200927480 九、發明說明 【發明所屬之技術領域】 本發明係關於即使不實施鉻酸鹽處理，耐蝕性、尤其 是端面之耐蝕性仍優異的樹脂塗裝金屬板。 【先前技術】 樹脂塗裝金屬板之切斷面（端面）及瑕疵部份係露出 〇 金屬板之金屬基材部份，此乃因鑛鋅或樹脂被膜而難以發 揮防銹效果的部份，但若於樹脂被膜中預先添加防銹顏料 時，自鍍鋅表面溶出的Zn離子與防銹顏料中的金屬形成 鈍化被膜，抑制鋅的腐蝕，能夠確保某程度的耐蝕性。 例如，在特開平6 — 9902號中揭示除了鉻酸鹽類防銹 顏料，亦可使樹脂被膜中含有釩/磷酸鹽系防銹顏料，提 高端面之耐蝕性的技術。於此專利文獻中揭示藉由磷酸離 子及溶解的鋅形成難溶性被膜之機能（沉澱機能）、以釩 G 酸離子的作用而顯示比鋅的腐蝕電位稍高之氧化還原電位 機能（氧化劑機能）等，於500小時之鹽水噴霧試驗中發 揮良好的耐蝕性。 另外，特開平11— 15 84 17號中揭示倂用鉻酸鹽系防 銹顏料與亞磷酸鹽系防銹顏料之基底用組成物。記載磷酸 鹽系之被膜係可提高端面耐鈾性（ 750小時之鹽水噴霧試 驗）。 此等2個專利文獻中記載的技術係任一種都使用鉻酸 鹽系防銹顏料，與最近不用鉻之潮流相違背。因此，本申 -5- 200927480 請者於特開2006 — 28582號中揭示，不使用鉻化合物，提 供端面腐蝕性優異之表面處理鍍鋅鋼板之技術。此專利文 獻之技術，其特徵在於使氧化鎂等之鹼土金屬（氫）氧化 物存在於樹脂被膜中，於腐蝕環境下，溶解成鹼離子，抑 制pH降低，可發揮控制Zn溶出之緩衝作用，周圍環境 變化成酸性和中性時，亦發揮長期的端面耐蝕性。 但是，對樹脂塗裝金屬板之端面耐蝕性要求進一步改 Q 善。例如，於經常暴露於水之潮濕環境下之端面或瑕疵部 份，因爲Zn離子或防銹顏料中之金屬離子因水而流失， 所以不能形成鈍態被膜，於短時間內產生紅銹，即使於如 此情況下，要求顯示良好的端面耐蝕性之樹脂塗裝金屬板 。上述傳統技術稱不上於假設如此嚴苛環境下提高端面耐 蝕性之技術。 【發明內容】 〇 發明之揭示 發明所欲解決之課題 於是，於本發明中，以提供例如即使經常暴露於水之 潮濕環境下之端面及瑕疵部份，亦可延緩紅銹之產生時間 之非鉻系樹脂塗裝金屬板爲課題。 課題之解決手段 爲解決上述課題，本發明提供樹脂塗裝金屬板，由金 屬板、及於前述金屬板表面所設置之非鉻系基底處理被膜 -6- 200927480 、及樹脂塗膜所形成’前述樹脂塗膜係相對於i 〇〇質量份 之緩釋性防録微粒子以外的塗膜成分，含有5〜40質量份 之多孔質無機微粒子與金屬化合物系防銹顏料所複合化而 成之緩釋性防錄微粒子’於前述樹脂塗裝金屬板上刻劃了 100個lmmx 1mm之方格後，浸漬於40 °C之碳酸鹽pH標 準液時，由前述防銹顏料中溶出金屬離子之溶出速度爲 0.001 〜1.0mg/l.m2_hr。 0 在此’於緩釋性防銹微粒子以外之塗膜成分中，含有 基底樹脂、防銹顏料、體質顏料、交聯劑等。亦即，意味 著有機樹脂整體。 本發明之樹脂塗膜，亦可以層合多種塗膜層之方式所 構成’只要該多種塗膜層中之至少一層含有前述緩釋性防 銹粒子即可。於該多種塗膜層中，含有前述緩釋性防銹粒 子的層係可以任一層。另外，具有多層含有前述緩釋性防 銹粒子之塗膜，可構成爲該含有緩釋性防銹微粒子之各塗 〇 膜層之緩釋性防銹微粒子之種類或含量係可彼此互異。 緩釋性防銹微粒子的平均粒徑若爲1〜10#m時，耐 蝕性及加工性的均衡將更良好。 浸漬緩釋性防銹微粒子於40 °C之pH 10之氫氧化鈉水 溶液時之金屬離子的溶出速度爲0.005〜OJing/l^hr時 ，因容易設定來自前述塗膜之金屬離子的溶出速度於適當 範圍內，所以適宜。 緩釋性防銹微粒子中複合化之防銹顏料係至少一種以 上選自氧化鎂、氫氧化鎂、磷酸鎂、碳酸鎂、氯化鎂、草 -7- 200927480 酸鎂、硫酸鎂及此等水合物所成群之鎂化合物，或至少一 種選自三聚磷酸鋁、磷酸鋁及磷酸鋁二水合物所成群之鋁 化合物時，因爲發揮優異的防銹效果，所以適宜。 緩釋性防銹微粒子所使用之多孔質無機微粒子係多孔 質二氧化矽微粒子時，因爲容易與防銹顏料複合化，所以 適宜。另外，於前述塗膜中，可再含有防銹顏料。藉此， 更進一步提高端面耐蝕性。 φ 本發明中，因爲樹脂塗裝金屬板之樹脂塗膜含有緩釋 性防銹微粒子，所以即使經常暴露於水中之潮濕環境下之 端面及瑕疵部份，防銹成分也會從此緩釋性防銹微粒子緩 緩溶於水中，長時間抑制紅銹的產生。因此，本發明之金 屬板係有效地使用於冷氣機室外機等之於比較嚴酷的腐蝕 環境下所使用之PCM (預塗金屬板）。 用以實施發明之最佳形態 〇 本發明具有之特徵係於非鉻系基底處理被膜上，形成 下塗塗膜及/或上塗塗膜之非鉻系樹脂塗裝金屬板，此下 塗塗膜及/或上塗塗膜係相對於100質量份之緩釋性防銹 微粒子以外的塗膜成分’含有5〜40質量份之多孔質無機 微粒子與金屬化合物系防銹顏料所複合而成之緩釋性防銹 微粒子’於樹脂塗裝金屬板上刻劃了 100個lmmxlmm之 方格後，浸漬於40 °C之碳酸鹽pH標準液時，自前述防銹 顏料溶出金屬離子的溶出速度爲0.001〜1.0mg/l.m2.hr。 本發明之樹脂塗裝金屬板係非鉻系樹脂塗裝金屬板。 -8 - 200927480 所謂非鉻系係指不施以鉻酸鹽系基底處理。本發明所使用 之金屬板之種類並無特別的限定，包含鋼板或非鐵金屬板 之金屬板、對此等施以單一金屬或各種合金之鍍敷之鍍敷 金屬板等。具體上，可舉例如熱軋鋼板、冷軋鋼板、不銹 鋼板等鋼板；熔融鍍鋅鋼板、合金化熔融鍍鋅鋼板、電鍍 鋅鋼板 '電鍍Zn — Ni合金鋼板等之鍍敷鋼板；鋁、鈦、 鋅等之非鐵金屬板或對此等施以鍍敷之鍍敷非鐵金屬板等 〇 。對上述金屬板，實施非鉻系基底處理。作爲基底處理係 只要爲非鉻系即可，可舉例如磷酸鹽處理、酸洗處理、鹼 處理、電解還原處理、矽烷交聯劑處理、無機矽酸鹽處理 等。若爲磷酸鹽處理，則以定0.05〜3. Og/m2之附著量爲 宜。 本發明之樹脂塗裝金屬板係具有下塗塗膜及/或上塗 塗膜。亦即，可爲僅有上塗塗膜的結構，亦可於下塗塗膜 上具有上塗塗膜的二層結構。另外，亦可爲進一步層合其 〇 他塗膜者。 下塗塗膜及上塗塗膜的主要成分係有機樹脂。作爲樹 脂，可舉例如聚脂系樹脂、丙烯樹脂、胺基甲酸乙酯樹脂 、聚烯烴系樹脂、氟系樹脂、矽氧系樹脂、及此等樹脂之 混合物或改性之樹脂等。其中，以有機溶劑可溶型（非晶 性）之聚脂樹脂爲宜。作爲有機溶劑可溶型（非晶性）之 聚脂樹脂，就可取得豐富種類者之觀點上，以東洋紡績公 司製之「VyIon (註冊商標）」系列爲宜。聚脂系樹脂係 可以三聚氰胺樹脂或環氧樹脂等進行交聯。作爲三聚氰胺 -9- 200927480 樹脂’有住友化學公司製之「Sumimal (註冊商標）」系 列、CYTECH公司製之「CYMEL (註冊商標）」系列。作 爲環氧樹脂，例如有Japan Epoxy Resins公司製之「jER (註冊商標）」系列。交聯劑係以配合成於乾燥後之樹脂 被膜中交聯劑（反應後）之質量爲0.5〜30% (以5〜25% 爲宜）尤佳。另外，此交聯劑（反應後）之質量比係以有 機樹脂整體（含有基底樹脂、防銹顏料、體質顏料、交聯 f) 劑等）之乾燥後之塗膜質量爲100%者。 本發明之樹脂塗裝金屬板係於下塗塗膜及/或上塗塗 膜中含有多孔質無機微粒子與金屬化合物系防銹顏料所複 合化而成之緩釋性防銹微粒子。所謂「多孔質無機微粒子 與金屬化合物系防銹顏料所複合化」係指於多孔質無機微 粒子的孔中或其表面，附著金屬化合物系防銹顏料之狀態 。所謂「緩釋性防銹微粒子」係指藉由前述複合化，自該 緩釋性防銹微粒子之金屬化合物防銹顏料之溶出速度比金 〇 屬化合物防銹顏料自身向水的溶出速度小。 防銹顏料係於腐蝕環境下（ΡΗ8·5〜10.5),溶出防 銹成分之金屬離子，具有pH變化之緩衝作用，並且與自 鍍Zn表面溶出的Zn離子形成鈍態被膜而抑制鋅的腐蝕 ，產生耐鈾性。形成鈍態被膜之防銹成分之金屬離子與 Zn離子的比率係一定。因此，於腐蝕環境下，若防銹成 分之金屬離子的溶出速度大時，未與Zn離子反應之金屬 離子亦溶出、流失，重新形成鈍態被膜用之金屬離子不足 ’因此腐蝕進行。但是，若塗膜中含有緩釋性防銹微粒子 -10- 200927480 時，即使塗膜與水接觸，亦可控制來自防銹材料之金屬離 子的溶出及流失於低水準，因此，長時間內自塗膜溶出金 屬離子，可控制端面或瑕疵部份產生紅銹（端面耐鈾性之 產生）。 爲長時間有效維持該端面耐蝕性，於樹脂塗裝金屬板 上刻劃100個lmmxlmm之方格後，浸漬於40°c之碳酸鹽 pH標準液（PH1 0.01 )時，自上述防銹顏料中溶出之金屬 D 離子的溶出速度必須爲0.001〜1.0η^/1·ιη2·ΙΐΓ。該溶出速 度未滿0.001ιηβ/1·πι2·1ιΓ時，於腐蝕環境下之金屬離子過 少，難以長時間防止端面及瑕疵部份的紅銹產生。但是， 金屬離子的溶出速度超過1.0π^/1·ιη2·1ιΓ時，不能得到端 面耐蝕性之持續性。溶出速度的下限係以0.005π^/1·ιη2·1ΐΓ ，上限爲〇.5mg/l.m2.hr尤佳。另外，傳統的二氧化矽系 防銹劑（鈣離子交換二氧化矽）中，腐蝕環境下之溶出速 度爲2·2ιηβ/1·ιη2·1ΐΓ，遠比本發明之緩釋性防銹微粒子大 G ’因此不能得到如本發明之提高端面耐蝕性之持續性的效 果。另外’於測定前述溶出速度時，方格係刻劃至基底金 屬板。碳酸鹽 pH値標準液係具有 0.21質量％ ( 0.02490mol/l)之碳酸氫鈉與 0.26 質量 ％ ( 0.0249 1 mol/1 )之碳酸鈉的水溶液，例如由關東化學公司等所銷售。 爲調節該金屬離子的溶出速度，例如可藉由調整緩釋 性防銹微粒子之含量以進行。倂用緩釋性防銹微粒子及傳 統的防銹顏料時，藉由調整此等之含量比率，可調整此金 屬離子的溶出速度。另外，使用層合含有緩釋性防銹微粒 -11 - 200927480 子的塗膜層與不含有緩釋性防銹微粒子的塗膜層時，藉由 調整此等膜厚的比率，可調整此金屬離子的溶出速度。 前述溶出速度，假設實際的腐蝕環境而規定金屬離子 自樹脂塗裝金屬板的溶出速度，但是浸漬本發明之緩釋性 防銹微粒子本身於40 °C的pHIO的氫氧化鈉水溶液時之金 屬離子的溶出速度係以0.00 5〜0.511^/11.111'爲宜。因爲 若於此範圍時，則可以容易設定金屬離子自樹脂塗裝金屬 〇 板的溶出速度於前述適合的範圍內。 要調整此金屬離子溶出速度，例如可藉由調整多孔質 無機微粒子之孔徑進行。或者藉由以樹脂等被覆於內包防 銹劑後之多孔質無機微粒子表面，亦可進行調整。 緩釋性防銹微粒子係藉由複合化多孔質無機微粒子及 金屬化合物系防銹顏料所得。作爲多孔質無機微粒子，以 二氧化矽、氧化鈦、氧化鐵、氧化鈷、氧化鋅、氧化鎳、 氧化錳、氧化鋁等之金屬氧化物；氫氧化鐵、氫氧化鎳、 ❹ 氫氧化鋁、氫氧化鈣、氫氧化鉻等之金屬氫氧化物：碳酸 鈣、碳酸鋇等之碳酸鹽；矽酸鈣、砂酸鋇、矽酸鎂等之砂 酸鹽；磷酸鈣、磷酸鋇、磷酸鎂、磷酸銷、磷灰石等之磷 酸鹽等所形成者爲宜。尤其就耐蝕性上，以二氧化矽微粒 子爲宜。 多孔質無機微粒子之平均粒徑係以1〜1()//ιη爲宜。 若小於1 // m時’因難以製造多孔質無機微粒子，耐蝕性 降低’所以不適宜。若超過時，因有加工性降低 之趨勢’因此不適宜。更適宜之平均粒徑爲1〜3ym。另 -12- 200927480 外，多孔質無機微粒子之平均粒徑及複合化後之緩釋性防 銹微粒子之平均粒徑幾乎不變。因此，緩釋性防銹微粒子 適合之平均粒徑亦爲1〜ΙΟ/zm (以1〜3//m爲宜）。平 均粒徑係例如使用掃描型電子顯微鏡（倍率5000倍）， 藉由計算視角中所觀察之微粒子之平均値而求出。或者亦 可使用島津製作所製「SA—P3」，藉由離心沉降法算出 〇 〇 多孔質無機微粒子之多孔質程度係以比表面積100〜 8 0 0m2/g爲宜。因爲與防銹顏料複合化後，成爲適當的溶 出速度》作爲如此多孔質無機微粒子，例如可得自「 godball (註冊商標）」系列（鈴木油脂工業公司製）、或多 孔質二氧化矽微粒子（ENEX公司製；SE MCB-FP/2 )。 於前述「go db all (註冊商標）」中，有非中空二氧化矽型 之E— 2C (平均粒徑爲0.9〜1.4 μ m，比表面積爲3 5 0〜 500m2/g) 、E-6C (平均粒徑爲2.0〜2.5//m，比表面積 〇 爲 250 〜400m2/g) 、E—2C (平均粒徑爲 0.9 〜1.4/zm， 比表面積爲350〜500m2/g) 、E — 16C (平均粒徑爲4.0〜 5·3/ζ m，比表面積爲 300〜550m2/g) 、D — 11C (平均粒 徑爲3_0〜4.0/zm，比表面積爲2 8 0〜5 00m2/g);中空二 氧化矽型之B—6C (平均粒徑爲2.0〜2.5ym，比表面積 爲 25 0 〜400m2/g) 、B— 25C (平均粒徑爲 8.0 〜10.0//m ，比表面積爲400〜5 50m2/g);超多孔質二氧化矽型之 AF—6C(平均粒徑爲 2.5〜3.5/^111、比表面積爲 600〜 700m2/g) 、AF — 16C (平均粒徑爲 4.0〜5.3μπι，比表面 -13- 200927480 積爲 600 〜700m2/g) 、SF — 16C(平均粒径 4.0 〜5.3/zm ，比表面積爲600〜700m2/g)等。 作爲金屬化合物系防銹顏料，以對水的溶解度不太大 ，溶出速度小者爲宜。可長期發揮端面耐飩性。具體上， 氧化鎂、氫氧化鎂、磷酸鎂、碳酸鎂、氯化鎂、草酸鎂、 硫酸鎂及此等之水合物等之鎂化合物；三聚磷酸鋁、磷酸 鋁、磷酸鋁二水合物等之鋁化合物適合。 φ 複合化時的多孔質無機微粒子與金屬化合物系防銹顏 料之質量比率係以95: 5〜50: 50爲宜。防銹顏料未滿5 質量％時，有時難以得到充分的端面耐蝕性及其持續性。 另外’使防銹顏料超過50質量％時，於多孔質無機微粒 子之結構上難以實現複合化。 緩釋性防銹微粒子可以藉由將比多孔質無機微粒子徑 小（根據需要進行破碎）之金屬化合物系防錄顏料與多孔 質無機微粒子一起進行機械混合而得到。以高剪斷力混合 〇 爲宜’認爲於此混合期間，防錄顏料進入多孔質無機微粒 子的孔中’兩者複合化。於混合時，亦可適當地進行加熱 •加壓。本發明中，因爲使用對水的溶解度小、溶出速度 小之金屬化合物系防銹顏料，所以難以浸漬多孔質無機微 粒子於防銹顏料的水溶液中而進行複合化，但若藉由調整 pH ’或使用其他溶劑以使防銹顏料溶液化，則藉由浸漬 多孔質無機微粒子於此溶液中後進行乾燥，可以進行兩者 的複合化。 相對於100質量份之塗膜成分’含有5〜40質量份之 -14 - 200927480 緩釋性防銹微粒子時，可得到良好的端面耐蝕性及其持續 性。亦即，於塗膜形成用組成物之固形成分中，相對於 1 00質量份之緩釋性防銹微粒子以外之固形成分，添加5 〜40質量份之緩釋性防銹微粒子，形成塗膜即可。緩釋 性防銹微粒子亦可包含於下塗塗膜及上塗塗膜中任何一方 或雙方。就耐蝕性之觀點係含於雙方塗膜中爲宜。 製造本發明之樹脂塗裝金屬板，以採用調製塗膜形成 〇 用組成物，將此塗佈於金屬板上進行乾燥的方法爲宜。塗 膜形成用組成物係使用成爲基底的有機樹脂及緩釋性防銹 微粒子、因應需要所添加之交聯劑等，以有機溶劑稀釋成 適於塗裝之黏度者。作爲有機溶劑並無特別的限定，可列 舉甲苯、二甲苯等之芳香族系烴；醋酸乙酯、醋酸丁酯等 之脂肪族酯系；環己烷等之脂環族烴系；己烷、戊烷等之 脂肪族烴系等；甲基乙基酮、環已酮等之酮系等。若考慮 塗裝適宜性時，推薦調整其黏度爲以福特杯No.4，30〜 © 1〇〇秒程度、或調節固形成分濃度爲5〜45質量％範圍之 原料組成物。 於前述塗膜形成用組成物中，亦可再添加眾知之防銹 顏料。另外，亦可添加消光劑、體質顏料、沉澱防止劑、 蠟等之於樹脂塗裝金屬板領域所使用之各種眾知的添加劑 〇 塗佈上述塗膜形成用組成物於金屬板之方法共無特別 的限定，可採用棒塗法、輥塗法、噴霧法、簾式流動塗佈 法等。於塗佈後進行乾燥，但於交聯劑添加系中，以交聯 -15- 200927480 劑可進行反應之溫度進行加熱乾燥爲宜。具體而言，於 100〜25(TC，進行加熱乾燥1〜5分鐘程度尤佳。 