1279452 九、發明說明： 【發明所屬之技術領域】 技術領域 本發明係有目於-種經無;^有;^複合處理之_糊板。 t先前技術】 背景技術 以往，為了提昇用於汽車、家電、建材等之鑛辞鋼板之财腐 錄或塗贿紐，-般係赌__麵祕酸魏理。特別 是於施行繼鹽處理後，藉鉻酸鹽進行密封處理之方法對於提昇 耐腐姓性或塗料密概有很大之效果，目此廣為實施。然而，進 年來’於减問題聽之背景下，傾向於開發不使用毒性大之絡 酸鹽之表面處理技術，而有如下之技術。 該技術係提供-種於鍍辞系鋼板之表面具有第i層之填酸辞 處理皮膜層，並於該第1層上具有第2層之有機系皮膜之磷酸辞複 合處理鋼板(參照例如日本專利公開公報2〇〇1_1〇5528號），而前述 魏辞處理賴齡魏自補、毅射之至少i種之附著量 0·2〜2.5g/m2者’且前述有機系皮膜係以選自於乙烯系樹脂、環氧 系樹脂、絲甲酸醋系樹脂及丙烯酸系樹脂中之至少增之有機 樹脂為主成分者。 另外有於鋼板表面依序形成鍍鋅皮膜、〇.3g/m2以上之碟酸 辞處理皮膜、G·3〜2g/m2之有機觀，雜雜齡魏，且，構 酸辞處理皮膜中之鎮/嶙(質量比)為〇15以上並且鎮量為施咖2 以上之有機複合鍍鋅鋼板（參照例如日本專利公開公報 200M31763號）。 1279452 ，通常於加壓成形並實施 。因此，需要無塗襞之耐 實施過如前述之處理之鍍鋅系鋼板， 鹼脫脂洗淨後直接使用或經塗裂後使用。 腐蝕性及塗裝後之耐腐蝕性兩者。 然而，顧如前述之方法等所得到之魏職合處理鋼板及 有機複合鑛鋅鋼板中’餐鋅皮膜與有機皮膜間於雜環境下之 結合不強，以業經«狀態放置於测率極高之魏巾時，魏 鋅皮膜與錢皮關會產《掃，而錢额之耐雜性不足之 情況發生。 L發明内容3 發明概要 鑑於前述現狀，本發明之目的在於提供一種於經過處理之皮 膜中不含有害之鉻酸鹽，且可得到優異之耐腐蝕性之經無機無機 複合處理之鍍辞鋼板。 本發明人專針對於鍵鋅且具有填酸鋅皮膜與有機皮膜之經 無機有機複合處理之鍛辞鋼板，檢討各種提昇填酸辞皮膜與有機 皮膜間於腐蝕環境下結合之方法後，發現麟s复鋅皮膜之底層之鍍 鋅層之狀態有很大之影響，而完成本發明。 本發明之要旨係提供一種經無機有機複合處理之鍍鋅鋼板，前述 經無機有機複合處理之鍍鋅鋼板係於鋼板上具有(002)面之結晶 定向為50%以上之鍍鋅層，並於該鍍鋅層上具有含有鎂之磷酸鋅 皮膜，且更於該磷酸鋅皮膜上具有有機皮膜層者。其中前述磷酸 鋅皮膜中之镁/磷(質量比)為0.1以上，且鎮量為20mg/m2。又，前 述有機皮膜層含有環氧樹脂及/或變性環氧樹脂，又，前述有機皮 膜層之附著量為0.3~5g/m2。 1279452 前述本發明之經無機有機複合處理之鍍辞鋼板，由於不使用 鉻酸鹽，可得職狀喊紐，製奴法亦襲，且成本亦低， 因此，可雜使用在汽車、家電、建财各種用途。 【-PC 】 較佳實施例之詳細說明 以下，詳細地說明本發明。 本發明之經無機核複合處理之__狀_層，㈣ 要電鍍、熱浸鍍方法，但需要(002)面之結晶定向為50%以上。其 中，所謂_面之結晶定向’係指藉X線繞設裝置繼鑛鋅結晶 之各峰強度再以各峰強度之和除以相當於(⑻^面之面之峰強度 之百分比者。鍍騎之_量並鱗繼定，_縣更高之耐 腐蝕性時係以20g/m2以上為佳。 將(002)面之結晶定向限定在5〇%以上係因為未滿獅時耐 雜性不佳。軸50%社可得敎好耐腐紐之理由並不非常 明確’ ^而可以推想其中一個理由為形成於如前述之狀態之電鑛 層上之顧辞越之性狀會改變，喃上層之有機皮膜層之密著 I·生變的良好又3外-個理由，可想到是因為即使有填酸辞皮 膜無被覆而使鍍鋅層露出之部分存在，亦可_形成舣之電鑛 層構造’使電顯與上層之有機皮輯之密著性變的良好。 欲使_)®之結晶⑽猶減，料崎讀丨過電位低 之條件進行電鍍即可。魏而言濃度、電流密度等 控制。透過使電鐘浴之鋅離子濃度高，或使電鑛電流密度低，可 提尚(002)面定向。 磷酸鋅處理皮膜可由含有磷酸離子及鋅離子之習知公知之 上279452 形成。前述璘酸離子之供給源，只要是含有鋅之化 有制限定，例如可舉财鋅、氧鱗、碳酸辞、 可述嶙酸離子之供給源，只要是含有顧之化合物即 鈉等。：?別限定，例如可舉例有魏、五氧化鱗、顧二氫 述雜如、可3有適里之制於磷酸辞處理狀其他成分。前 蝴。x，贿蝴、純、銅、 耐21或辦元錢合者。触，可更鄕雌鋼板之 、 且’可提昇與後處理皮膜之間之密著性。 旦前述磷酸鋅處理皮膜之皮膜中之鎭峨皮膜中之鎮與磷之質 =比)以O.m上為佳。小於叫，可能無法看_添加而提昇财 w生之放果。别述磷酸辞處理皮膜之皮膜中之鎮量係以2⑽以 上為佳。小於20mg/m2時，恐無法提昇耐雜性。 又，前述磷酸鋅處理皮膜，係以下限0.3gW、上限5g/m2之 皮膜量形成者為佳。小於a3g/m>，耐雜性可能不足，而超過 g/m時’於實施強烈加工時，皮膜恐會剝離。 域則述磷酸辞處理皮膜之處理液，可使用以雜離子、辞 離子為主成分’且於必要時亦添加辞以外之金屬離子、确酸離 氟化物離子等市售之處理液。欲使麟酸辞處理皮膜中含有鎮 時，係以使麟前述磷酸鋅處理液中添加有硝麵等之浴為佳。 皮膜中之㈣麟/磷之比可藉顧狀添加量控制。 藉Θ述磷酸辞處理瓣理鍍_板塌酸聽理方法，不管 使用反應型處理、塗布型處理巾任-種方法都可形成磷酸鋅處理 ^ °反’例如可於鍍鋅鋼板進行脫脂、祕、表面調 I後’使該峨與w述磷酸鋅處職賴，魏行祕、乾燥來 1279452 形成麟酸鋅處理麵。贿鋅處理皮膜 處理時間或處理劑濃度來調整。 之皮膜量，例如可藉改1279452 IX. Description of the Invention: [Technical Field to Which the Invention Is Alonged] TECHNICAL FIELD The present invention is directed to a type of composite material. BACKGROUND OF THE INVENTION In the past, in order to improve the financial record or bribery of the steel plate for automobiles, home appliances, building materials, etc., it is a gambling __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In particular, after the salt treatment, the method of sealing by