TW200934888A - Metal surface treatment composition, and surface-treated metal material with metal surface treatment layer obtained from the metal surface treatment composition - Google Patents
Metal surface treatment composition, and surface-treated metal material with metal surface treatment layer obtained from the metal surface treatment compositionInfo
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- TW200934888A TW200934888A TW97147484A TW97147484A TW200934888A TW 200934888 A TW200934888 A TW 200934888A TW 97147484 A TW97147484 A TW 97147484A TW 97147484 A TW97147484 A TW 97147484A TW 200934888 A TW200934888 A TW 200934888A
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200934888 六、發明說明: 【發明所屬之技術領域:| 技術領域 本發明係有關於一種金屬表面處理用組成物’以及從 5 該金屬表面處理用組成物獲得之具有金屬表面處理層的表 面處理金屬材。 【先前技術3 背景技術 過去’為使金屬表面的耐腐蝕性提高,一般進行鉻酸 ίο鹽處理及磷酸鹽處理。然而近年來鉻的毒性已成為社會問 題。使用鉻酸鹽的表面處理方法具有於處理工程中鉻酸鹽 的煙飛散之問題、在排水處理設備上需要魔大經費、更還 有自化學轉化處理外膜溶出鉻酸所造成的問題等等。而六 4貝絡化 口物被IARC (International Agency for Research on 15 Cance1· Review)為首的多數公家機關指定為對人體致癌物 質,是極為有害之物質。 而麟酸鹽處理通常進行磷酸辞系或磷酸鐵系的表面處 理。構酸鹽處理後,以赋予耐腐純為目的,通常會以鉻 酸進行/月洗處理。因此,有絡處理的問題以及麟酸鹽處理 2〇劑中的反應促進劑或金屬離子等的排水處理、自鱗酸鹽處 理金屬命出金屬離子所造成之軟泥處理等問題。 絡@夂鹽處理及鱗酸鹽處理以外的處理方法,錯系及欽 系表面處理劑是眾所皆知(參照曰本專利特公§48_24618號 A報等),主要實用化於銘系材料。然而對於辞系材料會有 3 200934888 <腐餘性較以往的鉻酸鹽處理低劣的問題。 錯系及鈦系以外尚有釩系處理劑被研究,日本專利特 開H9-95796號公報中揭露含有鈒酸鹽及/或無機酸飢鹽、 及具還原力之有機酸之金屬表面處理用電解化學轉化處理 5液。此為藉由進行負極化學轉化處理,於鋅材料亦能形成 優異耐腐蝕性外膜者。然而,所謂電解化學轉化處理之處 理方法有其界限存在,相較於只將材料浸泡或塗佈處理液 之處理成本較高,因此限定於特殊用途。 釩因耐腐蝕性優異,以偏釩酸銨等釩酸鹽利用作為防 ❹ 10鏽劑。然而’釩化合物在水中之安定性低劣,因此採用以 特疋水性有機樹脂分散,再分散於水中之方法。但即使是 此方法,亦無法將釩化合物大量加入至表面處理劑中,具 有由該表面處理劑形成的層之金屬表面的耐腐蝕性低下是 無法避免的。因此研究使用由釩化合物與過氧化氫反應而 15 成之過氧飢酸。 曰本專利特開S54-147141號公報中揭露一種使用了過 氧金屬含氧酸鹽的表面處理劑,該金屬係以釩為例《然而, Ο 過氧釩酸於水中的安定性雖優於前述釩酸鹽,但因容易產 生沉澱,故在貯藏安定性方面產生了問題。又,沒有任何 20 一個專利文獻記載使用過氧釩酸之實例,對此沒有進行充 分的研究。這被認為是因為處理劑的貯藏安定性尚未達到 實用上沒問題的程度。 【發明内容】 發明揭示 4 200934888 5 本發明之目的,在於提供一種具有與鉻酸鹽處理劑及 磷酸鹽處理劑匹敵之防鏽力,且貯藏安定性優異、無公害 型的金屬表面處理用組成物。 本發明之發明人為解決上述目的而經過仔細檢討後的 結果,發現含有過氧釩酸以及有機膦酸之金屬表面處理用 組成物具有與鉻酸鹽處理劑及磷酸鹽處理劑匹敵之防鏽 力,且貯藏安定性優異,進而完成本發明。 亦即,本發明係提供以下的金屬表面處理用組成物及 ❹ 具有從該金屬表面處理用組成物獲得之金屬表面處理層的 10 表面處理金屬材。 1. 一種金屬表面處理用組成物,其特徵在於,其包含 有: (A) 過氧釩酸;及 (B) 有機膦酸。 15 2.如上述第1項之金屬表面處理用組成物,該有機膦酸 (B)具有一帶有羥基之有機基團。 3.如上述第1或2項之金屬表面處理用組成物,其中該 有機膦酸(B)係含有選自1-羥甲基-1,1-二膦酸、1-羥乙基 -1,1-二膦酸、及1-羥丙基-1,1-二膦酸之至少一種化合物者。 20 4. 如上述第1至3項中任一項之金屬表面處理用組成 物,其含有該有機膦酸(B)相對於該過氧釩酸(A) 100 質量部在1〜250質量部範圍内。 5. 如上述第1至4項中任一項之金屬表面處理用組成 物,其中更含有一種水溶性或水分散性有機樹脂(C)。 5 200934888 6. 如上述第5項之金屬表面處理驗成物,其含有該水 ,合杜或水分散性有機樹脂(C)相對於該過氧叙酸(A) 100 質量部在1〜2〇,〇〇〇質量部之範圍内。 7. 如上述第1至6項中任-項之金屬表面處理用組成 5物,該金屬表面處理用組成物係用於經鋅或鋅合金電鑛之 鋼材。 8· -種表面金屬材,係具有位在經鑛鋅或辞合金之鋼 材上且由如第丨至6射任—項之金屬表喊理用組成物獲 得之金屬表面處理層者。 〇 9. 一種表面處理鋼板,係具有位在經鍍鋅或辞合金之 鋼板上且由如第㈤項中任一項之金屬表面處理賴成物 獲得之金屬表面處理層者。 10. -種表面金屬材料之製造方法’係形成有位在經 鍍鋅或鋅合金之材料上且由如第丨至6項中任—項之金屬表 15面處理用組成物獲得之金屬表面處理層者。 11_ 一種表面金屬鋼板之製造方法,係形成有位在鍍 辞或鋅合金之鋼板上且由如第丨至6項中任_項之金屬表面 處理用組成物獲得之金屬表面處理層者。 本發明之金屬表面處理用組成物係含有過氧釩酸(A) 20及有機膦酸(B)者。於以下詳細說明之。 過氧钒酸(A) 本發明(A)成分之過氧釩酸,可藉由例如將釩化合物 與過氧化氫反應而容易地製造。 上述釩化合物,可舉例如三氧化釩、五氧化釩等的釩 6 200934888 氧化物;氧二氣化釩、氧三氣化釩等的氧_化釩;三氣化 飢等的齒化釩;偏釩酸銨、偏釩酸鈉、正釩酸鈉、硫酸氧 釩、焦釩酸鈉等等。其中以製造容易度等觀點來看,特別 以五氧化鈒及偏飢酸錄為佳。 相對於釩化合物的過氧化氫添加量,係以相對於叙化 合物100質量部在10〜5,0〇〇質量部左右為佳。200934888 VI. Description of the Invention: [Technical Field] The present invention relates to a composition for metal surface treatment and a surface-treated metal having a metal surface treatment layer obtained from the composition for metal surface treatment material. [Prior Art 3] In the past, in order to improve the corrosion resistance of a metal surface, chromic acid salt treatment and phosphate treatment were generally performed. However, the toxicity of chromium has become a social problem in recent years. The surface treatment method using chromate has the problem of the smoke scattering of chromate in the treatment engineering, the need for the magic treatment of the drainage treatment equipment, and the problem caused by the dissolution of the outer membrane by the chemical conversion treatment. . Most of the public agencies, headed by the IARC (International Agency for Research on 15 Cance1·Review), are designated as carcinogenic to humans and are extremely harmful substances. The sulphate treatment is usually carried out by surface treatment of a phosphate or iron phosphate system. After the acidification treatment, it is usually treated with chromic acid/monthly for the purpose of imparting corrosion resistance. Therefore, there are problems such as the treatment of the enthalpy, the treatment of the reaction accelerator or the metal ion in the sulphate treatment, and the treatment of the scum from the sulphate treatment of the metal ions. The treatment methods other than the treatment of 夂@夂盐 and sulphate treatment, the miscellaneous and the surface treatment agent are well-known (refer to the 曰48_24618A newspaper, etc.), which is mainly used in Ming materials. . However, for the lexicographic material, there will be 3 200934888 < the problem of poor corrosion compared to the previous chromate treatment. A vanadium-based treatment agent has been studied in addition to the erroneous system and the titanium system. Japanese Patent Laid-Open Publication No. H9-95796 discloses a metal surface treatment containing a bismuth citrate and/or an inorganic acid hunger salt and a reducing organic acid. Electrolytic chemical conversion treatment of 5 liquids. This is because the negative electrode chemical conversion treatment can also form an excellent outer layer of the corrosion-resistant outer layer of the zinc material. However, the so-called electrolytic chemical conversion treatment method has its own limit, and is limited to a special use as compared with the case where only the material is immersed or the treatment liquid