下塗塗膜、上塗塗膜的厚度並無特別的限定，但任一 種皆在1〜100#m程度，以5〜30/zm程度尤佳。 【實施方式】 實施例 0 [實施例] 由下述實施例更詳細地說明本發明，但本發明並不侷 限於下述實施例，於不脫離本發明宗旨之範圍內之變更實 施亦包含於本發明。另外，以下無特別規定的情況下，「 %」表示“質量％ ” ， 「份」表示「質量份」，實施例中 使用之評估方法如下。 [橫切的耐蝕性] ❹ 於供試材料（50mmxl20mm)上，用切刀橫切（60°， 60mm)，依據 JIS Z237 1實施鹽水噴霧試驗，測定500 小時後之自橫切部份之塗膜膨脹寬度。評估基準如下所述 〇 ◎:膨脹寬度1mm以下 〇：膨脹寬度1mm以上，3mm以下 △:膨脹寬度3mm以上，5mm以下 X :膨脹寬度5mm以上 16- 200927480 [端面耐蝕性] 依據JIS Z2371實施鹽水噴霧試驗，測定500 之自端面部份之塗膜膨脹寬度。評價基準如下所述 ◎:膨脹寬度1mm以下 〇：膨脹寬度1mm以上，3mm以下 △:膨脹寬度3mm以上，5mm以下 X :膨脹寬度5mm以上 [人工雨水滴下試驗] 將試驗材料切割成50mmxl20mm，將圖1所不 方向的一端，彎曲成圓槽狀，使橫斷面成爲半圓形 部份的兩端密封。於圓槽部份的中央部切入 Φ =6mm )的切口，露出該半圓周圍部份的端面。 材料上方，以0.16〜0.17ml/min滴下人工雨水。人 的組成如表1所示，以硫酸調整成pH4.7。此乃依 廳調查的國內降雨的平均離子組成。試驗環境係 4〇°C，95%RH。於試驗裝置的下部放置紗布，每隔 時目視確認半圓切口部份的紅銹產生狀態，及紅銹 布的狀態。此確認時若產生紅銹，則以該時間爲紅 時間。 小時後 之長度 。圓槽 圓形（ 自試驗 工雨水 據環境 設定爲 24小 流入紗 銹產生 -17- 200927480[Technical Field] The present invention relates to a resin-coated metal sheet which is excellent in corrosion resistance, particularly in end surface corrosion resistance, even without chromate treatment. [Prior Art] The cut surface (end surface) and the ruthenium portion of the resin-coated metal sheet are exposed to the metal base material portion of the base metal sheet, which is a portion which is difficult to exert the rust-preventing effect due to the mineral zinc or the resin film. However, when a rust preventive pigment is added to the resin film in advance, the Zn ions eluted from the galvanized surface and the metal in the rust preventive pigment form a passivation film, which suppresses corrosion of zinc and ensures a certain degree of corrosion resistance. For example, Japanese Laid-Open Patent Publication No. Hei 6-9902 discloses a technique in which a vanadium/phosphate antirust pigment is contained in a resin film in addition to a chromate antirust pigment to improve the corrosion resistance of the end face. This patent document discloses a function of forming a poorly soluble film by a phosphate ion and dissolved zinc (precipitation function), and an oxidation-reduction potential function (oxidant function) which is slightly higher than a corrosion potential of zinc by the action of vanadium G acid ions. Etc., exerts good corrosion resistance in a 500 hour salt spray test. Further, a base composition for a chromate-based rust preventive pigment and a phosphite-based rust preventive pigment is disclosed in Japanese Laid-Open Patent Publication No. Hei. The phosphate-based coating system was described to improve the endurance resistance of the end face (the 750-hour salt spray test). Any of the techniques described in the two patent documents uses a chromate-based anti-rust pigment, which is contrary to the recent trend of not using chromium. The present invention discloses a technique of providing a surface-treated galvanized steel sheet excellent in end surface corrosion without using a chromium compound, as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2006-28588. The technique of the patent document is characterized in that an alkaline earth metal (hydrogen) oxide such as magnesium oxide is present in a resin film, and is dissolved in an alkali ion in a corrosive environment to suppress a decrease in pH, thereby exerting a buffering action for controlling Zn elution. When the surrounding environment changes to acidity and neutrality, it also exerts long-term end face corrosion resistance. However, the corrosion resistance of the end face of the resin-coated metal sheet is required to be further improved. For example, in the end face or the sputum portion which is often exposed to the humid environment of water, since the metal ions in the Zn ion or the rust preventive pigment are lost due to water, the passive film cannot be formed, and red rust is generated in a short time even if In such a case, a resin-coated metal sheet exhibiting good end face corrosion resistance is required. The above conventional techniques cannot be said to be techniques for improving the end face corrosion resistance under such a severe environment. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In the present invention, in order to provide, for example, an end face and a crucible portion in a humid environment which is often exposed to water, the generation time of red rust may be delayed. It is a problem to coat a metal plate with a chrome resin. In order to solve the above-mentioned problems, the present invention provides a resin-coated metal sheet which is formed of a metal plate and a non-chromium-based base treatment film 6-200927480 and a resin coating film provided on the surface of the metal plate. The resin coating film is a sustained release of a composite film containing 5 to 40 parts by mass of a porous inorganic fine particle and a metal compound-based rust preventive pigment, with respect to the coating component other than the i 〇〇 mass part of the sustained-release anti-recording fine particle. The anti-recording microparticles are etched into the above-mentioned resin-coated metal plate by 100 square meters of 1 mm x 1 mm, and then immersed in a carbonate pH standard solution at 40 ° C to dissolve the metal ions from the aforementioned anti-rust pigment. It is 0.001 to 1.0 mg/l.m2_hr. In the coating composition other than the sustained release rust preventive fine particles, a base resin, an rust preventive pigment, an extender pigment, a crosslinking agent, and the like are contained. That is, it means the organic resin as a whole. The resin coating film of the present invention may be formed by laminating a plurality of coating layers as long as at least one of the plurality of coating layers contains the above-mentioned sustained release rust preventive particles. In the plurality of coating layers, the layer containing the sustained release rust preventive particles may be either layer. Further, the coating film containing the multilayer release-preventing rust-preventing particles can be configured such that the types or contents of the sustained-release rust-preventing fine particles of the ruthenium-coated film layer containing the sustained-release rust-preventing fine particles can be different from each other. When the average particle diameter of the sustained release rust preventive fine particles is 1 to 10 #m, the balance between corrosion resistance and workability is further improved. When the elution rate of the metal ions in the sodium hydroxide aqueous solution of pH 10 at 40 ° C is 0.005 to OJing/l hr, the dissolution rate of the metal ions from the coating film is easily set. Suitable within the appropriate range. The rust preventive pigment compounded in the sustained release rust preventive particles is at least one selected from the group consisting of magnesium oxide, magnesium hydroxide, magnesium phosphate, magnesium carbonate, magnesium chloride, grass -7-200927480 magnesium