl acrylate 11.0 parts acrylic acid 1.9 parts 2,2'-azobisisobutyronitrile 1.7 parts Ο After complete instillation, add 0.5 part of 2,2'-azobisisobutyronitrile was further reacted at this temperature for 2 hours, and 35.0 parts of cyclohexanone was added to obtain a flexible acrylic resin AC1 solution having a solid content of 50%. The acid oxime of the acrylic resin AC1 solution was 15 mg K0H/g, the oxindole was 53 mg K0H/g, the glass transition temperature was 5 eC and the number average molecular weight was about 10,000. Synthesis Example 2-10 except that the formulation shown in Table 1 was used. In addition to the monomer composition, the procedure of Preparation Example 1 was repeated to obtain flexible-30-200948908 acrylic resins AC2 to AC10 having a solid content of 50%, respectively. Synthesis Example 1 1 A reactor equipped with a stirrer, a heater, a thermometer, a separator, and a distillate storage vessel was charged with a mixture of the following starting materials, followed by heating. Neopentyl glycol 105 parts 1,6-hexanediol 354 parts hexahydrophthalic anhydride 564 parts adipic acid 123 parts After stirring, heating can be started, stirring is started while the condensate is discharged, and the temperature is raised To 240 ° C, the reaction was further carried out at this temperature, and after the water was stopped to flow for 1.5 hours, 40 parts of xylene was charged to promote the reaction, and further dehydrogenation condensation was carried out until the acid hydrazine became 52, and it was cooled. 417 parts of cyclohexanone for dilution was added to obtain a polyester resin PE1 solution having a solid content of 70%. The number average molecular weight of the polyester resin PE1 was 2,100. φ Synthesis Example 1 2 - 1 5 The procedure of Preparation Example 11 was repeated except that the formulation shown in Table 1 was used to obtain a flexible polyester resin PE2 to PE5. The formulations shown in Table 1 represent the weight. -31- 200948908 ο ο Ο) ρ

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〇 Q SI« 合成實施例 r—H S v〇 寸 〇\ 寸 2200 3 S g ON CN CO 1〇 CS 卜 CS 〇〇 1400 CO \ 4 cn S $ CO 〇\ 〇〇 > < 1 4 r__H Οί 5300 C<1 \ < g D-. ON cs 卜 S 2200 < "Ή 1 < a o cn m CO CS 2100 〇\ 1 新戊二醇 1,6-己二醇 鮏 11 K) 六氫酞酸酐 趑 11 ίϋ 異酞酸 樹脂酸値（毫克ΚΟΗ/克） 數目平均分子量 玻璃轉移溫度（Tg)rc) 撓性聚酯樹脂溶名 起始材料 特徵性質 -eco- 200948908 製備實施例1 改質雙酚環氧樹脂ME1溶液的製備： 在裝配了攪拌器、冷凝器和溫度計的燒瓶中裝入60份 的環己酮和90份的jER 1007(商品名稱，由日本環氧樹脂公 司銷售的雙酚A環氧樹脂，環氧當量約1 8 00)，接著加熱至 1 30°C並且使環氧樹脂完全溶解，以獲得固體含量爲60%的 環氧樹脂溶液。將150份固體含量爲60%的環氧樹脂溶液 、20份由合成實施例1所獲得之50%撓性丙烯酸樹脂 〇 AC 1(10份爲固體含量）及0.5份溴化四乙銨所形成之混合物 在130°C下進行反應3至4小時，確認樹脂的酸値爲1或更 小，加入混合溶劑1 〔環己酮/SWASOL 1000(商品名稱，由 Maruzen石化公司銷售，高沸點的芳香石油溶劑）= 1/2(重量 比率）〕，以獲得固體含量爲40%的樹脂溶液ME1。 製備實施例2-37(提供製備實施例29-37係用於比較） 除了使用表2中所示的配方之外，重覆製備實施例1 之程序，以分別獲得固體含量爲40%的改質雙酚環氧樹脂 Ο ME2-37溶液。表2中所示的配方係代表重量。除了分別使 用如表2中所示之種類和數量的環氧樹脂來分別獲得固體 含量爲60%的環氧樹脂溶液之外，環氧樹脂的溶解係以相 同於製備實施例1的方式來進行。 在製備實施例34和37中所用的聚酯樹脂PE6係代表 ER-8101(商品名稱，由Unitika公司銷售，聚酯樹脂，酸値 約62，玻璃轉移溫度約64°C，數目平均分子量約2000)。 -34- 200948908 ❹ Ο 辑 Μ—. m _ co r—H | MED I Ο PE21 cs ME12 PE2 r"**H r_.H ME11 g 1—Η o I ME10 I ο AC8 ON |ME9 ο AC7 oo | ME8 ο AC6 卜 | ME7 冢 AC5 1 〇 m v〇 | ME6 | ο ^C4| V〇 | ME5 g AC3 1 寸 1 AC2 CO | ME3 s lAClJ 〇 CS | ME2 g LACil i 1 | ME1 | 〇 改質雙酚環氧樹脂溶液 jER 1007 (ii 1) jER4007P (註 2) jER 1004 (註 3) jER4004P (註 4) jER 1001 (ϋ 5) 己二酸 二聚物酸 癸二酸 1 種類 數量 魆 ΊΝΓΝ tlwrti P 數量 撓性丙烯酸樹脂溶液 撓性聚酯樹脂溶液 -se 200948908 ❹ο (m« 辑 v〇 CS | ME25 | Ο V£i AC8 1 i Ή ME24 〇 AC1 | CO CN ME23 o CN CS ME22 g ME21 s PE2 cn ME20 o PE2 1—^ Ρκ 撃 Os | ME19 | o i〇 AC2 γ··Η OO | ME18 | o AC1 | >〇 f—Η 1' 1 ^ ME17 _1 s CO PE2 t«**H ME16 s cn AC2 | cn m i i ME15 PE4 〇 ME14 〇 cn & Cl, 改質雙酣環氧樹脂溶液 jER 1007 (K 1) jER4007P (註 2) jER 1004 (註 3) JER4004P (註 4) jER 1001 (ϋ 5) m 1] ίΰ 二聚物酸 癸二酸 駿 P 數量 魃 ^Τ\ tlmil P 數量 撓性丙烯酸樹脂溶液 撓性聚酯樹脂溶液 _%· 200948908 ©o (co)csm 镯 cn | ME37 1 Ο v〇 & cu vn r·^ v〇 CO | ME36 s CO 甲 CU $ l〇 CO | ME35 ο AC10 1 | ME34 o MD s m CO ME33 Ο g Oh cs cn | ME32 ο g cu κ _ a 1 ΜΕ3Γ1 ο ! AC10I tfst? | ME30 | o | AC9 | 〇\ <N ME29 穿 fACl 1 oo cs ME28 l〇 VO CO CN a CS cn cs | ME27 ο 1 AC3 1 VO cs | ME26 | CS S 改質雙酣環氧樹脂溶液 jERK)07(註 1) jER4007P (註 2) jER 1004 (註 3) jER4004P (註 4) jER 1001 (註 5) 己二酸 二聚物酸 癸二酸 種類 數量 M P 數量 撓性丙烯酸樹脂溶液 撓性聚酯樹脂溶液 _ Li — 200948908 在表2中所示的（註1)至（註5)說明如下° (註1) jER 1007 :商品名稱’由日本環氧樹脂公司銷 售，雙酚A環氧樹脂，環氧當量約18〇〇)。 (註2) jER 4007P :商品名稱，由日本環氧樹脂公司 銷售，雙酚F環氧樹脂，環氧當量約227 0)。 (註3) jER 1004 :商品名稱，由日本環氧樹脂公司銷 售，雙酚A環氧樹脂，環氧當量約9 25) » (註4) jER 4004P :商品名稱，由日本環氧樹脂公司 © 銷售，雙酚F環氧樹脂，環氧當量約880)。 (註5) jER 1001 :商品名稱，由日本環氧樹脂公司銷 售，環氧當量約475)。 製備實施例38 可溶酚醛樹脂D1溶液的製備： 在反應器中裝入100份對-甲酚、178份37%的甲醛水 溶液及1份氫氧化鈉，接著在60°C進行反應3小時，在真 空及50 °C下進行脫水一小時，添加100份正丁醇及3份磷 〇 酸，在110至120°c進行反應2小時，將所得溶液予以過濾 ，濾掉所得的磷酸鈉，以獲得固體含量約50%的可溶酚醛 樹脂交聯劑溶液D1。如上所獲得之樹脂的數目平均分子量 爲880，每一個苯環平均有0.4個羥甲基且平均有1.0個烷 氧甲基。 製備實施例39 可溶酚醛樹脂D2溶液的製備： 在反應器中裝入100份石炭酸、178份37%的甲醛水溶 液及1份氫氧化鈉，接著在60°C進行反應3小時，在真空 -38- 200948908 及 5(Tc下進行脫水一小時，添加loo份正丁醇及3份磷酸 ’在Π0至120°C進行反應2小時，將所得溶液予以過濾， 胃掉所得的磷酸鈉，以獲得固體含量約50%的可溶酚醛樹 月旨交聯劑溶液D2。如上所獲得之樹脂的數目平均分子量爲 880’每一個苯環平均有〇.4個羥甲基且平均有1.〇個烷氧 甲基。 製備實施例40 含胺基環氧樹脂D3溶液的製備： ^ 在裝配了攪拌器及加熱溫度控制裝置的反應器中裝入 65份重的乙酸甲氧丁酯溶劑、35份重的jER 1002(商品名稱 ’由日本環氧樹脂公司銷售，雙酚A環氧樹脂，環氧當量 650)及1.09份重的2-胺基乙醇，接著在氮氣環境中，在攪 拌的情況下於90°C進行反應2小時，添加1.89份重的二乙 醇胺，在90°C進行反應1小時，並且以乙酸甲氧丁酯溶劑 予以稀釋，以獲得固體含量約35 %的含胺基環氧樹脂D3溶 液。 Ο 製備實施例4 1 含胺基環氧樹脂D4溶液的製備： 在裝配了攪拌器及加熱溫度控制裝置的反應器中裝入 65份重的乙酸甲氧丁酯溶劑、35份重的Araldite ECN 1299( 商品名稱，由旭化成化學股份有限公司銷售，甲酚酚醛環 氧樹脂，環氧當量225)及5.83份重的N-甲基乙醇胺，接著 在氮氣環境中，在攪拌的情況下於8(TC進行反應2小時， 添加1.89份重的二乙醇胺，在90°C進行反應1小時，並且 以乙酸甲氧丁酯溶劑予以稀釋，以獲得固體含量約35%的 -39- 200948908 含胺基環氧樹脂D4溶液。 製備實施例42 含胺基丙烯酸樹脂D5溶液的製備： 在裝配了攪拌器及加熱溫度控制裝置的反應器中裝入 40份丙二醇一甲醚，接著在氮氣環境中於90°C下加熱，以 3小時的時間將50份苯乙烯、50份甲基丙烯酸環氧丙酯、 1份2,2’-偶氮雙異丁腈和10份丙二醇一甲醚之混合溶液滴 入90°C的反應器中，添加0.2份的AIBN，在該溫度下進行 〇 反應30分鐘，並且加入50份丙二醇一甲醚，以獲得固體 含量爲50%的丙烯酸樹脂溶液。 在裝配了攪拌器及加熱溫度控制裝置的另一個反應器 中裝入200份前面所獲得固體含量爲50%的丙烯酸樹脂溶 液，接著在攪拌的情況下於85t下加熱，以30分鐘的時間 將26.4份的N-甲基乙醇胺和53.6份丙二醇一甲醚之混合 溶液滴入反應器中，在該溫度下進行反應5小時，並且加 入36份丙二醇一甲醚，以獲得固體含量爲40%的含胺基丙 © 烯酸樹脂D5溶液。 製備實施例43 含胺基丙烯酸樹脂D6溶液的製備： 在裝配了攪拌器及加熱溫度控制裝置的反應器中裝入 40份丙二醇一甲醚，接著在氮氣環境中於9(TC下加熱，以 3小時的時間將50份苯乙烯、30份丙烯酸乙酯、20份N，N-二甲基胺乙基丙烯酸酯、1份2,2’-偶氮雙異丁腈和10份丙 二醇一甲醚之混合溶液滴入90°C的反應器中，添加0.2份 的AIBN，在該溫度下進行反應30分鐘，加入0.2份2,2’- -40- 200948908 偶氮雙異丁腈，反應3小時，並且加入100份丙二醇一甲 醚，以獲得固體含量爲40%的含胺基丙烯酸樹脂D6溶液。 製備實施例44 背面用之塗布組成物的製備·· 將80份jER 1009F(商品名稱，由日本環氧樹脂公司銷 售的雙酚A環氧樹脂，環氧當量約2000)溶解於120份混合 溶劑2〔環己酮/乙二醇一丁酸/Swasol 1500(商品名稱，由 Maruzen石化公司銷售，高沸點的芳香烴系溶劑）= 3/1/1(重量 〇 比率）〕中所製備之200份環氧樹脂溶液與40份鈦白、40 份鋇氧及預定數量的混合溶劑3〔 Swasol 1500(商品名稱，由 Maruzen石化公司銷售，高沸點的芳香烴系溶劑）/環己酮 = 1/1(重量比率）〕所形成之混合物進行顔料分散，使得顆粒 大小，亦即顏料粗粒的粒徑能降低至20微米或更小，接著 力口入 26.7 份 Desmodur BL-3175(商品名稱，由 Sumika Bayer 胺 基甲酸酯公司銷售，甲基乙酮肟-阻斷HDI異氰脲酸酯型的 聚異氰酸酯化合物溶液，固體含量約75%)及2份Takenate Ο τκ-1(商品名稱，由武田製藥有限公司銷售，有機錫系阻斷 .