TW381108B - Resin coating metal plates and method for manufacturing the same - Google Patents

Resin coating metal plates and method for manufacturing the same Download PDF

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Publication number
TW381108B
TW381108B TW084114138A TW84114138A TW381108B TW 381108 B TW381108 B TW 381108B TW 084114138 A TW084114138 A TW 084114138A TW 84114138 A TW84114138 A TW 84114138A TW 381108 B TW381108 B TW 381108B
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TW
Taiwan
Prior art keywords
resin
weight
coating
particles
film
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TW084114138A
Other languages
Chinese (zh)
Inventor
Tadashige Nakamoto
Atsushi Kihara
Original Assignee
Kobe Steel Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention provides a kind of resin coating metal plate particularly the resin coating steel plate which possesses not only the characteristics of superior lubrication, but also high resistance to wearing, cutting, compression, corrosion, as well as anti-blackening during pressing, anti-corrosion, painting and earth properties, etc. wherein all the said characteristics are balanced; and the manufacturing of such kind of resin-coating metal plate particularly the resin coating steel plate. The resin coating metal plate is characterized in that the resin coating formed on the surface of metal plates has a dry weight of 0.2~2.5 g/square meter, the resin coating contains 5~30wt% of silicon dioxide particles, 0.5~20wt% of ball-shaped polyethylene wax particles, and 1~20wt% from solid portion of organic aziridine compound, which primarily contains a kind of polyethylene resin copolymer lactoprene associating with groups of free ions between molecules.

Description

A7 A7 經濟部中央標隼局員工消費合作社印製 B7 五、發明説明（1 ) 發明背景 發明铕域 本發明有關帶有樹脂塗層之金屬板，其具有優良之耐 磨蝕性’處理性，處理中之抗黑化性，穿孔性，抗腐蝕性 和塗料性，特別有關帶有樹脂塗層樹脂之鋼板，及此種樹 脂塗層金屬板之製法，特別是一種樹脂塗層鋼板者。 相關技藝敘沭 金屬板用於家用電子產品或建築材料之目的時，除了 鋁板和不銹鋼板外，表面經處理鋼板，諸如電鍍鋅鋼板， 熱浸鍍鋅鋼板具有廣泛用途。其中，進行鉻酸鹽處理或磷 酸鹽處理之鍍鋅表面處理鋼板迄今廣泛使用，主要用家用 電子產品和不同元件，諸如音響設備，電腦零件，電子範 圍底板等。但是，近來使用者對表面處理鋼板之需求因不 同膜之作用而變得愈來愈高。 例如，若以裸態使用該表面處理金屬板，必須有抗腐 蝕性’ 土特性，抗指紋性（即使形成指紋時不引人注意） ’對鹼，溶劑等之化學阻力，抗污染性等。此外，若其進 行壓製處理或穿孔處理，必須有潤滑特性，耐刮性，深度 抽絲處理性，耐磨塑腐蝕性，穿孔性，經處理滑動表面之 黑化性，快乾油之耐油性等。 此外，若該表面處理金屬板以線圏或鋼板製造機製之 片狀形式之產物運輸，其通常以卡車等運送。線圈實例中 ’產生磨擦，片狀實例中〃鋼板片片相疊，其中於鋼板表 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先《讀背面之注意事項再填寫本頁) -5A7 A7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs B7 V. Description of the invention (1) Background of the invention The invention relates to a metal plate with a resin coating, which has excellent abrasion resistance and handling characteristics. Blackening resistance, perforation resistance, corrosion resistance and coating properties during processing, especially for steel plates with resin coating resin, and the method for manufacturing such resin coated metal plates, especially for resin coated steel plates. Related arts When metal plates are used for the purpose of home electronics or construction materials, in addition to aluminum and stainless steel plates, surface-treated steel plates, such as galvanized steel plates, and hot-dip galvanized steel plates have a wide range of uses. Among them, chromate-treated or phosphate-treated zinc-coated surface-treated steel sheets have been widely used so far, mainly using household electronic products and different components, such as audio equipment, computer parts, electronic range floor boards, and the like. However, recently, users' demands for surface-treated steel sheets have become higher due to the effects of different films. For example, if the surface-treated metal plate is used in a naked state, it must have anti-corrosive properties, soil properties, and fingerprint resistance (even if it is not noticeable when fingerprints are formed). Chemical resistance to alkalis, solvents, etc., and pollution resistance. In addition, if it is pressed or perforated, it must have lubricating properties, scratch resistance, deep drawing treatment, wear-resistant plastic corrosion, perforation, blackening of the sliding surface after treatment, and oil resistance of quick-drying oil. Wait. In addition, if the surface-treated metal sheet is transported as a sheet in the form of a wire reel or a steel sheet manufacturing mechanism, it is usually transported by a truck or the like. In the coil example, friction occurs. In the sheet example, the steel sheets are stacked. The paper size of the steel sheet is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the "Notes on the back side before filling in" (This page) -5