silicate, magnesium sulfate, and the like. A group of magnesium compounds, or at least one aluminum compound selected from the group consisting of aluminum tripolyphosphate, aluminum phosphate, and aluminum phosphate dihydrate, is suitable because it exhibits an excellent rust preventing effect. When the porous inorganic fine particles used in the sustained release rust preventive particles are porous ceria particles, they are easily combined with the rust preventive pigment. Further, in the coating film, an anti-rust pigment may be further contained. Thereby, the end face corrosion resistance is further improved. φ In the present invention, since the resin coating film of the resin-coated metal sheet contains the sustained-release rust-preventing fine particles, the rust-preventing component can be prevented from being released even if it is often exposed to the end faces and the ruthenium portion in a humid environment of water. The rust particles are slowly dissolved in water and inhibit the generation of red rust for a long time. Therefore, the metal plate of the present invention is effectively used for a PCM (precoated metal plate) used in a relatively harsh corrosive environment such as an air conditioner outdoor unit. The best mode for carrying out the invention. The present invention is characterized in that it is formed on a non-chromium-based substrate-treated film to form a non-chromium-based resin-coated metal plate having a lower coating film and/or an upper coating film, and the lower coating film and/or And the coating film of the above-mentioned coating film is composed of a coating film component other than 100 parts by mass of the sustained-release rust-preventing particles, and contains 5 to 40 parts by mass of the porous inorganic fine particles and the metal compound-based rust-preventing pigment. The rust microparticles are etched into a square of 1 mm x 1 mm on a resin coated metal plate, and then immersed in a carbonate pH standard solution at 40 ° C, and the dissolution rate of the metal ions eluted from the rust preventive pigment is 0.001 to 1.0 mg. /l.m2.hr. The resin-coated metal sheet of the present invention is a non-chromium resin-coated metal sheet. -8 - 200927480 The so-called non-chromium system means that the chromate-based substrate treatment is not applied. The type of the metal plate used in the present invention is not particularly limited, and includes a metal plate of a steel plate or a non-ferrous metal plate, a plated metal plate to which a single metal or various alloys are applied, and the like. Specifically, for example, steel sheets such as hot-rolled steel sheets, cold-rolled steel sheets, and stainless steel sheets; plated steel sheets such as hot-dip galvanized steel sheets, alloyed hot-dip galvanized steel sheets, and electrogalvanized steel sheets 'electroplated Zn-Ni alloy steel sheets; aluminum and titanium Non-ferrous metal plates such as zinc, or non-ferrous metal plates coated with such plating. The metal plate was subjected to a non-chromium substrate treatment. The substrate treatment system may be a non-chromium system, and examples thereof include a phosphate treatment, a pickling treatment, an alkali treatment, an electrolytic reduction treatment, a decane crosslinking agent treatment, and an inorganic citrate treatment. Og/m2 is preferably used in an amount of 0.05 to 3. Og/m2. The resin-coated metal sheet of the present invention has a lower coating film and/or an upper coating film. That is, it may be a structure in which only the upper coating film is applied, or a two-layer structure having an upper coating film on the undercoating film. In addition, it is also possible to further laminate the film of the film. The main component of the undercoat film and the top coat film is an organic resin. The resin may, for example, be a polyester resin, an acrylic resin, a urethane resin, a polyolefin resin, a fluorine resin or a fluorene resin, or a mixture of these resins or a modified resin. Among them, an organic solvent-soluble (amorphous) polyester resin is preferred. It is preferable to use the "VyIon (registered trademark)" series manufactured by Toyobo Co., Ltd. as a polyester resin which is soluble in the organic solvent (amorphous). The polyester resin may be crosslinked by a melamine resin, an epoxy resin or the like. As a melamine -9- 200927480 resin, there is a "Sumimal (registered trademark)" series by Sumitomo Chemical Co., Ltd. and a "CYMEL (registered trademark)" series by CYTECH. As the epoxy resin, for example, the "jER (registered trademark)" series manufactured by Japan Epoxy Resins Co., Ltd. The crosslinking agent is preferably 0.5 to 30% by mass (equivalent to 5 to 25%) of the crosslinking agent (after the reaction) in the resin film after drying. Further, the mass ratio of the crosslinking agent (after the reaction) is 100% by mass of the coating film after drying of the entire organic resin (including the base resin, the rust preventive pigment, the extender pigment, and the crosslinking agent). The resin-coated metal sheet of the present invention is a sustained release rust-preventing fine particle obtained by combining a porous inorganic fine particle and a metal compound-based rust preventive pigment in a lower coating film and/or an upper coating film. The "composite of the porous inorganic fine particles and the metal compound-based rust preventive pigment" means a state in which a metal compound-based rust preventive pigment is adhered to the pores of the porous inorganic fine particles or the surface thereof. The term "sustained-release rust-preventing fine particles" means that the elution rate of the metal compound rust-preventing pigment from the sustained-release rust-preventing fine particles is smaller than the elution rate of the metal ruthenium-based compound rust-preventing pigment itself to water by the above-mentioned compounding. The anti-rust pigment is in a corrosive environment (ΡΗ8·5~10.5), dissolves the metal ions of the anti-rust component, has a buffering effect of pH change, and forms a passive film with the Zn ions eluted from the surface of the Zn-plated surface to inhibit the corrosion of zinc. , producing uranium resistance. The ratio of the metal ions to the Zn ions forming the rust-preventing component of the passive film is constant. Therefore, in the corrosive environment, if the elution rate of the metal ions of the rust-preventing component is large, the metal ions which are not reacted with the Zn ions are also eluted and lost, and the metal ions for re-forming the passive film are insufficient. However, if the coating film contains the sustained-release rust-preventing microparticles-10-200927480, even if the coating film is in contact with water, the elution and loss of metal ions from the