劑-解離觸媒，固體含量約10%)，均勻地攪拌，加入混合溶 劑3並且控制黏度約80秒（4號福特杯/25°C )，以獲得背面 用之塗布組成物。 抗腐鈾塗布組成物的製備： 實施例1 將200份（80份爲固體含量）在製備實施例1中以撓性 有機基元改質之改質雙酚環氧樹脂ME1與20份偏矽酸鈣 、20份磷酸鈣、20份鈦白、20份鋇氧及預定數量的混合溶 -41- 200948908 劑3〔 Swasol 1500(商品名稱，由Maruzen石化公司銷售，高 沸點的芳香烴系溶劑）/環己酮=1/1(重量比率）〕所形成之混 合物進行顏料分散’使得顆粒大小，亦即顔料粗粒的粒徑 能降低至20微米或更小，接著加入26.7份（2〇份爲固體含 量）Desmodur BL-3175(商品名稱，由Sumika Bayer胺基甲酸醋 公司銷售，甲基乙酮肟-阻斷HDI異氰脲酸酯型的聚異氰酸 酯化合物溶液，固體含量約75%)及2份Takenate TK-1(商品 名稱，由武田製藥有限公司銷售，有機錫系阻斷劑-解離觸 © 媒，固體含量約10%)，均句地攪拌，加入混合溶劑3並且 控制黏度約80秒（4號福特杯/25°C )，以獲得抗腐蝕塗布組 成物。 實施例2-51及比較實施例1-11 除了依照表3中所示的配方來使用改質雙酚環氧樹脂 、硬化劑、賦黏劑、抗腐蝕顏料、其它顏料等之外，重覆 實施例1之程序’以分別獲得抗腐蝕塗布組成物。在表3 中，改質雙酚環氧樹脂、硬化劑和顔料的個別數量係代表 Ο 固體含量。在實施例26-30中，係以1份的Nacure 5225(商 品名稱，由美國King Industries公司銷售，十二基苯磺酸的 胺中和溶液）來取代2份的Takenate TK-1。在表3中，如果 使用可溶酣醛樹脂及其它硬化劑時，可溶酚醛樹脂係做爲 賦黏劑’如果沒有使用其它硬化劑，則可溶酚醛樹脂係做 爲硬化劑。 -42- 200948908 ❺ ❹ CO 1 < I ME13 I cs 1 < ME12 § <τΉ ME11 o r_H ME10 ON ON I g OO OO Ϊ g 辑 κ 卜 i g v〇 i m I § 寸 i g CO CO s g 05 s g 1 t T—H s g 魅 ^T\ tlmll P 鋰 M 祕 mi 數量(份數） Desmodur BL3175 溢 键 N 1 〇〇 π _ 尾Ω 辑镲 _鋰 mu Cymel 303(註 6) 可溶酚醛樹脂溶液D1 可溶酚醋樹脂溶液D2 含胺基環氧樹脂D3 含胺基環氧樹脂D4 含胺基環氧樹脂D5 含胺基環氧樹脂D6 五氧化二釩 三聚磷酸二氫鋁 磷酸鈣 鈣離子交換二氧化矽(註7) 偏矽酸鈣 m 鋇氧 &银 硬化劑 (B成分） 賦黏劑 抗腐蝕 顏料 (C成分） 其它 顏料 200948908 ❹ (m«l〇Q SI« Synthesis Example r-HS v〇 inch〇\ inch 2200 3 S g ON CN CO 1〇CS BU CS 〇〇1400 CO \ 4 cn S $ CO 〇\ 〇〇>< 1 4 r__H Οί 5300 C<1 \ < g D-. ON cs 卜 S 2200 <"Ή 1 < ao cn m CO CS 2100 〇\ 1 neopentyl glycol 1,6-hexanediol 鮏11 K) hexahydrogen Ammonic anhydride 趑11 ϋ ϋ isophthalic acid strontium hydride (mg/g) number average molecular weight glass transition temperature (Tg) rc) flexible polyester resin melting name starting material characteristic property-eco- 200948908 Preparation Example 1 Modification Preparation of bisphenol epoxy resin ME1 solution: 60 parts of cyclohexanone and 90 parts of jER 1007 (trade name, double sold by Japan Epoxy Resin Co., Ltd.) were placed in a flask equipped with a stirrer, a condenser and a thermometer. A phenol A epoxy resin having an epoxy equivalent of about 1 8000), followed by heating to 130 ° C and completely dissolving the epoxy resin to obtain an epoxy resin solution having a solid content of 60%. 150 parts of an epoxy resin solution having a solid content of 60%, 20 parts of a 50% flexible acrylic resin 〇AC 1 obtained by Synthesis Example 1 (10 parts by solid content), and 0.5 part of tetraethylammonium bromide were formed. The mixture was subjected to a reaction at 130 ° C for 3 to 4 hours, and it was confirmed that the acid hydrazide of the resin was 1 or less, and a mixed solvent 1 [cyclohexanone / SWASOL 1000 (trade name, sold by Maruzen Petrochemical Co., Ltd., high-boiling aromatic) was added. Petroleum solvent) = 1/2 (weight ratio)] to obtain a resin solution ME1 having a solid content of 40%. Preparation Example 2-37 (Preparation Examples 29-37 are provided for comparison) The procedure of Preparation Example 1 was repeated except that the formulation shown in Table 2 was used to obtain a modification having a solid content of 40%, respectively. Bisphenol epoxy resin Ο ME2-37 solution. The formulations shown in Table 2 represent the weight. The dissolution of the epoxy resin was carried out in the same manner as in Production Example 1, except that the epoxy resin solution having a solid content of 60% was respectively obtained by using the kinds and amounts of epoxy resins as shown in Table 2, respectively. . The polyester resin PE6 used in Preparation Examples 34 and 37 represents ER-8101 (trade name, sold by Unitika Corporation, polyester resin, acid strontium about 62, glass transition temperature of about 64 ° C, number average molecular weight of about 2000 ). -34- 200948908 ❹ Ο Μ Μ —. m _ co r — H | MED I Ο PE21 cs ME12 PE2 r"**H r_.H ME11 g 1—Η o I ME10 I ο AC8 ON |ME9 ο AC7 oo | ME8 ο AC6 卜 | ME7 冢AC5 1 〇mv〇| ME6 | ο ^C4| V〇| ME5 g AC3 1 inch 1 AC2 CO | ME3 s lAClJ 〇CS | ME2 g LACil i 1 | ME1 | Epoxy resin solution jER 1007 (ii 1) jER4007P (Note 2) jER 1004 (Note 3) jER4004P (Note 4) jER 1001 (ϋ 5) Adipic acid dimer acid sebacic acid 1 Type of quantity tl tlwrti P Quantity Flexible Acrylic Resin Solution Flexible Polyester Resin Solution-se 200948908 ❹ο (m« 辑v〇CS | ME25 | Ο V£i AC8 1 i Ή ME24 〇AC1 | CO CN ME23 o CN CS ME22 g ME21 s PE2 cn ME20 o PE2 1—^ Ρκ 撃Os | ME19 | oi〇AC2 γ··Η OO | ME18 | o AC1 | >〇f—Η 1' 1 ^ ME17 _1 s CO PE2 t«**H ME16 s cn AC2 | cn mii ME15 PE4 〇ME14 〇cn & Cl, modified bismuth epoxy resin solution jER 1007 (K 1) jER4007P (Note 2) jER 1004 (Note 3) JER4004P ( Note 4) jER 1001 (ϋ 5) m 1] ΰ ΰ Dimer acid bismuth acid P quantity 魃^Τ\ tlmil P Quantity flexible acrylic resin solution flexible polyester resin solution _%· 200948908 ©o (co) Csm bracelet cn | ME37 1 Ο v〇& cu vn r·^ v〇CO | ME36 s CO A CU $ l〇CO | ME35 ο AC10 1 | ME34 o MD sm CO ME33 Ο g Oh cs cn | ME32 ο g Cu κ _ a 1 ΜΕ3Γ1 ο ! AC10I tfst? | ME30 | o | AC9 | 〇\ <N ME29 wear fACl 1 oo cs ME28 l〇VO CO CN a CS cn cs | ME27 ο 1 AC3 1 VO cs | ME26 | CS S modified double epoxy resin solution jERK) 07 (Note 1) jER4007P (Note 2) jER 1004 (Note 3) jER4004P (Note 4) jER 1001 (Note 5) Adipic acid dimer acid diacid type Quantity MP Quantity Flexible Acrylic Lipid solution flexible polyester resin solution_ Li — 200948908 The following (Note 1) to (Note 5) shown in Table 2 are as follows: (Note 1) jER 1007: Trade name 'sold by Japan Epoxy Co., Ltd., double Phenol A epoxy resin, epoxy equivalent weight of about 18 〇〇). (Note 2) jER 4007P: Trade name, sold by Japan Epoxy Resin Co., Ltd., bisphenol F epoxy resin, epoxy equivalent of about 227 0). (Note 3) jER 1004: Trade name, sold by Japan Epoxy Resin Co., Ltd., bisphenol A epoxy resin, epoxy equivalent of about 9 25) » (Note 4) jER 4004P: Trade name, by Japan Epoxy Resin Co., Ltd. © Sale, bisphenol F epoxy resin, epoxy equivalent of about 880). (Note 5) jER 1001: Product name, sold by Japan Epoxy Resin Co., Ltd., epoxy equivalent of approximately 475). Preparation Example 38 Preparation of Resole Phenolic Resin D1 Solution: 100 parts of p-cresol, 178 parts of 37% aqueous formaldehyde solution and 1 part of sodium hydroxide were charged in a reactor, followed by a reaction at 60 ° C for 3 hours. Dehydration was carried out under vacuum at 50 ° C for one hour, 100 parts of n-butanol and 3 parts of phosphonic acid were added, and the reaction was carried out