T -4 - 經濟部中央標準局員工消費合作社印製 A7 __._B7_ 1 五、發明説明（2 ) 面發生包裝磨擦或刮痕，二者實例係於運輸中之振動造成 '。該刮痕係一種缺陷，其中該部分變得呈現黑色。此種缺 陷稱作磨蝕，其導致一個問題，其中表面處理鋼板物品價 值惡化，因此使用者無法用其充作該物品。 這些不同.需求無法藉由慣用無機表面處理鋼板進行鉻 酸鹽處理或磷酸鹽處理反應之。有鑑於此，近來已提出許 多如下述之具有有機樹脂之樹脂塗覆鋼板。 例如，首先，日本專利申請案未公告 6 2 — 5 0 4 8 0號公告揭示一種鍍鋅鋼板，其係將鍍鋅 鋼板進行鉻酸鹽處理，之後形成一有機膜製成，該有機膜 包括一種羧酸化聚烯烴樹脂和一種環氧樹脂且含有一種膠 體二氧化矽，因此改善抗腐蝕性，塗料性，抗溶劑性，抗 鹼性和抗指紋性。第二，日本專利申請案Laid-Open 6 4_7 3 0 8 3號公告揭示一種表面處理鋼板，其係添 加一種可聚合乙烯不飽和化合物於一種乙烯- α，Θ -不 飽和羧酸共聚物樹脂之分散液體（含有一種膠體溶膠）中 以乳化聚合之，完成聚合作用後製備一種經處理液體交聯 該聚合物，並將該液體塗覆於一進行鉻酸鹽處理之鍍鋅板 製得，因此改善其黏附特性，抗指紋性，抗硬幣刮痕，抗 腐蝕性等。 第三，日本專利公告5 — 5 4. 8 2 3號公告，其揭示 一種樹脂塗覆鋼板，其係將一鍍鋅鋼板進行鉻酸鹽處理， 其後於其上塗覆一種含膠體二氧化矽乙烯-乙烯不飽和狻 酸共聚物樹脂和一種具有氮丙啶基之有機材料之樹脂液體 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）~ς _ 1_1 h —4— ml m n i ( (讀先閎讀背面之注意事項再填寫本頁) 訂 經濟部中央橾隼局員工消費合作社印製 A7 _____B7_1 五、發明説明（3) ，將其乾燥形成一交聯膜製得，因此改善塗料性’抗腐蝕 —.......'-·〆,、、 性，化學阻力和抗刮痕性。 第四，曰本專利申請案Laid-Open 6 — 2 4 6 2 2 9 號公告揭示一種有機組成物塗覆鋼板，其係將鍍鋅鋼板進 行鉻酸鹽，並於其上形成樹脂膜，其包括一種具有6 0至 8 0 %羧基以鈉離子中和之伸乙基異構物樹脂，使用伸乙 基和一種α，万-伸乙基不飽和羧酸充作主要組份製得， 因此改善抗黑化性，且維持良好抗腐蝕性。 此外，第五，日本專利公告5 — 1 3 8 2 9號公告揭 示一種樹脂塗覆鋼板，其係於鍍鋅鋼板上形成含有氟顆粒 和二氧化矽顆敏，使用丙烯化環氧樹脂充作主要組份之樹 脂膜製得，以得到該壓製模塑性良好之樹脂塗覆鋼板。 上述第一至第三項先前技藝已達到關於表現之某種程 度改善，諸如抗腐蝕性，塗料性，抗指紋性等使用者以裸 態使用之需求。亦可考慮關於使用省處理導致之耐刮性至 某程度效果。但是，因爲這些樹脂塗覆鋼板之膜硬度和潤 滑特性差，於壓製處理時仍有一個未解決問題，特別是， 彎曲處理和深度抽絲處理時，該樹脂膜因介於樹脂塗層鋼 板和該模之間的斜度而自該鋼板剝離，且該剝離之鍍層產 生一種黑化材料，其黏著於該產物或累積於模上。相同的 ’關於耐磨性，於極大壓力下，很難避免因振動導致介於 鋼板間之刮痕產生。 第四項先前技藝中，該具有羧基之乙烯樹脂以離子鈉 中和並離子鍵共聚之，因此產生該樹脂模之屏障效果，因 本紙張尺度逋用中國國家標準（CNS ) Α4規格（210 X 297公釐）-6 - (請先閎讀背面之注意事項再填寫本頁) .裝- 訂 ιί. 經濟部中央標準局員工消費合作社印裝 Α? Β7 五、發明説明（4) 此加強腐蝕環境下鍍鋅之黑化現象，即不使抗腐蝕性變質 之抗黑化性。此外，推定該膜表面之抗刮性可藉該樹脂膜 中樹脂組份之離子鍵共聚作用改善一些。但是，壓製處理 時之抗黑化性和耐磨性未改善。 第五項先前技藝有關強化壓製處理性目的用之潤滑鋼 板之技術，可預期該材料效應可抑制壓製處理中黑化材料 和磨蝕之產生。但是，使用氟樹脂顆粒充作潤滑劑之表面 不活潑且難以與該樹脂膜內部或表面化學鍵結。因此，當 塗層利用電解澱·積塗層，粉末塗層等施加於欲處理表面時 ，存在膜黏合性（塗料性）之問題。此外，在使用蠟顆粒 充作潤滑劑實例中，塗覆樹脂膜且乾燥時，若其加熱溫度 高，該樹脂膜中之蠟顆粒軟化升至該膜表面，且變得固化 ，致使塗料性和抗腐蝕性惡化。因此，樹脂之膜之乾燥和 製膜溫度限制在低於軟化點之溫度，因此導致無法得到充 分膜強度之問題。 發明摘要. 已完成本發明以解決上述關於慣用樹脂塗層金屬板， 特別是樹脂塗層鋼板之問題。本發明之一項目的係提出一 種樹脂塗層金屬板，特別是樹脂塗層鋼板，其不僅具有耐 磨蝕性亦具有良好之潤滑特性，抗刮性，穿孔性，壓製處 理性，及壓製中之穿孔性（諸如抗黑化性）：，抗腐蝕性， 塗料性，土特性等，此外，上述特性非常平衡，及製造此 種樹脂塗層金屬板，特別是樹脂塗層鋼板之方法。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）- Τ Γ .//1.. US l.- (請先W讀背面之注意事頃再填寫本頁) Γ 經濟部中央標準局員工消費合作社印製 A7 __.__B7 _ ' 五、發明説明（5 ) 如本發明，提出一種樹脂塗層金屬板’其特徵係於金 屬板表面形成之樹脂塗層重佔乾重0·2至2.5g/rri 範圍內，該樹脂膜含5至3 0重量％之二氧化矽顆粒， 0 . 5至2 0重量％之球形聚乙烯蠟顆粒及1至2 0重量 %之固體部分具有氮丙啶基之有機化合物，（其主要包括 聚烯烴共聚物樹脂乳膠，以分子間之離子團締合之）。 如本發明，另外提出製造樹脂塗層金屬板之製法，其 包括於金屬板表面塗覆一種水性樹脂塗層，其含5至3 0 重量％之二氧化矽顆粒，1至20重量％固體部分具有氮 丙啶基之有機化合物，其主要包括分子間以離子團締合之 聚烯烴共聚物樹脂，加熱該金屬板，乾燥該塗層，且於該 金屬板表面形成塗層重0.2至2.5g/ri之樹脂膜。 下文中，本發明將以鋼板代表性充作金屬板。 本發明中，使用一種分子間藉由離子團締合之聚烯烴 共聚物充作樹脂塗層中之樹脂組份。此處使用之聚烯烴共 聚物樹脂最好是一種聚烯烴樹脂，其中烯烴-乙烯不飽和 羧酸共聚物樹脂含有1至4 0重量％範圍之乙烯不飽和羧 酸組份’其可能含有藉交聯劑離子鍵共聚且交聯之（甲基 )丙烯酸酯組份以提供高分子量。 上述分子間藉離子團締合之聚烯烴共聚物樹脂乳膠可 經由第一步驟製備具有羧基之聚烯烴共聚物，第二步驟離 子鍵共聚該製得烯烴共聚物，和第三步驟將該製得離子鍵 共聚樹脂製成高分子量製得。 於分子間藉離子團締合之聚烯烴共聚物樹脂乳膠中添 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公^- (請先w讀背面之注意事項再填寫本頁) I n n ^ n II · a m immmw In m ΒΙ·_ι— m 經濟部中央標隼局員工消費合作社印製 A7 B7 ' 五、發明説明（6 ) 加預定數量之二氧化矽顆粒，球形聚乙烯蠟顆粒和具有氮 丙啶基之有機化合物以提供一種水性樹脂塗料。如本發明 ，該水性樹脂塗料塗覆於金屬板表面，該金屬板加熱至預 定板溫，且乾燥該塗層以形成一樹脂膜，因此得到不僅具 有耐磨蝕性之樹脂塗層鋼板，其亦具有良好，均衡之膜表 現，諸如處理性，壓製中之抗黑化性，穿孔性，抗腐触性 ，塗料性等。 首先，製備分子間藉離子團締合之聚乙烯共聚物樹脂 乳膠中，將解釋第一步驟，其係製備共聚物步驟。一種單 體混合物，其包括一種烯烴充作第一單體，1至4 0重量 %之乙烯不飽和羧酸充作第二單體，且視情況需要，一種 可共聚之第三單體，於溫度爲2 0 0至3 0 0 °C且大氣壓 力爲1 0 0 0至2 0 0 0之條件下於水性分散液中共聚之 ’製備一種具有羧基之烯烴共聚物樹脂乳膠。 最好使用，例如（甲基）丙烯酸，馬來酸，胡索延酸 ’衣康酸等’充作該乙烯不飽和羧酸，以（甲基）丙烯酸 更佳。其中，使用（甲基）丙烯酸較佳。最好使用，通常 ’ 一'種方族乙嫌基化合物’諸如苯乙嫌或一種脂族α —嫌 烴，諸如乙烯和丙烯充作該烯烴。因此，本發明使用之較 佳烯烴共聚物樹脂可包括’例如，一種乙烯一（甲基）两 烯酸共聚物樹脂’一種苯乙烯一（甲基）丙烯酸共聚物樹 脂’一種乙烯-苯乙烯（甲基）丙嫌酸共聚物樹脂。 本發明中，除了上述第一和第二單輝外，若情.況需要 可使用一種第三單體，例如一或二或多種（甲基）丙燦酸 本紙張尺度適用中國國家標準（CNS) Α4規格（21Q+X29·^董）~_ ~~— (讀先閲讀背面之注意事項再填寫本頁) 、裝- ,ίτ 經濟部中央標率局員工消費合作社印製 A7 B7 1 五、發明説明（7 ) 酯，諸如（甲基）丙烯酸乙酯，（甲基）丙烯酸甲酯，（ 甲基）丙烯酸丙酯，一種苯乙烯單體，諸如苯乙烯，乙烯 甲苯和氯苯乙烯，（甲基）丙烯酸羥烷酯，諸如丙烯基羥 乙酯和（甲基）丙烯酸羥丙酯，N —取代（甲基）丙烯醯 胺，諸如N —甲氧基（甲基）丙烯醯胺，含（甲基）丙烯 酸酯之環氧基，諸如（甲基）丙烯酸縮水甘油酯和（甲基 )丙烯睛。 此種聚嫌烴共聚物樹脂中，乙烯不飽和羧酸組份多於 4 0重量％時，即使使用稍後經由乳化離子鍵共聚步驟和 高分子量形成步驟製得之分子間藉離子團締合之聚烯烴共 聚物樹脂乳膠充作製膜材料，製得之樹脂塗層鋼板之抗腐 蝕性不夠充分。另一方面，該聚烯烴共聚樹脂中，該乙烯 不飽和羧酸組份少於1重量％時，難以提煉製得之聚烯烴 共聚物樹脂水性或水分散液，其不適用於本發明方法。 使用水或一種水混合物和親水有機溶劑充作該水性分 散液。使用，例如低脂醇，諸如甲醇，乙醇和η -丙醇， 乙二醇醚，諸如伸乙基乙二醇甲醚，乙二醇酯，諸如醋酸 伸乙基乙二醇酯，醚類，諸如四氫呋喃和二噁烷，二甲基 甲醯胺，二丙酮醇等充作親水有機溶劑。 將第一步驟製得之聚烯烴共聚物樹脂進行乳化離子鍵 共聚作用。該乳化離子鍵共聚作用通常使用適當之陽離子 且適情況需要使用銨水，於80至3 0 0°之溫度，1至 2 0之大氣壓力條件下進行。壓力下之離子鍵共聚作用中 ，視乳化作用和樹脂表現，以組合方式使用胺較佳。 本紙張尺度適用中國國家槺準（CNS ) Α4規格（210 X 297公釐） _ 1 〇 _ (請先閎讀背面之注意事項再填寫本頁) 裝. 訂 經濟部中央標隼局員工消費合作社印製 A7 B7 五、發明説明（8) 金屬離子充作該陽離子較佳。例如特別是使用諸如鋰 ’鉀’鎂，鋅，鈉，鈣，鐵和鋁離子較佳。 爲形成如本發明良好均衡之樹脂膜，其具有耐磨蝕性 以及處理性’壓製時抗黑化性，穿孔性，抗腐蝕性和鋼板 表面之塗料性，必須部分交聯樹脂塗層中之樹脂組份以提 高分子量。 因此，依本發明，可能藉由一種交聯劑另外部分交聯 該離子鍵共聚樹脂，因此製得一種分子間藉離子團締合之 烯烴共聚樹脂。此處不特別限制交聯劑，可使用使樹脂羧 基交聯之適當交聯劑。因此，該交聯劑包括，例如一種環 氧化合物’一種鈦化合物等。該交聯反應通常於3 0至 2 0 0°C溫度’正常至2 0大氣壓力之壓力條件下進行較 佳。 如本發明之樹脂塗層鋼板可藉於一金屬板上塗覆一種 水性樹脂塗層，其含有5至3 0重量％之二氧化矽顆粒， 0.5至20重量％之球形聚乙烯蠟顆粒和1茔20重量 %固體部份具有氮丙啶基之有機化合物，其主要包括一種 分子間由離子締合製得之聚烯烴共聚物樹脂乳膠，將該金 屬板加熱至預定溫度，乾燥該塗層，並於該金屬板表面乾 燥後形成0.2至2·5g/m樹脂膜重量之樹脂膜。 本發明中使用之水性樹脂塗層含有一種有機化合物， 其具有前述固體部分1至2 0重量％範圍之氮丙基，且當 曹樹脂塗層塗於鋼板上且加熱乾燥時，種分子間藉由離 子團締合之烯烴共聚物樹脂（其爲一種樹脂組份）係藉由 本紙張尺度適用中國國家標準（CNS ) A4規格（2!0X297公釐）一 ^ -- , ,' 豸 (請先E讀背面之注意事頃再填窩本頁)T -4-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 __._ B7_ 1 V. Description of the invention (2) Packaging friction or scratches occurred on the surface. The two examples are caused by vibration during transportation. The scratch is a defect in which the portion becomes black. Such a defect is called abrasion, and it causes a problem in which the value of the surface-treated steel sheet item deteriorates, so that the user cannot use it as the item. These differences. Demands cannot be reacted by chromate treatment or phosphate treatment by conventional inorganic surface-treated steel plates. In view of this, many resin-coated steel sheets having an organic resin as described below have recently been proposed. For example, first, Japanese Patent Application Publication No. 6 2-5 0 4 8 0 discloses a galvanized steel sheet, which is made by subjecting the galvanized steel sheet to chromate treatment, and then forming an organic film. The organic film includes A carboxylated polyolefin resin and an epoxy resin and containing a colloidal silicon dioxide, thereby improving corrosion resistance, coating properties, solvent resistance, alkali resistance, and fingerprint resistance. Secondly, Japanese Patent Application Laid-Open 6 4_7 3 0 8 3 discloses a surface-treated steel sheet, which is a polymerizable ethylene unsaturated compound added to an ethylene-α, Θ-unsaturated carboxylic acid copolymer resin. The dispersion liquid (containing a colloidal sol) is emulsified and polymerized. After the polymerization is completed, a treated liquid is prepared to crosslink the polymer, and the liquid is applied to a chromate-treated zinc-plated plate. Improve its adhesion properties, fingerprint resistance, coin scratch resistance, corrosion resistance, etc. Third, Japanese Patent Publication No. 5-5 4. 8 2 3 discloses a resin-coated steel plate, which is a chromate treatment of a galvanized steel plate, and then coated with a colloidal silicon dioxide Ethylene-Ethylene Unsaturated Acrylic Acid Copolymer Resin and a resin liquid of an aziridine-based organic material This paper is sized for China National Standard (CNS) A4 (210X297 mm) ~ _ 1_1 h —4— ml mni ((Please read the precautions on the back and then fill out this page) Order A7 printed by the Consumer Affairs Cooperative of the Central Government Bureau of the Ministry of Economic Affairs _____B7_1 V. Description of the invention (3), dried and formed into a crosslinked film, so it is improved Paintability 'Anti-corrosion —.........', 、, 性, chemical resistance, and scratch resistance. Fourth, the patent application Laid-Open 6 — 2 4 6 2 2 9 The announcement discloses an organic composition-coated steel sheet, which is obtained by subjecting a galvanized steel sheet to chromate and forming a resin film thereon, which includes a 60 to 80% carboxyl group neutralized with sodium ions and ethyl isopropyl groups. Structure resin, using ethylen and an alpha, ten-ethylen unsaturated The acid is prepared as the main component, thereby improving the blackening resistance and maintaining good corrosion resistance. In addition, the fifth, Japanese Patent Publication No. 5-1 3 8 2 9 discloses a resin-coated steel sheet, which is based on A resin film containing fluorine particles and silicon dioxide particles is formed on a galvanized steel sheet, and acrylated epoxy resin is used as a main component to obtain the resin-coated steel sheet having good press moldability. The third previous technique has reached a certain degree of improvement in performance, such as corrosion resistance, paint resistance, fingerprint resistance, etc. The user needs to use it in a naked state. It can also consider the scratch resistance caused by the use of provincial processing to a certain level. However, because of the poor hardness and lubricating properties of these resin-coated steel sheets, there is still an unresolved problem in the pressing process, especially when the bending process and the deep-drawing process are caused by the resin coating. The inclination between the steel sheet and the mold is peeled from the steel sheet, and the peeled plating layer produces a blackened material that adheres to the product or accumulates on the mold. The same 'about abrasion resistance Under extreme pressure, it is difficult to avoid scratches between steel plates due to vibration. In the fourth prior art, the vinyl resin having a carboxyl group was neutralized with ionic sodium and copolymerized with ionic bonds, so the resin mold was produced. Barrier effect, because this paper size uses Chinese National Standard (CNS) Α4 specification (210 X 297 mm) -6-(Please read the precautions on the back before filling this page). Equipment-Order ι. Central Ministry of Economic Affairs Standard Bureau employee consumer cooperative printed A? B7 V. Description of invention (4) This strengthens the blackening phenomenon of galvanization in a corrosive environment, that is, the blackening resistance that does not deteriorate the corrosion resistance. In addition, the resistance of the film surface is estimated The scratch resistance can be improved by the ionic bond copolymerization of the resin components in the resin film. However, the blackening resistance and abrasion resistance during the pressing treatment were not improved. The fifth prior art technique for lubricating steel plates for the purpose of strengthening the press processability can be expected to suppress the occurrence of blackened materials and abrasion during the press process. However, the surface using the fluororesin particles as a lubricant is inactive and difficult to chemically bond with the inside or the surface of the resin film. Therefore, when the coating is applied to the surface to be treated by electrolytic deposition, deposition coating, powder coating, etc., there is a problem of film adhesion (paintability). In addition, in the case where wax particles are used as a lubricant, when the resin film is coated and dried, if the heating temperature is high, the wax particles in the resin film soften to the surface of the film and become solidified, resulting in coating properties and Corrosion resistance deteriorates. Therefore, the drying and film forming temperature of the resin film is limited to a temperature lower than the softening point, so that a problem that a sufficient film strength cannot be obtained is caused. SUMMARY OF THE INVENTION The present invention has been completed to solve the above-mentioned problems regarding conventional resin-coated metal plates, especially resin-coated steel plates. One of the items of the present invention is to propose a resin-coated metal plate, especially a resin-coated steel plate, which has not only abrasion resistance but also good lubricating properties, scratch resistance, perforation, press-handling properties, and pressing properties. Perforation (such as blackening resistance): corrosion resistance, paintability, soil characteristics, etc. In addition, the above characteristics are very balanced, and a method for manufacturing such a resin-coated metal plate, especially a resin-coated steel plate. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm)-Τ Γ .//1 .. US l.- (Please read the notes on the back before filling out this page) Γ Central Standard of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau A7 __.__ B7 _ 'V. Description of the invention (5) According to the present invention, a resin-coated metal plate is proposed, which is characterized in that the resin coating formed on the surface of the metal plate accounts for dry weight 0.2 In the range of 2.5 g / rri, the resin film contains 5 to 30% by weight of silicon dioxide particles, 0.5 to 20% by weight of spherical polyethylene wax particles, and 1 to 20% by weight of the solid portion has nitrogen. Propidyl-based organic compounds (which mainly include polyolefin copolymer resin latex, associated with intermolecular ionic groups). According to the present invention, a method for manufacturing a resin-coated metal plate is further provided, which comprises applying an aqueous resin coating on the surface of the metal plate, which contains 5 to 30% by weight of silica particles, and 1 to 20% by weight of a solid portion. An organic compound having an aziridine group, which mainly includes a polyolefin copolymer resin associated with an ionic group between molecules, heating the metal plate, drying the coating, and forming a coating on the surface of the metal plate, weighing from 0.2 to 2.5 g / ri of resin film. Hereinafter, the present invention will be representative of a steel plate as a metal plate. In the present invention, a polyolefin copolymer intermolecularly associated with an ionic group is used as the resin component in the resin coating. The polyolefin copolymer resin used herein is preferably a polyolefin resin in which the olefin-ethylene unsaturated carboxylic acid copolymer resin contains an ethylene unsaturated carboxylic acid component in the range of 1 to 40% by weight, which may contain a loan. The crosslinker is ionically copolymerized and crosslinked (meth) acrylate components to provide a high molecular weight. The polyolefin copolymer resin latex associated with an intermolecular group by an ionic group can prepare a polyolefin copolymer having a carboxyl group through a first step, an olefin copolymer by a second step to obtain an olefin copolymer, and a third step to obtain the obtained olefin copolymer. Ionic bond copolymer resin is made of high molecular weight. This paper is added to the polyolefin copolymer resin latex associated with ionic groups by molecules. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297) ^-(please read the precautions on the back before filling this page) I nn ^ n II · am immmw In m ΒΙ · _ι— m Printed A7 B7 by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (6) Add a predetermined amount of silica particles, spherical polyethylene wax particles and An aziridine-based organic compound is used to provide an aqueous resin coating. According to the present invention, the aqueous resin coating is coated on the surface of a metal plate, the metal plate is heated to a predetermined plate temperature, and the coating is dried to form a resin film, so A resin-coated steel sheet having not only abrasion resistance is obtained, but it also has good and balanced film performance, such as handling, blackening resistance during pressing, perforation, corrosion resistance, paintability, etc. First, preparation In the polyethylene copolymer resin latex that is intermolecularly associated by an ionic group, the first step will be explained, which is a step of preparing a copolymer. A monomer mixture including an olefin as the first monomer, 1 to 40% by weight of the ethylenically unsaturated carboxylic acid is used as the second monomer, and if necessary, a copolymerizable third monomer at a temperature of 200 to 300 ° C and an atmospheric pressure of 1 'Preparing an olefin copolymer resin latex having a carboxyl group copolymerized in an aqueous dispersion under the conditions of 0 0 0 to 2 0 0. It is best to use, for example, (meth) acrylic acid, maleic acid, humic acid' Itaconic acid and the like are used as the ethylenically unsaturated carboxylic acid, and (meth) acrylic acid is preferred. Among them, (meth) acrylic acid is preferred. It is best to use, usually 'a' type of square ethyl ethynyl compound ' Such as styrene or an aliphatic alpha-hydrocarbon, such as ethylene and propylene, are used as the olefin. Therefore, the preferred olefin copolymer resin used in the present invention may include, for example, an ethylene mono (meth) dienoic acid copolymer Material resin 'a styrene (meth) acrylic copolymer resin' an ethylene-styrene (meth) acrylic acid copolymer resin. In the present invention, in addition to the above first and second single glow, if appropriate. If necessary, a third monomer can be used, such as one or two or Species of (meth) acrylic acid This paper is sized to the Chinese National Standard (CNS) Α4 (21Q + X29 · ^ 董) ~ _ ~~ — (Read the precautions on the back before filling this page), and install-, ίτ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 1 V. Description of the invention (7) Esters, such as ethyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, a Styrene monomers, such as styrene, vinyl toluene and chlorostyrene, hydroxyalkyl (meth) acrylates, such as hydroxyethyl acrylate and hydroxypropyl (meth) acrylate, N-substituted (meth) acrylic acid Amines, such as N-methoxy (meth) acrylamide, epoxy groups containing (meth) acrylates, such as glycidyl (meth) acrylate, and (meth) acrylamide. When the polyunsaturated hydrocarbon copolymer resin has an ethylenically unsaturated carboxylic acid component of more than 40% by weight, it is associated with an intermolecular ionic group even if it is prepared by an emulsion ion-bond copolymerization step and a high molecular weight formation step later. The polyolefin copolymer resin latex is used as a film-forming material, and the resin-coated steel plate obtained has insufficient corrosion resistance. On the other hand, in the polyolefin copolymer resin, when the ethylene unsaturated carboxylic acid component is less than 1% by weight, it is difficult to refine the obtained polyolefin copolymer resin aqueous or water dispersion, which is not suitable for the method of the present invention. Water or a water mixture and a hydrophilic organic solvent are used as the aqueous dispersion. Use, for example, low-fat alcohols, such as methanol, ethanol, and eta-propanol, glycol ethers, such as methylethylene glycol methyl ether, glycol esters, such as ethylene glycol acetate, ethers, Tetrahydrofuran and dioxane, dimethylformamide, diacetone alcohol and the like are used as hydrophilic organic solvents. The polyolefin copolymer resin obtained in the first step is subjected to emulsion ionic copolymerization. The emulsification ionic copolymerization is usually carried out using an appropriate cation and, where appropriate, using ammonium water at a temperature of 80 to 300 ° and an atmospheric pressure of 1 to 20. In the ionic copolymerization under pressure, depending on the emulsification and resin performance, it is better to use amines in combination. This paper size applies to China National Standards (CNS) Α4 size (210 X 297 mm) _ 1 〇_ (Please read the precautions on the back before filling out this page) Binding. Order the staff consumer cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Printing A7 B7 V. Description of the invention (8) It is better to use metal ions as the cation. For example, it is particularly preferable to use lithium, potassium, magnesium, zinc, sodium, calcium, iron, and aluminum ions. In order to form a well-balanced resin film according to the present invention, which has abrasion resistance and handleability, 'blackening resistance during pressing, perforation resistance, corrosion resistance, and coating properties on the surface of steel plates, it is necessary to partially crosslink the resin coating. Resin component to increase molecular weight. Therefore, according to the present invention, it is possible to partially cross-link the ionomer copolymer resin by a cross-linking agent, thereby preparing an olefin copolymer resin intermolecularly associated with an ionic group. The crosslinking agent is not particularly limited here, and a suitable crosslinking agent for crosslinking the carboxyl group of the resin can be used. Therefore, the crosslinking agent includes, for example, an epoxy compound ', a titanium compound, and the like. The cross-linking reaction is usually carried out preferably at a temperature of 30 to 200 ° C and a pressure of normal to 20 atmospheric pressure. For example, the resin-coated steel sheet of the present invention can be coated with a water-based resin coating on a metal plate, which contains 5 to 30% by weight of silica particles, 0.5 to 20% by weight of spherical polyethylene wax particles, and 1 ton. 20% by weight of an organic compound having an aziridinyl group, which mainly comprises a polyolefin copolymer resin latex prepared by ion association between molecules, heating the metal plate to a predetermined temperature, drying the coating, and A resin film having a resin film weight of 0.2 to 2.5 g / m is formed on the surface of the metal plate after drying. The aqueous resin coating used in the present invention contains an organic compound having an azopropyl group in the range of 1 to 20% by weight of the aforementioned solid portion, and when the Cao resin coating is coated on a steel plate and heated to dry, The olefin copolymer resin (which is a resin component) associated with the ion group is adapted to the Chinese National Standard (CNS) A4 specification (2! 0X297 mm) by this paper size. ^-,, '豸 (please first (E, read the notes on the back, and then fill in this page)