chromate has a great effect on improving the corrosion resistance or the coating, and is widely implemented. However, in the context of the problem of reducing the problem in the past year, there has been a tendency to develop a surface treatment technique that does not use a highly toxic complex, and has the following techniques. This technology provides a phosphoric acid-composite-treated steel sheet having an organic coating film of the second layer on the surface of the plated steel sheet having the i-th layer of the acid-filled coating layer (see, for example, Japan). Patent Publication No. 2〇〇1_1〇5528), and the above-mentioned Wei Xie treatment of Lai Ling Wei Zibu, Yi shot of at least i species of adhesion amount of 0·2~2.5g/m2 'and the aforementioned organic film system to choose The organic resin is mainly composed of at least an ethylene resin, an epoxy resin, a methyl formate resin, and an acrylic resin. In addition, a galvanized coating is formed on the surface of the steel sheet, a disk of acid coating of 3.3g/m2 or more, an organic view of G·3~2g/m2, and a mixed body age of Wei, and The town/rhodium (mass ratio) is an organic composite galvanized steel sheet having a 〇15 or more and a mass of 2 or more (see, for example, Japanese Patent Laid-Open Publication No. 200M31763). 1279452, usually formed and pressed under pressure. Therefore, it is necessary to carry out the galvanized steel sheet which has been subjected to the treatment as described above without being coated, and is used after being directly degreased and washed or after being cracked. Both corrosive and corrosion resistance after coating. However, the combination of the zinc-coated film and the organic film in the Wei-Jie-treated steel sheet and the organic composite zinc-coated steel sheet obtained by the method described above is not strong in the mixed environment, and the rate is extremely high. In the case of Wei towel, Wei Zinc film and Qianpiguan will produce "sweeping," and the lack of tolerance of money amount occurs. SUMMARY OF THE INVENTION 3 SUMMARY OF THE INVENTION In view of the foregoing, it is an object of the present invention to provide an inorganic inorganic composite treated plated steel sheet which does not contain harmful chromate in the treated film and which can provide excellent corrosion resistance. The present inventors have specifically targeted the zinc-bonded zinc-containing zinc oxide film and the organic film by the inorganic-organic composite treatment of the forged steel plate, and reviewed various methods for improving the combination of the acid-filled skin film and the organic film in a corrosive environment. The state of the galvanized layer of the underlying layer of the zinc film is greatly affected, and the present invention has been