is treated at a high cost. Vanadium is excellent in corrosion resistance and is used as a rust preventive 10 rust agent such as vanadate such as ammonium metavanadate. However, the vanadium compound has a poor stability in water, and therefore it is dispersed by a special aqueous organic resin and redispersed in water. However, even with this method, it is impossible to add a large amount of the vanadium compound to the surface treatment agent, and the corrosion resistance of the metal surface having the layer formed of the surface treatment agent is unavoidable. Therefore, it has been studied to use peroxic acid which is reacted with a hydrogen peroxide by a vanadium compound. A surface treatment agent using a peroxometal oxyacid salt is disclosed in the Japanese Patent Laid-Open Publication No. S54-147141, which is based on vanadium. However, the stability of yttrium vanadic acid in water is superior. The vanadate described above has a problem in terms of storage stability due to the tendency to precipitate. Further, no one of the patent documents describes an example of the use of peroxovanic acid, and sufficient research has not been conducted thereon. This is considered to be because the storage stability of the treating agent has not reached the point of practically no problem. DISCLOSURE OF INVENTION PROBLEMS TO BE SOLVED 4 200934888 5 The object of the present invention is to provide a metal surface treatment composition which has an anti-rusting property comparable to a chromate treatment agent and a phosphate treatment agent, and which has excellent storage stability and is non-polluting type. Things. The inventors of the present invention have carefully examined the above-mentioned objects and found that the metal surface treatment composition containing peroxovanaic acid and organic phosphonic acid has anti-rusting power comparable to chromate treating agent and phosphate treating agent. And the storage stability is excellent, and the present invention is completed. That is, the present invention provides the following composition for metal surface treatment and 10 10 surface-treated metal material having a metal surface treatment layer obtained from the metal surface treatment composition. A composition for metal surface treatment comprising: (A) peroxyvanadic acid; and (B) an organic phosphonic acid. The metal surface treatment composition according to the above item 1, wherein the organic phosphonic acid (B) has an organic group having a hydroxyl group. 3. The metal surface treatment composition according to the above item 1 or 2, wherein the organic phosphonic acid (B) contains a group selected from the group consisting of 1-hydroxymethyl-1,1-diphosphonic acid and 1-hydroxyethyl-1. And at least one compound of 1-diphosphonic acid and 1-hydroxypropyl-1,1-diphosphonic acid. The metal surface treatment composition according to any one of the above items 1 to 3, wherein the organic phosphonic acid (B) is contained in an amount of from 1 to 250 parts by mass relative to the mass of the peroxyvanadate (A) 100. Within the scope. 5. The metal surface treatment composition according to any one of items 1 to 4 above, which further comprises a water-soluble or water-dispersible organic resin (C). 5 200934888 6. The metal surface treatment composition according to item 5 above, which contains the water, the Du Du or the water-dispersible organic resin (C) relative to the peroxy sulphuric acid (A) 100 mass parts at 1 to 2 〇, within the scope of the quality department. 7. The metal surface treatment composition according to any one of the above items 1 to 6, wherein the metal surface treatment composition is used for a steel material which is subjected to zinc or zinc alloy electric ore. 8. A surface metal material having a metal surface treatment layer which is obtained on a steel material of a mineral or zinc alloy and which is obtained by a metal watch composition such as No. 6 to No. 6 . 〇 9. A surface-treated steel sheet having a metal surface treatment layer obtained by galvanizing or alloying a steel sheet and obtained by the metal surface treatment of any one of the items (5). 10. A method of producing a surface metal material by forming a metal surface obtained by a composition of a surface treatment of a metal sheet of the galvanized or zinc alloy and having a metal surface treatment according to any one of items 1-6 to 6. Processing layer. 11_ A method for producing a surface metal steel sheet which is formed by a metal surface treatment layer obtained by a metal surface treatment composition according to any one of Items 1-6 to 6 of the steel plated or zinc alloy. The metal surface treatment composition of the present invention contains peroxovanaic acid (A) 20 and an organic phosphonic acid (B). It is described in detail below. Peroxyvanadic acid (A) The peroxyvanadic acid of the component (A) of the present invention can be easily produced by, for example, reacting a vanadium compound with hydrogen peroxide. Examples of the vanadium compound include vanadium 6 200934888 oxide such as vanadium trioxide or vanadium pentoxide; oxygen vanadium such as oxygen vanadium pentoxide or vanadium oxysulfide; and vanadium vanadium such as three gasification hunger; Ammonium metavanadate, sodium metavanadate, sodium orthovanadate, vanadyl sulfate, sodium pyrovanadate, and the like. Among them, in view of ease of manufacture, it is preferable to record ruthenium pentoxide and hunger. The amount of hydrogen peroxide added to the vanadium compound is preferably about 10 to 5,0 Å by mass based on 100 parts by mass of the compound.