rust-preventing material can be controlled to a low level. The coating film dissolves metal ions, which can control the red rust on the end face or the enamel portion (the end face is resistant to uranium). In order to effectively maintain the corrosion resistance of the end face for a long time, 100 squares of lmmxlmm squares are scribed on the resin-coated metal plate, and then immersed in a carbonate pH standard solution (pH 1 0.01) at 40 ° C from the above-mentioned anti-rust pigment. The dissolution rate of the eluted metal D ion must be 0.001 to 1.0 η ^ / 1 · ιη 2 · ΙΐΓ. When the dissolution rate is less than 0.001 ηηβ / 1 · πι 2 · 1 Γ , the metal ions in the corrosive environment are too small, and it is difficult to prevent red rust on the end faces and the ruthenium portions for a long time. However, when the elution rate of metal ions exceeds 1.0 π ^ / 1 · ιη 2 · 1 Γ , the durability of the end surface corrosion resistance cannot be obtained. The lower limit of the dissolution rate is 0.005π^/1·ιη2·1ΐΓ, and the upper limit is preferably 〇5 mg/l.m2.hr. In addition, in the conventional cerium oxide rust preventive agent (calcium ion exchange ruthenium dioxide), the dissolution rate in a corrosive environment is 2·2ιηβ/1·ιη2·1ΐΓ, which is far larger than the sustained release rust preventive particles of the present invention. G' therefore does not provide the effect of improving the durability of the end face corrosion resistance as in the present invention. Further, when the above dissolution rate was measured, the checkered pattern was scored to the base metal plate. The carbonate pH standard solution has an aqueous solution of 0.21% by mass (0.02490 mol/l) of sodium hydrogencarbonate and 0.26 mass% (0.0249 1 mol/1) of sodium carbonate, for example, sold by Kanto Chemical Co., Ltd., and the like. In order to adjust the elution rate of the metal ions, for example, the content of the sustained release rust preventive particles can be adjusted. When the sustained release rust preventive particles and the conventional rust preventive pigment are used, the dissolution rate of the metal ions can be adjusted by adjusting the content ratio. Further, when a coating layer containing a controlled release rust preventive particle 11 - 200927480 and a coating layer containing no sustained release rust preventive particles are laminated, the metal can be adjusted by adjusting the ratio of the film thicknesses. The rate of dissolution of ions. The elution rate is determined by the actual corrosion environment, and the elution rate of the metal ions from the resin-coated metal sheet is specified, but the metal ions of the sustained release rust-preventing microparticles of the present invention are themselves in a pHIO aqueous sodium hydroxide solution at 40 ° C. The dissolution rate is preferably 0.005~0.511^/11.111'. When it is in this range, the elution rate of metal ions from the resin-coated metal ruthenium can be easily set within the above-mentioned suitable range. The metal ion elution rate is adjusted, for example, by adjusting the pore diameter of the porous inorganic fine particles. Alternatively, it may be adjusted by coating the surface of the porous inorganic fine particles coated with the rust inhibitor with a resin or the like. The sustained-release rust-preventing fine particles are obtained by combining porous inorganic fine particles and a metal compound-based rust preventive pigment. Examples of the porous inorganic fine particles include metal oxides such as cerium oxide, titanium oxide, iron oxide, cobalt oxide, zinc oxide, nickel oxide, manganese oxide, and aluminum oxide; iron hydroxide, nickel hydroxide, and hydrazine aluminum hydroxide; a metal hydroxide such as calcium hydroxide or chromium hydroxide: a carbonate such as calcium carbonate or barium carbonate; a calcium salt such as calcium citrate, barium silicate or magnesium citrate; calcium phosphate, barium phosphate, magnesium phosphate, It is preferable to form a phosphate such as a phosphoric acid pin or apatite. In particular, in terms of corrosion resistance, cerium oxide microparticles are preferred. The average particle diameter of the porous inorganic fine particles is preferably 1 to 1 () / / ηη. When it is less than 1 // m, it is unfavorable because it is difficult to produce porous inorganic fine particles and the corrosion resistance is lowered. If it exceeds, there is a tendency to decrease in workability, which is not preferable. A more suitable average particle size is from 1 to 3 ym. In addition, the average particle diameter of the porous inorganic fine particles and the average particle diameter of the delayed release rust preventive fine particles after the composite are almost unchanged. Therefore, the average particle diameter of the sustained release rust preventive particles is also 1 to ΙΟ/zm (preferably 1 to 3//m). The average particle diameter is obtained, for example, by using a scanning electron microscope (magnification: 5000 times) by calculating the average enthalpy of the fine particles observed in the viewing angle. Alternatively, the "SA-P3" manufactured by Shimadzu Corporation may be used, and the porosity of the porous inorganic fine particles of 〇 算出 may be calculated by a centrifugal sedimentation method to have a specific surface area of 100 to 800 m 2 /g. In the case of the above-mentioned porous inorganic fine particles, the "Godball (registered trademark)" series (made by Suzuki Oil & Fats Co., Ltd.) or porous cerium oxide microparticles (for example, it can be obtained as a suitable dissolution rate). ENEX company; SE MCB-FP/2). In the above "go db all (registered trademark)", there is a non-hollow ceria type E-2C (average particle size of 0.9 to 1.4 μm, specific surface area of 305 to 500 m2/g), E-6C (average particle size is 2.0~2.5//m, specific surface area 〇 is 250~400m2/g), E-2C (average particle size is 0.9~1.4/zm, specific surface area is 350~500m2/g), E-16C (the average particle diameter is 4.0 to 5·3/ζ m, the specific surface area is 300 to 550 m 2 /g), D 11 C (the average particle diameter is 3_0 to 4.0/zm, and the specific surface area is 280 to 5.00 m 2 /g) ; hollow ceria type B-6C (average particle size is 2.0~2.5ym, specific surface area is 25 0~400m2/g), B-25C (average particle size is 8.0~10.0//m, specific surface area is 400 ~5 50m2/g); super-porous ceria-type AF-6C (average particle size is 2.5~3.5/^111, specific surface area is 600~700m2/g), AF-16C (average particle size is 4.0~) 5.3 μπι, specific surface -13 - 200927480 product is 600 ~ 700 m2 / g), SF - 16C (average particle size 4.0 ~ 5.3 / zm, specific surface area of 600 ~ 700 m2 / g). As the metal compound-based rust preventive pigment, the solubility in water is not so large, and the dissolution rate is preferably