434 3 2 7 B7 濟 部 中 標 準 局 員 工 消 # 合 作 装 五、發明説明( 〔本發明所屬之技術領域〕 本發明爲關於罐蓋用樹脂覆蓋的鋁合金片,特別關於 一種樹脂覆蓋的鋁合金片,其成形後具有優良的樹脂膜黏 著度及抗蝕性。 〔先前技術〕 近幾年,罐頭原料因考慮環保前題,由傳統之金屬片 製成罐頭,罐頭再做被覆,轉移到預先在金屬片上覆蓋樹 脂’再製成罐頭。此預先覆蓋一層樹脂之金屬片,已特別 廣爲應用於罐體原料,在此之後則將詳述其在罐蓋原料上 之應用。 例如,在日本專利特開平-2-86433中所掲示,包含一 改質聚烯烴樹脂黏性層之罐頭原料用鋁,以及一層聚烯烴 樹脂*其透過黏著層熱層覆在鉻酸鹽處理鋁合金,使得在 試圖打開罐蓋時,幾乎不會造成搪瓷羽狀物(enamel-feathering)。 再如曰 本專利特開平 _3·258534 所掲示之鋁合 金複合材料,其經由烯烴類粘著劑,在磷酸鹽一鉻酸鹽處 理的鋁合金片表面上,層覆烯烴類樹脂膜,可避免鋁合金 片在刻劃部分厚度降低。 進—步在日本專利特開平-6-312234中所揭示,一包括 熱塑型樹脂覆蓋之鋼片的罐蓋原料,其中被覆的鋼片,或 經化學處理法如鉻酸鹽處理之表面處理的鋼片,加以刻劃 ,之後以熱塑型樹脂覆蓋,以增進刻劃部分的抗餽效果。 更進一步在日本專利特開平-8-224628中所揭示,一熱塑型 本紙浪尺度適用中國國家標卒(CNS ) Λ4規格(21〇Χ297公港) {請先閱讀背面*<:注意事唷再填寫本買) 訂 經濟部中央標準局員工消費合作社印製 4 343 2 7 五、發明説明(z ) 樹脂層覆的罐蓋,其包括隨後以鉻酸鹽處理一鍍鎳之鋼片 ,在該鋼片上鍍鎳後的一鍍錫/鎳鋼片,錫乃鍍於該鍍鎳 鋼片上,或金屬鉻及氫氧化鉻二層膜形成其上之電解鉻酸 鹽化鋼片,或是其他,並層覆一結晶飽和的聚酯樹脂膜。 在曰本專利特開平·2-86433中所揭不之錦罐原料*或 在曰本專利特開平4-258534中所揭示之用於罐蓋的鋁合金 複合材料,以化學處理法,如磷酸鹽一鉻酸鹽處理後的鋁 合金片’乃層覆以一樹脂膜,例如烯烴類樹脂膜_。但無論 如何’它們在樹脂膜與基底金屬片間的黏著度仍不夠,尤 其在成形後,其黏著度比上述利用樹脂膜層覆在電解鉻酸 鹽化之鋼片還差。在嚴格的加工情況下,例如鉚接罐蓋用 銘罐原料或鋁合金複合材料,樹脂便從其上剝落。 另一方面,日本專利特開平-6-312234揭示之熱塑型樹 脂覆蓋的鋼片,或日本專利特開平_8_224628揭示之熱塑型 樹脂層覆的褰子,乃包括鋼片做爲基片的罐蓋原料。與鋁 合金:片.爲基片者比較,雖然前者在成形後,樹脂膜之黏著 度優良’但卻不易打開,而且應用性受到限制。因此它們 並未廣泛地被使用。 〔本發明所荽解決的問題〕 #發明的目的,即提供一罐蓋用樹脂覆蓋之鋁合金片 ,甚成形後氧有芙庚π坑触性,丨田丨ff.罐芸 I -J α 〇/ u r-1- · 1 ^ J-J «ρκ JOL· 用樹脂覆蓋之鋁合金片製成的罐蓋。 ^^^^1 ^11^1 I - - - ml n t' (請先閱讀背面"注意事項再填商本頁)434 3 2 7 B7 Staff of the Bureau of Standards of the Ministry of Economic Affairs # Cooperative equipment V. Description of the invention ([Technical field to which the present invention belongs] The present invention relates to a resin-covered aluminum alloy sheet for a tank lid, and particularly to a resin-covered aluminum alloy Sheet, which has excellent resin film adhesion and corrosion resistance after forming. [Previous technology] In recent years, canned materials are made of traditional metal sheets in consideration of environmental protection issues. The metal sheet is covered with resin 'to make cans. This metal sheet previously covered with a layer of resin has been particularly widely used for can body materials, after which its application to can lid materials will be detailed. For example, in Japan Patent Publication No. Hei-2-86433 shows that aluminum for canned raw materials including an adhesive layer of modified polyolefin resin, and a layer of polyolefin resin * are coated with a chromate-treated aluminum alloy through a hot layer of the adhesive layer, so that When trying to open the can lid, it will hardly cause enamel-feathering. As another example of the aluminum alloy composite material shown in Japanese Patent Laid-Open No. Hei-3258258, An olefin-based adhesive is used to coat an olefin-based resin film on the surface of the phosphate-chromate-treated aluminum alloy sheet, which can prevent the thickness of the aluminum alloy sheet from being reduced in the scribed portion. As disclosed in 6-312234, a can lid material including a steel sheet covered with a thermoplastic resin, the coated steel sheet, or a surface-treated steel sheet subjected to a chemical treatment such as chromate treatment, is scribed, and thereafter Covered with a thermoplastic resin to enhance the anti-feedback effect of the engraved part. Further disclosed in Japanese Patent Laid-Open No. Hei-8-224628, a thermoplastic paper scale applies the Chinese National Standard (CNS) Λ4 specification ( 21〇Χ297 公 港) {Please read the back * <: Note before you fill in this purchase) Order printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 343 2 7 V. Description of the invention (z) Resin-coated cans Cover, which comprises subsequently treating a nickel-plated steel sheet with chromate, a tin / nickel steel sheet after nickel plating on the steel sheet, tin being plated on the nickel-plated steel sheet, or metallic chromium and chromium hydroxide A two-layer film forming an electrolytic chromate steel sheet thereon, or It is other, and is covered with a crystalline saturated polyester resin film. The raw materials of brocade cans not disclosed in Japanese Patent Laid-Open No. 2-86433 * or aluminum alloy composite materials for can lids disclosed in Japanese Patent Laid-open No. 4-258534, which are chemically treated, such as phosphoric acid The salt-chromate-treated aluminum alloy sheet is coated with a resin film, such as an olefin resin film. However, their adhesion between the resin film and the base metal sheet is still insufficient, especially after forming, the adhesion is worse than that of the above-mentioned steel sheet coated with electrolytic chromate using the resin film layer. Under strict processing conditions, such as the raw materials of cans for riveting can lids or aluminum alloy composite materials, the resin is peeled off. On the other hand, the steel sheet covered by a thermoplastic resin disclosed in Japanese Patent Laid-Open No. Hei-6-312234, or the thermoplastic resin layered dumpling disclosed by Japanese Patent Laid-open No. Hei_8_224628, includes a steel sheet as a substrate. Can lid material. Compared with the aluminum alloy: sheet. For the substrate, although the former has excellent adhesion after resin forming, it is not easy to open, and its applicability is limited. Therefore they are not widely used. [Problems Solved by the Present Invention] #The purpose of the invention is to provide an aluminum alloy sheet covered with a resin with a can lid. After forming, the aluminum oxide sheet has a pit-shaped contact. 丨 田 丨 ff. Can Yun I -J α 〇 / u r-1- · 1 ^ JJ «ρκ JOL · Can lid made of aluminum alloy sheet covered with resin. ^^^^ 1 ^ 11 ^ 1 I---ml n t '(Please read the back " note before filling in the supplier page)