10 又,過氧釩酸的製造,通常可藉由在過氧化氫水溶液 中添加飢化合物,於20〜l〇〇°C下加熱15〜12〇分鐘來進行 過氧凱酸(A)在該金屬表面處理用組成物中的濃声並 例 無特別限定,可依據使用形態改變適當稀釋率來使用 如以金屬表面處理用組成物中0.01〜l00g/L為宜,更以〇 i 〜30g/L為佳。當過氧釩酸(A)的濃度未達前述範圍時 將會有得不到充分的耐腐#性之傾向,而當超出前述範圍 時’液體貯藏安定性方面會有劣化的傾向。10 Further, the production of peroxovanic acid can be carried out by adding a hunger compound to an aqueous hydrogen peroxide solution and heating at 20 to 1 ° C for 15 to 12 minutes to carry out peroxoic acid (A). The thick sound in the composition for metal surface treatment is not particularly limited, and may be appropriately changed according to the use form, for example, 0.01 to 100 g/L in the composition for metal surface treatment, and more preferably 〇i to 30 g/ L is better. When the concentration of peroxovanaic acid (A) is less than the above range, there is a tendency that sufficient corrosion resistance is not obtained, and when it exceeds the above range, there is a tendency for deterioration in liquid storage stability.
本發明(B)成分之有機膦酸’適合者可舉例如κ輕甲 基-1,1-二膦酸、1·經乙基-1,1-二膦酸、κ經丙基鱗酸 荨帶有含經基之有機基團的有機膦酸;2_經基膦醜武 酸、2-膦酸丁烷-丨二‘三羧酸等帶有—種含羧基之有機 20的有機膦酸及其鹽類。 上述有機膦酸在使前述過氧飢酸(Α)水溶液的貯藏安 定性提升方面有優異的效果,其中從貯藏安定性觀點來 看,以帶有含羥基之有機基團的有機膦酸為宜,而以丨、羥 甲基-1,1-二膦酸、1_經乙基-1,1-二膦酸、丨-經丙基-i’l、二膦 7 200934888 酸為佳’特別以1-羥乙基-1,1-二膦酸為佳。 因過氧釩酸(A)在水中之安定性貧乏,有機膦酸(B) 之添加係於製造過氧釩酸後立刻添加為佳。 本發明之金屬表面處理用組成物因含有過氧釩酸(A) 5 及有機膦酸(B),在貯藏安定性方面優異。 從貯藏安定性觀點來看’有機膦酸(B)的添加量相對 於該過氧釩酸(A)固形分1〇〇質量部在1〜250質量部為宜, 而以5〜200質量部為佳’又以25〜160質量部為佳。 水溶性或米分散性有機樹脂(C) 10 本發明之金屬表面處理用組成物中,從在金屬表面處 理用組成物形成的層上塗佈塗料時之附著性提升及加工性 提升之觀點來看,更以添加一種水溶性或水分散性有機樹 脂(C)為佳。 所謂水溶性或水分散性有機樹脂(C),是一種可溶解 15 於水或在水中分散之有機樹脂。令有機樹脂可溶於水或令 其可在水中分散之方法可使用習知之技術以進行之。 具體而言,水溶性或在水中分散之樹脂可舉例如含有 可單獨溶於水中或在水中分散的官能基(例如羥基、聚氧 烷烯基、羧基、胺(亞胺)基、硫基、膦基等)之樹脂、 20 以及上述樹脂之官能基的一部份或全部因應需要被中和 者。上述官能基的一部份或全部因應需要被中和之樹脂, 若該樹脂為酸性樹脂(含有羧基之樹脂等),將其中和者可 舉例如以下化合物:乙醇胺、三乙胺等胺化合物;氨水; 氫氧化鋰、氫氧化鈉、氫氧化鉀等鹼金屬氫氧化合物。若 200934888 忒樹脂為鹼性樹脂(含有胺基之樹脂),將其中和者可舉例 如以下化合物:乙酸、乳酸等脂肪酸;磷酸等礦酸。 5 e 10 15 ❹ 20 遇水可溶解或分散於水中的有機樹脂之基體樹脂,可 舉例如環氧樹脂、酚樹脂、丙烯酸樹脂、雜酯樹脂、烯 叛酸樹脂、雜樹脂、具絲氧料鏈之職、聚乙稀 醇聚甘/由、叛曱基纖維素、經甲基纖維素、經乙基纖維 素等。上述樹脂可單獨❹或併用兩種顧上。從金屬表 面處理用組成物的貯藏安定性方面來看,其中特別以至少 =種選自水溶性或水分散性㈣酸樹脂、聚賴樹脂及環 氧樹脂所構成之群者為佳。 i)丙烯酸樹脂 水溶性或水分散性丙烯酸樹脂可由習知方法獲得,例 如乳化聚合個、懸浮聚合作用、將帶有親水性基的聚合 體以溶液聚合個合成,視需要中和,將其水溶液化等等 方法獲得。 上述帶有親水性基的聚合體,可藉由將帶有親水性基 例如緩基、胺基、聚氧輯基等的錢和單體及其衍生物 視需要與其它不飽和單體聚合而獲得。 上述帶有叛基之不飽和單體及其衍生物,可舉例如丙 婦酸、甲基丙烯酸、順丁烯二酸、順丁烯二岐、丁稀酸、 亞曱基丁二酸等。 帶有胺基之不飽和單體及其衍生物,可舉(甲 基)丙烯酸二甲胺乙酯、Ν,Ν-(甲基)丙烯酸二乙胺乙酯、 N-t-(甲基)丙烯酸丁胺乙醋等含氮(甲基)丙稀酸烧基^ 9 200934888 丙烯醯胺、甲基丙烯醯胺、N-曱基(甲基)丙烯醯胺、N-乙基(甲基)丙稀醯胺、N-經甲基(曱基)丙烯驢胺、N-甲氧甲(甲基)丙烯醯胺、N-丁氧甲(曱基)丙烯醯胺、 N,N-二甲基(甲基)丙烯醯胺、ν,Ν-二甲胺丙基(甲基) 5丙烯醯胺、Ν,Ν-二甲胺乙基(曱基)丙烯醯胺等可聚合醯 胺;丙烯胺等。 又,2-乙稀"比咬、1-乙稀基-2-η比洛酮、4-乙稀吼咬等 含氮單體也被利用作為帶有親水性基的不飽和單體。 帶有羥基之不飽和單體可舉例如(甲基)丙烯酸2-羥 10 乙酯、(曱基)丙浠酸經丙酯、(甲基)丙稀酸2,3-二經丁酯、 (甲基)丙烯酸4-羥丁酯等(甲基)丙烯酸羥烷酯等。 具有聚氧烷烯基之不飽和單體可舉例如聚乙二醇一 (曱基)丙烯酸酯、聚丙二醇一(曱基)丙烯酸酯等多元 醇與丙烯酸或甲基丙烯酸之單酯化物。 15 又’在上述(甲基)丙烯酸羥烧酯或多元醇與丙烯酸 或甲基丙稀酸之單酯化物中,e-己内酯經開環聚合之化合 物等亦可使用。 其他不飽和單體可舉例如(曱基)丙烯酸甲酯、(甲基) 丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙 20 酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基) 丙烯酸三級丁酯、(曱基)丙烯酸2-乙基己酯、(甲基)丙 烯酸正辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三 酯、(甲基)丙烯酸十八酯、(曱基)丙烯酸異硬脂酯等1〜 24碳之(甲基)丙烯酸烷基酯;乙酸乙烯酯等。該等化合 200934888 物可由一種或組合兩種以上以使用之。於本發明中,(曱基) 丙烯酸酯是指丙稀酸酯或甲基丙稀酸酷。 帶有親水性基的不飽和單體之含有量以全部單體中 100質量%以下為宜,而以80質量%以下為佳。 5 H耐雜性等誠來看,切性或水分散性丙稀 酸樹脂係由笨乙烯共聚合而成者為佳。全部不飽和單體中 苯乙烯的量是以60質量%以下為宜,又以1〇〜6〇質量%為 佳,更以15〜50質量%為佳。 又’從獲得之外膜的強韌性等觀點來看,由聚合而獲 10 得之丙烯酸樹脂的Tg (玻璃轉移點)是以3〇〜8〇°C為宜, 而以40〜70°C為佳。 上述丙烯酸樹脂之商品,可舉例如Aquabrid CC234 (Daicel Chemical Industries, Ltd.製造)。 ii)聚胺酯樹脂 15 上述水溶性或水分散性之聚胺酯樹脂,可適宜使用由 聚酯多元醇、聚醚多元醇等多元醇與二異氰酸酯而獲得之 聚胺酯,視需要於如二元醇、二元胺等帶有兩個以上活性 氫原子的低分子量化合物,即鏈伸長劑存在下進行鏈伸 長,進而在水中安定地分散或溶解者’可廣泛地使用周知 20 者(例如參照日本專利特公S42-24192號公報、特公 S42-24194號公報、特公S42-5118號公報、特公S49-986號公 報、特公S49-33104號公報、特公S50-15027號公報、特公 S53-29175號公報)。 水溶性或水分散性聚胺酯樹脂之製造方法可利用例如 11 200934888 以下的方法: 胺 ,透過自身乳化分散或 ⑴於合物之域或末铺由導入經基、 基、綾基等離子性基以賦予親水性 溶解於水中之方法。 ♦一口切墘禾端異氰酸基以如肟、乙醇 紛、硫醇、胺、亞械氫鈉等堵劑阻斷後之聚㈣聚合寺 利用乳化劑與機械性剪力令其強制分散於水中的方法。