completed. The invention provides a galvanized steel sheet which is treated by an inorganic organic composite treatment, wherein the galvanized steel sheet which has been subjected to an inorganic organic composite treatment is a galvanized layer having a (002) plane orientation of 50% or more on a steel sheet, and The galvanized layer has a zinc phosphate film containing magnesium and an organic film layer on the zinc phosphate film. The magnesium/phosphorus (mass ratio) in the zinc phosphate coating film is 0.1 or more, and the amount of the alloy is 20 mg/m2. Further, the organic film layer contains an epoxy resin and/or a denatured epoxy resin, and the adhesion amount of the organic film layer is 0.3 to 5 g/m2. 1279452 The above-mentioned inorganic-organic composite-treated plated steel plate of the present invention can obtain a job-like slogan because of the absence of chromate, and the slave-making method is also attacked, and the cost is also low, so that it can be used in automobiles, home appliances, Jiancai for various purposes. [-PC] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail. The inorganic core composite treatment of the present invention is __form_layer, (4) electroplating and hot dip plating methods, but the crystal orientation of the (002) plane is required to be 50% or more. Wherein, the so-called "crystal orientation" refers to the intensity of each peak of the zinc crystals by the X-ray winding device and then the sum of the peak intensities divided by the percentage of the peak intensity of the surface of the (8) surface. The amount of riding is limited and the scale is determined. The higher corrosion resistance of the county is better than 20g/m2. The orientation of the crystal of the (002) plane is limited to 5〇% or more because it is not full of lions. Poor. The reason why 50% of the shaft can get good corrosion resistance is not very clear. ^ It can be assumed that one of the reasons is that the traits formed on the electric ore layer as in the aforementioned state will change. The adhesion of the upper organic film layer is good and the other is a good reason. It is conceivable that even if there is no coating of the acid film, the exposed portion of the galvanized layer exists, and The layer structure 'is good for the adhesion between the electric display and the organic layer of the upper layer. To make the crystal of the _)® (10) substantiate, the material can be plated under the condition that the potential is low. Wei said the concentration, current density and other controls. By making the concentration of zinc ions in the electric clock bath high, or making the current density of the electric ore low, the orientation of (002) plane can be raised. The zinc phosphate treated film can be formed from the conventionally