T B7 五、發明説明（9) j 具有氮丙啶基之有機化合物交聯之形成一種交聯密度高之 .^^ -*—-------- '樹脂膜。該製得樹脂膜具有顯著改善硬度，高度韌性和耐 熱性。 本發明中使用之具有氮丙啶基之有機化合物包括，例 如，三甲氧基丙烷三（Θ —氮丙啶基丙酸酯），其以下列 化學式表示： ch2-ococh2ch2-n | 叫 CH3CH2 -c -ch2 -ococh2ch2 -n I /丨 CH2-OCOCH2CH2-N i ....._ ^...— 三—2，4，6 - ( 1 -氮丙啶基）—1，3，5 —三嗪 ，以下列化學式表示之： (請先閎讀背面之注意事項再填寫本頁)T B7 V. Description of the invention (9) j Crosslinking of organic compounds with aziridinyl groups to form a kind of high crosslink density. ^^-* --------- 'Resin film. The prepared resin film has markedly improved hardness, high toughness and heat resistance. The organic compound having aziridinyl group used in the present invention includes, for example, trimethoxypropanetri (Θ-aziridinylpropionate), which is represented by the following chemical formula: ch2-ococh2ch2-n | called CH3CH2 -c -ch2 -ococh2ch2 -n I / 丨 CH2-OCOCH2CH2-N i ....._ ^ ...— tri-2,4,6-(1-aziridinyl) -1,3,5 —tri The hydrazine is expressed by the following chemical formula: (Please read the precautions on the back before filling this page)

經濟部中央標隼局員工消費合作社印製 以及，三〔1_(2—甲基）氮丙陡基〕膦酸氧化物，其 係由下列化學式表示之： 、 vTCH3 : CHa^N-P-N^CHB 0 如上述具有氮丙啶基之有機化合物係以下列化學式表 示： 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）_ 12 - 五、發明説明（ίο) |^N-R-N^| + 共聚物 Ζ_Λ COOH 且具有該效應，因此該化合 反應形碎交聯密度高之樹 膜之硬度，高度韌性和耐熱 板進行壓製處理和穿孔處理 動，以及因模塑熱產生之樹 腐蝕性和化學阻力。 本發明中使用之樹脂塗 合物數量少於塗層中固體部 共聚物樹脂中羧基之交聯反 處理或穿孔處理後之Ρ脂步 鈉和離子鉀反應，達成膜親 和塗料性。另一方面，當有 時，該膜之交聯度過度增加 膜無法符合因壓製處理等造 等使抗腐蝕性和塗料性惡化 中具有氮丙啶基之有機化合 重量％範圍內。 本發明中使用之樹脂塗 量％範圍內之二氧化矽顆粒 製得之樹脂膜良好之抗腐蝕 膜之硬度，並控制運輸中震 Α7 Β7 共聚物 I -> coo-ch2ch2-nh-r-n~' I N~ 物與具有羧基之共聚物樹脂f 脂膜以顯著地強化該製得樹脂 性，因此當本發明樹脂塗層鋼 時，抑制因模塑斜度導致之震 脂膜軟化。此外，亦可強丨匕抗 層中，具有氮丙啶基之有機化 分之1重量％，不僅與如上述 應不充份，且該羧基與於壓製 驟中使用之鹼化合物中之離子 水性且明顯地惡办其抗腐蝕性 機化合物數量超過2 0重量％ 且該膜硬度過度增加，因此該 成之壓製變形，因此產生裂縫 。特別是本發明中，樹脂塗層 物數量佔固體部分中5.至1 〇 層含有佔固體部分5至3 0重 。該二氧化矽顆粒有助於賦予 性和塗料性，另外改善該樹脂 動造成之磨蝕產生，壓製中膜 (請先閲讀背面之注意事項备填寫本頁) 訂 • - · 經濟部中央標隼局員工消費合作社印製Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs and tris (1_ (2-methyl) azepine) phosphonic acid oxide, which is represented by the following chemical formula:, vTCH3: CHa ^ NPN ^ CHB 0 as The above organic compounds with aziridinyl are represented by the following chemical formulas: This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) _ 12-V. Description of the Invention (ίο) | ^ NRN ^ | + The copolymer Z_Λ COOH has this effect, so the compound reaction-shaped crushed cross-linking density of the tree film has high hardness, high toughness, and heat-resistant plate for pressing treatment and perforation treatment, as well as the tree's corrosiveness and chemistry due to molding heat. resistance. The amount of the resin coating compound used in the present invention is less than that in the solid portion of the copolymer resin in the coating layer after the cross-linking reverse treatment or perforation treatment of the carboxyl group. Sodium and ionic potassium react to achieve film affinity coating properties. On the other hand, the cross-linking degree of the film is excessively increased, and the film cannot meet the range of the weight percent of the organic compound having an aziridinyl group in the deterioration of the corrosion resistance and the coating properties due to press processing or the like. The resin film made of silicon dioxide particles in the range of the resin coating amount% used in the present invention has good hardness of the anti-corrosion film, and controls the shock of transportation A7 B7 copolymer I-> coo-ch2ch2-nh-rn ~ The resin film with a carboxyl group copolymer resin f significantly strengthens the resinous properties. Therefore, when the resin-coated steel of the present invention is used, the softening of the shock-induced lipid film due to the molding slope is suppressed. In addition, it is also possible that 1% by weight of the organic component of the aziridinyl group in the anti-drug layer is not only inadequate as described above, but also the carboxyl group and the ionic water in the alkali compound used in the pressing step And it is obviously mischievous that the amount of its anti-corrosive machine compound exceeds 20% by weight and the hardness of the film is excessively increased, so that the resulting compact is deformed and cracks are generated. In particular, in the present invention, the resin coating layer accounts for 5. to 10 of the solid portion, and the layer contains 5 to 30 weight of the solid portion. The silicon dioxide particles help to impart properties and coating properties. In addition, it improves the abrasion caused by the resin and suppresses the middle film (please read the precautions on the back to fill in this page) Order •-· Central Bureau of Standards, Ministry of Economic Affairs Printed by Employee Consumer Cooperative