j 有將帶有末端異氰酸基之_聚合物藉由與水、乳化劑 10The organic phosphonic acid of the component (B) of the present invention may be, for example, κ light methyl-1,1-diphosphonic acid, 1·ethyl-1,1-diphosphonic acid, κ propyl propyl sulphate. An organic phosphonic acid having a transbasic organic group; an organic phosphonic acid having a carboxyl group-containing organic 20 such as 2-phosphoric acid, 2-phosphonic butane-quinone di-tricarboxylic acid And its salts. The above organic phosphonic acid has an excellent effect in improving the storage stability of the above aqueous solution of peroxic acid (Α), wherein from the viewpoint of storage stability, it is preferred to use an organic phosphonic acid having a hydroxyl group-containing organic group. And 丨, hydroxymethyl-1,1-diphosphonic acid, 1_ethyl-1,1-diphosphonic acid, hydrazine-propyl-i'l, diphosphine 7 200934888 acid is preferred 'special Preferably, 1-hydroxyethyl-1,1-diphosphonic acid is used. Since the stability of peroxovanaic acid (A) in water is poor, the addition of the organic phosphonic acid (B) is preferably added immediately after the production of peroxyvanadate. The metal surface treatment composition of the present invention contains peroxyvanadate (A) 5 and an organic phosphonic acid (B) and is excellent in storage stability. From the viewpoint of storage stability, the amount of the organic phosphonic acid (B) added is preferably from 1 to 250 parts by mass, and from 5 to 200 parts by mass, based on the mass fraction of the peroxyvanadic acid (A). It is better to use the quality of 25~160. Water-soluble or rice-dispersible organic resin (C) 10 The metal surface treatment composition of the present invention is improved in adhesion and workability when coating a coating layer on a layer formed of a metal surface treatment composition. It is preferable to add a water-soluble or water-dispersible organic resin (C). The water-soluble or water-dispersible organic resin (C) is an organic resin which is soluble in water or dispersed in water. The method of making the organic resin soluble in water or dispersing it in water can be carried out using a conventional technique. Specifically, the water-soluble or water-dispersible resin may, for example, contain a functional group (for example, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, an amine (imine) group, a sulfur group, which may be dissolved in water alone or dispersed in water. The resin of the phosphino group, etc., 20 and some or all of the functional groups of the above resins are neutralized as needed. a part or all of the above-mentioned functional groups are required to be neutralized, and if the resin is an acidic resin (a carboxyl group-containing resin or the like), the neutralizing compound may, for example, be an amine compound such as ethanolamine or triethylamine; Ammonia; an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide. If the resin in 200934888 is a basic resin (a resin containing an amine group), the following compounds may be exemplified by the following compounds: fatty acids such as acetic acid and lactic acid; and mineral acids such as phosphoric acid. 5 e 10 15 ❹ 20 Base resin of organic resin which can be dissolved or dispersed in water, for example, epoxy resin, phenol resin, acrylic resin, heteroester resin, olefinic resin, hetero resin, silk oxide The chain, polyglycol polyglycol/yellow, renegade-based cellulose, methyl cellulose, ethyl cellulose, etc. The above resins may be used singly or in combination. From the viewpoint of storage stability of the metal surface treatment composition, among them, at least one selected from the group consisting of water-soluble or water-dispersible (tetra) acid resins, poly-resin resins and epoxy resins is preferred. i) Acrylic resin Water-soluble or water-dispersible acrylic resin can be obtained by a conventional method, for example, emulsion polymerization, suspension polymerization, polymerization of a polymer having a hydrophilic group by solution polymerization, neutralization as needed, and aqueous solution thereof And other methods are obtained. The above hydrophilic group-containing polymer can be polymerized with other unsaturated monomers as needed by using a hydrophilic group such as a buffer group, an amine group, a polyoxygen group, and the like, and a monomer and a derivative thereof. obtain. Examples of the above-mentioned unsaturated group-containing unsaturated monomer and its derivative include benzoic acid, methacrylic acid, maleic acid, maleic acid, butyric acid, and decylene succinic acid. The amine group-containing unsaturated monomer and its derivative may, for example, be dimethylaminoethyl (meth)acrylate, hydrazine, diethylaminoethyl hydrazine-(meth)acrylate, or Nt-(meth)acrylate. Nitrogen (meth)acrylic acid base such as amine vinegar ^ 9 200934888 acrylamide, methacrylamide, N-mercapto (meth) acrylamide, N-ethyl (meth) propylene Indoleamine, N-methyl (indenyl) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (decyl) acrylamide, N, N-dimethyl ( Methyl) acrylamide, ν, Ν-dimethylaminopropyl (methyl) 5 