known 279452 containing a phosphate ion and a zinc ion. The supply source of the citrate ion is not limited as long as it contains zinc. For example, it may be a supply source of zinc, an oxygen scale, a carbonated acid or a citrate ion, and may be a sodium or the like which contains a compound. It is not limited, for example, there may be mentioned Wei, pentoxide scale, Gu Dihydrogen, and the like. Before the butterfly. x, bribe, pure, copper, resistant 21 or dollar money. The touch can be more sturdy and the adhesion between the post-treated film and the post-treated film can be improved. Preferably, the ratio of the town to the phosphorus in the coating film of the zinc phosphate treated film is preferably O.m. Less than the call, may not be able to see _ add and improve the financial results. It is preferable that the amount of the film in the film of the phosphoric acid-treated film is 2 (10) or more. When it is less than 20 mg/m2, it may not improve the resistance to impurities. Further, it is preferable that the zinc phosphate-treated film is formed by a film thickness of 0.3 gW or an upper limit of 5 g/m 2 . Less than a3g/m>, the resistance may be insufficient, and when it exceeds g/m, the film may peel off when subjected to intense processing. In the case of the treatment liquid for the phosphoric acid treatment film, a commercially available treatment liquid such as a metal ion other than a hetero ion or a resonating ion and, if necessary, a metal ion or a deionized fluoride ion may be used. In order to contain a town in the film of the linonic acid, it is preferable to add a bath such as a nitric surface to the zinc phosphate treatment liquid. The ratio of (four) lin/phosphorus in the film can be controlled by the amount of addition. By means of the phosphoric acid treatment, the plating method is used to form a zinc phosphate treatment, for example, by using a reactive treatment or a coated treatment towel, for example, it can be degreased on a galvanized steel sheet. After the secret, the surface is adjusted to I, so that the sputum and the w zinc sulphate are used, and Wei Xing secret, dry to 1279452 to form a zinc sulphate treatment surface. Bribe zinc treatment film treatment time or treatment agent concentration to adjust. The amount of film, for example, can be changed
寸處理’除了可於鑛辞鋼板將對應必要之皮膜量之量之 =、=處理液贿塗特布以外，更錢浸潰 綠輕成轉之塗转之綠。將雜鋅處理劑 ^鋅鋼板後’藉姻乾等魏，形成磷酸鋅處理皮膜。 把、&域有輪麵理之麟鋪，胁前述鱗酸辞 处理皮膜上具有有機皮闕者，藉此可更進—步改善耐腐谢生。 有機皮輯含有麵_，且為了提料腐雜 ’可摻入各種防 鏽添加劑歧咖。又’亦可配合目的，摻人魏給予滑動性之 蠟成分或給予圖案性之顏料等。 由密著性之無來看，有鑛雜时有魏細旨及/或變 性環氧樹脂為佳。有機皮膜層之附著量係以a3〜5g/m2為佳，小於 下限時耐腐蝕性不足，而超過上限時不易熔接。 有機皮膜層可於藉塗裝、喷霧、電錢等方法塗布後，進行洪 烤乾燥來形成。 本發明之雜辞處理層，細於兩面處理為佳，然而對於有 機皮膜層，可於至少-面，即於最要求無塗裝之耐雜性之面進 行處理。 實施例1 以下，藉實施例詳細地說明本發明。 (鍍鋅鋼板） 於電鍍鋅鋼板製造線中，使辞附著量(每一單面)為40§/1112， 且藉調整電鍍浴濃度與電鍍電流密度，製成鋅結晶定向不同之各 1279452 種鍍鋅鋼板。 (鱗酸鋅處理） 於前述電鍍鋅處理鋼板進行鹼脫脂後，進行市售之Ti02膠體 系表面調整處理，並進行填酸鋅處理。構酸鋅處理液係使用含有 Zn離子2.5g/l、Ni離子2Og/l、Μη離子2.5g/l、Mg離子 15g/l、P〇4 離子14g/l者，藉嘴霧法以溫度45。及處理時間M〇秒進行洗滌並 乾燥。 (有機皮膜處理） 使用前述經磷酸鋅處理之鍍辞鋼板，進行有機皮膜處理。有 機皮膜處理係使用以水性樹脂為基底，並添加膠質氧化石夕固體且 使其成分重ϊ比為16%所構成之塗料，而前述水性樹脂係於乙烯 變性環氧酯樹脂摻合嵌段異氰酸酯硬化劑、變性聚乙烯蠟、縮合 偶氮系之紅色顏料(固體成分重量比分別為1〇〇: 1〇:5:3)者，又， 藉輥塗機塗布，且烘烤到板溫度15(rc，再以水冷卻。 (性能評價方法） (0〇2)面結晶定向：使用並以燈泡以、 40kV/20GMa進行2 6» 5〜90。之掃描(γ/πύη)，測量鋅之各結晶面之 峰強度’再以各結晶面峰強度之和除以〇〇2面強度來求出(〇〇2)面 定向比。 糊夂辞皮膜中鎮、嶙量：使皮膜全部溶解，並藉icp分析來 疋里 ^辞皮膜里係由前述構量假設Hopeite(鱗鋅礦)之構 造後計算而算出。 線分析定量Si，並由組成比換算成皮 膜量。 10 1279452 無塗裝耐腐蝕性：以市售之洗淨油洗淨樣品後，進行u邊緣 彎曲加工(樣品寬度70mm、BHF=lton、加工高度=7〇111111、邊緣 部衝壓R=5mm、邊緣部切割R=3mm、衝壓、切割 5mm、加工速度= 25spm)，切割其側面(切割面），並脫脂後，以 賽路紛膠帶密封端面與裡面，並進行CCT試驗*。觀察15循環後 之紅鏽產生狀況。「〇」：小於1%，「△」：；[〜；[〇%，「χ」：超過1〇%。 塗裝密著性：將樣品以市售之鹼脫脂液(ph=1〇 5、4(rc、浸 潰1分鐘）進行汽車用化合處理（日本PAINT公司製撒服旦_ 2500MZL)後’進行汽車用陽離子電沉積（日本ρΑΙΝΊν>司製、 20μ、170°且20分鐘之烘烤）。放置一天一夜後浸潰於5〇它溫水， 並於10天後取出’再製造間隔1]〇[皿之棋盤縫切割瑕疵，並以賽路 玢膠帶進行剝離。「〇」：沒有剝離，「△」··切割瑕疵之周邊之剝 離，「X /剝離。 塗裝後耐腐钱性：將樣品以市售之驗脫脂液 c、浸潰1分鐘)進行汽車用化合處理（日本PAINT公司製撒服旦一 2500MZL)後，進行汽車用陽離子電沉積（日本pAIN1^司製V2〇、 20μ、170。且20分鐘之烘烤）。製造通往地鐵之交叉切割瑕疵，並 進行cct試驗*。測量20循環後之膨脹寬度。「〇」：小於lmm， 「△」=1〜2mm ’「X」：超過2mm。 *CCT試驗條件：重複1循環之鹽水喷霧(5%NaCl，35)6小時 —乾燥(50°C45%RH)3 小時—濕潤(5〇°C95%RH)14 小時-> 乾燥(5〇 °C45%RH)1小時。 於表1顯示以上之評價結果。 11 1279452 ^1 磷酸鋅皮膜 性能評價結果 鍍鋅 (002)面定向 65 "72" 皮膜量 鎂/磷 質量比 鎂量mg/m2 有機皮膜 皮膜量g/m2 塗耐蝕 無裝腐 性 _L0 To" 0.17 0.17 23 裝#生 塗後腐+ 塗料密著性 實施例 84 ~96~ ~12 72 72 ~12 72 L0 To" ΤΓ 1.4 JLO^ To" 1.0 0.17 0.17 0.18 0.18 0.17 0.17 0.17 23 "23~ 23 *29" 34 23 23 _07_ "〇7~ 互 互 ~0?Γ 0.3 〇 〇 〇 〇 〇 〇 〇〇 00 〇| 〇 比較例 46 ~32~ ~65~ "72"In addition to the amount of film, the amount of film required to be used in the mine plate will be more than the amount of the film, and the treatment liquid will be smeared with green cloth. After the zinc-zinc treatment agent is used, the zinc-coated steel sheet is used to form a film of zinc phosphate. The && field has a round face Lin Lin, threatening the above-mentioned scales to deal with the organic skin on the film, so as to further improve the corrosion resistance Xie Sheng. The organic skin series contains noodles _, and various anti-rust additives can be incorporated in order to extract the rot. Further, it is also possible to incorporate a wax component which imparts slidability or a pigment which gives a pattern, etc., in accordance with the purpose. From the point of view of the lack of adhesion, it is preferable to have a fine-grained and/or variable epoxy resin when there is a mineral. The adhesion amount of the organic film layer is preferably from 3 to 5 g/m2, and when it is less than the lower limit, the corrosion resistance is insufficient, and when it exceeds the upper limit, it is not easily welded. The organic film layer can be formed by coating by a coating, a spray, a money, or the like, followed by baking and drying. The