、tT 本紙張尺度適用中國國^^ ( CNS ) 格(21〇><297公浼) ~~ 1 經濟部中央標準局員工消費合作社印製 4 34 3 2 7 五、發明説明(5 ) 〔解決問題的方法〕 本發明是罐蓋用樹脂覆蓋的鋁合金片,其特徵在此罐 蓋用樹脂覆蓋的鋁合金片包括一鋁合金片,該鋁合金片至 少在其對應罐蓋的內面上,有一層利用矽烷偶合之矽烷處 理膜,而此矽烷處理膜被樹脂覆蓋;本發明或是罐蓋用樹 脂覆蓋的鋁合金片,其特徵在此罐蓋用樹脂覆蓋的鋁合金 片包括一鋁合金片,該鋁合金片至少在其對應罐蓋的內面 上,有一層表面處理過的膜,而在表面處理過的膜上有一 層利用矽烷偶合之矽烷處理膜,此矽烷處理膜被樹脂覆蓋 本發明特徵在於上述之表面處理膜,是一層磷酸鹽一 鉻酸鹽膜,或鉻處理膜或者陽極氧化膜。 再者,本發明也與以罐蓋用樹脂覆蓋的鋁合金片所製 造的罐蓋有關,而此罐蓋用樹脂覆蓋的鋁合金片,爲後述 申請專利範圍中任何之罐蓋用樹脂覆蓋的鋁合金片。 〔本發明之進行方式〕 本發明中,利用矽烷偶合之矽烷處理,於對應罐蓋內 層之鋁合金片的一面上進行。或者利用磷酸鹽一鉻酸鹽處 理、銷處理或陽極氧化處理,於對應罐蓋內層之鋁合金片 的一面上進行。進行任一種處理之後,再對此鋁合金片, 以上述之矽烷處理法處理。最後再以熱塑型樹脂覆蓋在此 矽烷處理表面上’而製成罐蓋用樹脂覆蓋的鋁合金片。也 希望於對應罐蓋外層之鋁合金片的一面上,形成上述之表 面處理膜’然後再以上述之熱塑型樹脂覆蓋表面處理膜。 5 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210X297公浼) (請先閱讀背面‘之注意事唷再填寫本頁) ,ιτ 經濟部中央標率局負工消費合作钍印製 4 34 3 2 7 五、發明説明(4·) 再來有關本發明之罐蓋製造,是利用此罐蓋用樹脂覆蓋之 鋁合金片,以打印方式進行。 〔例子〕 在此將詳細解釋本發明。首先,任何可用於罐蓋製造 之鋁合金片,皆可適用於本發明,這也是本發明的主要目 的之一,因此本發明並無特定之限制。而由製造成本及成 形性上來看,5000系列而厚0.20至0.35mm可廣泛地用於 製造罐蓋之鋁合金片較佳β在本發明中,由於本發明之前 提爲熱塑型樹脂覆蓋在鋁合金片上,所以鋁合金片之選擇 ,必須考慮其成形性、表面處理時如化學處理之適應性、 以及成形後覆蓋在鋁合金片上膜之黏著度。 其次,在此說明本發明中,一種鋁合金表面處理方法 ◊首先,對此鋁合金片進行由去油、鹼處理及酸洗等步驟 組合成的前處理步驟。在去油脂步驟,是以市售之去油劑 對黏著於鋁合金片上的油脂,進行除油。此去油溶液之溫 度最好在30°C到90°C,而以40eC到80°C較佳。此種去油 處理方法,乃將鋁合金片浸入去油溶液中,或將去油溶液 噴灑於鋁合金片上。其充分之去油處理時間爲1到30秒, 而以3到15秒較佳。 隨後,將此鋁合金片以淸水沖洗,再進行鹼處理。在 此鹼處理,水溶液包含一種或二者或多種如鹼金屬或氨之 氫氧化物,碳酸鹽,草酸鹽,磷酸鹽,矽酸鹽及硼酸鹽等 化合物,可用之。在此鹼處理’將可除去形成在鋁合金片 6 本度適用中國國家標準(CNS ) Λ4规格(公趙) -------— ------ΐτ------乘J· r - * (請先閲讀背&之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 34 3 2 7 五、發明説明($ ) 上之氧化膜。在一些個案中,鋁合金片會被鹼性水溶液所 蝕刻。因此鹼液之濃度最好介於1到20%之間,而以2到 10%較佳。鹼液之溫度最好介於30到80°C之間,以40到 60°C較佳β此種鹼處理方法,鋁合金片是浸於鹼液中,或 將鹼液噴灑於鋁合金片上。其充分之鹼處理時間爲1到20 秒,以3到10秒較佳。 在此之後,此鋁合金片以水淸洗,再進行酸洗。此酸 洗步驟,可使用主要包含一種或二種以上之硫酸,硝酸, 氫氯酸及磷酸等無機酸之水溶液。此酸洗步驟乃是爲去除 銘合金片經驗處理時,在其表面生成之污斑。在一些個案 中,此酸洗將於鋁合金表面,同時生成細孔。所使用之酸 性水溶液,其濃度最好介於〖到10%之間’而以1到5% 間較佳。此酸洗水溶液的溫度,最好由室溫到60°c之間’ 以室溫到40°C間較佳。此酸洗處理方式,通常是將鋁合金 片浸於酸性水溶液內,或將此酸性水溶液,噴灑在鋁合金 片上。充分的酸洗時間爲1到1〇秒,以1到5秒間較佳。 前處理步驟,經由上述方法郎可完成。 經過上述前處理後,即可對鋁合金片進行主要處理。 在本發明中,主要處理是利用矽烷偶合之矽烷處理方法爲 之,如以下任一者:對磷酸鹽一鉻酸鹽處理後之鋁合金片 進行矽烷處理、對銷處理後之鋁合金片進行矽烷處堙、對 陽極氧化處理後之鋁合金片進行矽烷處理。首先將解釋矽 烷處理。在本發明之矽烷處理中’市售之矽烷偶合劑以溶 劑稀釋,而此矽烷偶合劑稀釋溶液’將用於鋁合金片上。 7 本紙張尺度適用中國國家標準(CNS ) Λ4规格(2丨OX297公浼) (請先閱讀背面之注意事嗔再填寫本頁), TT This paper size is applicable to the Chinese national standard ^^ (CNS) (21〇 > < 297 gong) ~~ 1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 34 3 2 7 V. Description of the invention (5) [Method for solving the problem] The present invention is a resin-covered aluminum alloy sheet for a can lid, which is characterized in that the resin-covered aluminum alloy sheet for the can lid includes an aluminum alloy sheet, and the aluminum alloy sheet is at least in a corresponding can lid. On the surface, there is a layer of a silane-treated film using a silane coupling, and the silane-treated film is covered with a resin. The present invention or a resin-covered aluminum alloy sheet with a can lid is characterized in that the resin-covered aluminum alloy sheet with the can lid includes An aluminum alloy sheet, the aluminum alloy sheet has a surface-treated film at least on the inner surface corresponding to the can lid, and the surface-treated film has a silane-coated silane-treated film, and the silane-treated film Covered with resin The present invention is characterized in that the above-mentioned surface treatment film is a phosphate monochromate film, or a chromium treatment film or an anodized film. Furthermore, the present invention also relates to a can lid made of an aluminum alloy sheet covered with a resin cover of the can lid, and the aluminum alloy sheet covered with the resin of the can lid is a resin cover of any of the cans covered by the patent application described later. Aluminum alloy sheet. [Procedure of the present invention] In the present invention, a silane-coupled silane treatment is performed on one side of the aluminum alloy sheet corresponding to the inner layer of the can lid. Alternatively, phosphate-chromate treatment, pin treatment, or anodizing treatment is performed on one side of the aluminum alloy sheet corresponding to the inner layer of the can lid. After performing any of the processes, the aluminum alloy sheet is processed by the above-mentioned silane treatment method. Finally, the silane-treated surface is covered with a thermoplastic resin to form an aluminum alloy sheet covered with a resin by a can lid. It is also desirable to form the above-mentioned surface treatment film 'on one side of the aluminum alloy sheet corresponding to the outer layer of the can lid, and then cover the surface treatment film with the above-mentioned thermoplastic resin. 5 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297). (Please read the “Notes on the back” and then fill out this page), ιτ Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperation and Printing 4 34 3 2 7 V. Description of the invention (4 ·) The production of the can lid of the present invention is carried out by printing the aluminum alloy sheet covered with the can lid with resin. [Example] The present invention will be explained in detail here. First, any aluminum alloy sheet that can be used in the manufacture of can lids can be applied to the present invention. This is also one of the main purposes of the present invention, and therefore the present invention is not particularly limited. From the perspective of manufacturing cost and formability, the 5000 series aluminum alloy sheet with a thickness of 0.20 to 0.35 mm can be widely used in the manufacture of can lids. In the present invention, because the thermoplastic resin was previously covered in the present invention, Aluminum alloy sheet, so the choice of aluminum alloy sheet must consider its formability, adaptability to chemical treatment during surface treatment, and the adhesion of the film covering the aluminum alloy sheet after forming. Next, in the present invention, an aluminum alloy surface treatment method will be described. First, this aluminum alloy sheet is subjected to a pretreatment step composed of steps such as degreasing, alkali treatment, and pickling. In the degreasing step, the grease adhered to the aluminum alloy sheet is degreased with a commercially available degreasing agent. The temperature of the degreasing solution is preferably 30 ° C to 90 ° C, and more preferably 40eC to 80 ° C. This degreasing treatment method is to immerse the aluminum alloy sheet in a degreasing solution, or spray the degreasing solution on the aluminum alloy sheet. Its sufficient degreasing treatment time is 1 to 30 seconds, and preferably 3 to 15 seconds. Subsequently, the aluminum alloy sheet was rinsed with rhenium water, and then subjected to an alkali treatment. In this alkali treatment, the aqueous solution contains one or two or more compounds such as hydroxides of alkali metals or ammonia, carbonates, oxalates, phosphates, silicates, and borates, and can be used. In this alkali treatment, it will be removed and formed in the aluminum alloy sheet 6 degrees applicable to