.i^i -H 本紙張尺度適用中國國家標隼（CMS ) Α4規格（210Χ297公釐） A7 _:_B7__ ’ 五、發明説明（11) 之刮痕，黑化現象產生等。但是，該樹脂膜中二氧化矽顆 粒數量少於固體部分5重量％時，製得之樹脂膜之抗腐蝕 性和塗料性之強化不足，且無法得到該膜之充分強度。因 此，不可能控制抗腐蝕性和壓製中刮痕之產生和黑化現象 。另一方面，當該數量超過3 0重量％時，該樹脂膜之硬 度明顯地強化，但是由樹脂膜佔用之二氧化矽顆粒部分過 度增加，惡化該樹脂膜之製膜特性，於該膜產生裂縫，惡 化其抗腐蝕性。 此外，該二氧化矽顆粒充作一種磨蝕增加劑之功能， 以增加該膜之磨擦係數，降低潤滑特性，於壓製中產生模 之磨蝕，加速該模之使用期限。特別是，該樹脂塗層中之 二氧化矽顆粒最好佔固體部分5至2 0重量％範圍》 經濟部中央標準局員工消费合作社印製 (請先閲讀背面之注意事項再填寫本頁) 爲使上述二氧化矽顆粒之效果最大化，該二氧化矽顆 粒直徑最好在1至2 0 0 nin範圔。二氧化矽顆粒直徑愈 小，該膜抗腐性增加愈多。該二氧化矽顆粒之效果使樹脂 膜稠密，且黏著性佳，此外加強該樹脂膜之抗腐蝕性。由 此種事實之觀點來看，二氧化矽顆粒之顆粒直徑愈小愈好 。但是，即使使用極細顆粒，上述效果無法相對地特別強 化。因此，本發明中該二氧化矽顆粒具有1 nm或更大之 顆粒直徑通常足夠。另一方面，二氧化矽顆粒之顆粒直徑 變得更大時，例如使用顆粒直徑爲4 0至2 0 0 nm之二 氧化矽，其已知爲鏈狀二氧化矽顆粒，因此該樹脂膜之塗 料性明顯地強化。因此，若顆粒直徑超過20 Onm，該 樹脂表面變得粗糙，因此無法形成細微之樹脂膜》此外， 本紙張尺度適用中國®家標準（CNS ) A4规格（210 X 297公漦）_ J 4 _ Α7 Β7 經濟部中央橾準局員工消費合作社印製 五、發明説明（l2) 二.氧化矽顆粒充作磨蝕增加劑時’導致處理性之惡化。特 別是本發明中，因抗磨蝕性之附帶童要性’例如依膜功用 所需，該二氧化矽顆粒直徑最好在4至2 0 n m範圍內。 因塗料性之附帶重要性，其最好在4至2 0 0 n m範圍內 〇 此種二氧化矽通常已知爲膠體二氧化矽。本發明中， 市售產物，例如，諸如SNOWTEX XS，SS, 40，N，UP·(由 NISSAN CHEMICAL INDUSTRIES LTD.)可適用。 本發明中使用之樹脂塗層另外含有佔固體部分Ο . 5 至2 0重量％之球形聚乙烯蠟頼粒。該球形聚乙烯蠟顆粒 有助於強化該製得樹脂膜之潤滑特性，強化抗腐蝕性和请 刮性。其另外於壓製處理和穿孔處理進行時，另外強化該 深度抽絲特性，穿孔性和模製磨蝕特性，且壓製時傾斜表 面之抗黑化性賦予良好之處理性。 但是，該樹脂塗層中，當球形聚乙烯蠟顆粒數量少於 0 · 5重量％時，製得之樹脂膜潤滑特性不足，無法得到 該耐磨蝕性和耐刮性之強化及令人滿意之處理性。另一方 面，該數量大於2 0重量％時，製得之樹脂膜具有充分潤 滑特性，但是於電解澱積塗覆，粉末塗覆或使用絲綢印花 塗覆時該塗層膜之黏著性差。原因之一係當樹脂塗層塗覆 ’烘烤和乾燥時，蠟變得軟化且液化，且介於樹脂膜和塗 一料間之介面變厚，使塗料之黏著性惡化。特別是本發明中 ’樹脂塗層中之球形聚乙烯蠟顆粒數量佔固體部分1至 10重量％範圍內較佳。 (請先閲讀背面之注意事項再填寫本頁) \裝· -訂 is. 本紙張尺度適用中國國家標準（CNS ) Μ規格（2丨〇><297公釐） 15 A7 B7 經濟部中央標準局員工消費合作社印製.i ^ i -H This paper size applies to China National Standard (CMS) A4 specification (210 × 297 mm) A7 _: _ B7__ ’5. Description of the invention (11) scratches, blackening phenomenon, etc. However, when the number of silica particles in the resin film is less than 5% by weight of the solid portion, the corrosion resistance and coating properties of the obtained resin film are insufficiently enhanced, and sufficient strength of the film cannot be obtained. Therefore, it is impossible to control the generation of corrosion resistance and the occurrence of scratches during pressing and blackening. On the other hand, when the amount exceeds 30% by weight, the hardness of the resin film is significantly enhanced, but the portion of the silicon dioxide particles occupied by the resin film is excessively increased, which deteriorates the film-forming characteristics of the resin film, and results in the film. Cracks that deteriorate its corrosion resistance. In addition, the silicon dioxide particles function as an abrasion enhancer to increase the friction coefficient of the film, reduce the lubricating characteristics, generate mold abrasion during pressing, and accelerate the life of the mold. In particular, the silicon dioxide particles in the resin coating preferably occupy 5 to 20% by weight of the solid portion. "Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) as To maximize the effect of the above silicon dioxide particles, the diameter of the silicon dioxide particles is preferably in the range of 1 to 200 nin. The smaller the diameter of the silica particles, the more the film has increased corrosion resistance. The effect of the silicon dioxide particles makes the resin film dense and has good adhesion, and further enhances the corrosion resistance of the resin film. From the viewpoint of this fact, the smaller the particle diameter of the silica particles, the better. However, even if extremely fine particles are used, the above effects cannot be relatively particularly enhanced. Therefore, it is usually sufficient that the silicon dioxide particles have a particle diameter of 1 nm or more in the present invention. On the other hand, when the particle diameter of the silicon dioxide particles becomes larger, for example, silicon dioxide having a particle diameter of 40 to 200 nm is used, which is known as chain-shaped silicon dioxide particles. The coating properties are significantly enhanced. Therefore, if the particle diameter exceeds 20 Onm, the surface of the resin becomes rough, so a fine resin film cannot be formed. In addition, the paper size applies the Chinese Standard (CNS) A4 (210 X 297 mm) _ J 4 _ Α7 Β7 Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (l2) 2. When the silica particles are used as an abrasion enhancer, it leads to deterioration of handling properties. In particular, in the present invention, the abrasion resistance is incidental, such as the film function, and the diameter of the silicon dioxide particles is preferably in the range of 4 to 20 nm. Due to the incidental importance of paintability, it is preferably in the range of 4 to 2000 nm. This type of silica is generally known as colloidal silica. In the present invention, commercially available products such as SNOWTEX XS, SS, 40, N, and UP (by NISSAN CHEMICAL INDUSTRIES LTD.) Are applicable. The resin coating used in the present invention additionally contains spherical polyethylene wax particles having a solid content of 0.5 to 20% by weight. The spherical polyethylene wax particles help to strengthen the lubricating properties of the obtained resin film, and enhance the corrosion resistance and scratch resistance. It also strengthens the deep-drawing characteristics, perforation properties, and mold abrasion characteristics during the pressing and perforating processes, and the blackening resistance of the inclined surface during pressing gives good reason. However, in the resin coating, when the number of spherical polyethylene wax particles is less than 0.5% by weight, the lubricating characteristics of the obtained resin film are insufficient, and the abrasion resistance and scratch resistance cannot be enhanced and satisfactory. Its handling. On the other hand, when the amount is more than 20% by weight, the obtained resin film has sufficient lubricating properties, but the adhesion of the coating film is poor when electrolytic deposition coating, powder coating or silk printing coating is used. One of the reasons is that when the resin coating is applied and baked and dried, the wax becomes soft and liquefied, and the interface between the resin film and the coating material becomes thicker, which deteriorates the adhesiveness of the coating. In particular, the number of spherical polyethylene wax particles in the 'resin coating layer in the present invention is preferably in the range of 1 to 10% by weight of the solid portion. (Please read the precautions on the back before filling in this page) \ Installation · -Order is. This paper size is applicable to Chinese National Standard (CNS) M specifications (2 丨 〇 > < 297 mm) 15 A7 B7 Central Ministry of Economic Affairs Printed by Standards Bureau's Consumer Cooperative