at 110 to 120 ° C for 2 hours, and the resulting solution was filtered, and the obtained sodium phosphate was filtered off to A resol phenol resin crosslinker solution D1 having a solid content of about 50% was obtained. The number of the resins obtained as above was an average molecular weight of 880, and each of the benzene rings had an average of 0.4 methylol groups and an average of 1.0 alkoxymethyl groups. Preparation Example 39 Preparation of Soluble Phenolic Resin D2 Solution: The reactor was charged with 100 parts of carbolic acid, 178 parts of 37% aqueous formaldehyde solution and 1 part of sodium hydroxide, followed by reaction at 60 ° C for 3 hours in a vacuum - 38- 200948908 and 5 (dehydration for one hour under Tc, adding loo part of n-butanol and 3 parts of phosphoric acid' at Π0 to 120 °C for 2 hours, filtering the resulting solution, and removing the obtained sodium phosphate to obtain the sodium phosphate obtained. A resol-type phenolic resin cross-linking agent solution D2 having a solid content of about 50%. The number average molecular weight of the resin obtained as above is 880', and each benzene ring has an average of 44 hydroxymethyl groups and an average of 1. Alkoxymethyl. Preparation Example 40 Preparation of a solution containing an amine-based epoxy resin D3: ^ A reactor equipped with a stirrer and a heating temperature control device was charged with 65 parts by weight of a solvent of methoxybutyl acetate, 35 parts. Heavy jER 1002 (trade name 'sold by Japan Epoxy Co., Ltd., bisphenol A epoxy resin, epoxy equivalent 650) and 1.09 parts by weight of 2-aminoethanol, then under nitrogen, with stirring The reaction was carried out at 90 ° C for 2 hours, adding 1.89 parts by weight of two The alcoholamine was reacted at 90 ° C for 1 hour, and diluted with a methoxybutyl acetate solvent to obtain an amine-containing epoxy resin D3 solution having a solid content of about 35%. 制备 Preparation Example 4 1 Amine-containing ring Preparation of Oxygen Resin D4 Solution: In a reactor equipped with a stirrer and a heating temperature control device, 65 parts by weight of methoxybutyl acetate solvent and 35 parts by weight of Araldite ECN 1299 (trade name, by Asahi Kasei Chemicals Co., Ltd.) were charged. The company sells cresol novolac epoxy resin, epoxy equivalent 225) and 5.83 parts by weight of N-methylethanolamine, and then reacts at 8 (TC for 2 hours, adding 1.89 parts by weight under stirring in a nitrogen atmosphere). The diethanolamine was reacted at 90 ° C for 1 hour, and diluted with a methoxybutyl acetate solvent to obtain a -39-200948908 amine-containing epoxy resin D4 solution having a solid content of about 35%. Preparation Example 42 Preparation of Amino Acrylic Resin D5 Solution: In a reactor equipped with a stirrer and a heating temperature control device, 40 parts of propylene glycol monomethyl ether was charged, followed by heating at 90 ° C in a nitrogen atmosphere for 3 hours. 50 copies A mixed solution of ethylene, 50 parts of glycidyl methacrylate, 1 part of 2,2'-azobisisobutyronitrile and 10 parts of propylene glycol monomethyl ether was dropped into a reactor at 90 ° C, and 0.2 part of AIBN was added. The hydrazine reaction was carried out at this temperature for 30 minutes, and 50 parts of propylene glycol monomethyl ether was added to obtain an acrylic resin solution having a solid content of 50%. The reactor was charged in another reactor equipped with a stirrer and a heating temperature control device. 200 parts of the previously obtained acrylic resin solution having a solid content of 50%, followed by heating at 85t with stirring, and a mixed solution of 26.4 parts of N-methylethanolamine and 53.6 parts of propylene glycol monomethyl ether in 30 minutes It was dropped into the reactor, the reaction was carried out at this temperature for 5 hours, and 36 parts of propylene glycol monomethyl ether was added to obtain a solution of the amino group-containing acrylate resin D5 having a solid content of 40%. Preparation Example 43 Preparation of Amino Acrylic Resin D6 Solution: A reactor equipped with a stirrer and a heating temperature control device was charged with 40 parts of propylene glycol monomethyl ether, followed by heating at 9 (TC) under a nitrogen atmosphere. 50 parts of styrene, 30 parts of ethyl acrylate, 20 parts of N,N-dimethylamine ethyl acrylate, 1 part of 2,2'-azobisisobutyronitrile and 10 parts of propylene glycol-A for 3 hours The mixed solution of ether was dropped into a reactor at 90 ° C, 0.2 part of AIBN was added, and the reaction was carried out at this temperature for 30 minutes, and 0.2 part of 2,2'- -40-200948908 azobisisobutyronitrile was added, and the reaction 3 was carried out. Hour, and 100 parts of propylene glycol monomethyl ether was added to obtain a solution containing the amino group-containing acrylic resin D6 having a solid content of 40%. Preparation Example 44 Preparation of Coating Composition for Back Surface · 80 parts of jER 1009F (trade name, Bisphenol A epoxy resin sold by Japan Epoxy Resin Co., Ltd., epoxy equivalent of about 2000) dissolved in 120 parts of mixed solvent 2 [cyclohexanone / ethylene glycol monobutyric acid / Swasol 1500 (trade name, by Maruzen Petrochemical Company) Sale, high boiling point aromatic hydrocarbon solvent) = 3/1/1 (weight ratio) 200 parts of epoxy resin solution prepared with 40 parts of titanium dioxide, 40 parts of xenon and a predetermined amount of mixed solvent 3 [Swolsol 1500 (trade name, sold by Maruzen Petrochemical Company, high boiling point aromatic hydrocarbon solvent) / The mixture formed by cyclohexanone = 1/1 (weight ratio) is subjected to pigment dispersion so that the particle size, that is, the particle size of the pigment coarse particles can be reduced to 20 μm or less, and then 26.7 parts of Desmodur BL- 3175 (trade name, sold by Sumika Bayer urethane company, methyl ethyl ketone oxime - blocking HDI isocyanurate type polyisocyanate compound solution, solid content about 75%) and 2 parts Takenate Ο τκ- 1 (trade name, sold by Takeda Pharmaceutical Co., Ltd., organic tin-based blocking agent-dissociation catalyst, solid content about 10%), uniformly stirred, added mixed solvent 3 and controlled viscosity for about 80 seconds (No. 4 Ford Cup) /25 ° C) to obtain a coating composition for the back surface. Preparation of a coating composition for resisting uranium: Example 