the Chinese National Standard (CNS) Λ4 specifications (Gong Zhao) --------- ------ ΐτ ------ Multiply J · r-* (Please read the notes on the back & then fill out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 34 3 2 7 V. The oxide film on the description of the invention ($). In some cases, aluminum alloy sheets are etched by alkaline aqueous solutions. Therefore, the concentration of lye is preferably between 1 and 20%, and more preferably between 2 and 10%. The temperature of the lye is preferably between 30 and 80 ° C, preferably 40 to 60 ° C. This is an alkali treatment method. The aluminum alloy sheet is immersed in the alkali solution, or the alkali solution is sprayed on the aluminum alloy sheet. . Its sufficient alkali treatment time is 1 to 20 seconds, preferably 3 to 10 seconds. After that, the aluminum alloy sheet was washed with water and then pickled. In this pickling step, an aqueous solution mainly containing one or two or more inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid can be used. This pickling step is to remove the stains on the surface of the Ming alloy sheet during the empirical treatment. In some cases, this pickling will produce fine pores on the surface of the aluminum alloy. The concentration of the acidic aqueous solution used is preferably between "to 10%" and more preferably from 1 to 5%. The temperature of the pickling aqueous solution is preferably from room temperature to 60 ° c ', and more preferably from room temperature to 40 ° C. In this pickling treatment, the aluminum alloy sheet is usually immersed in an acidic aqueous solution, or the acidic aqueous solution is sprayed on the aluminum alloy sheet. The sufficient pickling time is 1 to 10 seconds, and preferably 1 to 5 seconds. The pre-processing steps can be completed through the above method. After the above pretreatment, the main treatment of the aluminum alloy sheet can be performed. In the present invention, the main treatment is a silane-coupled silane treatment method, such as any one of the following: performing silane treatment on an aluminum alloy sheet treated with phosphate monochromate, and performing aluminum alloy sheet treatment with a pin treatment Silane treatment is performed, and the anodized aluminum alloy sheet is subjected to silane treatment. The silane treatment will be explained first. In the silane treatment of the present invention, a 'commercially available silane coupling agent is diluted with a solvent, and this silane coupling agent diluted solution' is used on an aluminum alloy sheet. 7 This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (2 丨 OX297) 浼 (Please read the precautions on the back before filling this page)
五、發明説明(G) 水可單獨做爲溶劑使用。但無論如何,利用乙醇和水的混 合液做爲溶劑,是較爲理想Θ例如,當此混合溶劑中,水 比乙醇之比例爲水:乙醇=i : 4到4 : 1時,以1 : 2到2 :1較佳,可得滿意之結果。當水比乙醇之比例大於丨:4 時,矽烷偶合劑在溶液中’呈現充分的分布性及均一性。 但因爲乙醇是高價物品,從成本效益的觀點來看,是較不 爲人所接受。另一方面’當水對乙醇之比例比4 : 1小時, 矽烷偶合劑在溶液中’將無法充分地散布,且不具均一性 ’而且鋁合金片在經矽烷偶合劑處理後,需要芘一段長時 間進行乾燥。矽烷偶合劑在混合溶劑的濃度最好在0.5到 20%之間,而以1到10%間較佳。 當矽烷偶合劑的濃度,小於0.5%時,覆蓋在鋁合金片 上的矽烷偶合劑在乾燥後,將無法達成均一性,以及不具 充分之黏著度。當其濃度超過20%時,其黏著度可增加至 飽和程度,但從成本效益來看,則不受歡迎《此處理溶液 之溫度最好爲室溫到60°C之間,而以室溫到40°C間較佳。 此矽烷處理法是將鋁合金片,浸入處理的溶液中,過量的 溶液則利用滾筒將其壓擠出來,再將鋁合金片烘乾。充分 的含浸時間爲1到15秒之間,而以3到10秒間較佳。以 矽表示的處理量最好爲0.3到30 mg/m2,而以1到10 mg /m2較佳。 其次解釋磷酸鹽一鉻酸鹽處理後,所進行之矽烷處理 0磷酸鹽一鉻酸鹽處理法是使用市售之磷酸鹽一鉻酸鹽處 理劑’進行含浸處理或噴灑處理。處理溶液的溫度最好從 8 本紙浪尺度適用中國國家標準(CNS ) Λ4規格(210.x297公婕〉 4 經濟部中央標準局員工消費合作社印製 3432 7 Λ7 _- _ Η 7 五、發明説明(7 ) 室溫到80°C間,而以室溫到60°C較佳。充分的處理時間是 1到10秒之間,而以3到10秒間較佳。以鉻表示的使用 量最好爲3到50 mg/m2,而以5到30 較佳a當以 鉻表示之膜量小於3 mg/m2時,對黏著度的增加,幾乎無 法觀察到。當其用量超過50 mg/m2時,則使用的量將增 加,而且形成的膜部分變成凹凸不平,除了降低其黏著度 之外,也產生不欲發生之深棕色外觀。當鋁合金片以磷酸 鹽一鉻酸鹽處理之後,隨即以上述之矽烷處理法處理之。 再來解釋銷處理後,所進行之矽烷處理法。鉻處理是 以市售之銷處理劑,進行含浸處理或噴灑處理◊處理劑之 溫度最好爲室溫到60°C之間,而以室溫到45°C間較佳。充 分的處理時間爲3到40秒之間,以10到30秒間較佳。以 銷表示之膜量最好爲3到30 mg/m2之間,而以7到15 mg /m2間較佳。 當鋁合金片以鉻處理之後,隨即以上述之矽烷處理法 處理之。 再來解釋陽極氧化處理法後,進行矽烷處理。本發明 之陽極氧化處理法與傳統形成厚膜的方法不同,後者不需 要一般成形所需的加工性。層覆在陽極氧化層上的樹脂膜 ,經嚴袼的成彤之後,仍須維持優良之黏著度,而且必需 在一短時間內,經連續處理之後,可以得到一層薄的處理 膜。關於符合此種需求的陽極氧化處理法,利用直電流電 解使鋁合金片陽極化,是最好的方法。利用鹼液處理鋁合 金的方法,除了需花一段較長的時間去淸洗殘存在鋁合金 請 先 閱- 背 意 填' 寫、 本 頁 本紙張尺度適用中國國家標举 ( CNS ) Λ4規格(2[〇X297公浼) 434327 A 7 B7 五、發明説明(y ) 片表面之鹼溶液外,而且層覆在鋁合金片上的膜,亦不具 充分之黏著度°再者’利用交流電電解鋁合金片的方法, 需要花長時間在陽極氧化膜之形成’因此也不適用於高速 之處理。本發明中陽極氧化處理法的具體實施例,乃是以 加入硼砂之硼酸水溶液做爲酸液。此硼酸溶液之濃度最好 爲5到1〇〇 g /1閭β當硼酸濃度小於5 g /1之時,此處理 液之導電性就比較低’使得處理的電流密度不能增加。因 此將花一段不樂見之長時間’在形成所需厚度之處理膜。 另一方面,當硼酸溶液的濃度超過i〇〇g/i時,由於連續 處理鋁片之故,因此從處理浴中’因附著於鋁片而拿出的 硼酸量就隨著增加,這從成本效益上來看,較不受喜歡。 加入硼酸溶液的硼砂濃度介於1到之間時,將有 助於處理浴之穩定。處理浴的溫度最好由室溫到60°c之間 ,陽極電流密度最好爲2.5到50A/dm2之間,以3到20A /dm2間較隹。當陽極電流密度小於2.5A/dm2時,膜的 生成將花較長的時間,從生產力觀點來看,較不受喜歡, 而且較難形成均勻的薄膜。另一方面,當陽極電流密度大 於50A/dm2時,電解的電壓變得太高,這使得不外表不 平坦的情況易於發生,例如燃燒,而且均一薄膜難以生成 。欲得足夠膜厚的電解時間爲〇·1到10秒之間。經過陽極 氧化處理後,即可對鋁合金片,進行上述之矽烷處理。 在本發明中,鋁合金片經上述之表面處理後,進行熱 塑型樹脂覆蓋時,在聚乙烯,聚丙烯,聚酯,聚醯胺,聚 碳酸酯,聚氯乙烯,聚偏氯乙烯,丙烯酸樹脂,任二種或 10 本紙張尺度適用中國國家標卒(CNS ) Λ4規格(2)0X297公处) " (請先閱讀背负之注意事項再填莴本買) 訂 經濟部中央標準局Λ工消费合作社印製 經濟部中央標準局員工消費合作社印策 434327 五、發明説明(?) 二種以上之共聚物中之任一種,或者二種或二種以上之樹 脂調和,都可做爲熱塑型樹脂用。在本發明中,聚酯是特 別符合需要,而由聚對苯二甲酸乙二酯,對苯二甲酸乙二 酯單體爲主體的共聚合之聚酯,對苯二甲酸丁酯單體爲主 體之聚酯,以及彼此調和而成的複合樹脂,所做成之膜, 皆可應用於本發明中。在上述樹脂中,雙軸方向膜較符合 實際之使用。再者’當需有抗衝擊力時,最好使用由上述 聚酯和雙酚A聚碳酸酯調合組成的複合樹脂膜,或由上述 複合樹脂在上層而上述聚酯在下層所組成之二層式膜,或 者由上述聚酯在上層及下層而上述雙酚A聚碳酸酯在中間 層所組成之三層式膜。 上述熱塑型樹脂之厚度,視實際需要而定。一般厚度 最好在5到300# m,而以10到250 間較佳。當上述 熱塑型樹脂的厚度小於5μιη時,熱塑型樹脂明顯地比較 難覆蓋在鋁合金片上。且在覆蓋後或樹脂覆蓋鋁合金片成 形後’易於產生針扎,使得無法得到充分之抗触力。另— 方面,當上述熱塑型樹脂層的厚度超過300#m時,此熱 塑型樹脂層和塗膜比較,在成本效益上就較不受歡迎》 可視需要’額外加入一些如穩定劑,抗氧化劑,抗靜 電劑,顏料,潤滑劑或腐蝕抑制劑於上述之熱塑型樹脂》 當上述熱塑型樹脂對鋁合金片的黏著度不夠,特別是 當鋁金合片嚴格加工後的黏著度已不充分時,或者單獨的 熱塑型樹脂無法獲得充分之抗蝕時,則可應用一些熱固型 黏蓍劑,如環氧酚黏著劑,在鋁合金片上,然後,熱塑型 11 ---------U.------11------烺 - (請先'閲讀背面之注意事項再4·寫本頁) ' 本紙張尺度埼用中國國家標华< CNS ) Λ4規格(210X 297公浼) 經濟部十央標準局員工消费合作社印製 434327 五、發明説明(川) 樹脂即可層覆在熱固型黏著劑層上,或者上述黏著劑可預 先使用在將覆蓋在鋁合金片上之熱塑型樹脂,即熱塑型樹 脂將和鋁合金接觸那一面’然後熱塑型樹脂與上述黏著劑 •,即可層覆在鋁合金片上。_ 可利用任何擠壓法,將熔化之熱塑型樹脂直接擠壓至 鋁合金片上,而將熱塑型樹脂覆蓋在鋁合金片上。或者利 用膜層覆法’將熱塑型樹脂之雙軸向膜與加熱到超過樹脂 熔化溫度的鋁合金片接觸,然後,再利用一對滾筒將二者 壓緊,使得鋁合金片和雙軸方向膜互相層覆。 以下將利用例子來詳細說明本發明。 〔例子〕 在下列條件下,對厚度爲〇.26mm之鋁合金片(JIS 5052)進行去油脂、鹼處理及酸洗等前處理步驟。然後在如 表1到7所示之條件下,對鋁合金片進行表面處理。 〔前處理之條件〕 •去油 將上述鋁合金片含浸於3%之市售去油劑(Surf Cleaner,322N-8,Nippon Paint Inc.製造)的水溶液,其加熱 到80°C持續1〇秒鐘,再將此鋁合金片淸洗並乾燥之。 •鹼處理 在鋁合金片經上述去油步驟後,將其浸入5%氫氧化 鈉水溶液中,加熱至50°C持續1〇秒鐘,再將此鋁合金片 進行淸洗及乾燥。 12 (諳先閱讀背面'之注意事項再填寫本頁) 訂 声丨 @張尺度適用中國國家標準(CNS ) Λ4蚬格(210X297公t ) 經濟部中央橾準局員工消費合作社印製 ’4 34327 λ 7 H? 丨· 1 ^ 1 .......—— 五、發明説明(") ^ 將表面處理過之鋁合金片’加熟到240°C。