五、發明説明（13) 爲使上述球形聚乙烯蠘顆粒之效果最大化，該蠟顆粒 之顆粒直徑爲0.1至3較佳。當蠘顆粒之顆粒直徑 小於1時，不可能製得具有良好潤滑特性之樹脂膜，且不 能得到不足以樹脂膜爲基準亦以膜中之蠟顆粒爲基準之穿 孔性，模塑耐磨蝕性和深度抽絲特性之強化。. 另一方面，當蠟顆粒之顆粒直徑大於3>m時，難以 將蠘顆粒均匀分散於樹脂塗層中，無法製得蠟均匀分散之 > 樹脂膜使該膜對鋼板之黏著性惡化。另外，以電解澱積塗 覆，粉末塗覆或絲綢印花等方法之膜黏著性惡化。 特別是本發明中，該樹脂·塗層中球形聚乙烯蟣顆粒之 顆粒直徑在0 · 3至1 . Ομπι範圍內較佳》 本發明中，球形聚乙烯蠟顆粒之軟化點在80至 1 4 0 °C範圍內較佳。當軟化點低於8 0 °C時，該蠟顆粒 軟化且液化，如模塑溫度升高，於壓製處理或穿孔處理進 行時，因介於樹脂塗覆鋼板和該模間之傾斜表面，產生液 體流出現象而降低處理性，產生刮痕或以該模烘烤時，黑 化材料黏著於傾斜部分，明顯地使產品外觀惡化。另一方 面，當軟化點高於1 4 0 °C時，該蠟顆粒之潤滑特性不足 ，因此沒有加強穿孔性，模塑耐磨蝕性和深度抽絲性，無 法得到良好之處理性。 本發明中，此種球形聚乙烯蠟顆粒爲市售產品，諸如 DIEJET E-17 (GOO CHEMICAL LTD.所製），KUE-1，KUE - 5 和 KUE-8 (SANYO KASEI INDUSiRIES LTD.所製）， CHEMIPEARL W-100, CHEMIPEARL W-200, CHEMIPEARL (請先閲讀背面之注意事項再填寫本頁) > ·4— m- 1. 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（2i〇X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（14) W-300, CHEMIPEARL W-400, CHEMIPEARL W-500, CHEMIPEARL W-640, CHEMIPEARL W-700 (MITSUI PETROLEUM CHEMICAL INDUSTRIES LTD.，所製），和 EREPON E-20 (NIKKA CHEMICAL LTD.所製）。 如本發明，當上述水性樹脂塗層塗覆於鋼板表面，並 加熱乾燥時，其係以低於球形蠘顆粒軟化點之板溫加熱。 然後，形成一樹脂膜，並維持樹脂膜中之球形聚乙烯蠟顆 粒，且製得之樹脂膜之潤滑特性另外強化，以再強化製得 樹脂塗覆鋼板之壓製處理性和穿孔處理性。此外，維持該 樹脂膜中之球形聚乙烯蠟顆粒之球形，可使該蠟顆粒於樹 脂膜中更均勻分散。再者，該樹脂膜表面中，可減少樹脂 膜曝露出之由蠟顆粒表面部分佔用之部分，且其可輕易地 完全以該樹脂覆蓋，得到良好之抗腐蝕性和塗料性。 必須於鋼板表面形成慣用熱塑樹脂膜以進行高溫長時 間之烘烤和乾燥。但是本發明中使用之樹脂塗層塗覆於金 屬板表面，並以相對低溫短時間加熱乾燥，因此交聯形成 膜，因此形成具有體型網狀結構之樹脂膜。先前技藝之高 溫長時間烘焙乾燥並非必要’因此’如本發明’可以簡易 之乾燥設備製備一種交聯樹脂塗層鋼板，且具有該鋼板可 於其生產線製備之優點。 例如，於電鍍鋅生產線中，可藉輥狀塗覆器塗覆樹脂 塗層，並以簡易乾燥設備短時間乾燥以製備一樹脂塗層鋼 板》如上述，因爲利用線上方式生產，可以使設備之投資 低廉，亦可預期相當程度之成本下降。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I.Μ-ΙΓΙΓ---^-- (請先閎讀背面之注意事項再填寫本頁) 、νβ 經濟部中央標準局員工消費合作社印製 A7 _____B7__ 五、發明説明（15) .本發明中，該樹脂膜對鋼板之塗層重量在0.2至 2 · 5 g / rri乾燥膜較佳。當樹脂膜塗覆重量少於0 . 2 g /rrf時，該樹脂塗層無法均勻塗於鋼板上，此外，無法 充分顯示欲得到之良好均衡膜功用，諸如處理性，抗黑化 性，抗腐餓性，塗料性等，以及耐磨蝕性。另一方面，該 樹脂膜之塗層重大於2 . 5 g / nf時，該土特性（其係電 腦實例特所需特性之一），即傳導性惡化。此外，壓製處 理中，該樹脂膜之剝離數量增加，因此剝^離之膜黏附且累 積於模中，致使壓模不便，增加生產成本。由實用觀點來 看，特別是，該樹脂膜之塗覆重在0 . 3至1 .〇g/nf 範圍內較佳。 本發明中樹脂塗層金屬板中使用之金屬板原料無法特 別限制，但是例如可提及鋅或銨鋅鋼板，鋁板，鋁合金板 ，鈦板等。該鋅或鍍鋅鋼板，鋁板，鋁合金板等進行成形 處理，諸如鉻酸鹽處理和磷酸鹽處理較佳。特別是進行鉻 酸鹽處理者較佳。如該鉻酸鹽處理，使用任何洗式（反應 型）鉻酸鹽處理，塗覆式鉻酸鹽處理及電解式鉻酸鹽處理 〇 如上述，如本發明，將一種水樹脂塗覆於鋼板，然後 以相對低溫短時間加熱且乾燥之，因此製得一種具有交聯 樹脂膜之樹脂塗層鋼板。 該製得之樹脂塗層鋼板不僅於耐磨蝕性特別良好，其 於潤滑特性，耐刮性，穿孔性，壓製處理性和穿孔處理性 ，諸如壓製時之抗黑化性亦良好，此外抗腐蝕性，塗料性 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐）β _ (請先閎讀背面之注意事項再填寫本頁) 、裝. 訂 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（16) ~ 及土特性等佳》此外，這些特性非常均衡。 更具體化實例敘述 本發明於下文中以實施例敘述，但並不完全由該實施 例限制。下文中，使用一種電鍍鋅鋼板進行鉻酸鹽處理（ 鋅之塗層重係2 0 g/rri，鉻之塗層重係2 Omg/πί)充 作金屬板原料，以進行實施例間之相對評估。 實施例中評估項目和試驗方法如下述。五項評價中， 評價5最佳，評價1最差。 (1 )抗腐蝕性 關於製得之樹脂塗層金屬板，於邊緣封閉之平板及 J I s Z 2 3 7 1之Ericksen處理材料進行鹽水噴霧試 驗，並於1 %白色銹產生時進行評估。Ericksen推出之高 度爲6 ΙιιΓ。 (2 )塗料性 藉噴霧於製得樹脂塗層鋼板塗覆2 0从m厚之三聚氰 胺塗料。之後，該鋼板於1 5 0°C烘烤3 0分鐘並浸於沸 水中1小時。移去鋼板後1小時，於其上以切刀製成 1 0 0格1画度量方格。進行帶狀剝離試驗，且以殘留之 塗料度量數量評估該膜之黏著性。 (3 )動態摩擦係數 爲評估製得之樹脂塗層鋼板潤滑特性，使用傾斜試驗 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）一 1 q _ ~~ IJ.-------裝------訂------广4._ - (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標率局員工消費合作社印製 A7 _____B7_ 1 五、發明説明（1” 裝置測量於1 5 0 kg施加壓力之傾斜造成之載重以計算動 態摩擦係數。 (4 )穿孔性 爲評估製得樹脂塗層鋼板之穿孔性，於模塑材料 S K D - 1 1，模塑形狀1 0 ram正方’清潔度2 5 % ’穿 孔速度8 0片/分，及不使用穿孔油之條件下’使用連續 穿孔試驗裝置進行穿孔試驗以評估之，直到送回高度到達 5 0以m爲止。穿1 5 0 0 0 0 0孔之後可由視範圍觀察 該模之磨蝕狀況以評估5個階段中之耐磨蝕性。 (5 )處理性 爲評估製得樹脂塗層鋼板之深度抽絲等壓製處理性， 以8 0噸曲柄壓製裝置進行單一壓製試驗以視覺評估五個 階段中之模塑後該產物傾斜表面之刮痕，模塑刮痕及抗黑 化性。 (6)膜硬度 於樹脂塗層鋼板表面進行J I s K 5 4 0 0之鉛筆 抓刮試驗以評估樹脂塗層鋼板表面之樹脂膜於鉛筆硬度中 之硬度。 (7 )碾磨 將試驗器之終端鉛板（+，-）置於與製得之樹脂塗 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-20 - ~ (諳先閎讀背面之注意事頃再填寫本頁)V. Description of the invention (13) In order to maximize the effect of the above-mentioned spherical polyethylene rhenium particles, the particle diameter of the wax particles is preferably 0.1 to 3. When the particle diameter of the gadolinium particles is less than 1, it is impossible to obtain a resin film with good lubricating properties, and it is not possible to obtain a perforation that is not based on the resin film but also based on the wax particles in the film, and the mold wear resistance And deep drawing characteristics. On the other hand, when the particle diameter of the wax particles is larger than 3 > m, it is difficult to uniformly disperse the gadolinium particles in the resin coating layer, and it is not possible to obtain a wax uniformly dispersed resin film which deteriorates the adhesion of the film to the steel plate. In addition, the film adhesion is deteriorated by electrolytic deposition coating, powder coating, or silk printing. In particular, in the present invention, the particle diameter of the spherical polyethylene hafnium particles in the resin · coating is preferably in the range of 0.3 to 1.0 μm. In the present invention, the softening point of the spherical polyethylene wax particles is 80 to 1 4 0 ° C is preferred. When the softening point is lower than 80 ° C, the wax particles are softened and liquefied. For example, when the molding temperature is increased, the pressing or perforating treatment is performed due to the inclined surface between the resin-coated steel plate and the mold. The liquid outflow phenomenon reduces the handleability, produces scratches or bakes with this mold, the blackening material sticks to the inclined part, which obviously deteriorates the appearance of the product. On the other hand, when the softening point is higher than 140 ° C, the lubricating properties of the wax particles are insufficient, so there is no enhancement of perforation, molding abrasion resistance and deep drawability, and no good reason can be obtained. In the present invention, such spherical polyethylene wax particles are commercially available products such as DIEJET E-17 (made by GOO CHEMICAL LTD.), KUE-1, KUE-5 and KUE-8 (made by SANYO KASEI INDUSiRIES LTD.) , CHEMIPEARL W-100, CHEMIPEARL W-200, CHEMIPEARL (Please read the precautions on the back before filling out this page) > · 4— m- 1. The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (2i〇) X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (14) W-300, CHEMIPEARL W-400, CHEMIPEARL W-500, CHEMIPEARL W-640, CHEMIPEARL W-700 (MITSUI PETROLEUM CHEMICAL INDUSTRIES LTD., And EREPON E-20 (manufactured by NIKKA CHEMICAL LTD.). According to the present invention, when the above-mentioned water-based resin coating is coated on the surface of a steel plate and dried by heating, it is heated at a plate temperature lower than the softening point of the spherical slag particles. Then, a resin film is formed, and the spherical polyethylene wax particles in the resin film are maintained, and the lubricating properties of the obtained resin film are further strengthened to further strengthen the press-treatability and perforation-treatability of the resin-coated steel sheet obtained. In addition, by maintaining the spherical shape of the spherical polyethylene wax particles in the resin film, the wax particles can be more uniformly dispersed in the resin film. In addition, in the surface of the resin film, the portion occupied by the surface of the wax particles exposed by the resin film can be reduced, and it can be easily and completely covered with the resin to obtain good corrosion resistance and paintability. It is necessary to form a conventional thermoplastic resin film on the surface of the steel plate for baking and drying at high temperature and for a long time. However, the resin coating used in the present invention is coated on the surface of a metal plate, and is heated and dried at a relatively low temperature for a short time, so that it is crosslinked to form a film, and thus a resin film having a bulk network structure is formed. The high temperature and long time baking and drying of the prior art is not necessary. Therefore, as in the present invention, a crosslinked resin-coated steel plate can be prepared by simple drying equipment, and has the advantage that the steel plate can be prepared on its production line. For example, in an electro-galvanizing production line, a resin coating can be applied by a roll coater and dried with a simple drying device for a short time to prepare a resin-coated steel sheet. With low investment, considerable cost reductions can also be expected. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) I.M-ΙΓΙΓ --- ^-(Please read the precautions on the back before filling this page), νβ Staff of the Central Bureau of Standards, Ministry of Economic Affairs Printed by the consumer cooperative A7 _____B7__ 5. Description of the invention (15). In the present invention, the coating weight of the resin film on the steel plate is preferably 0.2 to 2.5 g / rri dry film. When the coating weight of the resin film is less than 0.2 g / rrf, the resin coating cannot be uniformly coated on the steel plate, and in addition, it cannot fully display the desired balanced film functions such as handling, blackening resistance, and resistance. Sterility, paintability, etc., and abrasion resistance. On the other hand, when the coating of the resin film is greater than 2.5 g / nf, the properties of the soil (which is one of the characteristics specifically required for a computer example), that is, the conductivity deteriorates. In addition, in the pressing process, the peeling amount of the resin film increases, so the peeled-off film adheres and accumulates in the mold, resulting in inconvenience to the mold and increasing production costs. From a practical point of view, in particular, the coating weight of the resin film is preferably in the range of 0.3 to 1.0 g / nf. The metal plate raw material used in the resin-coated metal plate in the present invention cannot be specifically limited, but, for example, zinc or ammonium zinc steel plates, aluminum plates, aluminum alloy plates, titanium plates, and the like can be mentioned. The zinc or galvanized steel sheet, aluminum sheet, aluminum alloy sheet, etc. are subjected to a forming treatment, such as a chromate treatment and a phosphate treatment. Especially, it is preferable to perform chromate treatment. As for the chromate treatment, use any washing (reactive) chromate treatment, coating chromate treatment, and electrolytic chromate treatment. As described above, as in the present invention, a water resin is applied to the steel plate. Then, it is heated and dried at a relatively low temperature for a short time, so a resin-coated steel sheet having a crosslinked resin film is prepared. The obtained resin-coated steel sheet is not only particularly good in abrasion resistance, but also good in lubricating properties, scratch resistance, perforation, pressing properties, and perforating properties, such as blackening resistance during pressing, and also has excellent resistance to blackening. Corrosive and paintable This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) β _ (Please read the precautions on the back before filling this page), packaging. Order the Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperatives Printed A7 B7 V. Description of the invention (16) ~ and good soil properties. In addition, these properties are very balanced. DETAILED DESCRIPTION OF EXAMPLES The present invention is described below by way of example, but is not limited in any way by the examples. In the following, an electro-galvanized steel sheet is used for chromate treatment (zinc coating weight is 20 g / rri, chromium coating weight is 2 Omg / πί) as the metal plate raw material for the comparison between the examples. Evaluation. The evaluation items and test methods in the examples are as follows. Of the five evaluations, 5 was the best and 1 was the worst. (1) Corrosion resistance Regarding the obtained resin-coated metal plate, a salt spray test was performed on the edge-enclosed flat plate and the Ericksen-treated material of J Is Z 2 3 71, and evaluated when 1% white rust occurred. Ericksen launched a height of 6 ΙιΓ. (2) Coating property The resin-coated steel plate obtained by spraying was coated with a 20-m thick melamine coating. After that, the steel plate was baked at 150 ° C for 30 minutes and immersed in boiling water for 1 hour. One hour after the steel plate was removed, a 100 squares and a measuring square were made on the cutting board with a cutter. A strip peel test was performed, and the adhesiveness of the film was evaluated by the amount of paint remaining. (3) The dynamic friction coefficient is used to evaluate the lubricating properties of the resin-coated steel plate. The paper scale is used in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm)-1 q _ ~~ IJ .---- --- Installation ------ Order ------ Canton 4._-(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 _____B7_ 1 5 2. Description of the invention (1 ”The device measures the load caused by the inclination of 150 kg of applied pressure to calculate the dynamic friction coefficient. (4) Perforability To evaluate the perforation of the resin-coated steel sheet, the mold material SKD-1 1. Molded shape 1 0 ram square 'Cleanliness 25%' Perforation speed 80 pieces / min, and without using perforating oil 'Perforation test using a continuous perforation test device to evaluate until the return height reaches 50 to m. After a hole is drilled through 15 0 0 0 0 0, the abrasion condition of the mold can be observed from the visual range to evaluate the abrasion resistance in 5 stages. (5) The handleability is to evaluate the resin-coated steel sheet. For deep press processing such as deep drawing, a single pressing test was performed with an 80 ton crank pressing device. Visually evaluate the scratches on the inclined surface of the product after molding in five stages, molding scratches, and blackening resistance. (6) Film hardness The pencil of JI s K 5 4 0 0 was applied to the surface of the resin-coated steel sheet. Scratch test to evaluate the hardness of the resin film on the surface of the resin-coated steel plate in pencil hardness. (7) Grind and place the terminal lead plate (+,-) of the tester with the prepared resin-coated paper. This paper is suitable for China. National Standard (CNS) A4 specification (210X297 mm) -20-~ (谙 Please read the notes on the back before filling this page)

、tT Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明（18) 層鋼板表面輕接觸以測量該傾斜表面之阻力。 (8 )耐磨蝕性 使用PWO型平曲疲勞試驗裝置造成磨蝕以肉眼評估 5個步驟中之耐磨蝕性。 (9)樹脂膜強度 製備4 Ο Μ m厚之樹脂膜使用張力試驗裝置測量該膜 之張力強度（膜寬1 5画，裂縫間距1 5麵，測量時溫度 2 0。。）。 實施例1 將一種具有狻基之聚烯烴共聚物，其含0 . 5至5 0 重量％之仲乙基不飽和羧酸組份，藉氫氧化鈉離子鍵共聚 . 之，並另外藉交聯劑形成高聚合物分子，以製備一種分子 間藉離子團鍵結之聚烯烴共聚物樹脂乳膠。 該形成乳膠中添加佔固體部分1 0重'量％之直徑爲 1 0至2 0 nm之二氧化矽顆粒，5重量％軟化點爲 1 0 0°C_且顆粒直徑爲〇 . 6 之球形聚乙烯蠟顆粒， 及.1 0重量％之三甲氧基丙烷三（点-氮丙啶基丙酸酯） 以製備一種水性樹脂塗料。 將該樹脂塗料塗於進行鉻處理之電鍍鋅鋼板表面，並 於9 0 °C加熱乾燥，製得一具有1 g / πί樹脂膜塗層重之 樹脂塗層鋼板。 (請先閎讀背面之注意事項再填寫本瓦), TT Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) The surface of the steel sheet is lightly touched to measure the resistance of the inclined surface. (8) Abrasion resistance The abrasion resistance in the 5 steps was evaluated with the naked eye caused by abrasion using a PWO type flat bending fatigue test device. (9) Resin film strength A resin film with a thickness of 40 μm was prepared using a tensile tester to measure the tensile strength of the film (film width 15 strokes, crack spacing 15 sides, and temperature 20 during measurement). Example 1 A polyolefin copolymer having a fluorenyl group, which contains 0.5 to 50% by weight of a secondary ethyl unsaturated carboxylic acid component, is copolymerized by means of sodium hydroxide ion bonding, and is additionally crosslinked by The agent forms high polymer molecules to prepare a polyolefin copolymer resin latex bonded by an ionic group between molecules. The spherical latex is formed by adding 10% by weight of the solid portion with silica particles having a diameter of 10 to 20 nm, a 5% by weight softening point of 100 ° C_ and a spherical diameter of 0.6. Polyethylene wax particles and .10% by weight of trimethoxypropanetri (point-aziridinylpropionate) to prepare an aqueous resin coating. The resin coating was coated on the surface of a galvanized steel sheet subjected to chromium treatment, and heated and dried at 90 ° C to obtain a resin-coated steel sheet having a resin film coating weight of 1 g / π. (Please read the notes on the back before filling in this tile)