1 200 parts (80 parts by solid content) were modified in the preparation example 1 with a flexible organic element Quality modified bisphenol epoxy resin ME1 and 20 Calcium metasilicate, 20 parts calcium phosphate, 20 parts titanium dioxide, 20 parts helium oxygen and a predetermined amount of mixed solution -41- 200948908 agent 3 [ Swasol 1500 (trade name, sold by Maruzen Petrochemical Company, high boiling aromatic hydrocarbon system) Solvent) / cyclohexanone = 1 / 1 (by weight)] The resulting mixture is subjected to pigment dispersion' such that the particle size, that is, the particle size of the pigment coarse particles can be reduced to 20 microns or less, followed by the addition of 26.7 parts (2 〇parts as solid content) Desmodur BL-3175 (trade name, sold by Sumika Bayer Amino Acid vinegar company, methyl ethyl ketone oxime - blocking HDI isocyanurate type polyisocyanate compound solution, solid content about 75% ) and 2 copies of Takenate TK-1 (trade name, sold by Takeda Pharmaceutical Co., Ltd., organotin-based blocker-dissociation catalyst, solid content of about 10%), stir evenly, add mixed solvent 3 and control viscosity Approximately 80 seconds (No. 4 Ford Cup / 25 ° C) to obtain a corrosion resistant coating composition. Example 2-51 and Comparative Example 1-11 Repeated except that the modified bisphenol epoxy resin, hardener, tackifier, anti-corrosive pigment, other pigment, etc. were used according to the formulation shown in Table 3. The procedure of Example 1 was carried out to obtain a corrosion-resistant coating composition, respectively. In Table 3, the individual quantities of the modified bisphenol epoxy resin, hardener and pigment represent the solids content of Ο. In Examples 26-30, 2 parts of Takenate TK-1 was replaced with 1 part of Nacure 5225 (trade name, sold by King Industries, USA, amine neutralization solution of dodecylbenzenesulfonic acid). In Table 3, if a soluble furfural resin and other hardeners are used, the resol resin is used as a binder. If no other hardener is used, the resol resin acts as a hardener. -42- 200948908 ❺ ❹ CO 1 < I ME13 I cs 1 < ME12 § <τΉ ME11 o r_H ME10 ON ON I g OO OO Ϊ g compilation ig igv〇im I § inch ig CO CO sg 05 sg 1 t T—H sg Charm ^T\ tlmll P Lithium M Secret mi Quantity (parts) Desmodur BL3175 Overflow N 1 〇〇π _ Tail Ω Collection 镲 Lithium mu Cymel 303 (Note 6) Resolusol phenolic resin solution D1 Solvent phenol vinegar resin solution D2 Amine-containing epoxy resin D3 Amine-containing epoxy resin D4 Amine-containing epoxy resin D5 Amine-containing epoxy resin D6 Vanadium pentoxide tripolyphosphate dihydrogen aluminum phosphate calcium ion exchange two Cerium oxide (Note 7) Calcium metasilicate calcium 钡 Oxygen & silver hardener (Part B) Adhesive anti-corrosive pigment (Component C) Other pigments 200948908 ❹ (m«l

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I 200948908 οο (寸)e嗽 ί〇 I ΜΕ28 1 g 1〇 v〇 〇 ΜΕ25 卜 〇 ON ΜΕ22 vn (N 〇 ΜΕ13 g in CS 〇 ΜΕ24 g ΙΤί cs 〇 ΜΕ24 Ό cs ΜΕ24 w-> CN ΜΕ24 g CS CO 1 ΜΕ24 g CN 〇 〇 〇 ΜΕ24 g CS CO CO »—Η ΜΕ28 ___j g VO ο 1 ΜΕ25 g ν〇 VO 魅 卿 數量(份數） Desmodur BL3175 t? N ^ Q |〇( _ 筆趟 坩铤 Cymel 303(註 6) 可溶酚醒樹脂溶液D1 可溶酚醛樹脂溶液D2 含胺基環氧樹脂D3 含胺麵氧樹脂D4 含胺基環氧樹脂D5 含胺纖氧樹脂D6 五氧化二釩 1三聚磷酸二氫鋁 磷酸鈣 鈣離子交換二氧化矽(註7) 偏矽酸鈣 •m 鋇氧 改質雙酣環氧樹脂 (A成分） 硬化劑 (B成分） 賦黏劑 抗腐蝕 顔料 (C成分） 1其它1 1 19寸， 200948908 ❹ ο 5ε嗽 比較實施例 1—Η | ME24 | 8 ι—Η 〇 ME37 g ME36 g oo ME35 g 卜 ME34 g v〇 ME33 g VO ME32 g 寸 ME31 g CO ME30 g cs ME29 g jER 1007 (K 1) M ΊΝ Γ\ ilmil w 數量(份數） Desmodur BL3175 赵S 癍 _趙 Cymel 303(註 6) 可溶酚醛樹脂溶液D1 可溶酚醛樹脂溶液D2 含胺基環氧樹脂D3 含胺基環氧樹脂D4 含胺基環氧樹脂D5 含胺基環氧樹脂D6 五氧化二釩 三聚磷酸二氫鋁 磷酸鈣 二氧化矽(註7) 偏矽酸鈣 m 鋇氧 改質雙酣環氧樹脂 鈣離子交換. (A成分） 硬化劑 (B成分） 賦黏劑 抗腐蝕 顏料 (C成分） 其它 顏料 丨/，寸 .200948908 在表3中，（註6)和（註7)說明如下。 (註 6) Cymel 303:商品名稱，由 Nihon Cytec Industries 公司銷售，甲基醚化三聚氰胺樹脂。 (註7) 鈣離子交換二氧化矽：SHIELDEX(商標）C303 ，由W.R. Grace公司銷售。 塗布測試板的製備 將實施例1-51、比較實施例1-11所獲得各個的抗腐蝕 塗布組成物及面漆組成物塗布在個別的基板上，並且依照 以下塗布規範說明予以硬化，以獲得個別的塗布測試板。 塗布規範說明： 將製備實施例44所獲得之背面用塗布組成物塗布在 曾接受金屬表面處理方法之鍍鋁鋅（galvalume)鋼片上，鋼片 厚度爲0.35毫米，它是一種鍍鋁-鋅合金鋼片，合金中的鋁 含量約爲55%，電鍍的合金量爲150克/平方公尺，在表2 中被稱爲“GL鋼片”，其係使用塗布棒來形成8微米的乾 膜厚，接著在基板最大溫度18(TC下硬化30秒，而形成背 面塗布薄膜；將上述實施例中所獲得之抗腐蝕塗布組成物 個別塗布在具有鋼片背面塗布薄膜之鋼片背面的另一面， 其係使用塗布棒來形成5微米的乾膜厚，接著在基板最大 溫度220 °C下硬化40秒，而獲得個別的底漆塗布薄膜；予 以冷卻，並且將KP Color 1580B40(商品名稱，由關西 塗料股份有限公司銷售，聚酯系面漆組成物，藍色，硬化 塗布薄膜的玻璃轉移溫度約爲70°C)塗布在個別的底漆塗 布薄膜之上，其係使用塗布棒來形成約15微米的乾膜厚， 並且在基板最大溫度220°C下硬化40秒，以獲得個別的塗 布測試板。 -48- .200948908 塗布薄膜功能測試 依照以下的測試方法，將先前製備塗布測試板所獲得 的個別塗布測試板施以塗布薄膜功能測試。測試結果如表 4中所示。 測試方法 製造性質： 將各個塗布測試板切割成6公分xl 2公分的大小，並施 以4T折疊製造，也就是說，包含以塗布板外側表面的該側 來折疊塗布板的製造方法，其中在塗布板的內側置入4片 與塗布板厚度相同的薄板，並且利用老虎鉗將所得的塗布 板彎折180°角，使得折叠部分的長度在20°C的室溫下爲6 公分，並且依照以下方式分別評估在4T折疊製造部分之塗 布薄膜的裂縫阻抗和黏附性質。折叠製造部分之附著性質 的評估係將玻璃紙膠帶黏著在折疊製造部分之上，接著將 膠帶強力分離，再觀察折叠製造部分之塗布薄膜的剝離程 度。 ◎:在製造部分沒有形成薄膜裂縫也沒有薄膜剝離。 〇：在製造部分同時有梢微形成薄膜裂縫及薄膜剝離，或 者是兩者之一有稍微形成。 △:在製造部分同時有明顯形成薄膜裂縫及薄膜剝離，或 者是兩者之一有明顯形成。 X:在製造部分同時有非常明顯形成相當多薄膜裂縫及薄 膜剝離，或者是兩者之一有非常明顯形成。 耐沸水性：將各個塗布測試板切割成5公分Χίο公分的 大小，並浸入約100 °C的沸水中5小時，接著將其取出並評 估在塗布板表面上所形成之塗布薄膜的外觀，並且分別進 -49- .200948908 行百格測試（cross cut-tape method)評估。百格測試法是依照 113〖-5400 8.5.2(1990)所定義。也就是將玻璃紙膠帶黏著在 各個塗布測試板的表面上，其切割間隔爲1毫米且切成1〇〇 個方格，接著將膠帶強力分離，再依照以下方式評估具有 方格的塗布薄膜。 ◎:在塗布薄膜上沒有異常（如形成起泡和白化），留有1〇〇 個方格。 〇：在塗布薄膜上沒有異常（如形成起泡和白化），留有91-99 0 個方格。 △:在塗布薄膜上有稍微形成起泡或白化，留有91-99個 方格；或者是在塗布薄膜上沒有異常（如形成起泡和白化） ，但留有71-90個方格。 X:在塗布薄膜上有明顯或非常明顯的形成起泡和白化， 或是留有70或更少個方格。 耐鹼性： 以抗腐蝕塗布組成物來密封被切割成5公分χΙΟ公分 φ 大小之各個塗布測試板的背面及切削表面，並且在塗布板 表面的中心處形成交叉切口，其切口可延伸至基板。將所 得的塗布板浸入25°C的5%氫氧化鈉水溶液中48小時，接 著將其取出，予以沖洗，並在室溫下乾燥，以評估塗布薄 膜表面上的塗布薄膜外觀，並且進一步地將玻璃紙膠帶黏 著在交叉切口部分，接著將膠帶強力分離，以評估其在所 得塗布薄膜中自交叉切口部分分離的寬度（一側）。 ◎:沒有形成起泡，自切口部分的膠帶分離寬度爲1.5毫 米或更小。 〇：沒有形成起泡，自切口部分的膠帶分離寬度大於1.5 -50- .200948908 毫米，但等於3毫米或更少。 △:有稍微形成起泡，自切口部分的膠帶分，離寬度大於3 毫米或更少，或者是沒有形成起泡，但是自切口部分的膠 帶分離寬度大於3毫米。 X:有形成起泡，並且自切口部分的膠帶分離寬度大於3 毫米。 抗刮性質：在室溫20°C下，將10元銅板（日幣）的邊緣以45° 角放在各個塗布測試板表面的塗布薄膜上，接著在加壓3 φ 公斤負荷的同時，以10毫米/秒的速度將10元銅板拖行約 30毫米，而在塗布薄膜上形成損傷，並且依照以下方式來 評估損傷的程度。 ◎:在損傷部分沒有露出基板金屬。 〇：在損傷部分有稍微露出基板金屬。 △:在損傷部分有明顯露出基板金屬。 X :幾乎沒有塗布薄膜殘留，並且在損傷部分清楚地露出 基板金屬。 0 循環腐蝕測試：以下測試係依照JASO M609-9K汽車車體用 材料腐蝕測試，1991)之規定來進行。使用裁切刀的刀背在 各個被切割成6公分χ12公分大小的塗布測試板表面中心 處形成交叉切口，此切口可延伸至基板，並且夾角爲30° 且線寬爲0.5毫米，使得各個塗布測試板長側邊緣部分的 毛邊面對表面上之塗布薄膜右側上的表面，並且面對表面 上之塗布薄膜右側上的背面，接著以抗腐蝕組成物來密封 塗布板上端邊緣部分，並且將此上緣部分施以4T折疊製造 ’也就是包含以塗布板外側表面的該側來折叠塗布板的製 造方法，其中在折疊塗布板的內側置入4片與塗布板厚度 -51- .200948908 相同的薄板，並且利用老虎鉗將所得的塗布板彎折180。角 ，將所製得的塗布板進行循環腐蝕測試，總共包含1 200小 時的150次循環，每一次循環係包括以下連續步驟：在35°C 進行5%鹽霧測試2小時，在相對濕度爲95%的條件下，於 60t乾燥4小時，並且在相對濕度爲95%的條件下，於5(TC 下濕潤2小時。分別針對所得塗布板的邊緣部分、交叉切 口部分及4T折疊製造部分進行評估。 4T製造部分：針對4T製造部分中生鏽部分的總長度來進 Λ 行評估。 〇 ◎:沒有形成生鏽。 〇：形成白鏽，但少於20毫米。 △:形成白鏽20毫米或更長，但少於40毫米。 