再將由88 莫耳%之聚對苯二甲酸乙二酯及12莫耳%之聚異苯二甲酸 乙二酯組成之共聚合的聚醋’利用雙軸延伸及熱固化所得 之膜(此膜層覆在罐蓋之內面’在鋁合金片經膜層覆並成 形成罐蓋時,其厚度爲25/im ’此膜層覆在罐蓋外面之厚 度爲15^m),同時與鋁合金片兩面接觸。利用一對滾筒 將膜和鋁合金片壓緊,使得膜層覆在鋁合金片上,然後立 即將此覆蓋膜之銘合金片浸入水中丨卒火,並乾燥之。 將上述製成之聚酯膜覆蓋之鋁合金片,利用下列測試 方法評估,其結果如表8和9所示。 〔成形後樹脂膜之黏著度〕 片型測試片之寬爲20麵,長爲100 nun,是從覆蓋聚酯 膜之鋁合金片上切下來。將此測試片的一尾端折彎180°_ 使對應鋁合金罐蓋的內面朝向外面,再以肉眼觀察形成於 該處的聚酯樹脂剝離之情況,並評估之° 〔抗蝕力〕 上述測試片成形部分,將其含浸於3°c並以擰檬酸及 檸檬酸鈉調pH値爲3.0之氯化鈉水溶液30天,再以肉眼 評估其腐蝕狀況。 其評佶結果如表8及9所示。 樣品編號1到21 (例子)是膜覆蓋在合金片上,即聚 醋膜覆蓋在利用本發明表面處理法處理之鋁合金片上’在 13 1 . (請先閲讀背面•之注意事項再填荇本頁)5. Description of the invention (G) Water can be used alone as a solvent. However, in any case, it is better to use a mixture of ethanol and water as the solvent. For example, in this mixed solvent, the ratio of water to ethanol is water: ethanol = i: 4 to 4: 1, and 1: 2 to 2: 1 is preferable, and satisfactory results can be obtained. When the ratio of water to ethanol is greater than 丨: 4, the silane coupling agent in the solution ′ exhibits sufficient distribution and uniformity. But because ethanol is an expensive item, it is less acceptable from a cost-effective point of view. On the other hand, when the ratio of water to ethanol is 4: 1 hour, the silane coupling agent in the solution will not be able to spread sufficiently and is not homogeneous. In addition, after the aluminum alloy sheet is treated with the silane coupling agent, it needs a long period of time. Time to dry. The concentration of the silane coupling agent in the mixed solvent is preferably 0.5 to 20%, and more preferably 1 to 10%. When the concentration of the silane coupling agent is less than 0.5%, after drying, the silane coupling agent covered on the aluminum alloy sheet cannot achieve uniformity and insufficient adhesion. When its concentration exceeds 20%, its viscosity can increase to saturation, but it is unpopular from the viewpoint of cost-effectiveness. The temperature of this treatment solution is preferably between room temperature and 60 ° C. It is better to reach 40 ° C. In the silane treatment method, an aluminum alloy sheet is immersed in a treated solution, and an excessive amount of the solution is extruded out by a roller, and then the aluminum alloy sheet is dried. A sufficient impregnation time is between 1 and 15 seconds, and preferably between 3 and 10 seconds. The processing amount expressed in silicon is preferably 0.3 to 30 mg / m2, and more preferably 1 to 10 mg / m2. Next, the silane treatment performed after the phosphate monochromate treatment is explained. The phosphate monochromate treatment method is an impregnation treatment or a spray treatment using a commercially available phosphate monochromate treatment agent '. The temperature of the treatment solution is best from 8 paper waves to the Chinese National Standard (CNS) Λ4 specification (210.x297). 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 3432 7 Λ7 _- _ Η 7 V. Description of the invention (7) Room temperature to 80 ° C, and preferably room temperature to 60 ° C. The sufficient processing time is between 1 and 10 seconds, and preferably between 3 and 10 seconds. The amount of use in terms of chromium is the most It is preferably from 3 to 50 mg / m2, and from 5 to 30 is preferred. When the film amount expressed in chromium is less than 3 mg / m2, the increase in adhesion is almost unobservable. When the amount exceeds 50 mg / m2 When it is used, the amount used will increase, and the formed film part becomes uneven, in addition to reducing its adhesion, it also produces an undesired dark brown appearance. When the aluminum alloy sheet is treated with phosphate monochromate, Then use the silane treatment method described above. Let's explain the silane treatment method after the pin treatment. The chromium treatment is a commercially available sales treatment agent. The temperature of the impregnation treatment or spray treatment is preferably room temperature. Temperature to 60 ° C, but preferably from room temperature to 45 ° C. Sufficient The treatment time is between 3 and 40 seconds, preferably between 10 and 30 seconds. The film amount expressed as a pin is preferably between 3 and 30 mg / m2, and more preferably between 7 and 15 mg / m2. When aluminum After the alloy sheet is treated with chromium, it is then treated with the above-mentioned silane treatment method. After explaining the anodic oxidation treatment method, the silane treatment is performed. The anodic oxidation treatment method of the present invention is different from the traditional thick film formation method, and the latter does not require general The processability required for forming. The resin film layered on the anodized layer must still maintain excellent adhesion after strict formation, and it must be obtained in a short period of time after continuous processing. Thin processing film. Regarding the anodizing method that meets this requirement, the direct current electrolysis is the best method to anodize aluminum alloy sheets. The method of treating aluminum alloy with alkali solution takes a long time Decontamination and washing of residual aluminum alloy, please read it first-write it on the back, and the paper size on this page applies to China National Standards (CNS) Λ4 specifications (2 [〇X297 公 浼) 434327 A 7 B7 V. Description of the invention (y ) Of the surface Outside the solution, and the film laminated on the aluminum alloy sheet does not have sufficient adhesion degree. Furthermore, the method of “alternating the aluminum alloy sheet by alternating current requires long time to form the anodized film”, so it is not suitable for high-speed Treatment. A specific embodiment of the anodizing method in the present invention is to use a boric acid aqueous solution containing borax as the acid solution. The concentration of the boric acid solution is preferably 5 to 100 g / 1 β when the boric acid concentration is less than 5 When g / 1, the conductivity of this treatment liquid is relatively low 'so that the current density of the treatment cannot be increased. Therefore it will take an unpleasant time' to form a treatment film of the required thickness. On the other hand, when the concentration of the boric acid solution exceeds 100 g / i, since the aluminum sheet is continuously processed, the amount of boric acid taken out from the processing bath due