acrylamide, hydrazine, hydrazine-dimethylamine ethyl (fluorenyl) acrylamide, etc., polymerizable guanamine; acrylamide, etc. . Further, a nitrogen-containing monomer such as 2-ethene "bite, 1-ethlyl-2-n-piperone or 4-ethyl acetonate is also utilized as an unsaturated monomer having a hydrophilic group. The hydroxyl group-containing unsaturated monomer may, for example, be 2-hydroxy10 ethyl (meth)acrylate, propyl (mercapto)propionate or 2,3-dibutyl butyl (meth)acrylate. (hydroxy) (meth) acrylate such as 4-hydroxybutyl (meth)acrylate. The polyoxyalkylene group-containing unsaturated monomer may, for example, be a monoester of a polyhydric alcohol such as polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(decyl)acrylate and acrylic acid or methacrylic acid. Further, in the above-mentioned monoethyl ester of (meth) acrylate or a monoester of a polyhydric alcohol and acrylic acid or methyl acrylic acid, a compound obtained by ring-opening polymerization of e-caprolactone or the like may be used. Examples of other unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl 20 (meth) acrylate, and n-butyl (meth) acrylate. Ester, isobutyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, An alkyl (meth)acrylate of 1 to 24 carbons such as tridecyl (meth)acrylate, octadecyl (meth)acrylate or isostearyl (mercapto)acrylate; vinyl acetate or the like. These compounds 200934888 may be used alone or in combination of two or more. In the present invention, (mercapto) acrylate means acrylate or methyl acrylate. The content of the unsaturated monomer having a hydrophilic group is preferably 100% by mass or less based on the total of the monomers, and preferably 80% by mass or less. 5 H is resistant to impurities, etc. It is preferred that the cleavable or water-dispersible acrylic resin is copolymerized with stupid ethylene. The amount of styrene in all the unsaturated monomers is preferably 60% by mass or less, more preferably 1 to 6 % by mass, still more preferably 15 to 50% by mass. Further, from the viewpoint of obtaining the toughness of the outer film, etc., the Tg (glass transition point) of the acrylic resin obtained by the polymerization is preferably 3 Torr to 8 〇 ° C, and 40 to 70 ° C. It is better. The commercial product of the above acrylic resin may, for example, be Aquabrid CC234 (manufactured by Daicel Chemical Industries, Ltd.). Ii) Polyurethane resin 15 As the above-mentioned water-soluble or water-dispersible polyurethane resin, a polyurethane obtained by using a polyol such as a polyester polyol or a polyether polyol and a diisocyanate can be suitably used, such as a diol or a binary. A low molecular weight compound having two or more active hydrogen atoms such as an amine, that is, a chain elongation in the presence of a chain extender, and then stably dispersed or dissolved in water can be widely used (for example, refer to Japanese Patent Special S42). -24192, and the public S42-24194, the special public S42-5118, the special public S49-986, the special public S49-33104, the special public S50-15027, and the special public S53-29175 Bulletin). The method for producing a water-soluble or water-dispersible polyurethane resin can be carried out, for example, by the method of 11 200934888: an amine, dispersed by self-emulsification or (1) by introducing a base group, a base group, or a thiol group to give a hydrophilic group in the domain or at the end of the compound. A method of dissolving in water. ♦After cutting off the isocyanate group, the poly(4-) polymerization temple is blocked by a plugging agent such as hydrazine, ethanol, thiol, amine, sodium sulfoxide, etc. The emulsifier and mechanical shear force force it to be dispersed. The method in the water. j has a polymer with a terminal isocyanate group with water, emulsifier 10
鏈伸長_合制職械性剪力來㈣進行分散化及& 子量化之方法。 (3)使用例如聚乙二醇之水溶性多元醇作為聚胺酯主 原料之多元醇,進而使聚胺醋如同可溶於水之聚胺醋聚合 物般分散或溶解於水中之方法。 上述聚胺醋樹脂中,對於前述之分散或溶解方法並非 15限定為單一方法者’而是由各種方法獲得之混合物亦可使 用0Chain Stretching _ Combining Occupational Shear Forces (4) Decentralization and & sub-quantization methods. (3) A method in which a water-soluble polyol such as polyethylene glycol is used as a polyol of a polyurethane main raw material, and then the polyurethane is dispersed or dissolved in water like a water-soluble polyamine vinegar polymer. In the above polyamine resin, the above-mentioned dispersion or dissolution method is not limited to a single method, but a mixture obtained by various methods may also be used.