X :形成白鏽40毫米或更長，或者是形成紅鏽。 交叉切口部分：依照以下方式，以白鏽在具有0.5毫米切 割寬度之基板金靥外露部分中延伸長度的程度爲基準，來 評估交叉切口部分的腐蝕情況以及在切割部分的左右兩側 ©起泡寬度的平均値 ◎:在基板金屬外露部分中之白鏽延伸長度的程度小於 5 0%，並且起泡寬度少於3毫米。 〇：白鏽延伸長度的程度爲5 0%或更大，並且起泡寬度少 於3毫米，或者是启鏽延伸長度的程度少於50%，並且起 泡寬度爲3毫米或更大，但少於5毫米。 △:白鏽延伸長度的程度爲50%或更大，並且起泡寬度爲5 毫米或更長，但少於10毫米。 X :白鏽延伸長度的程度爲50%或更大，並且起泡寬度爲 1 0毫米或更長 -52- 200948908 邊緣部分：同時量測左側長邊和右側長 的平均値，並且依下述方式來評估。 ◎:少於5毫米。 〇：5毫米或更長，但少於1〇毫米。 △ : 10毫米或更長，但少於20毫米。 X : 20毫米或更長。 耐候鹽霧測試： 將切割成5公分χΙΟ公分的塗布測 候試驗機500小時的照射，其係依照用 的方法A，在潤濕18分鐘接著乾燥102 件下進行，且以JIS K-5600 7.7中所定義 耐候性，接著再以抗腐蝕塗布組成物來 面，在塗布板中心處形成交叉切口，其 ，讓所得的塗布板接受鹽霧測試UIS Z- 且依照下列標準來評估平坦部分的外觀 ◎:平均而言，在跨越切口處從切口部 •生鏽處的寬度爲3毫米或更小，並且 〇：從切口部分所延伸形成起泡•生鏽 米，及5毫米或更少，在平坦部分和其 或者是在平坦部分有形成一些起泡，但 成起泡•生鏽處的寬度爲3毫米或更少 △:從切口部分所延伸形成起泡•生鏽 米’但是5毫米或更少，並且在平坦部 〇 X:從切口部分所延伸形成起泡•生鏽 米，或者明顯地形成起泡。 邊之邊緣潛變寬度 試板接受氙弧燈耐 於長期耐久性測試 分鐘的重要循環條 的氙燈方法來加速 密封背面及切削表 切口可延伸至基板 237 1 )500小時，並 〇 分所延伸形成起泡 沒有其它異常。 處的寬度大於3毫 它部分沒有異常， 是從切口部分所形 〇 處的寬度大於3毫 分有形成一些起泡 處的寬度大於5毫 -53- 200948908 表 4(1) 實施 列 1 2 3 4 5 6 7 8 9 10 11 12 13 折疊製造性質 〇 ◎ 〇 〇 ◎ 〇 〇 〇 〇 〇 ◎ 〇 〇 水性(浸入沸水5小時） ◎ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐鹼性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 抗刮性質 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 CCT 測試 4T折疊製造部分 〇 〇 〇 〇 ◎ 〇 〇 〇 〇 〇 ◎ 〇 〇 交叉切口部分 〇 〇 〇 〇 〇 〇 〇 〇 〇 ◎ 〇 〇 〇 邊緣部分 〇 ◎ ◎ 〇 ◎ 〇 〇 〇 〇 ◎ ◎ ◎ ◎ 耐候鹽霧測試 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ❹I 200948908 οο (inch)e嗽ί〇I ΜΕ28 1 g 1〇v〇〇ΜΕ25 卜〇ON ΜΕ22 vn (N 〇ΜΕ13 g in CS 〇ΜΕ24 g ΙΤί cs 〇ΜΕ24 Ό cs ΜΕ24 w-> CN ΜΕ24 g CS CO 1 ΜΕ24 g CN 〇〇〇ΜΕ24 g CS CO CO »—Η ΜΕ28 ___j g VO ο 1 ΜΕ25 g ν〇VO Number of enchantments (parts) Desmodur BL3175 t? N ^ Q |〇( _ pen 趟坩铤Cymel 303 (Note 6) Soluble phenol waking resin solution D1 Resolute phenolic resin solution D2 Amine-containing epoxy resin D3 Amine-containing oxy-resin D4 Amine-containing epoxy resin D5 Amine-containing oxy-resin D6 Vanadium pentoxide 1 III Calcium dihydrogen aluminum phosphate calcium ion exchange cerium oxide (Note 7) Calcium metasilicate ••m 钡Oxygen modified bismuth epoxy resin (component A) Hardener (component B) Adhesive anti-corrosion pigment (C Ingredients) 1 Others 1 1 19 inches, 200948908 ❹ ο 5ε嗽Comparative Example 1—Η | ME2 4 | 8 ι—Η 〇ME37 g ME36 g oo ME35 g 卜 ME34 gv〇ME33 g VO ME32 g inch ME31 g CO ME30 g cs ME29 g jER 1007 (K 1) M ΊΝ Γ\ ilmil w Quantity (parts) Desmodur BL3175 Zhao S 癍 _ Zhao Cymel 303 (Note 6) Resolute phenolic resin solution D1 Resolute phenolic resin solution D2 Amine-containing epoxy resin D3 Amine-containing epoxy resin D4 Amine-containing epoxy resin D5 Amine-containing epoxy Resin D6 vanadium pentoxide tripolyphosphate aluminum dihydrogen phosphate calcium dioxide (Note 7) calcium metasilicate calcium 钡 oxygen modified double bismuth epoxy resin calcium ion exchange. (A component) hardener (B component) Adhesive anti-corrosive pigment (component C) Other pigments ,/, inch. 200948908 In Table 3, (Note 6) and (Note 7) are explained below. (Note 6) Cymel 303: trade name, sold by Nihon Cytec Industries, methyl etherified melamine resin. (Note 7) Calcium ion exchange ruthenium dioxide: SHIELDEX (trademark) C303, marketed by W.R. Grace. Preparation of Coating Test Plate Each of the anti-corrosion coating composition and the topcoat composition obtained in Example 1-51, Comparative Example 1-11 was coated on an individual substrate, and hardened according to the following coating specification. Individual coated test panels. Description of Coating Specification: The coating composition for the back surface obtained in Preparation Example 44 was coated on a galvalume steel sheet which had been subjected to a metal surface treatment method, and the thickness of the steel sheet was 0.35 mm, which was an aluminum-zinc alloy. The steel sheet, the aluminum content of the alloy is about 55%, and the amount of alloy plating is 150 g/m 2 . It is called “GL steel sheet” in Table 2, which uses a coating rod to form a dry film of 8 μm. Thick, and then hardened at a maximum substrate temperature of 18 (TC for 30 seconds to form a back coating film; the anti-corrosion coating composition obtained in the above examples was individually coated on the other side of the back surface of the steel sheet having the steel back coating film , using a coating bar to form a dry film thickness of 5 microns, followed by hardening at a substrate maximum temperature of 220 ° C for 40 seconds to obtain a separate primer coating film; cooling, and KP Color 1580B40 (trade name, by Kansai Paint Co., Ltd. sells, polyester topcoat composition, blue, hard coated film with a glass transfer temperature of about 70 ° C) coated on individual primer coated films, which are coated The rod was used to form a dry film thickness of about 15 microns and hardened at a substrate maximum temperature of 220 ° C for 40 seconds to obtain individual coated test panels. -48- .200948908 Coating film functional test was prepared according to the following test method The individual coated test panels obtained by coating the test panels were subjected to a coated film functional test. The test results are shown in Table 4. Test Methods Manufacturing Properties: Each coated test panel was cut to a size of 6 cm x 2 cm and applied 4T Folding manufacturing, that is, a manufacturing method including folding the coated sheet with the side of the outer surface of the coated sheet, wherein 4 sheets of the same thickness as the coated sheet are placed inside the coated sheet, and the resulting coated sheet is obtained by using a vise The 180° angle was bent so that the length of the folded portion was 6 cm at room temperature of 20 ° C, and the crack resistance and adhesion properties of the coated film at the 4T folded manufacturing portion were respectively evaluated in the following manner. Adhesive properties of the folded manufacturing portion The evaluation is to attach the cellophane tape to the folded manufacturing part, then separate the tape strongly, and then observe the folding manufacturing part. Degree of peeling of the coated film. ◎: No film crack or film peeling was formed in the production portion. 