• 1^1 m m m nn m i \·* /1.0¾ 、T ——IB nn ^ϋ9Β ^mc nn · 4 本紙張尺度適用中國國家榉準（CMS ) Α4規格（2〗0 X 297公釐）_ 21 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（19) 該製得之樹脂塗層鋼板之抗腐蝕性和塗料性如表 (請先W讀背面之注意事頃再填寫本頁) -22 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） 經濟部中央標準局員工消費合作社印製 五、發明説明（2〇) 表 1 伸乙基不飽和羧酸組份 (w t · % ) 抗腐蝕性（小時） 塗料性 (剩餘方格數） 平板 Er i cksen 本發明 1 892 744 99 5 960 744 100 10 984 792 100 20 984 792 100 40 888 792 100 對照實例 0.5 不良水分散液 45 42 0 360 82 (請先閎讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） Α7 Β7 五、發明説明(21) 實施例2 將一種具有羧基之聚烯烴共聚物樹脂，其含2 〇重量 %之伸乙烯不飽和羧酸組份，以氫氧化鈉離子鍵共聚，另 外以交聯劑形成高聚合物分子，以製備分子間以離子團鍵 合之聚烯烴共聚物樹脂乳膠。 β 於該形成乳膠中加入佔固體部份1 0重量％，且顆粒 直徑爲1 0至2 0 nm之二氧化矽顆粒，5重量％軟化點 爲1 0 0°C，且顆粒直徑爲0 . 6jm之球形聚乙烯蠟顆 粒，及三甲氧基丙烷三（y3_氮丙啶基丙酸酯）（ TAZM)在〇.5至25重量％範圍內以製備一種水性 樹脂塗覆物。 將該樹脂塗覆物塗於進行鉻處理之電鍍鋅鋼板表面， 於9 0°C溫度加熱並乾燥，製得一種樹脂膜塗層重1 m2之樹脂塗層鋼板。 (請先閲讀背面之注意事項再填寫本I·) 1 言• 1 ^ 1 mmm nn mi \ · * /1.0¾, T ——IB nn ^ ϋ9Β ^ mc nn · 4 This paper size is applicable to China National Beech Standard (CMS) Α4 specification (2〗 0 X 297 mm) _ 21 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (19) The corrosion resistance and coating properties of the resin-coated steel plate produced are as shown in the table (please read the precautions on the back before filling this page) ) -22 This paper size applies to China National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (20) Table 1 Ethyl Unsaturated Carboxylic Acid Components ( wt ·%) Corrosion resistance (hours) Paintability (remaining number of squares) Plate Er i cksen The present invention 1 892 744 99 5 960 744 100 10 984 792 100 20 984 792 100 40 888 792 100 Comparative example 0.5 Poor water dispersion Liquid 45 42 0 360 82 (Please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) Α7 Β7 V. Description of the invention (21) Example 2 will be A polyolefin copolymer resin having a carboxyl group, which Contains 20% by weight of ethylenically unsaturated carboxylic acid components, copolymerized with sodium hydroxide ion bonds, and high-molecule molecules are formed with cross-linking agents to prepare polyolefin copolymer resin latexes that are bonded with ionic groups between molecules . β is added to the latex-forming latex to account for 10% by weight of the solid portion, and particle diameter of 10 to 20 nm of silicon dioxide particles, 5% by weight softening point of 100 ° C, and the particle diameter of 0. 6jm spherical polyethylene wax particles, and trimethoxypropane tris (y3-aziridinylpropionate) (TAZM) were in the range of 0.5 to 25% by weight to prepare an aqueous resin coating. The resin coating was coated on the surface of an electro-galvanized steel sheet subjected to chromium treatment, heated and dried at 90 ° C. to obtain a resin-coated steel sheet having a resin film coating weight of 1 m 2. (Please read the notes on the back before completing this I ·) 1 Comment

經濟部中央標隼局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS.) A4規格.ί _2_10 X 297公釐） A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（22 ) 表 2 數量 (w t · %) 張力強度 (kg/ηί) 抗腐蝕性（小時） 塗料性 膜硬度 處理性 平板 Ericksen 本發明 0.5 722 888 768 100 Η 4 1 766 888 768 100 2Η 5 5 786 912 792 100 3Η 5 10 780 960 816 100 3Η 5 15 790 912 768 100 3Η 5 20 · 812 912 744 100 4Η 5 對照實例 0.3 132 720 480 85 ΗΒ 2 25 890 624 96 36 5Η 1 null In —l·— — ^ϋΜ— ^/11 .士 I nn nn HI— —^n 一OJ (請先閎讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（ CNS ) A4#l格（210X297公釐） A7 B7 五、發明説明（23) 實施例3 將一種具有羧基之聚烯烴共聚物樹脂，其含2 〇重量 %之伸乙烯不飽和羧酸組份，以氫氧化鈉離子鍵共聚，另 外以交聯劑形成高聚合物分子，以製備分子間以離子團鍵 合之聚烯烴共聚物樹脂乳膠。 於該形成乳膠中加入佔固體部份3至3 5重量％，且 顆粒直徑爲1 0至2 0 n m之二氧化矽顆粒，5重量％軟 f. 化點爲1 0 0°C，且顆粒直徑爲0 · 6 jam之球形聚乙烯 蠟顆粒，及1 0重量％三甲氧基丙烷三（召—氮丙啶基丙 酸酯）（TAZM)以製備一種樹脂塗覆物。 將該樹脂塗料塗於進行鉻處理之電鍍鋅鋼板表面，並 於9 0°C加熱乾燥，製得一具有1 g/nf樹脂塗層重之樹 脂塗層鋼板。 該製得之樹脂塗層鋼板之抗腐蝕性和塗料性如表3。 (請先閲讀背面之注意事項再填寫本頁) '袭-Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper size is applicable to the Chinese National Standard (CNS.) A4 specifications. Ί _2_10 X 297 mm) A7 B7 ) Table 2 Quantity (wt ·%) Tensile strength (kg / ηί) Corrosion resistance (hours) Paintability Film hardness Handling flat Ericksen The present invention 0.5 722 888 768 100 Η 4 1 766 888 768 100 2 Η 5 5 786 912 792 100 3Η 5 10 780 960 816 100 3Η 5 15 790 912 768 100 3Η 5 20 · 812 912 744 100 4Η 5 Comparative Example 0.3 132 720 480 85 ΗΒ 2 25 890 624 96 36 5Η 1 null In —l · — — ^ ϋΜ — ^ / 11. 士 I nn nn HI— — ^ n One OJ (Please read the precautions on the reverse side before filling out this page) The paper size is applicable to Chinese National Standard (CNS) A4 # l grid (210X297 mm) A7 B7 V. Description of the invention (23) Example 3 A polyolefin copolymer resin having a carboxyl group, which contains 20% by weight of an ethylenically unsaturated carboxylic acid component, is copolymerized with sodium hydroxide ion bonds, and further crosslinked Agent to form high polymer molecules to make Polyolefin copolymer resin latex with intermolecular bonds. To the latex-forming latex, silicon dioxide particles with a solid content of 3 to 35% by weight and a particle diameter of 10 to 20 nm are added, and 5% by weight is soft. The chemical point is 100 ° C, and the particles are Spherical polyethylene wax particles with a diameter of 0.6 jam, and 10% by weight of trimethoxypropane tris (z-aziridinylpropionate) (TAZM) to prepare a resin coating. This resin coating was applied to the surface of an electro-galvanized steel sheet subjected to chromium treatment, and heated and dried at 90 ° C to obtain a resin-coated steel sheet having a resin coating weight of 1 g / nf. The corrosion resistance and coating properties of the obtained resin-coated steel sheet are shown in Table 3. (Please read the notes on the back before filling out this page) ''-

、1T 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4&格公釐） A7 A7 經濟部中央標準局員工消費合作社印製 B7 五、發明説明（24) 表3 二氧化矽顆粒 添加數量 (w t · %) 抗腐蝕性（小時） 塗料性 膜硬度 處理性 耐磨蝕性 動態摩 擦係數 平板 Ericksen 本發明 5 912 792 100 2H 5 4 0.080 10 960 816 100 3H 5 5 0.070 15 960 840 100 3H 5 5 0.065 20 960 816 100 3H 5 5 0.072 25 936 792 100 3H 5 5 0.100 30 888 744 100 3H 5 5 0.120 對照實例 3 520 240 66 HB 3 3 0.100 35 240 72 27 4H 4 1 0.386 n· —^—1— mu n BUI mV -m^ nf— fm m· ims ml \ .. .. /(V 、言 (請先閲讀背面之注意事項再填寫本k ) 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐）-27 - A7 ___B7_ 五、發明説明（25) 實施例4 將一種具有羧基之聚烯烴共聚物樹脂，其含2 0重量 %之伸乙烯不飽和羧酸組份，以氫氧化鈉離子鍵共聚，另 外以交聯劑形成高聚合物分子，以製備分子間以離子團鍵 合之聚烯烴共聚物樹脂乳膠。 於該形成乳膠中加入佔固體部份1 0重量％，且顆粒 直徑爲4至4 0 0 nm之二氧化矽顆粒，5重量％軟化點 爲1 0 0°C，且顆粒直徑爲0 ·6 μιη之球形聚乙烯蠘顆 粒，及1 0重量％之三甲氧基丙院三（召-氮丙啶基丙酸 酯）（T A Z Μ )製備一種水性樹脂塗覆物。 將該樹脂塗料塗於進行鉻處理之電鍍鋅鋼板表面，於 90°C加熱乾燥，製得一具有1 g/rri樹脂膜塗層重之樹 脂塗層鋼板》 該製得之樹脂塗層鋼板之抗腐蝕性和塗料性如表4。 (請先閎讀#面之注意事項再填寫本頁)， 1T Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper is printed in accordance with Chinese National Standards (CNS) A4 & GMM A7 A7 Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economics Addition amount of silicon dioxide particles (wt ·%) Corrosion resistance (hours) Coating film hardness Hardness wear resistance Dynamic friction coefficient flat plate Ericksen The invention 5 912 792 100 2H 5 4 0.080 10 960 816 100 3H 5 5 0.070 15 960 840 100 3H 5 5 0.065 20 960 816 100 3H 5 5 0.072 25 936 792 100 3H 5 5 0.100 30 888 744 100 3H 5 5 0.120 Comparative Example 3 520 240 66 HB 3 3 0.100 35 240 72 27 4H 4 1 0.386 n · — ^ — 1— mu n BUI mV -m ^ nf— fm m · ims ml \ .. .. / (V, word (please read the notes on the back before filling in this k) This paper size is applicable to China Standard (CNS) A4 specification (210X297 mm) -27-A7 ___B7_ V. Description of the invention (25) Example 4 A polyolefin copolymer resin having a carboxyl group, which contains 20% by weight of ethylenically unsaturated carboxylic acid Components with sodium hydroxide ion bond Polymer, and a high polymer molecule is formed with a cross-linking agent to prepare a polyolefin copolymer resin latex intermolecularly bonded with an ionic group. To the formed latex, 10% by weight of the solid portion is added, and the particle diameter is 4 Silicon dioxide particles up to 400 nm, spherical polyethylene fluorene particles with a 5% softening point of 100 ° C and a particle diameter of 0.6 μm, and 10% by weight of trimethoxypropane (Zo-aziridinyl propionate) (TAZ M) A water-based resin coating was prepared. The resin coating was coated on the surface of a galvanized steel sheet subjected to chromium treatment, and dried by heating at 90 ° C to obtain a product having 1 g / rri resin coated steel plate with heavy resin coating "The corrosion resistance and coating properties of the resin coated steel plate produced are shown in Table 4. (Please read the precautions on the # side before filling out this page)