small. Long-term endurance resistance can be achieved. Specifically, magnesium compounds such as magnesium oxide, magnesium hydroxide, magnesium phosphate, magnesium carbonate, magnesium chloride, magnesium oxalate, magnesium sulfate, and the like; aluminum of aluminum tripolyphosphate, aluminum phosphate, aluminum phosphate dihydrate, and the like The compound is suitable. The mass ratio of the porous inorganic fine particles to the metal compound-based rust-preventing pigment at the time of φ compounding is preferably 95:5 to 50:50. When the rust preventive pigment is less than 5% by mass, it may be difficult to obtain sufficient end face corrosion resistance and sustainability. In addition, when the rust preventive pigment is more than 50% by mass, it is difficult to achieve compositing in the structure of the porous inorganic fine particles. The sustained-release rust-preventing fine particles can be obtained by mechanically mixing a metal compound-based anti-recording pigment having a smaller diameter than that of the porous inorganic fine particles (crushed if necessary) together with the porous inorganic fine particles. It is preferable to mix 〇 with a high shearing force, and it is considered that the anti-recording pigment enters the pores of the porous inorganic fine particles during the mixing. When mixing, it is also possible to appropriately heat and pressurize. In the present invention, since a metal compound-based rust preventive pigment having a small solubility in water and a small elution rate is used, it is difficult to immerse the porous inorganic fine particles in an aqueous solution of the rust preventive pigment, but by adjusting the pH 'or When a solvent is used to dissolve the rust preventive pigment, the porous inorganic fine particles are immersed in the solution and then dried to form a composite of the two. When the coating film component ' contains 5 to 40 parts by mass of -14 - 200927480 sustained-release rust-preventing fine particles, good end face corrosion resistance and durability can be obtained. In the solid content of the composition for forming a coating film, 5 to 40 parts by mass of the sustained release rust-preventing fine particles are added to the solid component other than the 100 parts by mass of the sustained release rust preventive fine particles to form a coating film. Just fine. The sustained release rust preventive particles may be contained in either or both of the undercoat film and the overcoat film. The viewpoint of corrosion resistance is preferably contained in both coating films. It is preferred to produce the resin-coated metal sheet of the present invention to form a composition by using a coating film, and to apply it to a metal plate for drying. The composition for forming a coating film is an organic resin to be used as a base, a controlled release rust preventive fine particle, a crosslinking agent to be added as needed, and the like, and is diluted with an organic solvent to have a viscosity suitable for coating. The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and xylene; aliphatic esters such as ethyl acetate and butyl acetate; and alicyclic hydrocarbons such as cyclohexane; and hexane; An aliphatic hydrocarbon such as pentane or the like; a ketone system such as methyl ethyl ketone or cyclohexanone. When considering the suitability for coating, it is recommended to adjust the viscosity to a raw material composition in the range of Ford Cup No. 4, 30 to © 1 sec, or a solid concentration of 5 to 45% by mass. Further, a known rust preventive pigment may be added to the composition for forming a coating film. In addition, various known additives used in the field of resin-coated metal sheets, such as a matting agent, an extender, a precipitation inhibitor, and a wax, may be added, and the coating film-forming composition may be applied to a metal sheet. Particularly, a bar coating method, a roll coating method, a spray method, a curtain flow coating method, or the like can be employed. Drying is carried out after coating, but in the crosslinking agent addition system, it is preferred to carry out heat drying at a temperature at which the crosslinking can be carried out by crosslinking -15-200927480. Specifically, it is preferably 100 to 25 (TC, heat-drying for 1 to 5 minutes. The thickness of the undercoat film and the overcoat film is not particularly limited, but any one is in the range of 1 to 100 #m, [Embodiment] Embodiment 0 [Embodiment] The present invention will be described in more detail by the following examples, but the present invention is not limited to the following examples, without departing from the spirit of the invention. The change implementation within the scope is also included in the present invention. In the following, unless otherwise specified, "%" means "% by mass", and "part" means "parts by mass", and the evaluation methods used in the examples are as follows. Cross-cut corrosion resistance] 横 On the test material (50mmxl20mm), cross-cut with a cutter (60°, 60mm), perform a salt spray test in accordance with JIS Z237 1 and measure the coating from the cross-section after 500 hours. Expansion width. The evaluation criteria are as follows: 〇 ◎: expansion width 1 mm or less 〇: expansion width 1 mm or more, 3 mm or less △: expansion width 3 mm or more, 5 mm or less X: expansion width 5 mm or more 16-200927480 [end surface corrosion resistance] According to JIS Z2371 Implement salt spray The test film was measured for the expansion width of the coating film from the end surface portion of 500. The evaluation criteria were as follows: ◎: expansion width: 1 mm or less 〇: expansion width: 1 mm or more, 3 mm or less Δ: expansion width: 3 mm or more, 5 mm or less, X: expansion width: 5 mm or more [Artificial rain drop test] The test material was cut into 50 mm x 20 mm, and one end of the non-directional direction of Fig. 1 was bent into a circular groove shape, and the cross section was sealed at both ends of the semicircular portion. The slit is cut into Φ = 6 mm) to expose the end face of the portion around the semicircle. Above the material, artificial rainwater was dripped at 0.16 to 0.17 ml/min. The composition of the human was as shown in Table 1, and the pH was adjusted to 4.7 with sulfuric acid. This is the average ion composition of domestic rainfall surveyed by the Department. The test environment was 4 ° C, 95% RH. Gauze was placed in the lower part of the test apparatus, and the red rust generation state of the semicircular cut portion and the state of the red rust cloth were visually confirmed at intervals. If red rust is generated during this confirmation, the time is red time. The length after hours. Round groove round (Self-test rainwater according to the environment is set to 24 small inflow yarn rust generation -17- 200927480