〇: Film cracks and film peeling were formed at the same time in the production portion, or one of them was slightly formed. △: In manufacturing At the same time, there are obvious film cracks and film peeling, or one of them is formed. X: There are quite a lot of film cracks and film peeling at the same time in the manufacturing part, or one of them is very obvious. Boiling water resistance: Each coated test sheet was cut into a size of 5 cm ο 公 cm and immersed in boiling water of about 100 ° C for 5 hours, and then taken out and evaluated for the appearance of the coated film formed on the surface of the coated sheet, and Into the -49-.200948908 cross cut-tape method evaluation. The Baige test method is defined in accordance with 113 〖-5400 8.5.2 (1990). That is, the cellophane tape was adhered to the surface of each of the coated test sheets with a cutting interval of 1 mm and cut into 1 square squares, and then the tape was strongly separated, and the coated film having a checkered color was evaluated in the following manner. ◎: There was no abnormality on the coated film (such as foaming and whitening), and 1 square was left. 〇: There are no abnormalities on the coated film (such as foaming and whitening), leaving 91-99 0 squares. △: There is slight foaming or whitening on the coated film, leaving 91-99 squares; or there is no abnormality on the coated film (such as foaming and whitening), but 71-90 squares are left. X: There is a significant or very pronounced formation of blistering and whitening on the coated film, or 70 or fewer squares are left. Alkali resistance: The back surface and the cutting surface of each coated test board which are cut into 5 cm χΙΟ cm φ are sealed with a corrosion-resistant coating composition, and a cross-cut is formed at the center of the surface of the coating sheet, and the slit can be extended to the substrate . The resulting coated plate was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C for 48 hours, then taken out, rinsed, and dried at room temperature to evaluate the appearance of the coated film on the surface of the coated film, and further The cellophane tape was adhered to the cross-cut portion, and then the tape was strongly separated to evaluate the width (one side) of the separation from the cross-cut portion in the obtained coated film. ◎: No foaming was formed, and the tape separation width from the slit portion was 1.5 mm or less. 〇: No blistering is formed, and the tape separation width from the slit portion is greater than 1.5 - 50 - .200948908 mm, but equal to 3 mm or less. △: There was slight formation of foaming, and the tape from the slit portion was separated by a width of more than 3 mm or less, or no foaming was formed, but the tape separation width from the slit portion was more than 3 mm. X: Foaming was formed, and the tape separation width from the slit portion was more than 3 mm. Scratch resistance: The edge of a 10-yuan copper plate (Japanese yen) was placed at a 45° angle on a coated film on the surface of each coated test plate at room temperature 20 ° C, followed by a load of 3 φ kg at a pressure of At a speed of 10 mm/sec, a 10-yuan copper plate was towed by about 30 mm to form a damage on the coated film, and the degree of damage was evaluated in the following manner. ◎: The substrate metal was not exposed in the damaged portion. 〇: The substrate metal is slightly exposed in the damaged portion. △: The substrate metal was clearly exposed in the damaged portion. X: Almost no coating film remains, and the substrate metal is clearly exposed in the damaged portion. 0 Cyclic Corrosion Test: The following tests were carried out in accordance with JASO M609-9K Automotive Body Material Corrosion Test, 1991). A knife-back was used to form a cross-cut at the center of each of the coated test panels cut to a size of 6 cm to 12 cm, which slit was extended to the substrate at an angle of 30° and a line width of 0.5 mm, so that each coating test The burr of the long side edge portion of the plate faces the surface on the right side of the coated film on the surface, and faces the back surface on the right side of the coated film on the surface, and then seals the end edge portion of the coated plate with the anti-corrosion composition, and this is The edge portion is subjected to 4T folding manufacturing, that is, a manufacturing method including folding the coated sheet with the side of the outer surface of the coated sheet, wherein four sheets of the same thickness as the coated sheet thickness -51-.200948908 are placed on the inner side of the folded coated sheet. And the resulting coated panel was bent 180 using a vise. The coated panels were subjected to cyclic corrosion testing for a total of 150 cycles of 1 200 hours. Each cycle consisted of the following sequential steps: 5% salt spray test at 35 ° C for 2 hours at relative humidity Under the conditions of 95%, dried at 60t for 4 hours, and wetted at 5 (TC) for 2 hours under the condition of relative humidity of 95%. For the edge portion, the intersecting slit portion and the 4T folding manufacturing portion of the obtained coated sheet, respectively. Evaluation. 4T Manufacturing Section: The total length of the rusted part in the 4T manufacturing section was evaluated. 〇 ◎: No rust was formed. 〇: White rust was formed, but less than 20 mm. △: White rust 20 mm was formed. Or longer, but less than 40 mm. X: Forms white rust 40 mm or longer, or forms red rust. Cross-cut portion: White rust exposed on a substrate with a 0.5 mm cutting width in the following manner The extent of the intermediate extension length is used as a reference to evaluate the corrosion of the cross-cut portion and the average of the bubble width on the left and right sides of the cut portion. ◎: The length of white rust extension in the exposed portion of the substrate metal The degree is less than 50%, and the foaming width is less than 3 mm. 〇: The degree of white rust extension is 50% or more, and the foaming width is less than 3 mm, or the degree of rust extension is less than 50%, and the foaming width is 3 mm or more, but less than 5 mm. △: The degree of white rust extension is 50% or more, and the foaming width is 5 mm or more, but less than 10 Mm. X: The degree of white rust extension is 50% or more, and the foaming width is 10 mm or longer -52- 200948908. Edge portion: Simultaneously measure the average length of the long side and the right side of the left side, and It is evaluated in the following manner: ◎: less than 5 mm. 