20 可使用於上述聚胺醋樹脂合成之二異氛酸醋,可列舉 如脂環族、脂肪族及芳香族之二異氰酸醋,具體而言可列 舉如六亞甲二異氰酸黯、四亞甲二異氰酸m(二異氣 酸甲)環己剩、1,4仁異氰酸甲)環己綱、4,4異氰酸環己 嗣、4,4’·亞甲基雙(環己異氰酸醋)、二異氰酸異佛爾嗣·3,3,_ 二甲氧基_4,4’_聯苯二異氰酸醋、對苯二尹基二異氰酸醋、 間苯二甲基二異氰酸δ旨、2,"苯二異氰酸醋、¥甲苯二 異氰酸醋、對苯二異氰酸醋、二苯基甲烧二異氰酸醋、間 12 200934888 苯二異氰酸酯、2,4-萘二異氰酸酯、3,3’-二甲基-4,4’ -聯苯 二異氰酸酯、4,4’ -聯苯二異氰酸酯等。其中特別以2,4-甲 苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲二異氰酸酯、 二異氰酸異佛爾酮為佳。 5 φ 10 15 ❹ 20 上述聚胺酷樹脂商品,可舉例如Adeka Bontiter UX206 (由 ADEKA公司所製造)、Hydran HW-330、HW-340、及 HW-350 (皆由 Dainippon Ink & Chemicals, Inc所製造)、 Superflex 100 ' i5〇、e-2500、以及F-3438D (皆由Dai-Ichi Kogyo Seiyaku Co.,Ltd所製造)。 iii)環氧樹脂 上述水溶性或水分散性環氧系樹脂,可舉例如將胺附 加入環氧樹脂而成的陽離子環氧樹脂;丙烯酸改質環氧樹 脂、以及胺酯改質環氧樹脂等的改質環氧樹脂。 改質環氧樹脂,20 The diisocyanic acid vinegar which can be used for the synthesis of the above polyamine resin may, for example, be an alicyclic, aliphatic or aromatic diisocyanate, and specifically, for example, bismuth methylene diisocyanate , tetramethylene diisocyanate m (diiso-hydrogen acid) ring, 1,4 isocyanic acid methyl) cyclohexene, 4,4 isocyanate cyclohexanide, 4,4'· Base double (cyclohexyl isocyanate), isophorar diisocyanate, 3,3,_dimethoxy-4,4'-biphenyldiisocyanate, p-phenylenedione diiso Cyanate vinegar, m-xylylene diisocyanate δ, 2, " benzene diisocyanate vinegar, toluene diisocyanate vinegar, p-phenylene diisocyanate vinegar, diphenyl carbaryl Cyanic acid vinegar, interlayer 12 200934888 phenyl diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, and the like. Among them, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable. 5 φ 10 15 ❹ 20 The above polyamine-based resin products include, for example, Adeka Bontiter UX206 (manufactured by ADEKA), Hydran HW-330, HW-340, and HW-350 (all by Dainippon Ink & Chemicals, Inc Manufactured), Superflex 100 'i5〇, e-2500, and F-3438D (all manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.). Iii) Epoxy resin The water-soluble or water-dispersible epoxy resin may, for example, be a cationic epoxy resin obtained by adding an amine to an epoxy resin; an acrylic modified epoxy resin; and an amine ester modified epoxy resin. Equivalent epoxy resin. Modified epoxy resin,
、以及 陽離子環氧樹脂,可舉例如環氧化合物與一級單體或 聚胺、二級單體絲胺…二級混合聚料之加成物(例 如參照美國專利第3984299號說明書);環氧化合物與已轉 化成酮亞胺的具有—級胺基之二級單體或聚胺之加成物 (例如參照美國專利第彻期魏明f);環氧化合物與 已轉化成啦胺的具有-級胺基錢化合細化反應之生 成物(例如參照日本專利特開抓43013號公報)等。 衣乳樹脂與帶有羧基之 以及在環氧樹脂上以帶有 丙烯酸改質環氧樹脂可舉例如環 丙稀酸樹脂反應而獲得之樹脂; 13 200934888 含羧基單體之可聚合不飽和單體混合物進行接枝聚合或共 聚合而成之樹脂等。 ' 胺酯改質環氧樹脂可舉例如以胺類與環氧化合物反應 而成的含胺環乳樹脂與聚異氰酸醋化合物或單異氰酸醋化 5合物反應而獲得之樹脂;以環氧化合物與聚烯烴基二醇以 及聚異氰酸酯化合物反應所獲得之胺酯改質環氧樹脂的環 氧基因應需要而加入烧醇胺等之胺類後所獲得的樹脂;以 及將雙酚A型環氧樹脂等環氧化合物與聚烯烴基二醇二環 氧丙基醚混合之混合物以雙酚八與之反應,再以異氰酸酯化 〇 10合物與之反應所獲得之胺酯改質環氧樹脂的環氧基因應需 要而附加烷醇胺等之胺類後所獲得的樹脂等。 胺酯改質環氧樹脂因應需要利用中和劑中和一部份或 全部的陰離子基或陽離子基進而溶解或分散至水中。 上述環氧化合物之數量平均分子量係以4〇〇〜4〇〇〇為 15宜,而以800〜2,000為佳。又,環氧當量係以190〜2,000為宜, 而以400〜1,000為佳。 此類環氧化合物可由例如多盼化合物與環氧氣丙烧t 〇 反應而獲得。 多酚化合物,可舉例如雙(4_羥苯)_2,2丙烷、4,4二羥 20二苯基酮、雙(4-經苯)-1,1-乙燒、雙(4_經笨^山異丁烷、 雙(4-髮基二級丁苯)_2,2_丙烷、雙(2·羥萘)甲烷、μ二羥 萘、雙(2,4-二經苯)甲烧、四(4·經笨乙烧、4,4_二 經基二苯硪、笨紛酸、曱紛經等。 上述壞氧樹脂之商品可舉例如Adeka Resin EM-0718 14 200934888 (由ADEKA公司製造)等。 5 10 15 20 從塗料附著性等的觀點來看,水溶性或水分散性有機 樹脂(c)之添加量相對於該過氧飢酸(A)議質量部, 在20,000質里部以下為宜,而在卜加,刪質量部為佳,更以 5〜10’_質量部為佳’特別㈣〜5,刪質量部為佳。水溶性 或水分散性有機樹脂(c)之添加量若未達前述範圍,盘外 層塗料之附著性及處理膜加工性有劣化之傾向 ,而超出前 述範圍則耐腐蝕性有劣化之傾向。 其他成分 本發明之金屬表面處理用組成物中,可因應需要而更 包含有過氧織以外的峽化合物、氟化錄化合物、碳酸 錯化合物、氟化鈦化合物等金屬化合物。 上述飢酸化合物,可舉例如偏叙酸裡、偏叙酸鉀、偏 鈒酸納、偏減錄、銳酸肝等。其中㈣麟性等觀點來 看,特別以偏釩酸銨為佳。 氟化錯化合物可舉例如氫氟酸錯,以及氫氟酸錯的 鈉鉀、裡、铵等鹽類。其中從耐腐钱性等觀點來看,以 氟化錯銨、氫氟酸鍅為佳。 碳酸錄化合物可舉例如碳酸錯_ m 類。其中從耐雜料㈣來看,叫祕錄為佳。 * i化鈦化合物可舉例如,氫氣酸鈦的鈉、鉀、鐘 專鹽類。其中從耐腐紐等觀點來看,以氟化鈦錢為佳。 該等金屬化合物之添加量,從耐腐純等觀點來看, 相對於過氧減u) _量部,可舉例如2,麵質量部以 15 200934888 5 10 15 20 下為宜,而以卜2,_質量部為佳,又以叫,卿質量 佳,更以2_質量部為佳,特別錢〜3崎量部為佳: 本發明之金屬表面處理用組成物可因應需要添加妙偶 合劑。該矽偶合劑可舉例如(胺乙基)[胺丙 氧魏、料(胺乙基)r_胺丙基甲基二甲氧妙貌土、— 甲基丙_氧基丙基三甲氧㈣、^ (乙稀基笨甲美胺 乙基)卜丙基三甲氧㈣氫級鹽、r_去水甘油氧基丙基 二甲軋矽烷、r-硫醇基丙基三甲氧矽烷、卜硫醇基丙基甲 基二甲氧雜、甲基三甲氧矽烷、乙烯基三乙醯氧矽烷、 r-氣三甲氧基丙錢、六曱基二销烧、卜苯胺基丙基三 甲氧械、乙稀基三甲氧雜、乙稀基三乙氧㈣、二甲 ^十八膚·(三甲氧魏基)丙基]氣倾、三甲氣魏 4。 從將外膜經驗脫脂處理後之耐腐钱性等觀點酸u)⑽質量部’典型地是 傷質量部以下’而以量部、1〇〜4⑻質量部為佳。在本發明之金屬表面處理用組成物中,可因應需要再 =加有機《子及/或無機微粒子。藉添加祕粒子使得 塗膜透明性下降,可抑制在薄膜容易產生的干涉色 (mterfereneeeGlG〇,適合祕重視外觀的用途。 上述微粒子之粒徑係在平均粒子徑,嶋齡特別以 ^〜5〇〇ηη^_者係從粒子沉降安定性及耐腐錄觀點 看較適合。 上述有機微粒子可舉例如丙烯酸、聚胺醋、尼龍、聚And a cationic epoxy resin, for example, an adduct of an epoxy compound and a primary monomer or a polyamine, a secondary monomeric silk amine, a secondary mixed polymer (for example, refer to US Pat. No. 3,984,299); An adduct of a compound with a secondary monomer or a polyamine having a ketimine (for example, see U.S. Patent No. 2004); an epoxy compound having a conversion to a amide The product of the hydrazine-based compounding and refining reaction (for example, see Japanese Patent Laid-Open No. 43013). a resin obtained by reacting a latex resin with a carboxyl group and an epoxy resin modified epoxy resin, for example, a cycloacrylic acid resin; 13 200934888 A polymerizable unsaturated monomer having a carboxyl group-containing monomer The mixture is subjected to graft polymerization or copolymerization of a resin or the like. The amine ester-modified epoxy resin may, for example, be a resin obtained by reacting an amine-containing cyclic latex resin obtained by reacting an amine with an epoxy compound with a polyisocyanate compound or a monoisocyanate 5 compound; An epoxy group obtained by reacting an epoxy