[表i] 離子種 "eq/L NH/ 21 Ca2+ 26 K+ 5 Mg2+ 22 Na+ 88 no3" 15 Cl— 110 [加工性A] 切割試驗材料成50mrnx50mm，將評估的面設定爲外 側且彎曲，於低溫（〇°C )環境下，以老虎鉗進行1 80。（ 0Τ彎曲）彎曲加工後，以目視及放大鏡（倍率1 〇倍）觀 察發生於彎曲部份塗膜之裂紋的發生狀態。評估基準如下 所述。 ◎:沒有發生裂紋（即使目視及放大鏡任一種觀察， 〇 皆無裂紋） 〇:裂紋發生少（雖目視不能看到，但以放大鏡觀察 . 時可確認有少許裂紋） △:裂紋發生（目視能夠看到龜裂小的裂紋） X :裂紋大（目視能夠看到龜裂大的裂紋） [加工性Β] 除了於非低溫（〇 t )環境下，而於常溫（2 0 °C )環 境下進行以外，與加工性A同樣地觀察彎曲部份的裂紋 -18- 200927480 發生狀態。評估基準亦相同。 [溶出速度測定試驗] 切割試驗材料成Φ 50mm的圓形’用切刀刻劃100個 1mm xl mm的方格。於4 0 °C、9 5 % RH之環境下，浸漬於 100ml之碳酸鹽pH標準液（ΡΗ=10·01，碳酸氫鈉+碳酸鈉 水溶液）。將此水溶液每隔24小時採取l〇ml，以ICP發 0 光分析法定量分析自方格刻劃部份及端面溶出的離子量， 測定防銹成分之溶出速度。 [製造緩釋性防銹微粒子A] 混合5 0份之中空多孔質二氧化矽微粒子（「godball (註冊商標）B- 6C」：鈴木油脂工業公司製：平均粒徑約 爲2.0#m(2〜2.5/zm) ) 、50份之相當氧化镁（「 STARMAG L— 10」之高活性品：神島化學工業公司製： 〇 平均粒徑爲0.63/z m )，製造緩釋性防銹微粒子A。另外 ，預先粉碎氧化鎂後，與中空多孔質二氧化矽微粒子混合 。混合時，於加溫下以高剪斷力混合。 [製造緩釋性防銹微粒子B] 除改變爲氧化鎂，使用三聚磷酸鋁（「K— WAHITE #G1 05」：平均粒徑爲 2.3 // m : TAYCA公司製）以外’ 與緩釋性防銹微粒子A同樣地操作，製造緩釋性防鍵微 粒子B。 -19- 200927480 [製造緩釋性防銹微粒子c] 除改變爲氧化鎂，使用碳酸鎂（工業用（輕質）：協 和化學工業公司製）以外，與緩釋性防銹微粒子A同樣 地操作，製造緩釋性防銹微粒子C。 [製造緩釋性防銹微粒子D] 〇 除改變爲氧化鎂，使用氫氧化鎂（「1 〇 a」：神島化 學工業公司製：平均粒徑爲3.5 # m )以外，與緩釋性防 銹微粒子A同樣地操作，製造緩釋性防銹微粒子D。 [製造緩釋性防銹微粒子E] 除改變爲氧化鎂，使用磷酸鎂（御國色素公司製）以 外’與緩釋性防銹微粒子A同樣地操作，製造緩釋性防 錄微粒子E。 ❹ [製造緩釋性防銹微粒子F ] 除改變爲氧化鎂，使用釩酸鈣（新興化學工業公司製 )以外，與緩釋性防銹微粒子A同樣地操作，製造緩釋 性防銹微粒子F。 實驗No.l (防銹成分的溶出速度） 添加、攪拌上述各緩釋性防銹微粒子A〜F於調整成 40°C、pHl 0之NaOH水溶液中，使成爲2%，從第24小 -20- 200927480 時至第120小時，每隔24小時以ICP發光分析法定量分 析水溶液中溶出的離子量，測定自微粒子之防銹成分的溶 出速度。結果如表2所示。 〇 〇 [表2] 緩釋性防銹 微粒子的· 溶出速度 (mg/1-g · hr) 離子種 參考 A 0.013 Mg2+ 實施例用 B 0.017 Al3+ 實施例用 C 0.32 Mg2+ 實施例用 D 0.019 M^+ 實施例用 E 0.040 Mg2+ 實施例用 F 0.61 Ca2+ 比較例用 實驗No.2 (溶出速度的影響） 作爲金屬板，使用板厚爲〇.8mm，鍍敷附著量每單面 4 5g/m2之熔融鍍鋅鋼板。於此鍍鋅鋼板之表裏面，塗裝非 鉻酸鹽系基底處理劑之日本 Parkerizing公司製之「 CTE220」，使附著量成爲100mg/m2。鍛燒條件係到達板 溫爲100°C，加熱時間爲12秒，煅燒時風速爲5m/秒。 充分混合57份之基底樹脂（「Vylon (註冊商標） 3〇〇」：東洋紡績公司製之有機溶劑可溶型聚脂樹脂：Tg7 -21 - 200927480 °C ··分子量（Μη) 23x 1 03 )、作爲交聯劑之2 5質量份之 三聚氰胺樹脂（「CYMEL(註冊商標）325」：CYTECH公 司製）、及3份之環氧樹脂（“ jER (註冊商標）100L” (Japan Epoxy Resins公司製））、作爲體質顏料之14.5 份之二氧化鈦（「JR— 603」：TAYCA公司製：平均粒徑 爲〇.28//m)、及0.5份之二氧化矽系黏土（「Clayl號 」：九尾鈣公司製）。相對於1 0 0份之此混合物的固形成 ❺ 分，配合20份之表3、4所示之緩釋性防銹微粒子，調製 下塗塗膜用樹脂組成物。 於前述基底處理後之金屬板單面，進行棒塗塗裝該下 塗塗膜用樹脂組成物，使乾燥後厚度成爲l〇#m。熘燒條 件係到達板溫爲2 1 0 °C，乾燥時間爲5 0秒，锻燒時風速 爲5 m /秒。 相對於100份之聚脂•三聚氰胺類塗料（「FLC5 000 」：日本FINE COATINGS公司製）（固形成分），添加 〇 15份之二氧化鈦（「JR— 603」：TAYCA公司製：平均 粒徑爲0.28 " m) 、50份之二氧化矽系黏土（「Clay 1號 」：九尾鈣公司製）、20份之表3、4所示之緩釋性防銹 微粒子，調製上塗塗膜用樹脂組成物。 於下塗塗膜形成後之板的兩面，進行棒塗塗裝此上塗 塗膜用樹脂組成物，使乾燥後厚度成爲1 7 " m。煅燒條件 係到達板溫爲2 1 0 °C，乾燥時間爲5 0秒，煅燒時風速爲 5m/秒。如下塗塗膜及上塗塗膜所形成的面之評估結果如 表3所示。 -22- 200927480 另外，不形成下塗塗膜，於基底處理後之金屬板的兩 面’塗佈上塗塗膜用樹脂組成物之樹脂塗裝金屬板，亦與 前述同樣地製造。評估結果如表4所示。 [表3] 緩釋性防 銹微粒子 耐蝕性 加工性A 讎溶出速度 (mg/l-m2-hr) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例1 A ◎ ◎ ◎ 0.06 240 實施例2 B 〇 〇 ◎ 0.6 192 比較例1 F Δ △ ◎ 3 96 [表4] 緩釋性防 銹微粒子 耐Ιί &性 加工性A 被膜溶出速度 (mg/l-m2-hr) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例3 A ◎ ◎ ◎ 0.5 168 實施例4 B 〇 〇 ◎ 0.9 72 比較例2 F X X ◎ 4.4 <24[Table i] Ion species "eq/L NH/ 21 Ca2+ 26 K+ 5 Mg2+ 22 Na+ 88 no3" 15 Cl— 110 [Processability A] The test material was cut into 50 mrnx50 mm, and the evaluated surface was set to the outside and bent. In a low temperature (〇°C) environment, use a vise to perform 1 80. (0Τbend) After the bending process, the occurrence of cracks occurring in the curved portion of the coating film was observed by a visual observation and a magnifying glass (magnification: 1 〇). The evaluation criteria are as follows. ◎: No crack occurred (even if it was observed by any of the visual observation and the magnifying glass, there was no crack in the crucible). 〇: There was little crack occurrence (although it could not be seen by visual observation, but it was confirmed by a magnifying glass. A slight crack was confirmed) △: Crack occurred (visually visible) To cracks with small cracks) X: Large cracks (visible cracks can be seen by visual observation) [Processability Β] Except in a non-low temperature (〇t) environment, at normal temperature (20 °C) In the same manner as in the case of the workability A, the state of the crack of the bent portion -18-200927480 was observed. The evaluation criteria are also the same. [Dissolution speed measurement test] The test material was cut into a circular shape of Φ 50 mm. 100 squares of 1 mm x l mm were scored with a cutter. Immersed in 100 ml of carbonate pH standard solution (ΡΗ=10·01, sodium bicarbonate + sodium carbonate aqueous solution) at 40 ° C, 9 5 % RH. This aqueous solution was taken at intervals of 24 hours, and the amount of ions eluted from the square portion and the end surface was quantitatively analyzed by ICP light emission analysis to determine the elution rate of the rust preventive component. [Production of the release-release rust-preventing particles A] 50 parts of hollow porous cerium oxide microparticles ("godball (registered trademark) B-6C": manufactured by Suzuki Oil & Fats Co., Ltd.: average particle size is about 2.0 #m (2 ~2.5/zm)), 50 parts of magnesium oxide ("STARMAG L-10" high activity product: manufactured by Shendao Chemical Industry Co., Ltd.: 〇 average particle size 0.63/zm), and produced slow release rust preventive particles A. Further, after the magnesium oxide is previously pulverized, it is mixed with the hollow porous ceria particles. When mixing, mix with high shear force under heating. [Production of the release-release rust-preventing microparticles B] In addition to the change to magnesium oxide, use of aluminum tripolyphosphate ("K-WAHITE #G1 05": average particle size of 2.3 // m: manufactured by TAYCA) The rust-preventing fine particles A are operated in the same manner to produce sustained-release anti-bonding fine particles B. -19- 200927480 [Production of the release-release rust-preventing microparticles c] In the same manner as the slow-release rust-preventing microparticles A, except for the use of magnesium carbonate (industrial (lightweight): manufactured by Kyowa Chemical Industry Co., Ltd.) , production of sustained release rust preventive particles C. [Production of the release-release rust-preventing microparticles D] In addition to the change to magnesium oxide, magnesium hydroxide ("1 〇a": manufactured by Shendao Chemical Industry Co., Ltd.: average particle size: 3.5 # m), and sustained-release rust prevention The fine particles A were similarly operated to produce sustained-release rust-preventing fine particles D. [Production of the release-release rust-preventing fine particles E] In the same manner as in the case of the slow-release rust-preventing fine particles A, the use of magnesium phosphate (manufactured by Royal Pharmaceutical Co., Ltd.) was carried out to produce a sustained-release anti-microparticle E. ❹ [Production of the release-preventive rust-preventing fine particles F] In the same manner as the slow-release rust-preventing fine particles A, a slow-release rust-preventing fine particle F is produced, except that it is changed to magnesium oxide, and calcium vanadate (manufactured by Shin-Etsu Chemical Co., Ltd.) is used. . Test No. 1 (dissolution rate of rust-preventing component) The above-mentioned slow-release rust-preventing fine particles A to F were added and stirred in an aqueous NaOH solution adjusted to 40° C. and pH 10 to be 2%, from the 24th small- 20-200927480 From the time of the 120th hour, the amount of ions eluted in the aqueous solution was quantitatively analyzed by ICP emission analysis every 24 hours, and the elution rate of the rust-preventing component from the fine particles was measured. The results are shown in Table 2. 