word processing layer of the present invention is preferably finer than two-side treatment, whereas for the organic film layer, it can be treated at least on the surface, i.e., on the surface which is most resistant to coating. Embodiment 1 Hereinafter, the present invention will be described in detail by way of examples. (galvanized steel sheet) In the electro-galvanized steel sheet manufacturing line, the amount of adhesion (each side) is 40§/1112, and by adjusting the plating bath concentration and the plating current density, each of the 1279452 types of zinc crystal orientation is made. Galvanized steel. (Zinc sulphate treatment) After the alkali degreasing of the electrogalvanized steel sheet, a commercially available TiO2 colloidal surface conditioning treatment was carried out, and zinc sulphate treatment was carried out. Zinc acid treatment liquid system uses Zn ion 2.5g / l, Ni ion 2Og / l, Μ η ion 2.5g / l, Mg ion 15g / l, P 〇 4 ion 14g / l, by mouth fog method with temperature 45 . The treatment time is M 〇 second for washing and drying. (Organic film treatment) The organic film treatment was carried out using the zinc phosphate-treated plated steel sheet. The organic film treatment uses a coating composed of an aqueous resin and a colloidal oxidized oxide solid with a composition weight ratio of 16%, and the above aqueous resin is blended with an ethylene-modified epoxy ester resin blended block isocyanate. Hardener, denatured polyethylene wax, condensed azo red pigment (solid content weight ratio: 1〇〇: 1〇: 5:3, respectively), and coated by a roll coater, and baked to a plate temperature of 15 (rc, then cooled with water. (Performance evaluation method) (0〇2) Surface crystal orientation: Use and scan with a bulb at 40kV/20GMa for 2 6» 5~90. (γ/πύη), measure zinc The peak intensity of each crystal plane' is obtained by dividing the sum of the intensity of each crystal plane peak by the intensity of the 〇〇2 plane to obtain the (定向2) plane orientation ratio. The paste and the amount of the film in the film: the amount of the film is completely dissolved. The icp analysis is used to calculate the structure of the Hopeite (scale zinc ore) from the above-mentioned structure. The line analysis quantifies Si and converts the composition ratio into the amount of film. 10 1279452 No coating resistance Corrosive: After washing the sample with commercially available washing oil, the u-edge bending process is performed ( Product width 70mm, BHF=lton, machining height=7〇111111, edge part punching R=5mm, edge part cutting R=3mm, punching, cutting 5mm, processing speed=25spm), cutting the side (cutting surface), and degreasing After that, seal the end face and the inside with the tape, and carry out the CCT test*. Observe the red rust generation after 15 