Bn.— mfl ^ an—— I— n^i 1^1-1 l^v Bn 一WJn nn 經濟部中央標隼局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐）_ 28 _ 五、發明説明（26 ) 表4 經濟部中央標隼局員工消費合作社印製 二氧化矽顆粒 之顆粒直徑 (/zm) 抗腐蝕性（小時） 塗料性 膜硬度 處理性 耐磨蝕性 動態摩 擦係數 平板 Ericksen 本發明 4-6 960 816 100 3H 5 5 0.070 10-20 960 816 100 3H 5 5 0.065 30-50 936 792 100 3H 5 5 0. 080 40-200 912 792 100 3H . 5 5 0.098 對照實例 1 or less 936 792 95 2H 4 4 0.080 200 or more 240 72 27 4H 2 2 0.146 JI'— — ^--'__ Γ'.裝-- (請先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明（27) 實施例5 將一種具有羧基之聚烯烴共聚物樹脂，其含2 0重量 %之伸乙烯不飽和羧酸組份，以氫氧化鈉離子鍵共聚，另 外以交聯劑形成高聚合物分子，以製備分子間以離子圑鍵 合之聚烯烴共聚物樹脂乳膠。 於該形成乳膠中加入佔固體v部份1 〇重量％，且顆粒 直徑爲10至20nm之二氧化矽顆粒，〇 . 3至25重 量％軟化點爲1 0 0°C，且顆粒^徑爲〇 . 6/zm之球形 聚乙烯蠟顆粒，及1 0重量％三甲氧基丙烷三（石一氮丙 啶基丙酸酯）（T A Z Μ )以製備一種水性樹脂塗覆物。 將該樹脂塗料塗於進行鉻處理之電鍍鋅鋼板表面，並 於9 0°C加熱乾燥，製得一具有1 g/nf樹脂膜塗層重之 樹脂塗層鋼板。 該製得之樹脂塗層鋼板之抗腐蝕性和塗料性如表5。 I-^--*---^---— Γ'裝------訂 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐）Bn.— mfl ^ an—— I— n ^ i 1 ^ 1-1 l ^ v Bn_WJn nn Printed by the staff consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297) (Mm) _ 28 _ V. Description of the invention (26) Table 4 Particle diameter (/ zm) of silica particles printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Corrosion resistance (hours) Coating film hardness Handling resistance Abrasive dynamic friction coefficient plate Ericksen The present invention 4-6 960 816 100 3H 5 5 0.070 10-20 960 816 100 3H 5 5 0.065 30-50 936 792 100 3H 5 5 0. 080 40-200 912 792 100 3H. 5 5 0.098 Comparative Example 1 or less 936 792 95 2H 4 4 0.080 200 or more 240 72 27 4H 2 2 0.146 JI'— — ^ --'__ Γ '. Install-(Please read the precautions on the back before filling (This page) The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) A7 B7 V. Description of the invention (27) Example 5 A polyolefin copolymer resin having a carboxyl group, which contains 20% by weight Ethylene unsaturated carboxylic acid component is copolymerized with sodium hydroxide ion bond, and crosslinked by Forming a high polymer molecule, a polyolefin molecule prepared between the ionic bonding of Pu copolymer resin emulsion. 10% by weight of the solid v part is added to the latex-forming silica particles having a particle diameter of 10 to 20nm, 0.3 to 25% by weight of the softening point is 100 ° C, and the particle diameter is 0.6 / zm spherical polyethylene wax particles, and 10% by weight of trimethoxypropane tris (stilbaziridinylpropionate) (TAZM) to prepare an aqueous resin coating. This resin coating was applied to the surface of an electro-galvanized steel sheet subjected to chromium treatment, and heated and dried at 90 ° C to obtain a resin-coated steel sheet having a resin film coating weight of 1 g / nf. The corrosion resistance and coating properties of the obtained resin-coated steel sheet are shown in Table 5. I-^-* --- ^ ----- Γ 'installed ------ Order (please read the precautions on the back before filling out this page) The paper standard printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Applicable to China National Standard (CNS) A4 specification (210X297 mm)

B 五、發明説明（28) 表5 經濟部中央標準局員工消費合作社印製 蠟顆粒添加數量 (w t · %) 動態摩 擦係數 處理性 耐磨蝕性 穿孔性* 塗料性 膜硬度 穿孔數 模磨損 本發明 0.5 0.085 2H 5 5 150 5 5 1 0.070 3H 5 5 >150 5 5 5 0.065 3H 5 5 >150 5 5 10 0. 065 3H 5 5 >150 5 5 15 0.065 3H 5 5 >150 5 5 20 0.065 4H 5 5 >150 5 4 對照實例 0.3 0.125 Η 2 2 80 2 4 25 0.065 4Η 5 5 >150 5 1 (註）*該孔數目係恢復高度到達5 0 /zm爲止之孔數目（1萬單位）。 至於模磨損係評估穿1 5 0 0 0 0 0?L後該模之抗磨蝕性' 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） 31 - (請先閎讀背面之注意事項再填寫本頁) 訂 A7 B7 五、發明説明（29) 實施例6 將一種具有羧基之聚烯烴共聚物，其含2 〇重量％之 伸乙基不飽和羧酸組份’以氫氧化鈉離子鍵共聚，另外以 交聯劑形成高聚合物分子，以製備分子間以離子團鍵合之 聚烯烴共聚物樹脂乳膠。 於該形成乳膠中加入佔固體部分1 0重量％，且顆粒 直徑爲1 0至2 0 nm之二氧化矽顆粒，1 〇重量％軟化 點爲10 0°C且顆粒直徑爲〇 . 1至3#m之球形聚乙烯 蠟顆粒，及1 0重量％之三甲氧基丙烷三（沒一氮丙啶基 丙酸酯）（TAZM)以製備一種水性樹脂塗覆物。. 將該樹脂塗料塗於進行鉻處理之電銨鋅鋼板表面，並 於9 0°C加熱乾燥，製得一具有1 g/iri樹脂膜塗層重之 樹脂塗層鋼板。 該製得之樹脂塗層鋼板之抗腐蝕性和塗料性如表6。 I- i— n3— I I I rn Λ n I {'/ί,Λ^ (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標隼局員工消費合作社印製 -32 - 本紙張尺度適用中國國家標隼（CNS ) A4規格（.210X297公釐） A7 A7 經濟部中央標準局員工消費合作社印製 B7 五、發明説明（3〇) 表6 蠟顆粒之顆粒 直徑 (^m) 動態摩 擦係數 膜硬度 處理性 耐磨蝕性 穿孔性* 塗料性 穿孔數 模磨損 本發明 0.1 0.085 3H 5 5 >150 5 5 0.3 0.065 3H 5 5 >150 5 5 0.5 0.065 3H 5 5 >150 5 5 1.0 0.065 3H 5 5 >150 5 5 1.5 0. 077 " 3H 5 5 >150 5 5 3.0 0.085 3H 5 5 >150 5 4 對照實例 <0.1 0.248 Η 1 2 65 2 4 3.5 0.125 2Η 2 3 120 3 1 (註)木該穿孔數係恢復高度到達5 Ο μm爲止之穿孔數（1萬單位)。 至於該模磨損係評估穿1 5 0 0 0 0 0 ?L後該模之模耐磨蝕性。 m.-!......一 mu - - - 1 In I !i Λ/( » --- - 111 - 〜aJ (請先閎讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -33 - A7 B7 五、發明説明（31) 實施例7 將一種具有狻基之聚烯烴共聚物樹脂，其含2 〇重量 %之伸乙烯不飽和羧酸組份，以氫氧化鈉離子鍵共聚，另 外以交聯劑形成高聚合物分子，以製備分子間以離子團鍵 合之聚烯烴共聚物樹脂乳膠。 於該形成乳膠中加入佔固體部份1 〇重量％，且顆粒 直徑爲1 0至2 0 nm之二氧化矽顆粒，5重量％軟化點 爲7 0至15 0/C且顆粒直徑爲0 . 6#m之球形聚乙烯 蠟顆粒’及1 〇重量％之三甲氧基丙烷三（/3—氮丙陡基 丙酸酯）（TAZM)以製備一種水性樹脂塗覆物。. 將該樹脂塗料塗於進行鉻處理之電鍍鋅鋼板表面，並 於9 0°C加熱乾燥，製得一具有i g/nf樹脂膜塗層重之 > 樹脂塗層鋼板。 該製得之樹脂塗層鋼板之抗腐蝕性和塗料性如表7。 (誇先閲讀背面之注意事項再填寫本頁)B V. Description of the invention (28) Table 5 Addition of wax particles (wt.%) Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, dynamic friction coefficient, processing resistance, abrasion resistance, and perforation properties Invention 0.5 0.085 2H 5 5 150 5 5 1 0.070 3H 5 5 > 150 5 5 5 0.065 3H 5 5 > 150 5 5 10 0. 065 3H 5 5 > 150 5 5 15 0.065 3H 5 5 > 150 5 5 20 0.065 4H 5 5 > 150 5 4 Comparative Example 0.3 0.125 Η 2 2 80 2 4 25 0.065 4Η 5 5 > 150 5 1 (Note) * The number of holes is the number of holes until the recovery height reaches 50 / zm (10,000 units). As for the mold wear, the wear resistance of the mold is evaluated after wearing 15 0 0 0 0 0? L. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 31-(Please read the note on the back first Please fill in this page again) Order A7 B7 V. Description of the invention (29) Example 6 A polyolefin copolymer having a carboxyl group, which contains 20% by weight of an ethylenically unsaturated carboxylic acid component 'as sodium hydroxide Ion-bond copolymerization, and in addition, high-polymer molecules are formed with a cross-linking agent to prepare polyolefin copolymer resin latexes in which molecules are bonded with ionic groups. 1 to 3 are added to the latex-forming latex to account for 10% by weight of the solid portion and particles having a particle diameter of 10 to 20 nm, a 10% by weight softening point of 100 ° C and a particle diameter of 0.1 to 3 #m of spherical polyethylene wax particles, and 10% by weight of trimethoxypropane tris (triazine propionate) (TAZM) to prepare an aqueous resin coating. The resin coating was coated on the surface of an electro-ammonium-zinc steel plate subjected to chromium treatment, and heated and dried at 90 ° C to obtain a resin-coated steel plate having a coating weight of 1 g / iri resin film. The corrosion resistance and coating properties of the obtained resin-coated steel sheet are shown in Table 6. I- i— n3— III rn Λ n I {'/ ί, Λ ^ (Please read the notes on the back before filling out this page) Order printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -32-This paper size applies China National Standards (CNS) A4 specification (.210X297 mm) A7 A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs B7 V. Description of the invention (30) Table 6 Wax particle diameter (^ m) Dynamic friction coefficient Film hardness, processing resistance, abrasion resistance, perforation property *, coating perforation, digital mold wear, the present invention 0.1 0.085 3H 5 5 > 150 5 5 0.3 0.065 3H 5 5 > 150 5 5 0.5 0.065 3H 5 5 > 150 5 5 1.0 0.065 3H 5 5 > 150 5 5 1.5 0. 077 " 3H 5 5 > 150 5 5 3.0 0.085 3H 5 5 > 150 5 4 Comparative example < 0.1 0.248 Η 1 2 65 2 4 3.5 0.125 2Η 2 3 120 3 1 (Note) The number of perforations is the number of perforations (10,000 units) until the height reaches 50 μm. As for the wear of the mold, the mold abrasion resistance of the mold after the penetration of 15 00 0 0? L was evaluated. m .-! ...... 一 mu---1 In I! i Λ / (»----111-~ aJ (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 specification (210X297 mm) -33-A7 B7 V. Description of the invention (31) Example 7 A polyolefin copolymer resin having a fluorene group was used, which contained 20% by weight Saturated carboxylic acid components are copolymerized with sodium hydroxide ion bonds, and high-molecule molecules are formed with cross-linking agents to prepare polyolefin copolymer resin latexes in which molecules are bonded with ionic groups. To the latex is added to account for solids. Part of a spherical polyethylene wax with 10% by weight and a particle diameter of 10 to 20 nm, a 5% by weight softening point of 70 to 15 0 / C and a particle diameter of 0.6 # m Granules' and 10% by weight of trimethoxypropane tris (/ 3-aziridinopropionate) (TAZM) to prepare an aqueous resin coating. The resin coating was applied to chromium electroplated zinc plating The surface of the steel plate was heated and dried at 90 ° C to obtain a resin-coated steel plate having an ig / nf resin film coating weight. Paint and corrosion resistance of the coated steel lipid are shown in Table 7. (Note boast read and then fill the back of the page)

、tT 經濟、坪中央標隼局貞工消費合作社印製 -34 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） BSiiQS at B7 五、發明説明（32 ) 表 7 蠟顆粒之軟化 溫度 (°〇 動態摩 擦係數 處理性 耐磨蝕性 穿孔性* 塗料性 膜硬度 穿孔數 模磨損 本發明 80 0.068 3H 5 5 >150 5 5 100 0.064 3H 5 5 >150 5 5 120 0.067 3H 5 5 >150 5 5 140 0. 072 3H 5 5 >150 5 5 對照實例 70 0.070 2H 2 3 32 1 4 150 0.262 2H 1 1 43 2 3 (請先閎讀背面之注意事頃再填寫本頁) 訂 經濟部中央標隼局員工消費合作社印製 (註广該穿孔數係恢復高度到達5 0 /zm爲止之穿孔數（1萬單位）。 至於該模磨損係評估該模穿1 5 0 0 0 0 0 ?L後之模耐磨触性。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ % — A7 B7 經濟部中央標準局員工消費合作社印製 S8ii08 五、發明説明（33 ) 表8 樹脂膜之塗層重 (g /m) 動態摩 擦係數 處理性 耐磨蝕性 抗腐触性（小時） 塗料性 土特性 膜硬度 平板 Ericksen 本發明 0.2 0.074 2H 4 4 888 744 5 5 0.5 0. 067 3H 5 5 936 792 5 5 1.0 0.064 3H 5 5 960 816 5 5 1.5 0.065 3H 5 5 1032 912 5 5 2.0 0. 068 3H 5 5 1260 936 5 4 2.5 0.072 3H 4 5 1380 936 5 3 對照實例 <0.2 0.364 B 1 1 480 360 4 5 3.0 0.092 2H 1 3 780 480 1 1 (請先聞讀背面之注意事項再填寫本頁) ί 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 36 - S8ii08 A7 B7 五、發明説明（34) 實施例8 將一種具有竣基之聚烯烴共聚物樹脂，其含2 0重量 %之伸乙烯不飽和羧酸組份，以氫氧化鈉離子鍵共聚，另 外以交聯劑形成高聚合物分子，以製備分子間以離子團鍵 合之聚烯烴共聚物樹脂乳膠。 於該形成乳廖中加入佔固體部份1 0.重量％，且顆粒 直徑爲1 0至2 0 nm之二氧化矽顆粒，5重量％軟化點 爲1 0 0°C且顆粒直徑爲0 . 6 μπι之球形聚乙烯蠟顆粒 ，及1 0重量之三甲氧基Η院三（万-氮丙B定基丙酸酯 )(T A Z Μ )以製備一種水性樹脂塗覆物。 將該樹脂塗料塗於進行鉻處理之電鍍鋅鋼板表面，並 於9 0 °C加熱乾燥，製得一具有0 . 2至2 . 5 g / πί樹 脂膜塗層重之樹脂塗層鋼板。 該製得之樹脂塗層鋼板之抗腐蝕性和塗料性如表8。 (請先閱讀背面之注意事項再填寫本頁) 裝- 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）_ 37Printed by Zhengong Consumer Cooperative, TT Economy, Ping Central Bureau of Standards-34-This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210 × 297 mm) BSiiQS at B7 V. Description of the invention (32) Table 7 Softening temperature (°° Dynamic friction coefficient, processing resistance, abrasion resistance, perforation resistance *, paintability, film hardness, perforation, digital mold wear, etc.) 80 0.068 3H 5 5 > 150 5 5 100 0.064 3H 5 5 > 150 5 5 120 0.067 3H 5 5 > 150 5 5 140 0. 072 3H 5 5 > 150 5 5 Comparative example 70 0.070 2H 2 3 32 1 4 150 0.262 2H 1 1 43 2 3 (Please read the notes on the back before filling out this Page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (note that the number of perforations is the number of perforations (10,000 units) up to a recovery height of 50 / zm. As for the wear of the mold, it is evaluated that the mold penetrates 1 5 0 The wear resistance of the mold after 0 0 0 0 L. This paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) _% — A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs S8ii08 5. Invention Explanation (33) Table 8 Coating weight of resin film (g / m) Dynamic Coefficient of friction Handling abrasion resistance Corrosion resistance (hours) Paintable soil characteristic Film hardness flat plate Ericksen The present invention 0.2 0.074 2H 4 4 888 744 5 5 0.5 0. 067 3H 5 5 936 792 5 5 1.0 0.064 3H 5 5 960 816 5 5 1.5 0.065 3H 5 5 1032 912 5 5 2.0 0. 068 3H 5 5 1260 936 5 4 2.5 0.072 3H 4 5 1380 936 5 3 Comparative example < 0.2 0.364 B 1 1 480 360 4 5 3.0 0.092 2H 1 3 780 480 1 1 (Please read the precautions on the back before filling out this page) ί The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 36-S8ii08 A7 B7 V. Description of the invention (34) Example 8 A polyolefin copolymer resin having an end group, which contains 20% by weight of an ethylene-unsaturated carboxylic acid component, is copolymerized with sodium hydroxide ion bonds, and a high polymer molecule is formed with a crosslinking agent. In order to prepare a polyolefin copolymer resin latex intermolecularly bonded with an ionic group. To the formed milk cell was added 10.2% by weight of the solid portion of the silicon dioxide particles with a particle diameter of 10 to 20 nm, a 5% by weight softening point of 100 ° C and a particle diameter of 0. 6 μm of spherical polyethylene wax particles and 10 weight of trimethoxypyridine tris (10,000-azapropane-B-propyl propionate) (TAZ M) to prepare an aqueous resin coating. The resin coating was coated on the surface of an electro-galvanized steel sheet subjected to chromium treatment, and heated and dried at 90 ° C to obtain a resin-coated steel sheet having a resin film coating weight of 0.2 to 2.5 g / π. The corrosion resistance and coating properties of the obtained resin-coated steel sheet are shown in Table 8. (Please read the precautions on the back before filling out this page.) Binding-Order Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economics This paper size applies to China National Standard (CNS) Α4 size (210X297 mm) _ 37