to adhesion to the aluminum sheet increases, which is from In terms of cost-effectiveness, it is less popular. Adding a borax concentration of 1 to between boric acid solution will help stabilize the treatment bath. The temperature of the treatment bath is preferably from room temperature to 60 ° C, and the anode current density is preferably between 2.5 and 50 A / dm2, and between 3 and 20 A / dm2. When the anode current density is less than 2.5A / dm2, it takes a long time to form the film, from the viewpoint of productivity, it is less preferred, and it is more difficult to form a uniform film. On the other hand, when the anode current density is greater than 50A / dm2, the voltage of electrolysis becomes too high, which makes the appearance of unevenness prone to occur, such as combustion, and it is difficult to form a uniform film. The electrolysis time for a sufficient film thickness is between 0.1 and 10 seconds. After the anodizing treatment, the aluminum alloy sheet can be subjected to the above-mentioned silane treatment. In the present invention, when the aluminum alloy sheet is subjected to the above-mentioned surface treatment and covered with a thermoplastic resin, the polyethylene, polypropylene, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, Acrylic resin, any two or 10 paper sizes are applicable to Chinese National Standards (CNS) Λ4 specifications (2) 0X297 public place) " (Please read the precautions for the burden before filling in lettuce to buy) Order the Central Bureau of Standards of the Ministry of Economic Affairs Printed by Λ Industrial Consumer Cooperative, printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperative, printed by 434327 V. Description of the invention (?) Any of two or more copolymers, or a blend of two or more resins, can be used as For thermoplastic resin. In the present invention, the polyester is particularly suitable, and the copolymerized polyester mainly composed of polyethylene terephthalate and ethylene terephthalate monomers, and the butyl terephthalate monomer is Both the main polyester and the composite resin blended with each other can be used in the present invention. Among the above resins, a biaxially oriented film is more suitable for practical use. Furthermore, when impact resistance is required, it is best to use a composite resin film composed of the above polyester and bisphenol A polycarbonate blend, or a two-layer composed of the above composite resin on the upper layer and the above polyester on the lower layer. Film, or a three-layer film composed of the polyester above and below and bisphenol A polycarbonate above. The thickness of the above-mentioned thermoplastic resin depends on the actual needs. Generally, the thickness is preferably from 5 to 300 # m, and more preferably from 10 to 250. When the thickness of the above-mentioned thermoplastic resin is less than 5 µm, it is significantly difficult for the thermoplastic resin to cover the aluminum alloy sheet. And after the covering or the formation of the resin-coated aluminum alloy sheet, it is easy to cause pinning, so that it is impossible to obtain sufficient contact resistance. On the other hand, when the thickness of the above-mentioned thermoplastic resin layer exceeds 300 # m, compared with the coating film, the thermoplastic resin layer is less cost-effective compared with the coating film. "If necessary, add some additional stabilizers, Antioxidants, antistatic agents, pigments, lubricants or corrosion inhibitors to the above thermoplastic resins "When the above thermoplastic resins do not have sufficient adhesion to aluminum alloy sheets, especially when the aluminum alloy sheet is processed strictly When the degree is insufficient, or when the thermoplastic resin alone cannot obtain sufficient corrosion resistance, some thermosetting adhesives, such as epoxy phenol adhesives, can be applied on the aluminum alloy sheet. Then, the thermoplastic type 11 --------- U .------ 11 ------ 烺-(Please 'read the notes on the back before writing this page 4' Biaohua < CNS) Λ4 specification (210X 297 gong) Printed by the Consumers' Cooperative of Shiyang Standard Bureau of the Ministry of Economic Affairs 434327 5. Description of the invention (Sichuan) The resin can be coated on the thermosetting adhesive layer, or the above-mentioned adhesion The agent can be used in advance on the thermoplastic resin that will be covered on the aluminum alloy sheet, that is, the thermoplastic tree The side where the grease will come into contact with the aluminum alloy ’, then the thermoplastic resin and the above-mentioned adhesive can be laminated on the aluminum alloy sheet. _ You can use any extrusion method to directly extrude the molten thermoplastic resin onto the aluminum alloy sheet, and cover the aluminum alloy sheet with the thermoplastic resin. Or use the film coating method to contact the biaxial film of the thermoplastic resin with the aluminum alloy sheet heated above the resin melting temperature, and then use a pair of rollers to compact the two, so that the aluminum alloy sheet and the biaxial The orientation films are layered on each other. Hereinafter, the present invention will be described in detail using examples. [Example] Under the following conditions, pre-treatment steps such as degreasing, alkali treatment and pickling were performed on an aluminum alloy sheet (JIS 5052) with a thickness of 0.26 mm. The aluminum alloy sheet was then subjected to a surface treatment under the conditions shown in Tables 1 to 7. [Conditions of Pretreatment] • Degreasing The above aluminum alloy sheet was impregnated with an aqueous solution of 3% of a commercially available degreasing agent (Surf Cleaner, 322N-8, manufactured by Nippon Paint Inc.), which was heated to 80 ° C for 1 °. Second, rinse and dry the aluminum alloy sheet. • Alkali treatment After the aluminum alloy sheet has been degreased, it is immersed in a 5% sodium hydroxide aqueous solution, heated to 50 ° C for 10 seconds, and then the aluminum alloy sheet is washed and dried. 12 (谙 Please read the “Notes on the back” before filling out this page) Ordering 丨 @ 张 标 Applies to Chinese National Standards (CNS) Λ4 蚬 Grid (210X297gt) Printed by the Employees 'Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs' 4 34327 λ 7 H? 