cycles. "〇": less than 1%, "△":; [~; [〇%, "χ ”: more than 1%. Coating adhesion: The sample was treated with a commercially available alkali degreasing solution (ph=1〇5, 4 (rc, dipping for 1 minute) for car compounding (sprinkling by PAINT, Japan) After _ 2500MZL), 'Carbon cation electrodeposition (made by Japan ρΑΙΝΊν>, 20μ, 170° and 20 minutes of baking) was carried out. After being placed for one day and one night, it was immersed in 5 〇 of warm water and taken out after 10 days. 'Remanufacturing interval 1】〇[The dish of the dish is cut and cut, and peeled off with Sai Lulu tape. "〇": no peeling, "△" · peeling around the cutting edge, "X / peeling. Painting Post-corrosion resistance: the sample is treated with commercially available degreased liquid c, impregnated for 1 minute) for automotive compounding treatment After the Japanese PAINT company made a service of 2500 MZL), it carried out cationic electrodeposition for automobiles (V2〇, 20μ, 170, and 20 minutes of baking in Japan), and manufactured a cross-cutting raft to the subway. Cct test*. Measure the expansion width after 20 cycles. "〇": less than lmm, "△" = 1~2mm 'X': more than 2mm. *CCT test conditions: repeat 1 cycle of salt spray (5% NaCl , 35) 6 hours - dry (50 ° C, 45% RH) for 3 hours - wet (5 ° C 95% RH) 14 hours - > Dry (5 ° C 45% RH) for 1 hour. The above evaluation results are shown in Table 1. 11 1279452 ^1 Zinc phosphate film performance evaluation results galvanized (002) plane orientation 65 "72" Film amount Magnesium/phosphorus mass ratio Magnesium amount mg/m2 Organic film film amount g/m2 Coating corrosion resistance without rotability _L0 To" ; 0.17 0.17 23 loaded #生涂腐腐 + coating adhesion Example 84 ~96~ ~12 72 72 ~12 72 L0 To" ΤΓ 1.4 JLO^ To" 1.0 0.17 0.17 0.18 0.18 0.17 0.17 0.17 23 "23~ 23 *29" 34 23 23 _07_ "〇7~ Mutual ~0?Γ 0.3 〇〇〇〇〇〇〇〇00 〇| 〇Comparative Example 46 ~32~ ~65~ "72"
"oT 1.0 0.17 0.17 0.17 23 23 23 限 * —23 本小於lmg/n 1.2 "10" 0.7 "〇?Γ 0.7 -(無） 〇 〇 〇 〇〇 〇〇 IO一〇 〇 〇 〇〇 與本發明之實施例之良好特性者相比較下，超過本發明之範 圍以外之比較例之特性不佳。 產業上之可利用性 本發明之經無機有機複合處理之鑛辞鋼板，由於不使用鉻酸 鹽’可传到良好之耐腐紐，製造方法亦簡易，且成本亦低，因 此’可適於使用在汽車、家f、雜等各種用途。"oT 1.0 0.17 0.17 0.17 23 23 23 Limit* —23 This is less than lmg/n 1.2 "10" 0.7 "〇?Γ 0.7 -(none) 〇〇〇〇〇〇〇IO〇〇〇〇〇 In comparison with the good characteristics of the examples of the present invention, the characteristics of the comparative examples beyond the scope of the present invention are not good. INDUSTRIAL APPLICABILITY The mineral-inorganized composite steel sheet of the present invention can be transferred to a good anti-corrosion button without using chromate, and the manufacturing method is simple and low in cost, so that it can be adapted It is used in various applications such as automobiles, home f, and miscellaneous.
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