〇〇[Table 2] Release rate of sustained-release rust-preventing microparticles (mg/1-g · hr) Ion species reference A 0.013 Mg2+ Example B = B7 7 Al3 + Example C 0.32 Mg2+ Example D 0.019 M^ + E 0.040 Mg2+ for the example. F 0.61 Ca2+ for the example. Experiment No. 2 for the comparative example (effect of dissolution rate) As a metal plate, the plate thickness was 〇.8 mm, and the plating adhesion amount was 4 5 g/m2 per one side. Hot-dip galvanized steel sheet. In the surface of the galvanized steel sheet, "CTE220" manufactured by Parkerizing Co., Ltd. of Japan, which is a non-chromate base treatment agent, was applied to make the adhesion amount 100 mg/m2. The calcination conditions reached a plate temperature of 100 ° C, a heating time of 12 seconds, and a wind speed of 5 m / sec during calcination. 57 parts of base resin ("Vylon (registered trademark) 3"": Organic solvent soluble polyester resin manufactured by Toyobo Co., Ltd.: Tg7 - 21 - 200927480 °C · Molecular weight (Μη) 23x 1 03 ) 25 parts by mass of melamine resin ("CYMEL (registered trademark) 325": manufactured by CYTECH) and 3 parts of epoxy resin ("jER (registered trademark) 100L" (manufactured by Japan Epoxy Resins Co., Ltd.) )), 14.5 parts of titanium dioxide as a body pigment ("JR-603": TAYCA company: average particle size 〇.28//m), and 0.5 parts of cerium oxide clay ("Clayl": nine Tail calcium company). The resin composition for a coating film was prepared by mixing 20 parts of the solid-phase aging particles of the mixture shown in Tables 3 and 4 with respect to 100 parts by weight of the mixture. On the single side of the metal sheet after the substrate treatment, the resin composition for the undercoat film was applied by bar coating to have a thickness of l〇#m after drying. The simmering condition reached a plate temperature of 2 1 0 ° C, a drying time of 50 seconds, and a wind speed of 5 m / sec during calcination. Adding 15 parts of titanium dioxide ("JR-603": TAYCA company: average particle size 0.28) to 100 parts of polyester/melamine coating ("FLC5 000": manufactured by FINE COATINGS, Japan) (solid component) " m) 50 parts of cerium oxide clay ("Clay No. 1": manufactured by Jiuwei Calcium Co., Ltd.), 20 parts of the sustained release rust-preventing granules shown in Tables 3 and 4, and a resin for coating a coating film Composition. On both sides of the plate after the formation of the undercoat film, the resin composition for the upper coating film was applied by bar coating to have a thickness of 1 7 " m after drying. The calcination conditions reached a plate temperature of 2 1 0 ° C, a drying time of 50 seconds, and a wind speed of 5 m/sec during calcination. The evaluation results of the faces formed by the following coating film and the upper coating film are shown in Table 3. -22-200927480 In addition, a resin coated metal plate coated with a resin composition for a coating film on both sides of a metal plate after the substrate treatment is formed without forming a lower coating film. The evaluation results are shown in Table 4. [Table 3] Slow release rust preventive fine particles Corrosion resistance Processability A 雠 Dissolution speed (mg/l-m2-hr) Rain drop test (production time) Transverse end face Example 1 A ◎ ◎ ◎ 0.06 240 Example 2 B 〇〇◎ 0.6 192 Comparative Example 1 F Δ △ ◎ 3 96 [Table 4] Sustained release rust preventive particles resistant to Ιί & processability A film dissolution rate (mg/l-m2-hr) Rain drop test (production time Cross-cut end face Example 3 A ◎ ◎ ◎ 0.5 168 Example 4 B 〇〇 ◎ 0.9 72 Comparative Example 2 FXX ◎ 4.4 <24
實驗Νο·3 (緩釋性防銹微粒子之平均粒徑之影響） 於製造緩釋性防銹微粒子Α時，藉由改變中空多孔 質二氧化矽微粒子之平均粒徑，製造平均粒徑爲0.5〜20 〆m之緩釋性防銹微粒子。與實驗No. 2同樣地，將各緩 釋性防銹微粒子，配合各20份於下塗塗膜用樹脂組成物 及上塗塗膜用樹脂組成物，製造下塗塗膜及上塗塗膜所形 成之樹脂塗裝金屬板。評估結果如表5所示。另外，比較 例3係改變爲使用20份之緩釋性防銹微粒子，使用1 0份 -23- 200927480 之未與中空多孔質二氧化矽微粒子複合化之氧化鎂（「 STARMAG L—10」：神島化學工業公司製）之例。Experiment Νο·3 (Impact of the average particle size of the sustained-release rust-preventing fine particles) When the sustained-release rust-preventing fine particles are produced, the average particle diameter is 0.5 by changing the average particle diameter of the hollow porous cerium oxide fine particles. ~20 〆m of sustained-release rust-preventing particles. In the same manner as in the experiment No. 2, each of the sustained-release rust-preventing fine particles was mixed with 20 parts of the resin composition for the undercoating coating film and the resin composition for the upper coating film to prepare a resin formed by the lower coating film and the upper coating film. Painted metal plates. The evaluation results are shown in Table 5. Further, in Comparative Example 3, it was changed to use 20 parts of the sustained-release rust-preventing fine particles, and 10 parts of -23-200927480 of magnesium oxide which was not composited with the hollow porous ceria particles ("STARMAG L-10": Example of Shendao Chemical Industry Co., Ltd.).
[表5] 緩釋性防銹 微粒子之粒 徑(jczm) 耐蝕性 加工性A 加工性B 讎溶出速度 (mgA.m^hr) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例5 1.0 〇 〇 ◎ ◎ 0.07 216 實施例1 2.0 ◎ ◎ ◎ ◎ 0.06 240 實施例6 4.0 ◎ ◎ 〇 ◎ 0.04 264 實施例7 5.0 ◎ ◎ 〇 ◎ 0.03 288 實施例8 6.0 ◎ ◎ Δ 〇 0.02 288 實施例9 8.0 ◎ ◎ Δ 〇 0.02 312 實施例10 9.0 ◎ ◎ Δ 〇 0.01 312 實施例11 10.0 ◎ ◎ Δ 〇 0.01 336 參考例1 0.5 △ Δ ◎ ◎ 0.08 168 參考例2 15.0 ◎ ◎ X 〇 0.009 360 參考例3 20.0 ◎ ◎ X 〇 0.005 384 比較例3 注1) X X ◎ ◎ 0.11 144 注1) 直接添加氧化鎂「STARMAG L·-10」於被膜組成物中。 實驗No .4 (緩釋性防銹微粒子之添加量之影響） 除了變更緩釋性防銹微粒子A之添加量如表6、7所 示以外，與實驗No .2同樣地操作，製造形成下塗塗膜及 上塗塗膜所形成之樹脂塗裝金屬板（表6)、及僅形成上 塗塗膜之樹脂塗裝金屬板（表7)。評估結果如表6、7 所示。 -24- 200927480 [表6] 緩釋性防銹微 粒子之添加量 (份） 性 加工性A 被膜溶出速度 (mg/l*m2-hr) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例12 5 〇 〇 ◎ 0.07 216 實施例13 10 〇 〇 ◎ 0.05 240 實施例 20 ◎ ◎ ◎ 0.06 240 實施例Η 30 ◎ ◎ 〇 0.01 264 實施例15 35 ◎ ◎ 〇 0.01 264 實施例16 40 ◎ ◎ Δ 0.009 288 比較例4 3 Δ △ ◎ 0.08 192 比較例5 50 ◎ ◎ X 0.009 312 比較例ό 0 X X ◎ 0 48 [表7] 緩釋性防銹微 粒子之添加量 (份） 纖性 加工性A 被膜溶出速度 (mg/l*m2*hr) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例Π 10 〇 〇 ◎ 0.7 96 實施例3 20 ◎ ◎ ◎ 0.5 168 實施例18 40 ◎ ◎ Δ 0.4 168 比較例7 3 X X ◎ 0.9 24 比較例8 50 ◎ ◎ X 0.4 168 比較例9 0 X X ◎ 0 <24 Ο 實驗No. 5 (緩釋性防銹微粒子之種類之影響） 除了改變緩釋性防銹微粒子之種類如表8、9所示以 外，與實驗No.2同樣地操作，製造形成下塗塗膜及上塗 塗膜的樹脂塗裝金屬板（表8)、及僅形成上塗塗膜之樹 脂塗裝金屬板（表9)。評估結果如表8、9所示。 -25- 200927480 [表8] 緩釋性防 銹微粒子 耐蝕性 加工性A 被膜溶出速度 (mg/l-m2*!^) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例1 A ◎ ◎ ◎ 0.06 240 實施例19 C ◎ ◎ ◎ 0.5 144 實施例20 D ◎ ◎ ◎ 0.08 192 實施例21 E ◎ ◎ ◎ 0.9 144 比較例9 F △ Δ ◎ 3.0 96 [表9] 緩釋性防 銹微粒子 耐蝕性 加工性A 被膜溶出速度 (mg/l*m2*hr) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例3 A ◎ ◎ ◎ 0.5 168 實施例22 C 〇 〇 ◎ 1.0 96 實施例23 D 〇 〇 ◎ 0.9 72 實施例24 E 〇 〇 ◎ 1.0 72 比較例10 F X X ◎ 4.4 <24[Table 5] Particle size of sustained-release rust-preventing fine particles (jczm) Corrosion-resistant workability A Processability B 雠 Dissolution speed (mgA.m^hr) Rain drop test (production time) Transverse end face Example 5 1.0 〇〇 ◎ ○ 0.07 216 Example 1 2.0 ◎ ◎ ◎ ◎ 0.06 240 Example 6 4.0 ◎ ◎ 〇 ◎ 0.04 264 Example 7 5.0 ◎ ◎ 〇 ◎ 0.03 288 Example 8 6.0 ◎ ◎ Δ 〇 0.02 288 Example 9 8.0 ◎ ◎ Δ 〇 0.02 312 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施X 〇0.005 384 Comparative Example 3 Note 1) XX ◎ ◎ 0.11 144 Note 1) Magnesium oxide "STARMAG L·-10" is directly added to the film composition. In the same manner as in Experiment No. 2, the production of the undercoating was carried out in the same manner as in Experiment No. 2 except that the amount of the delamination-preventing rust-preventing granules A was changed as shown in Tables 6 and 7. A resin-coated metal plate (Table 6) formed by coating a film and an upper coating film, and a resin-coated metal plate (Table 7) in which only the upper coating film was formed. The evaluation results are shown in Tables 6 and 7. -24- 200927480 [Table 6] Addition amount of sustained release rust preventive particles (parts) Processability A Film dissolution rate (mg/l*m2-hr) Rain drop test (production time) Transverse end face Example 12 5 〇〇 ◎ 0.07 216 Example 13 10 〇〇 ◎ 0.05 240 Example 20 ◎ ◎ ◎ 0.06 240 Example Η 30 ◎ ◎ 〇 0.01 264 Example 15 35 ◎ ◎ 〇 0.01 264 Example 16 40 ◎ ◎ Δ 0.009 288 Comparison Example 4 3 Δ △ ◎ 0.08 192 Comparative Example 5 50 ◎ ◎ X 0.009 312 Comparative Example ό 0 XX ◎ 0 48 [Table 7] Addition amount of sustained-release rust-preventing fine particles (parts) Fibrous workability A film dissolution rate ( Mg/l*m2*hr) Rain drop test (production time) Transverse end face example Π 10 〇〇 ◎ 0.7 96 Example 3 20 ◎ ◎ ◎ 0.5 168 Example 18 40 ◎ ◎ Δ 0.4 168 Comparative Example 7 3 XX ◎ 0.9 24 Comparative Example 8 50 ◎ ◎ X 0.4 168 Comparative Example 9 0 XX ◎ 0 < 24 Ο Experiment No. 5 (Impact of types of sustained-release rust-preventing fine particles) In addition to changing the types of sustained-release rust-preventing fine particles Except as shown in Tables 8 and 9, the same operation as Experiment No. 2 was performed. The coating film on the coating film and the coating film is formed for producing a resin coated metal sheet (Table 8), and only the resin coated metal sheet is formed (Table 9). The evaluation results are shown in Tables 8 and 9. -25- 200927480 [Table 8] Slow release rust-preventing fine particles Corrosion resistance Process A Film dissolution rate (mg/l-m2*!^) Rain drop test (production time) Cross-cut end face Example 1 A ◎ ◎ ◎ 0.06 240 Example 19 C ◎ ◎ ◎ 0.5 144 Example 20 D ◎ ◎ ◎ 0.08 192 Example 21 E ◎ ◎ ◎ 0.9 144 Comparative Example 9 F Δ Δ ◎ 3.0 96 [Table 9] Slow release rust-preventing microparticle corrosion resistance processing A-film dissolution rate (mg/l*m2*hr) Rain drop test (production time) Transverse end face Example 3 A ◎ ◎ ◎ 0.5 168 Example 22 C 〇〇 ◎ 1.0 96 Example 23 D 〇〇 ◎ 0.9 72 Example 24 E 〇〇 ◎ 1.0 72 Comparative Example 10 FXX ◎ 4.4 <24
實驗No.6 (緩釋性防銹微粒子之種類之影響） 除了改變緩釋性防銹微粒子種類如表1 0、1 1所示以 外，與實驗No.2同樣地操作，製造形成下塗塗膜及上塗 塗膜之樹脂塗裝金屬板（表1〇)、及僅形成上塗塗膜之 樹脂塗裝金屬板（表1 1 )。評估結果如表1 〇、1 1所示。 -26- 200927480 [表 ι〇] 緩釋性防 銹微粒子 耐鈾性 加工性A 被膜溶出速度 (mg/l-m2-hr) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例2 B 〇 〇 ◎ 0.6 192 比較例11 F Δ Δ ◎ 3.0 96 [表 11] 緩釋性防 銹微粒子 耐蝕性 加工性A 被膜溶出速度 (mg/l-m2-hr) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例4 B 〇 〇 ◎ 0.9 72 比較例12 F X X ◎ 4.4 <24 實驗No.7 (非緩釋性防銹顏料之影響） 相對於1〇〇份之實驗Νο·2調製之下塗塗膜用樹脂組 成物，另外，作爲防銹顏料，除了追加添加表12所示的 量之氧化鎂（「STARMAG L— 10」：神島化學工業公司 〇 製）以外，與實驗No .2同樣地操作，製造形成下塗塗膜 及上塗塗膜之樹脂塗裝金屬板。因此，測定表1 2的溶出 速度時之溶出離子量亦加上追加添加之氧化鎂的溶出分。 評估結果如表1 2所示。 -27- 200927480 [表 12]Test No. 6 (Impact of the type of the sustained-release rust-preventing fine particles) The same procedure as in Experiment No. 2 was carried out except that the types of the controlled release rust-preventing fine particles were changed as shown in Tables 10 and 11. And a resin-coated metal plate coated with a coating film (Table 1), and a resin-coated metal plate on which only the upper coating film was formed (Table 1 1). The evaluation results are shown in Table 1 〇, 1 1 . -26- 200927480 [Table 〇] Sustained-release rust-preventing fine particles uranium-resistant workability A Film dissolution rate (mg/l-m2-hr) Rain drop test (production time) Cross-cut end face Example 2 B 〇〇 ◎ 0.6 192 Comparative Example 11 F Δ Δ ◎ 3.0 96 [Table 11] Slow release rust preventive fine particles Corrosion resistance Process A Film dissolution rate (mg/l-m2-hr) Rain drop test (production time) Cross-cut end face example 4 B 〇〇 ◎ 0.9 72 Comparative Example 12 FXX ◎ 4.4 <24 Experiment No. 7 (Impact of non-release-release anti-rust pigment) The composition of the coating film was made with respect to 1 part of the experiment Νο·2 In addition to the addition of the amount of magnesium oxide ("STARMAG L-10": manufactured by Shendao Chemical Industry Co., Ltd.) shown in Table 12, the rust-preventing pigment was produced in the same manner as in Experiment No. 2. The coating film and the resin coated with the coating film are coated with a metal plate. Therefore, the amount of eluted ions when the elution rate of Table 12 is measured is also added to the elution fraction of the additionally added magnesium oxide. The evaluation results are shown in Table 12. -27- 200927480 [Table 12]
防銹顏料 之添加量 (份） 耐蝕性 加工性A 被膜溶出速度 y (mg/l-m -hr) 雨水滴下試驗 (產生時間） 橫斷 端面 實施例25 10 ◎ ◎ ◎ 0.146 288 實施例26 20 ◎ ◎ ◎ 0.260 312 實施例27 30 ◎ ◎ ◎ 0.356 312 實施例28 40 ◎ ◎ ◎ 0.439 336 實施例29 45 ◎ ◎ ◎ 0.476 336 實施例30 50 ◎ ◎ ◎ 0.510 360 實施例31 60 ◎ ◎ ◎ 0.573 384 實施例32 70 ◎ ◎ ◎ 0.628 360 實施例33 100 ◎ ◎ ◎ 0.760 360 實施例1 0 ◎ ◎ ◎ 0.060 240 【圖式簡單說明】 圖1是人工雨水滴下試驗之測定方法之說明圖。Anti-rust pigment addition amount (parts) Corrosion resistance Processability A film dissolution rate y (mg/lm - hr) Rain drop test (production time) Transverse end surface Example 25 10 ◎ ◎ ◎ 0.146 288 Example 26 20 ◎ ◎ ◎ 0.260 312 Example 27 30 ◎ ◎ ◎ 0.356 312 Example 28 40 ◎ ◎ ◎ 0.439 336 Example 29 45 ◎ ◎ ◎ 0.476 336 Example 30 50 ◎ ◎ ◎ 0.510 360 Example 31 60 ◎ ◎ ◎ 0.573 384 Example 32 70 ◎ ◎ ◎ 0.628 360 Example 33 100 ◎ ◎ ◎ 0.760 360 Example 1 0 ◎ ◎ ◎ 0.060 240 [Simplified description of the drawings] Fig. 1 is an explanatory diagram of a measurement method of the artificial rain drop test.
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