〇: 5 mm or longer, but less than 1 mm. △: 10 mm or longer, but less than 20 mm X: 20 mm or longer. Weathering salt spray test: 500 hours of irradiation of a coating tester cut into 5 cm χΙΟ cm, according to Method A, followed by wetting for 18 minutes followed by drying of 102 pieces, and JIS K-5600 7.7 Weather resistance as defined in the coating, followed by corrosion-resistant coating composition, at the center of the coated plate A cross-cut was made, and the resulting coated plate was subjected to a salt spray test UIS Z- and the appearance of the flat portion was evaluated according to the following criteria. ◎: On average, the width from the cut portion to the rust at the slit was 3 mm. Or smaller, and 〇: from the slit portion to form foaming / rusted rice, and 5 mm or less, in the flat portion and its or in the flat portion, some foaming, but into foaming / rusting The width is 3 mm or less △: foaming from the slit portion is formed to form a blistering rusted rice but 5 mm or less, and at the flat portion 〇X: blistering from the slit portion to form a blistering/rusting rice , or blistering is clearly formed. The edge-to-edge creeping width test panel accepts a xenon arc lamp that is resistant to the long-term durability test minute of the important cycle of the xenon lamp method to accelerate the seal back surface and the cut-table cut can be extended to the substrate 237 1) for 500 hours, and the branch is extended to form There are no other abnormalities in foaming. Where the width is greater than 3 millimeters, there is no abnormality in the part, the width from the shape of the slit portion is greater than 3 millimeters, and the width of some foaming is formed to be greater than 5 milli-53-200948908. Table 4(1) Implementation column 1 2 3 4 5 6 7 8 9 10 11 12 13 Folding manufacturing properties 〇 ◎ 〇〇 ◎ 〇〇〇〇〇 ◎ Water repellency (immersed in boiling water for 5 hours) ◎ 〇〇〇〇〇〇〇〇〇〇〇〇 alkali resistance 〇 〇〇〇〇〇〇〇〇〇〇〇〇 scratch resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇CCT test 4T folding manufacturing part 〇〇〇〇 ◎ 〇〇〇〇〇 〇〇 〇〇 cross cut section 〇〇〇〇〇〇〇〇〇 ◎ 〇〇〇 edge part 〇 ◎ ◎ 〇 ◎ 〇〇〇〇 ◎ ◎ ◎ ◎ weathering salt spray test 〇〇〇〇〇〇〇〇〇〇〇〇〇❹

表 4(2) 實施例 14 15 16 17 18 19 20 21 22 23 24 25 26 折疊製造性質 ◎ 〇 〇 〇 〇 〇 〇 〇 ◎ ◎ 〇 〇 〇 耐沸水性(浸入沸水5小時） 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐鹼性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 抗刮性質 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 CCT 測試 4T折疊製造部分 〇 〇 〇 〇 〇 〇 〇 〇 ◎ ◎ 〇 〇 〇 交叉切口部分 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 邊緣部分 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 耐候鹽霧測試 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 -54- 200948908 表 4(3) 實施 列 27 28 29 30 31 32 33 34 35 36 37 38 39 折疊製造性質 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 耐沸水性(浸入沸水5小時） 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 耐鹼性 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 抗刮性質 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ CCT 測試 4T折疊製造部分 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 交叉切口部分 ◎ 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 邊緣部分 ◎ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ◎ 〇 耐候鹽霧測試 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ❹Table 4 (2) Example 14 15 16 17 18 19 20 21 22 23 24 25 26 Folding manufacturing properties ◎ 〇〇〇〇〇〇〇 ◎ ◎ 〇〇〇 boiling water resistance (immersed in boiling water for 5 hours) 〇〇〇〇〇 〇〇〇〇〇〇〇〇 alkali resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇 scratch resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇 CCT test 4T folding manufacturing part 〇〇〇〇 〇〇〇〇 ◎ ◎ 〇〇〇 Cross-cut part 〇〇〇〇〇〇〇〇〇〇〇〇〇 edge part 〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 weathering salt spray test 〇〇〇〇〇〇 〇〇〇〇〇〇〇-54- 200948908 Table 4 (3) Implementation column 27 28 29 30 31 32 33 34 35 36 37 38 39 Folding manufacturing properties 〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Resistance to boiling water (Immersed in boiling water for 5 hours) 〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ CCT test 4T folding manufacturing part 〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Cross-cut part ◎ 〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Edge part ◎ 〇〇〇〇〇〇〇〇〇〇 ◎ 〇 weathering salt spray test 〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ❹ ❹

表 4(4) 實施例 40 41 42 43 44 45 46 47 48 49 50 51 折疊製造性質 ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 水性(浸入沸水5小時） ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 耐鹼性 ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 抗刮性質 ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ CCT 測試 4T折疊製造部分 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 交叉切口部分 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇 邊緣部分 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇 耐候鹽霧測試 ◎ ◎ 〇 〇 ◎ ◎ ◎ 〇 〇 〇 〇 〇 -55- 200948908 表 4(5)Table 4 (4) Example 40 41 42 43 44 45 46 47 48 49 50 51 Folding property ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Water (immersed in boiling water for 5 hours) ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ CCT test 4T folding manufacturing part ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Cross-cut part ◎ ◎ 〇 ◎ ◎ ◎ ◎ 〇〇〇〇〇 edge part ◎ ◎ 〇 ◎ ◎ ◎ ◎ 〇〇〇〇〇 weathering salt spray test ◎ ◎ 〇〇 ◎ ◎ ◎ 〇〇〇〇〇-55- 200948908 Table 4 (5)

實施例 1 2 3 4 5 6 7 8 9 10 11 折疊製造性質 Δ 〇 Δ ◎ 〇 ◎ Δ ◎ ◎ Δ Δ 耐沸水性(浸入沸水5小時） 〇 △ 〇 〇 Δ Δ 〇 〇 〇 ◎ X 耐鹼性 Δ Δ 〇 X X Δ 〇 Δ △ 〇 X 抗刮性質 〇 Δ 〇 Δ Δ Δ 〇 Δ △ 〇 Δ CCT 測試 4T折疊製造部分 Δ 〇 Δ 〇 〇 〇 Δ ◎ ◎ Δ Δ 交叉切口部分 〇 Δ 〇 Δ △ 〇 〇 Δ Δ 〇 〇 邊緣部分 〇 〇 △ 〇 〇 〇 Δ 〇 〇 Δ 〇 耐候鹽霧測試 〇 Δ 〇 Δ Δ Δ 〇 Δ Δ 〇 X 【圖式簡單說明】 ❹ 無。 【主要元件符號說明】 無0 -56-Example 1 2 3 4 5 6 7 8 9 10 11 Folding manufacturing property Δ 〇 Δ ◎ 〇 ◎ Δ ◎ ◎ Δ Δ boiling water resistance (immersion in boiling water for 5 hours) 〇 △ 〇〇 Δ Δ 〇〇〇 ◎ X alkali resistance Δ Δ 〇 XX Δ 〇 Δ Δ 〇 X Scratch resistance 〇 Δ 〇 Δ Δ Δ Δ Δ 〇 Δ CCT test 4T folding manufacturing part Δ 〇 Δ 〇〇〇 Δ ◎ ◎ Δ Δ cross-cut part 〇 Δ 〇 Δ Δ 〇 〇Δ Δ 〇〇 edge part 〇〇 △ 〇〇〇 Δ 〇〇 Δ 〇 weathering salt spray test 〇 Δ Δ Δ Δ 〇 Δ Δ 〇 X [Simple diagram] ❹ None. [Main component symbol description] No 0 -56-

Claims (1)