丨 · 1 ^ 1 .......—— V. Description of the invention ^ Add the surface-treated aluminum alloy sheet to 240 ° C. Then a copolymerized polyester consisting of 88 mol% polyethylene terephthalate and 12 mol% polyethylene isophthalate was used to obtain a film obtained by biaxial stretching and thermal curing (this film Layered on the inner surface of the can lid 'When the aluminum alloy sheet is laminated with a film to form a can lid, its thickness is 25 / im' The thickness of this film layer is 15 ^ m on the outside of the can lid), and simultaneously with aluminum The alloy sheet is in contact with both sides. Use a pair of rollers to compact the film and the aluminum alloy sheet, so that the film layer is covered on the aluminum alloy sheet, and then immediately immerse the alloy sheet of the cover film in water, fire, and dry it. The aluminum alloy sheet covered with the polyester film prepared above was evaluated by the following test methods, and the results are shown in Tables 8 and 9. [Adhesion of the resin film after molding] The sheet-shaped test piece has a width of 20 sides and a length of 100 nun, and is cut from an aluminum alloy sheet covered with a polyester film. Bend one end of this test piece 180 ° so that the inner surface of the corresponding aluminum alloy can lid faces outward, and then observe the peeling of the polyester resin formed there with the naked eye, and evaluate the ° 〔Corrosion resistance〕 The formed part of the test piece was immersed in a sodium chloride aqueous solution adjusted to pH 3.0 with citric acid and sodium citrate for 30 days at a temperature of 3 ° C, and the corrosion condition was evaluated with the naked eye. The evaluation results are shown in Tables 8 and 9. Samples Nos. 1 to 21 (examples) are films coated on alloy sheets, that is, polyacetate films are coated on aluminum alloy sheets treated with the surface treatment method of the present invention 'at 13 1. (Please read the precautions on the back side before filling in the transcript page)
本紙張尺度適用中國國家標準(CNS ) Λ4规格(21〇乂 297公#-) r 4 343 2 7 Λ7 ___ _IT__一_______ 五、發明説明(a ) 其中任一例,成形後都具有良好之黏著度’以及良好之抗 蝕力。另一方面,樣品編號22到35 (比對例子)是膜覆 蓋在合金片上,即聚酯膜覆蓋在傳統表面處理之鋁合金片 上,與本發明比較,可發現在成形後,黏著度與抗蝕力都 比較差。 C本發明效果〕 本發明爲罐蓋用樹脂覆蓋之鋁合金片,此鋁合金片在 對應罐蓋內面部分,有一層利用砂焼偶合之较院處理膜, 且樹脂層覆在此膜上;或樹脂覆蓋在罐蓋用鋁合金片上, 而此鋁合金片經過磷酸鹽一鉻酸鹽處理,鉻處理或陽極氧 化處理後,矽烷處理膜再於上述處理膜上成形,最後樹脂 層覆於其上。它們在成形後之黏著度及抗蝕性,都相當優 良,甚至於製成罐蓋時亦同β 經濟部中央標準局員工消費合作社印製 (請先閱讀背&之注意事項再填寫本頁)This paper size applies the Chinese National Standard (CNS) Λ4 specification (21〇 乂 297 公 #-) r 4 343 2 7 Λ7 ___ _IT__ 一 _______ V. Description of the invention (a) Any one of the examples has good properties after forming. 'Adhesion' and good corrosion resistance. On the other hand, sample numbers 22 to 35 (comparative examples) are films covered with alloy sheets, that is, polyester films are covered with conventional surface-treated aluminum alloy sheets. Compared with the present invention, it can be found that after forming, the adhesion and resistance Erosion is relatively poor. C Effect of the present invention] The present invention is an aluminum alloy sheet covered with a resin by a can lid. The aluminum alloy sheet has a layer of a comparative film treated with sand sand on the inner portion of the corresponding can lid, and the resin layer is coated on the film. Or the resin is covered on the aluminum alloy sheet for can lid, and the aluminum alloy sheet is treated with phosphate monochromate, chromium or anodized, and then a silane treatment film is formed on the above treatment film, and finally the resin layer is coated on On it. They have excellent adhesion and corrosion resistance after forming. They are printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs even when they are made into can lids (please read the precautions on the back and fill out this page). )
本紙張尺度適用十國國家標準(CNS ) Λ4规格(2ΙΟΧ297公心) 4 3432 7 B7五、發明説明(/3 ) 說明書中提到的化學配方及其他 [表1]鋁合金片之表面處理(矽烷處理) 品 編號 處理浴成分 浴液 溫度 (0〇 處理方法 區分 種類 濃度 種類 處理時 間(秒) 1 矽烷偶合劑 _ 903* 0.5%+ 30 含浸 15 例子 2 矽烷偶合劑 KBM 903* W 30 含浸 10 例子 3 矽烷偶合劑 KBM 903* 5矿 30 含浸 5 例子 4 矽烷偶合劑 KBM 903* 10%+ 30 含浸 2 例子 5 矽烷偶合劑 KBM 903* 20%+ 30 含浸 1 例子 經濟部中失標準局員工消费合从 (附注)*:由 Shin-etsu Chemical Industry CO.,Ltd 製造。 +:溶劑水/乙醇=2/1 15 (請先阶讀背而之注意事項再t取本頁)This paper size applies to the ten national standards (CNS) Λ4 specifications (2ΙΟχ297 public heart) 4 3432 7 B7 V. Description of the invention (/ 3) The chemical formula mentioned in the description and other [Table 1] surface treatment of aluminum alloy sheet (silane Treatment) Product No. Treatment bath ingredients Bath temperature (0 〇 Treatment method Different types Concentration types Treatment time (seconds) 1 Silane coupling agent_ 903 * 0.5% + 30 Impregnation 15 Example 2 Silane coupling agent KBM 903 * W 30 Impregnation 10 Example 3 Silane coupling agent KBM 903 * 5 ore 30 impregnation 5 Example 4 Silane coupling agent KBM 903 * 10% + 30 impregnation 2 Example 5 Silane coupling agent KBM 903 * 20% + 30 impregnation (Note) *: Manufactured by Shin-etsu Chemical Industry CO., Ltd. +: Solvent water / ethanol = 2/1 15 (Please read the precautions before reading this page)
甩中國國家標準(CNS ) Λ4规格(210X297公釐) ^ 34 3 2 7 λ? Η 7 五、發明説明(iy·) [表2]鋁合金片之表面處理(磷酸處理+矽烷處理) 樣品 處理浴成分 浴液 溫度 處理方法 鉻附著量 區分 編號 種類與濃度 (°C) 種類 處理時 間(秒) (nig/in2) 雄酸-銘酸鹽 A1surf 401* 2% 30 含浸 1 3 6 Alsurf 45$ 0. 5¾ 例子 矽烷偶合劑 KBM 903* 5^ 30 含浸 5 磷酸-鉻酸鹽 Alsurf 401s 2¾ 45 含浸 1 5 7 Alsurf 45s 0. 5% 例子 矽烷偶合劑 KBM 903* 5%+ 30 含浸 5 磷酸-鉻酸鹽 Alsurf 401s 2% 70 含浸 1 8 8 Alsurf 45s 0.5% 例子 矽烷偶合劑 KBM 903* 5%+ 30 含浸 5 磷酸-銘酸鹽 Alsurf 401$ 2% 45 含浸 5 23 9 Alsurf 45s 0.5¾ 例子 矽烷偶合劑 腿 903* 5V 30 含浸 5 磷酸-鉻酸鹽 Alsurf 401s 2¾ 45 含浸 10 45 10 Alsurf 45$ 0. 5% 例子 矽烷偶合劑 KBM 903* 5%+ 30 含浸 5 經濟部中央標準局員工消費合作社印製 (附注)$ :由 Nippon Paint CO., Ltd 製造 ° + :溶劑水/乙醇=2/1 *:由 Shin-etsu Chemical Industry CO.,Ltd 製造。 16 本紙張尺度適用中國國家標準(CNS ) Λ4规格(21〇><297公货) 4 34 3 2 Λ: \Υ 五、發明説明() 經濟部中央標準局員工消費合作社印聚 [表3]鋁合金片之表面處理(錯處理+石夕烷處理) 樣品 處理浴成分 浴液 溫度 處理方法 锆附著量 區分 編號 種類與濃度 (0〇 種類 處理時 間(秒) (mg/πι2) 錘處理 30 含浸 3 3 11 Alsurf 404s 2% 矽烷偶合劑 KBM 903* 5%+ 30 含浸 5 - 例子 錯處理 45 含浸 3 4 12 Alsurf 404* 2% 矽燒偶合劑 KBM 903* 5%+ 30 含浸 5 一 例子 锆處理胃 60 含浸 3 5 13 Alsurf 404s 2% 矽烷偶合劑 KBM 903* 5%+ 30 含浸 5 - 例子 錯處理 45 含浸 20 17 14 Alsurf 404s 2% 矽烷偶合劑 KBM 903* 5%+ 30 含浸 5 - 例子 錯處理· 45 含浸 40 28 15 Alsurf 404s 2% 矽烷偶合劑 30 含浸 5 - 例子 KBM 903* δ%·" (請先閱讀背面之注意事項再#寫本頁) •裝· 丁 -V0 腺 (附注)$ :由 Nippon Paint CO.,Ltd 製造。 + :溶劑水/乙醇=2/1 * :由 Shin-etsu Chemical Industry CO·,Ltd 製造。 17 本紙張尺度適用中國國家標莘(CNS ) Λ4规格(210X297公錄) 4 34 32 Λ7 Η ? 五、發明説明( 經濟部中央標準局員工消費合作社印製 [表4]鋁合金片之表面處理(鋁陽極氧化+矽烷處理) 樣品 處理浴成分 浴液 處理方法 編號 溫度 區分 種類與濃度 (0〇 種類 處理時 間(秒) 硼酸5g/l 30 陽極電解 1.5 16 硼砂3. 5g/l 30 20A/dm2 例子 矽烷偶合劑 KBM 903* 5%+ 含浸 5 硼酸20g/l 30 陽極電解 5 17 硼砂5g/l 矽烷偶合劑 KBM 903* 30 20A/dm2 含浸 5 例子 硼酸50g/l 30 陽極電解 8 18 硼砂5g/l 矽烷偶合劑 KBM 903* 5%+ 30 20A/dm2 含浸 5 例子 硼酸100g/l 30 陽極電解 10 19 硼砂5g/l 矽烷偶合劑 KBM 903* 5%+ 30 3A/dm2 含浸 5 例子 4 酸 20g/i 30 陽極電解 5 20 硼砂5g/l 矽烷偶合劑 KBM 903* 5%+ 30 30A/dm2 含浸 5 例子 硼酸20g/l 30 陽極電解 2 21 硼砂5g/l 矽烷偶合劑 KBM 903* 5%+ 30 50A/dm2 含浸 5 例子 (請先Μ讀背面之注意事項再填寫本頁)Chinese National Standard (CNS) Λ4 specification (210X297 mm) ^ 34 3 2 7 λ? Η 7 V. Description of the invention (iy ·) [Table 2] Surface treatment of aluminum alloy sheet (phosphoric acid treatment + silane treatment) Sample treatment Bath composition Bath temperature treatment method Chromium adhesion amount classification number and concentration (° C) Kind of processing time (seconds) (nig / in2) Androic acid-aluminate A1surf 401 * 2% 30 Impregnated 1 3 6 Alsurf 45 $ 0 5¾ Example Silane Coupler KBM 903 * 5 ^ 30 Impregnated 5 Phosphoric Acid-Chromate Alsurf 401s 2¾ 45 Impregnated 1 5 7 Alsurf 45s 0. 5% Example Silane Coupler KBM 903 * 5% + 30 Impregnated 5 Phosphoric Acid-Chromic Acid Salt Alsurf 401s 2% 70 Impregnated 1 8 8 Alsurf 45s 0.5% Example Silane Coupling KBM 903 * 5% + 30 Impregnated 5 Phosphoric Acid-Amin Salt Alsurf 401 $ 2% 45 Impregnated 5 23 9 Alsurf 45s 0.5¾ Example Silane Coupling Leg 903 * 5V 30 Impregnated 5 Phosphate-Chromate Alsurf 401s 2¾ 45 Impregnated 10 45 10 Alsurf 45 $ 0.5% Example Silane Coupler KBM 903 * 5% + 30 Impregnated 5 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Note) $: . Nippon Paint CO, Ltd manufactured ° +: solvent of water / ethanol = 2/1 *: manufactured by Shin-etsu Chemical Industry CO, Ltd manufactured. 16 This paper size applies the Chinese National Standard (CNS) Λ4 specification (21〇 > < 297 public goods) 4 34 3 2 Λ: \ Υ V. Description of the invention () Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs [Table 3] Surface treatment of aluminum alloy sheet (wrong treatment + petrolatum treatment) Sample treatment bath ingredients Bath temperature treatment method Zirconium adhesion amount division number type and concentration (0 type treatment time (seconds) (mg / πι2) hammer treatment 30 impregnated 3 3 11 Alsurf 404s 2% silane coupling agent KBM 903 * 5% + 30 impregnated 5-example mistreatment 45 impregnated 3 4 12 Alsurf 404 * 2% sintered coupling KBM 903 * 5% + 30 impregnated 5 an example Zirconium-treated stomach 60 impregnated 3 5 13 Alsurf 404s 2% silane coupling agent KBM 903 * 5% + 30 impregnation 5-example wrong treatment 45 impregnation 20 17 14 Alsurf 404s 2% silane coupling agent KBM 903 * 5% + 30 impregnation 5- Examples of wrong handling 45 impregnation 40 28 15 Alsurf 404s 2% silane coupling agent 30 impregnation 5-Example KBM 903 * δ% · (Please read the precautions on the back before #write this page) • Packing • Ding-V0 gland (Note) $: Made by Nippon Paint CO., Ltd +: Solvent water / ethanol = 2/1 *: Manufactured by Shin-etsu Chemical Industry CO ·, Ltd. 17 This paper size is applicable to China National Standard (CNS) Λ4 specification (210X297) 4 34 32 Λ7 Η? V. Description of the invention ([Table 4] Surface treatment of aluminum alloy sheet (aluminum anodized + silane treatment) printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics) Sample treatment bath ingredients Bath treatment method number Type of processing time (seconds) Boric acid 5g / l 30 Anodizing 1.5 16 Borax 3.5g / l 30 20A / dm2 Example Silane coupling agent KBM 903 * 5% + Impregnation 5 Boric acid 20g / l 30 Anodizing 5 17 Borax 5g / l Silane coupling agent KBM 903 * 30 20A / dm2 Impregnation 5 Example of boric acid 50g / l 30 Anodization 8 18 Borax 5g / l Silane coupling agent KBM 903 * 5% + 30 20A / dm2 Impregnation 5 Example of boric acid 100g / l 30 Anodization 10 19 Borax 5g / l Silane coupling agent KBM 903 * 5% + 30 3A / dm2 Impregnation 5 Example 4 Acid 20g / i 30 Anodizing 5 20 Borax 5g / l Silane coupling agent KBM 903 * 5% + 30 30A / dm2 Impregnation 5 Example boric acid 20g / l 30 anode 221 Borax Solution 5g / l Silane coupling agent KBM 903 * 5% + 30 50A / dm2 impregnated example 5 (Please Note Μ read back surface of the page and then fill)
'1T (附注)* :由 Shin-etsu Chemical Industry CO.,Ltd 製造。 + :溶劑水/乙醇=2/1 18 本紙張尺度適用中國國家標隼(CNS ) Λ4規格(210Χ 297公浼) 434327 經濟部中央標準局一貝工消費合作社印製 五、發明説明(丨7) [表5]鋁合金片之表面處理(磷酸-銘酸鹽處理) 樣品 編號 處理浴成分 浴液 溫度 (°C) 處理方法 鉻附著量 (mg/in2) 區分 種類與濃度 種類 處理時 間(秒) 22 磷酸-鉻酸鹽 Alsurf 4015 2% Alsurf 45* 0.5¾ 30 含浸 1 3 比對用 之例子 23 填酸錯 Alsurf 401s 2% Alsurf 45s 0. 5¾ 45 含浸 1 5 比對用 之例子 24 磷酸銷 Alsurf 401s 2% Alsurf 45$ 0.5% 70 含浸 1 8 比對用 之例子 (附注)$:由 Nippon Paint CO.,Ltd 製造。 it 种^I H 、17. Λ^.、- 1 (請先閱讀背面;之注意4項再矿¾本頁) . -'1T (note) *: Manufactured by Shin-etsu Chemical Industry CO., Ltd. +: Solvent water / ethanol = 2/1 18 This paper is scaled to the Chinese National Standard (CNS) Λ4 specification (210 × 297 gong) 434327 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, a Bayer Consumer Cooperative, V. Description of the invention (丨 7 ) [Table 5] Surface treatment of aluminum alloy sheet (phosphoric acid-aluminate treatment) Sample No. Treatment bath ingredients Bath temperature (° C) Treatment method Chromium adhesion amount (mg / in2) Differentiated type and concentration type Treatment time (seconds) ) 22 Phosphate-chromate Alsurf 4015 2% Alsurf 45 * 0.5¾ 30 Example of impregnation 1 3 comparison 23 Acid filled Alsurf 401s 2% Alsurf 45s 0. 5¾ 45 Example of impregnation 1 5 comparison 24 Phosphoric acid pin Alsurf 401s 2% Alsurf 45 $ 0.5% 70 Example of impregnation 1 8 comparison (note) $: Manufactured by Nippon Paint CO., Ltd. it species ^ I H, 17. Λ ^.,-1 (Please read the back first; pay attention to 4 items before you mine this page)-