compound with a polyolefin-based diol and a polyisocyanate compound, and an epoxy group obtained by adding an amine such as an alcoholic amine; and a bisphenol A mixture of an epoxy compound such as a type A epoxy resin and a polyolefin-based diol diepoxypropyl ether is reacted with bisphenol VIII, and an amine ester modified by reacting an isocyanate oxime compound with the same The epoxy resin of the epoxy resin is required to be added with a resin such as an alkanolamine or the like. The amine ester-modified epoxy resin is neutralized or dispersed in water by neutralizing a part or all of an anionic group or a cationic group with a neutralizing agent. The number average molecular weight of the above epoxy compound is preferably from 4 to 4, and preferably from 800 to 2,000. Further, the epoxy equivalent is preferably from 190 to 2,000, more preferably from 400 to 1,000. Such an epoxy compound can be obtained, for example, by reacting a polypane compound with an epoxidized t oxime. The polyphenol compound may, for example, be bis(4-hydroxyphenyl)_2,2 propane, 4,4 dihydroxy 20 diphenyl ketone, bis(4-benzene)-1,1-ethyl benzene, bis (4_经Stupid mountain isobutane, bis(4-fluorenyl-tert-butylbenzene)_2,2-propane, bis(2-hydroxynaphthalene)methane, μ-dihydroxynaphthalene, bis(2,4-di-benzene)-methyl , four (4 · stupid Ethylene, 4,4_ di-based dibenzoquinone, stupid acid, sputum, etc.. For the above-mentioned products of the bad oxygen resin, for example, Adeka Resin EM-0718 14 200934888 (by ADEKA) (manufacturing), etc. 5 10 15 20 The amount of the water-soluble or water-dispersible organic resin (c) added is 20,000 in terms of the quality of the peroxy oxo acid (A) from the viewpoint of paint adhesion and the like. The following is appropriate, but in Bujia, the quality department is better, and the 5~10'_mass is better 'special (four)~5, the quality part is better. Water-soluble or water-dispersible organic resin (c) When the amount of addition is less than the above range, the adhesion of the outer coating material and the processability of the treated film tend to deteriorate, and the corrosion resistance tends to deteriorate beyond the above range. Other components The metal surface treatment composition of the present invention Can be used as needed Further, a metal compound such as a gorge compound, a fluorinated compound, a carbonic acid compound, or a titanium fluoride compound other than peroxy woven fabric is further included. The hunth acid compound may, for example, be a meta-acid, a potassium citrate or a bismuth citrate. Nano, partial subtraction, sharp acid liver, etc. Among them, (iv) lining and other viewpoints, especially ammonium metavanadate. Fluorinated compounds can be, for example, hydrofluoric acid, and sodium and potassium hydrofluoric acid, Salts such as lysine and ammonium, etc., from the viewpoint of corrosion resistance and the like, fluorinated ammonium amide and cesium hydrofluoric acid are preferred. The carbonic acid recording compound may, for example, be a carbonic acid _ m type, which is derived from the resistant material (four) It is preferable to refer to the secret book. * The titanium compound may, for example, be a sodium, potassium or a bell salt of titanium hydrogen hydride. Among them, from the viewpoint of corrosion resistance, etc., it is preferable to use titanium fluoride. The amount of the metal compound to be added is, for example, 2 from the viewpoint of corrosion resistance and the like, and is 2, and the surface quality portion is preferably 15 200934888 5 10 15 20 , and is 2, _The quality department is better, and it is called, the quality of the Qing is good, and the quality is better than the 2_ quality department. The metal surface treatment composition of the present invention may contain a wonderful coupling agent as needed. The oxime coupling agent may, for example, be (aminoethyl) [amine propoxy oxime, (aminoethyl) r-aminopropyl methyl dimethyl Oxygen-excellent soil, - methyl propyloxypropyltrimethoxy (tetra), ^ (ethyl bromide), propyltrimethoxy (tetra) hydrogen salt, r_dehydroglyceryloxypropyl Decane, r-thiol propyl trimethoxy decane, bromopropyl propyl dimethyl dimethyl oxalate, methyl trimethoxy decane, vinyl triethoxy decane, r-gas trimethoxy propylene, six曱基二销烧, Buaniline propyl trimethoxide, Ethylene trimethoxy, Ethyl triethoxy (tetra), Dimethyl 18 (trimethoxy oxi) propyl] gas, three Gas Wei 4. From the viewpoint of the anti-corrosion property after degreasing treatment of the outer film, etc., the acid (i) mass portion 'typically below the damage mass portion' is preferably the mass portion and the mass portion of 1 〇 to 4 (8). In the metal surface treatment composition of the present invention, organic "sub- and/or inorganic fine particles" may be added as needed. By adding the secret particles, the transparency of the coating film is lowered, and the interference color which is likely to occur in the film (mterfereneee GlG〇, which is suitable for the appearance of the appearance) can be suppressed. The particle diameter of the above-mentioned fine particles is in the average particle diameter, and the age is particularly limited to ^5. 〇ηη^_ is suitable from the viewpoint of particle sedimentation stability and corrosion resistance. The above organic fine particles may, for example, be acrylic acid, polyurethane, nylon, poly