200948908 七、申請專利範圍： 1. 一種抗腐蝕塗布組成物，其含有（A)撓性有機基元改質之 雙酚環氧樹脂，其係將5至50重量％的撓性有機基元與 95至50重量％的雙酚環氧樹脂反應而得，（B)硬化劑及（C) 抗腐蝕顏料，此種撓性有機基元至少一種係選自由具有 4至36個碳原子的脂肪族多元酸、具有-20至50°C玻璃 轉移溫度的丙烯酸樹脂及具有-20至50°C玻璃轉移溫度 的聚酯樹脂所構成之組群。 ❹ 2.如申請專利範圍第1項之抗腐蝕塗布組成物，其中樹脂 (A)爲雙酚環氧樹脂，其係以具有4至36個碳原子的脂 肪族多元酸及具有-20至50°C玻璃轉移溫度的丙烯酸樹 脂改質。 3. 如申請專利範圍第1項之抗腐蝕塗布組成物，其中具有4 至36個碳原子的脂肪族多元酸爲二聚物酸。 4. 如申請專利範圍第1項之抗腐蝕塗布組成物，硬化劑（B) 爲至少一種交聯劑，其係選自胺基樹脂、酚樹脂和選用 Q 的阻斷聚異氟酸酯化合物。 5. 如申請專利範圍第1項之抗腐蝕塗布組成物，其中抗腐 蝕顏料（C)爲無鉻抗腐蝕顏料。 6. 如申請專利範圍第5項之抗腐蝕塗布組成物，其中抗腐 蝕顏料包含（1)至少一種釩化合物，其係選自五氧化二 釩、釩酸鈣和偏釩酸銨，（2)至少一種含矽化合物，其係 選自金屬矽酸鹽和二氧化矽微粒，以及（3)磷酸鹽系金屬 鹽。 7. 如申請專利範圍第1項之抗腐蝕塗布組成物，其中抗腐 -57- 200948908 蝕塗布組成物還進一步包含至少一種選自含二級或三級 胺基的環氧樹脂、含二級或三級胺基的丙烯酸樹脂及可 溶粉'酵樹脂。 8. —種經塗布的金屬片，在此金屬片表面的一側或兩側之 上具有由申請專利範圍第1項之抗腐蝕塗布組成物形成 的硬化塗布薄膜，該金屬表面被施以選用之金屬處理方 法。 9. 一種經塗布的金屬片，其具有多層塗布薄膜，包括在此 ❹ 金屬片表面的一側或兩側之上由申請專利範圍第1項之 抗腐蝕塗布組成物形成的硬化塗布薄膜，該金屬表面被 施以選用之金屬處理方法，以及在此硬化塗布薄膜的至 少一側形成之面漆塗布薄膜。 ❹ -58- 200948908 四、指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： te 〇 Μ、、200948908 VII. Patent application scope: 1. A corrosion-resistant coating composition comprising (A) a flexible organic element modified bisphenol epoxy resin, which is 5 to 50% by weight of a flexible organic element and 95 to 50% by weight of a bisphenol epoxy resin obtained by reacting (B) a hardener and (C) a corrosion-resistant pigment, at least one selected from the group consisting of aliphatic having 4 to 36 carbon atoms A group consisting of a polybasic acid, an acrylic resin having a glass transition temperature of -20 to 50 ° C, and a polyester resin having a glass transition temperature of -20 to 50 ° C. ❹ 2. The corrosion-resistant coating composition according to claim 1, wherein the resin (A) is a bisphenol epoxy resin, which is an aliphatic polybasic acid having 4 to 36 carbon atoms and has -20 to 50 °C glass transfer temperature of acrylic resin modified. 3. The anticorrosive coating composition of claim 1, wherein the aliphatic polybasic acid having 4 to 36 carbon atoms is a dimer acid. 4. The anti-corrosion coating composition of claim 1, wherein the hardener (B) is at least one crosslinking agent selected from the group consisting of an amine resin, a phenol resin, and a blocking polyisofluoride compound selected from Q. . 5. The anti-corrosion coating composition of claim 1, wherein the anticorrosive pigment (C) is a chromium-free anticorrosive pigment. 6. The anticorrosive coating composition of claim 5, wherein the anticorrosive pigment comprises (1) at least one vanadium compound selected from the group consisting of vanadium pentoxide, calcium vanadate and ammonium metavanadate, (2) At least one cerium-containing compound selected from the group consisting of metal citrate and cerium oxide microparticles, and (3) a phosphate metal salt. 7. The anti-corrosion coating composition of claim 1, wherein the anti-corrosion-57-200948908 etching coating composition further comprises at least one epoxy resin selected from the group consisting of a secondary or tertiary amine group, and a secondary layer Or a tertiary amino-based acrylic resin and a soluble powder 'enzyme resin. 8. A coated metal sheet having a hardened coating film formed on one or both sides of the surface of the metal sheet by the corrosion-resistant coating composition of claim 1 of the patent sheet, the metal surface being applied Metal treatment method. A coated metal sheet comprising a multilayer coated film comprising a hard coat film formed on one or both sides of the surface of the tantalum sheet by the anticorrosive coating composition of claim 1 The metal surface is subjected to a metal treatment method selected, and a topcoat coating film formed on at least one side of the hardened coating film. ❹ -58- 200948908 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: te 〇 Μ, 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
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CN107227051A (en) * 2017-06-20 2017-10-03 合肥太通制冷科技有限公司 A kind of evaporator of refrigerator aluminium sheet corrosion resistant coating and preparation method thereof
CN109777184A (en) * 2017-11-15 2019-05-21 马锐 The production technology of natural organic functions paint ceramic tile
CN108997902A (en) * 2018-09-03 2018-12-14 王劲 A kind of resistance to deep-draw high temperature resistant does not adhere to coil coating and preparation method thereof
EP3666842B1 (en) * 2018-12-12 2021-09-15 3M Innovative Properties Company High chemical resistant coating as protection against aggressive environment
WO2021002139A1 (en) * 2019-07-03 2021-01-07 中国塗料株式会社 Heat-resistant coating composition, heat-resistant coating film, heat-resistant coating film-attached substrate, and method for preparing same
CN113891918B (en) * 2019-09-17 2022-07-15 关西涂料株式会社 Two-pack type coating composition
CN112341796A (en) * 2020-11-27 2021-02-09 浙江长鸿纺织科技有限公司 TPU membrane with corrosion resistance

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61276861A (en) * 1985-05-31 1986-12-06 Nippon Paint Co Ltd Primer composition for metallic material
JP2697883B2 (en) * 1989-01-23 1998-01-14 ダウ・ケミカル日本株式会社 Method for producing high molecular weight epoxy dimer acid ester resin
JPH0692559B2 (en) * 1989-02-10 1994-11-16 東洋インキ製造株式会社 Paint composition
JP2864546B2 (en) * 1989-08-09 1999-03-03 日本鋼管株式会社 Pre-coated steel sheet
JPH05255636A (en) * 1992-03-11 1993-10-05 Origin Electric Co Ltd Material having film excellent in adhesion
JPH06228497A (en) * 1993-02-01 1994-08-16 Kansai Paint Co Ltd Water-based coating composition
JPH0751620A (en) * 1993-08-18 1995-02-28 Kawasaki Steel Corp Harmless precoated steel excellent in corrosion resistance
JP3076496B2 (en) * 1994-03-29 2000-08-14 関西ペイント株式会社 Paint composition
JP2002012820A (en) * 2000-06-29 2002-01-15 Nippon Yushi Basf Coatings Kk Primer coating composition
JP2002188041A (en) * 2000-12-20 2002-07-05 Toray Ind Inc Coating composition
JP4890688B2 (en) * 2001-07-23 2012-03-07 関西ペイント株式会社 Aqueous epoxy resin dispersion
JP4061050B2 (en) * 2001-11-01 2008-03-12 関西ペイント株式会社 Primer coating composition
JP2003166071A (en) * 2001-11-29 2003-06-13 Kansai Paint Co Ltd Surface finishing composition for lubricative steel sheet, and lubrictive steel sheet
CN1286927C (en) * 2002-05-30 2006-11-29 关西涂料株式会社 Coating composition
CN1215137C (en) * 2002-07-30 2005-08-17 关西涂料株式会社 Paint composition and coating method
JP2004190111A (en) * 2002-12-12 2004-07-08 Kansai Paint Co Ltd Corrosion prevention method for edge part
JP5250859B2 (en) * 2006-05-22 2013-07-31 関西ペイント株式会社 Water-based paint composition
JP5547376B2 (en) * 2008-03-19 2014-07-09 関西ペイント株式会社 Rust preventive paint composition
JP5547375B2 (en) * 2008-03-19 2014-07-09 関西ペイント株式会社 Rust preventive paint composition
JP5086288B2 (en) * 2009-02-05 2012-11-28 関西ペイント株式会社 Chromium-free painted metal sheet coating method and painted metal sheet
JP5366628B2 (en) * 2009-04-16 2013-12-11 関西ペイント株式会社 MULTILAYER COATING FORMATION METHOD AND COATED METAL PLATE

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