Claims (1)

4.^ss. θ· 1¾ A8 B8 C8 D8 MMJ 六、申請專利範圍 ^81108 第84 1 1 4 1 38號專利申請案 中文申請專利範圍修正本 民國8 8年 9月修正 經濟部智葚財產局員工消費合作杜印製 一金屬板 2 · 5 g 徑介於1 量％顆粒 佔固體部 其主要包 ，該聚烯 不飽和羧 烯烴一乙 以交聯劑 2 . 該烯烴至 一種樹 表面， / m2範 至2 0 直徑介 分1至 括分子 烴共聚 酸組份 烯不飽 交聯成 如申請 少爲乙 如申請 該球形聚乙烯蠟 4 · 一種製 於金屬板表 3 0重量％顆粒 ，0 · 5 至 2 0 脂塗層 其塗層 圍內， 0 n m 於0 · 2 0重 間以離 物樹脂 ，其中 和羧酸 高聚合 專利範 烯或苯 專利範 顆粒之 備樹脂 面塗覆 直徑介 重量％ 金屬板 重以乾 該樹脂 之二氧 1至3 量％具 子團締 乳膠含 一種含 ，其特徵係 重爲基準， 膜含5至3 化矽顆粒， A m之球形 有氮丙聢基 合之聚烯烴 有1至4 0 有.（甲基） 樹脂係離子 該樹脂 係於0 0重量 0 . 5 聚乙烯 之有機 共聚物 重量％ 丙燦敗 鍵共聚 膜形成於 • 2至 %顆粒直 至2 0重 蠟顆粒及 化合物， 樹脂乳膠 之伸乙基 n組份之 ，且另外 共聚物 物分子。 圍第1項之樹脂塗層金屬板，其中 乙燦之一。胃 圍第1 軟化點 塗層鋼 一種水 於1至 顆粒直 項之樹脂塗 在8 0至1 板之方法， 性樹脂塗覆 2 0 Ο n m 徑介於Ο · 層金屬板，其中 4 0 °C範圍內。 其包括： 物，其包含5至 之二氧化矽顆粒 1至3 μ m之球 (請先閱讀背面之注意事項再填寫本頁) 孝 、1.τ- i氣. 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -1 一 4.^ss. θ· 1¾ A8 B8 C8 D8 MMJ 六、申請專利範圍 ^81108 第84 1 1 4 1 38號專利申請案 中文申請專利範圍修正本 民國8 8年 9月修正 經濟部智葚財產局員工消費合作杜印製 一金屬板 2 · 5 g 徑介於1 量％顆粒 佔固體部 其主要包 ，該聚烯 不飽和羧 烯烴一乙 以交聯劑 2 . 該烯烴至 一種樹 表面， / m2範 至2 0 直徑介 分1至 括分子 烴共聚 酸組份 烯不飽 交聯成 如申請 少爲乙 如申請 該球形聚乙烯蠟 4 · 一種製 於金屬板表 3 0重量％顆粒 ，0 · 5 至 2 0 脂塗層 其塗層 圍內， 0 n m 於0 · 2 0重 間以離 物樹脂 ，其中 和羧酸 高聚合 專利範 烯或苯 專利範 顆粒之 備樹脂 面塗覆 直徑介 重量％ 金屬板 重以乾 該樹脂 之二氧 1至3 量％具 子團締 乳膠含 一種含 ，其特徵係 重爲基準， 膜含5至3 化矽顆粒， A m之球形 有氮丙聢基 合之聚烯烴 有1至4 0 有.（甲基） 樹脂係離子 該樹脂 係於0 0重量 0 . 5 聚乙烯 之有機 共聚物 重量％ 丙燦敗 鍵共聚 膜形成於 • 2至 %顆粒直 至2 0重 蠟顆粒及 化合物， 樹脂乳膠 之伸乙基 n組份之 ，且另外 共聚物 物分子。 圍第1項之樹脂塗層金屬板，其中 乙燦之一。胃 圍第1 軟化點 塗層鋼 一種水 於1至 顆粒直 項之樹脂塗 在8 0至1 板之方法， 性樹脂塗覆 2 0 Ο n m 徑介於Ο · 層金屬板，其中 4 0 °C範圍內。 其包括： 物，其包含5至 之二氧化矽顆粒 1至3 μ m之球 (請先閱讀背面之注意事項再填寫本頁) 孝 、1.τ- i氣. 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -1 一 Α8 Β8 C8 D8 六、申請專利範圍 形聚乙烯蠟顆粒和佔固體部分1至2 0重量％具有氮丙啶 基之有機化合物，其主要包括一種分子間藉離子團締合之 聚.烯烴共聚物樹脂乳膠」該聚烯烴共聚物樹腊乳..麗含有1 至4 0重量％之伸乙基不飽和羧酸組份，其中一種含有（ 甲基）丙烯酸酯組份之烯烴-乙烯不飽和羧酸共聚物樹脂 係離子鍵共聚，且另外以交聯劑交聯成高聚合物分子；， 加熱該金廍板， 乾燥該塗層，且 於該金屬板表面形成塗層重爲0 . 2至2 „ . J g / πί 之樹脂膜。 5 ·如申請專利範圍第4項之方法，其中該烯烴至少 是乙烯或苯乙烯之一。 6 .如申請專利範圍第4項之方法，其中該金屬板以 低於球形聚乙烯蠟顆粒之軟化點溫度加熱，且該球形聚乙 烯蠟顆粒以球形保留於該樹脂膜中。 (清先閱讀背面之注意事項再填寫本頁) --裝--------旬！ 經濟部智慧財產局員工消費合作社印製 ' n n n n n I n I n - 本紙張尺度適用中國國家標準（CNS)A4規格（210x 297公釐）-2 -4. ^ ss. Θ · 1¾ A8 B8 C8 D8 MMJ 6. Scope of Patent Application ^ 81108 Patent Application No. 84 1 1 4 1 38 Chinese Application for Patent Scope Amendment September 1988 Amendment to the Intellectual Property Office of the Ministry of Economic Affairs Consumption cooperation with employees Du printed a metal plate 2.5 g with a diameter between 1% by weight and the solid portion of the main package, the polyunsaturated carboxylic olefin with ethyl crosslinker 2. The olefin to a tree surface, / m2 range to 2 0 diameter 1 to molecular hydrocarbon copolymeric acid component olefinic unsaturated cross-linking, if the application is less than B, such as the application of the spherical polyethylene wax 4 · a kind made on a metal sheet 3 0% by weight particles, 0 5 to 20 lipid coatings, with a coating resin diameter of 0 nm and weights between 0 and 20, and a resin coating that neutralizes the prepared resin surface of carboxylic acid polymerized patented vinyl or benzene patented particles. The weight% of the metal plate is based on 1 to 3% of the dry oxygen of the resin. The content of the latex contains one kind. The characteristic weight is based on the film. The film contains 5 to 3 silicon particles. Basic polyolefins are 1 to 40. Yes. (Methyl) resin ions The resin is based on 0% by weight, 0.5% by weight of an organic copolymer of polyethylene, and a copolymer of acrylic copolymer formed from 2 to% particles up to 20 heavy wax particles and compounds, and the ethylenic component of resin latex. And also copolymer molecules. The resin-coated metal sheet surrounding item 1, one of which is Yi Chan. Stomach circumference No. 1 softening point coated steel A method of applying water to 1 to particle straight resin on 80 to 1 plate, resin coating 20 0 〇 nm diameter between 0 · layer metal plate, of which 40 ° C range. It includes: objects, which contain 5 to 2 spheres of silicon dioxide particles of 1 to 3 μm (please read the precautions on the back before filling out this page) Xiao, 1.τ-i gas. This paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) -1 4. ^ ss. Θ · 1¾ A8 B8 C8 D8 MMJ VI. Patent application scope ^ 81108 No. 84 1 1 4 1 38 Chinese Patent Application Amendment September 1988 Amendment to the Consumer Consumption Cooperation of the Intellectual Property Office of the Ministry of Economic Affairs of the People ’s Republic of China Du printed a metal plate 2 · 5 g with a diameter between 1% and 1% by weight of the solid package. Crosslinking agent 2. The olefin to a tree surface, / m2 range to 20 diameter diameter 1 to molecular hydrocarbon copolymeric acid component olefin unsaturated cross-linking, if the application is less than B, such as the spherical polyethylene wax 4 · A 30% by weight particle made on a sheet of metal sheet, with a thickness of 0.5 to 20 within the coating envelope, and a resin of 0 nm at a weight of 0 to 20, which neutralizes the carboxylic acid highly polymerized patent vanillin Or benzene patented particles prepared resin surface coating diameter weight% gold The weight of the board is 1 to 3% by weight based on the dry oxygen of the resin. The latex contains a kind of rubber. The characteristic weight is based on the film. The film contains 5 to 3 silicon particles. The spherical shape of A m has aziridinyl group. Polyolefins range from 1 to 40. (Methyl) resin ions. The resins are based on 0. 0. 0. 0.5% by weight of organic copolymers of polyethylene. The acrylic copolymer film is formed from 2 to% particles up to 2%. 0 Heavy wax particles and compounds, the ethylene n component of resin latex, and other copolymer molecules. The resin-coated metal sheet surrounding item 1, one of which is Yi Chan. Stomach circumference No. 1 softening point coated steel A method of applying water to 1 to particle straight resin on 80 to 1 plate, resin coating 20 0 〇 nm diameter between 0 · layer metal plate, of which 40 ° C range. It includes: objects, which contain 5 to 2 spheres of silicon dioxide particles of 1 to 3 μm (please read the precautions on the back before filling out this page) Xiao, 1.τ-i gas. This paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) -1 A A8 B8 C8 D8 6. Patent application scope Shaped polyethylene wax particles and organic compounds with aziridinyl group occupying 1 to 20% by weight of the solid portion, which mainly include a Poly.olefin copolymer resin latex associated with ionic groups between molecules. The polyolefin copolymer wax emulsion .. Lai contains 1 to 40% by weight of ethylenically unsaturated carboxylic acid component, one of which contains (A Base) olefin-ethylene unsaturated carboxylic acid copolymer resin-based ionomer copolymerization of an acrylic ester component, and further cross-linking with a cross-linking agent to form a high polymer molecule; heating the gold plate, drying the coating, and A resin film with a coating weight of 0.2 to 2 „. J g / πί is formed on the surface of the metal plate. 5 · The method according to item 4 of the patent application, wherein the olefin is at least one of ethylene or styrene. 6. For the method of applying for the scope of patent No. 4, in which The metal plate is heated at a temperature lower than the softening point of the spherical polyethylene wax particles, and the spherical polyethylene wax particles are retained in the resin film in a spherical shape. (Please read the precautions on the back before filling this page) --pack- ------- Xun! Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs' nnnnn I n I n-This paper size applies to China National Standard (CNS) A4 (210x 297 mm)-2-
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