9 IX 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公競) 4 34 3 2 7 五、發明説明(/&) [表6]鋁合金片之表面處理(磷酸錯處理) 樣品 編號 處理浴成分 浴液. 溫度 (°C) 處理方法 锆附著量 (mg/m2) 區分 種類與濃度 種類 處理時 間(秒) 25 锆處理 Alsurf 401$ 2% 30 含浸 3 3 比對用 之例子 26 锆處理 Alsurf 401* 2% 45 含浸 3 4 比對用 之例子 27 結處理 Alsurf 401* 2% 60 含浸 3 5 比對用 之例子 28 锆處理 Alsurf 401s 2% 45 含浸 20 17 比對用 之例子 29 锆處理 Alsurf 401s 2% 45 含浸 40 28 比對用 之例子 (請先閲讀背面之注意事項再填岛本頁) 經濟部中央標準局員工消費合作社印製 (附注)$ :由 Nippon Paint CO.,Ltd 製造。 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210X 297公麓) hi Γ34 3 2 7 五、發明説明(丨,) 經濟部中央標準局®ί工消費合作杜印製 [表7]鋁合金月之表面處理(鈕陽極氧化) 樣品 編號 處理浴成分 浴液' 溫度 (0〇 處理方法 區分 種類與濃度 種類 處理時 間(秒) 30 硼酸5g/l 硼砂3. 5g/l 30 陽極電解, 20A/dm2 2 比對用 之例子 31 硼酸20g/l 硼砂5g/l 30 陽極電解, 20A/dm2 7 比對用 之例子 32 硼酸50g/l 硼砂5g/l 30 陽極電解, 20A/dm2 10 比對用 之例子 33 硼酸100g/l 硼砂5g/l 30 陽極電解, 3A/dm2 13 比對用 之例子 34 硼酸20g/l 硼砂5g/l 30 陽極電解, 30A/dm2 8 比對用 之例子 35 硼酸20g/l 领砂5g/l 30 陽極電解, 50A/dm2 5 比對用 之例子 21 請 先 閱— 讀 背 意 事 項 再 填 寫 本 頁 訂 pt 本紙張尺度適用中國國家標準(CNS ) Λ4規格(2丨0X297公釐) 4 343 2 7 λ7 Β] 五、發明説明(加) 經濟部中央標準局員工消費合作社印製 [表8]樣品片特性評估結果(1) 樣品編號 形成樣品之黏著性 抗 钮 區 分 1 無剝離現象 良 好 例 子 2 無剝離現象 良 好 例 子 3 無剝離現象 良 好 例 子 4 無剝離現象 良 好 例 子 5 無剝離現象 良 好 例 子 6 無剥離現象 良 好 例 子 7 無剝離現象 良 好 例 子 8 無剝離現象 良 好 例 子 9 無剝離現象 良 好 例 子 10 無剥離現象 良 好 例 子 11 無剝離現象 良 好 例 子 12 無剥離現象 良 好 例 子 13 無剝離現象 良 好 例 子 14 無剥離現象 良 好 例 子 15 無剝離現象 良 好 例 子 16 無剝離現象 良 好 例 子 17 無剝離現象 良 好 例 子 18 無剝離現象 良 好 例 手 19 無剝離現象 良 好 例 子 20 無剝離現象 良 好 例 子 21 無剝離現象 良 好 例 子 22 (請先閱讀背面;之注意^項再轳筠本頁) " 本紙張尺度適用中國國家標隼(CNS ) Α4規格(210X297公簸) 經濟部宁央標準局員工消費合作社印製 4 3432? Λ7 ___B1 五、發明説明(Μ ) [表9]樣品片特性評估結果(2) 樣品編號 形成樣品之黏著性 抗 .蚀 區分 22 發現剝離現象 不 佳 比對用之例子 23 發現剝離現象 不 佳 比對用之例子 24 發現剝離現象 不 佳 比對用之例子 25 發現剝離現象 不 佳 比對用之例子 26 發現剝離現象 不 佳 比對用之例子 27 發現剥離現象 不 佳 比對用之例子 28 發現剝離現象 不 佳 比對用之例子 29 發現剝離現象 不 佳 比對用之例子 30 發現剝離現象 不 佳 比對用之例子 31 發現剝離現象 不 佳 比對用之例子 32 發現制離現象 不 佳 比對用之例子 33 發現剝離現象 不 佳 比對用之例子 34 發現剝離現象 不 佳 比對用之例子 35 發現剝離現象 不 佳 比對用之例子 ----1----裝—— 、^·. ί C請先閱讀背面之注意亭項再項爲本頁) 訂 " 3 2 本紙張尺度適用中國國家標隼(CNS ) Λ4規格(210X297公釐)9 IX This paper size applies Chinese National Standard (CNS) A4 specification (210X297) 4 34 3 2 7 V. Description of the invention (/ &) [Table 6] Surface treatment of aluminum alloy sheet (phosphoric acid mistreatment) Sample number Treatment bath composition bath. Temperature (° C) Treatment method Zirconium adhesion amount (mg / m2) Differentiated type and concentration type Treatment time (seconds) 25 Zirconium treatment Alsurf 401 $ 2% 30 Impregnated 3 3 Comparison example 26 Zirconium Treatment Alsurf 401 * 2% 45 Impregnated 3 4 Comparison Example 27 Junction treatment Alsurf 401 * 2% 60 Impregnation 3 5 Comparison Example 28 Zirconium treatment Alsurf 401s 2% 45 Impregnation 20 17 Comparison Example 29 Zirconium Processing Alsurf 401s 2% 45 Impregnation 40 28 Example of comparison (please read the precautions on the back before filling in this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (note) $: by Nippon Paint CO., Ltd Manufacturing. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 feet) hi Γ34 3 2 7 V. Description of the invention (丨,) Central Standards Bureau of the Ministry of Economics®, industrial and consumer cooperation Du printed [Table 7] aluminum alloy Moon's surface treatment (button anodizing) Sample No. Treatment bath composition bath liquid 'Temperature (0 〇 Treatment method to distinguish type and concentration type Treatment time (seconds) 30 Boric acid 5g / l Borax 3. 5g / l 30 Anodization, 20A / Example for dm2 2 comparison 31 Boric acid 20g / l Borax 5g / l 30 for anode electrolysis, 20A / dm2 7 Example for comparison 32 Boric acid 50g / l Borax 5g / l 30 for anode electrolysis, 20A / dm2 10 for comparison Example 33 Boric acid 100g / l Borax 5g / l 30 Anodizing, 3A / dm2 13 Example for comparison 34 Boric acid 20g / l Borax 5g / l 30 Anodizing, 30A / dm2 8 Example 35 for comparison 35Bric acid 20g / l Collar sand 5g / l 30 Anodizing, 50A / dm2 5 Comparison example 21 Please read first — Read the notes before filling in this page to order pt This paper size applies to Chinese National Standard (CNS) Λ4 specification (2 丨 0X297) (Centi) 4 343 2 7 λ7 Β] 5. Description of the invention (plus) Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China [Table 8] Sample sheet characteristic evaluation results (1) Sample No. Adhesion resistance of the sample forming the sample 1 Good example of no peeling phenomenon 2 Good example of no peeling phenomenon 3 Good example of no peeling phenomenon 4 Good example of no peeling phenomenon 5 Good example of no peeling phenomenon 6 Good example of no peeling phenomenon 7 Good example of no peeling phenomenon 8 Good example of no peeling phenomenon 9 Good example of no peeling phenomenon 10 Good example of no peeling phenomenon 11 Good example of no peeling phenomenon 12 No peeling Good examples 13 Good examples without peeling good examples 14 Good examples without peeling good examples 15 Good examples without peeling good examples 17 Good examples without peeling good examples 18 Good examples without peeling good examples 19 Good examples without peeling good examples 20 No peeling Good example 21 No peeling phenomenon Good example 22 (Please read the back side; note the ^ item before this page) " This paper size applies to China House Standard 隼 (CNS) Α4 size (210X297). Printed by Ningyang Standard Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. 4 3432? Λ7 ___B1 V. Description of the invention (M) [Table 9] Sample sheet characteristic evaluation results (2) Sample number Form the sample's adhesion resistance. Erosion classification 22 Example with poor peeling comparison Example 23 with poor peeling comparison Example 24 with poor peeling comparison Example 25 with poor peeling comparison Example 26 found that the peeling phenomenon is poor compared with the example 27 Comparison example that the peeling phenomenon is poor compared with the example 28 Discovery that the peeling phenomenon is poor compared with the example 29 Discovery that the peeling phenomenon is poor compared with the found 30 Example for comparison of poor phenomenon 31 Example for comparison of poor peeling phenomenon Example for comparison of poor peeling phenomenon Example for comparison of poor peel phenomenon 33 Example of comparison of poor peel phenomenon 34 Comparison of poor peeling phenomenon Example of use 35 Found that the peeling phenomenon is not good. Example of comparison ---- 1 ---- installing ——, ^ ·. Ί C Please read the note on the back first Entry for this page) book " 3 2 Ben paper scale applicable Chinese national standard Falcon (CNS) Λ4 size (210X297 mm)