16 200934888 乙二醇等樹脂微粒子。又,無機微粒子可舉例如二氧化石夕、 4化鈦、硫酸鋇、碳酸料。從成本等觀點來看,以二 氧化矽、二氧化鈦、硫酸鋇等為佳。 5 10 15 Ο 20 從耐腐触性觀點來看,有機微粒子及/或無機微粒子 之添加量在金屬表面處理驗成物的固形分中 3〇質量%以下,以^0質量%】如傲真。/ 也係 負重/ΰ、1〜20質量%的範圍為佳。 在本發明之金屬表面處理用組成物中,因應需要除上 述成分外可含有例如無機錢化合物、氫氟酸等糊劑、 本發明成份以外之重金屬化合物、增_、界面活_、 潤滑劑(聚乙稀蟻、含氟蟻、棕觸等)、防鏽劑、著色顏 料、體質顏料、防鏽顏料、染料等。 上述無⑽酸化合物可舉例如正璘酸、偏魏、亞磷 酸、偏亞磷酸、低魏、次碟酸、焦碟酸、三聚魏、四 磷酸、六概、三偏細、焦亞魏、及魏衍生物等。 可組合使用一種或兩種Μ之鱗化合物。又,該等磷酸 化合物與祕化合物形成_亦可。該驗性化合物可舉例 ^有鋰鈉鉀銨之有機或無機鹼性化合物。無 酸鹽化合物係以使用具右料 有對水之溶解性者為佳。 重金屬化合物可舉例如 銦酸、鑛酸及其鹽類。t鐵'錄、銦等金屬之鹽類; 其他防鏽劑可舉例如 類、《絲等切衫彳=料Μ雜合物;硫醇 物4補、仁麵、/物;三_等含氮原子化合 子化合物;麟子交換^碳醯賴等含硫原子及氮原 矽等含鈣原子化合物;及硼 17 200934888 酸、偏硼酸等。 因應需要 丙一醇系溶 又,在本發明之金屬表面處理用組成物中, 可利用甲醇、乙醇、異丙醇、乙二醇 之:、親水二: 劑之使用量係二變來用,例如親水性有機溶 佳 金屬表面處理用組成物㈣質量%以下為16 200934888 Resin microparticles such as ethylene glycol. Further, examples of the inorganic fine particles include cerium oxide, titanium hydride, barium sulfate, and carbonic acid. From the viewpoint of cost and the like, it is preferred to use ruthenium dioxide, titanium oxide, barium sulfate or the like. 5 10 15 Ο 20 From the viewpoint of corrosion resistance, the amount of organic fine particles and/or inorganic fine particles added is not more than 3% by mass in the solid content of the metal surface treatment test, and is 0% by mass. . / It is also a load/ΰ, and a range of 1 to 20% by mass is preferable. In the metal surface treatment composition of the present invention, in addition to the above components, a paste such as an inorganic money compound or hydrofluoric acid, a heavy metal compound other than the component of the present invention, an increase in the amount of the interface, and a lubricant may be contained. Polyethylene ants, fluorine-containing ants, brown touches, etc.), rust inhibitors, coloring pigments, body pigments, anti-rust pigments, dyes, etc. The above-mentioned (10) acid-free compound may, for example, be n-decanoic acid, partial Wei, phosphorous acid, metaphosphoric acid, low Wei, hypotriic acid, pyroic acid, trimeric Wei, tetraphosphoric acid, hexa-, tri-negative, and pyro-wei And Wei derivatives. One or two sputum scale compounds may be used in combination. Further, these phosphoric acid compounds are formed together with the secret compound. The test compound can be exemplified by an organic or inorganic basic compound having lithium sodium potassium ammonium. The acid-free compound is preferably one which has a right-handed material and is soluble in water. The heavy metal compound may, for example, be indium acid, mineral acid or a salt thereof. t iron 'record, indium and other metal salts; other rust inhibitors can be mentioned, for example, "silk and other sputum 彳 = mash complex; thiol 4 supplement, ren face, / material; three _ and so on Nitrogen compound; sulphide exchange; carbon-containing compound such as sulfur atom and nitrogen atom; and boron 17 200934888 acid, metaboric acid, and the like. In the metal surface treatment composition of the present invention, methanol, ethanol, isopropanol, ethylene glycol: and hydrophilic two: the amount of use of the agent may be used for two changes. For example, a hydrophilic organic solvent-soluble metal surface treatment composition (4)% by mass or less is
本發明之金屬表面處理用組成物之製造方法並非 別限制者,可用魏峨⑷、有機舰⑻、因應以 配合其他成分後,因應需要以水稀釋調整_分為〇 Μ 質量% (以0.5〜40質量%為佳)而製造之。 表面處理合Μ村 本發明之表面處理金屬材係於金屬材上具有從本發明 之金屬表面處理用組成物獲得之金屬表面處理層的表面處 Η理金屬材。具體而言,可用本發明之金屬表面處理用組成 物於基材上塗佈並烘培㈣獲得表面處理金屬材。The manufacturing method of the metal surface treatment composition of the present invention is not limited thereto, and Wei Wei (4), organic ship (8), and other components may be used, and if necessary, water dilution adjustment _ is divided into 〇Μ mass % (to 0.5~) 40% by mass is better). Surface Treatment Μ村 The surface-treated metal material of the present invention is a ruthenium metal material having a surface of a metal surface treatment layer obtained from the metal surface treatment composition of the present invention on a metal material. Specifically, the surface-treated metal material can be obtained by coating and baking (4) the metal surface treatment composition of the present invention on a substrate.
適用於上述金屬表面處理用組成物之基材,只要是金 屬基板即不受任何限制。可舉例如鐵、銅、鋁、錫、鋅及 含有該等金屬之合金,以及由該等金屬電鍍之鋼材或者由 2〇該金屬沉積而成之製品。其中使用由辞或辞合金電鍍之鋼 材’特別是使用鍍辞之鋼板或鍍鋅合金之鋼板時在耐腐蝕 性等的提升效果顯著。 此處所謂鋼材,係指包含鐵(包含合金)的塊或成型 物、板狀、棒狀者,鋼板則是將鐵(包含合金)製成板狀 18 200934888 者。 =之金屬表面處理用組成物塗布於基材上之方 法’並非钟職制者,可依f知之塗布方法進行。 該塗布方法可舉例如浸塗裝、噴塗裝 面處理膜之供培(乾燥)條件係通常㈣=表 為峨〜約撕之條件下乾細秒,秒間為^度 又’金屬表面處理用組成物之處理媒厚通常係以乾燥 膜厚為〇.001〜10g/m2者為佳,更以〇.〇5〜3g/nf者為佳。處 理膜厚若過薄,耐腐钮性、耐水性等性能有低落之傾向, 10而處理膜厚若過厚,表面處理膜會裂開或有加工性低落之 傾向。The substrate suitable for the above metal surface treatment composition is not limited as long as it is a metal substrate. For example, iron, copper, aluminum, tin, zinc, and alloys containing the metals, and steels plated from the metals or deposited from the metal may be mentioned. Among them, the steel material which is electroplated by rhetoric or alloying is used, and in particular, when a steel plate of a plated steel or a steel plate of a galvanized alloy is used, the effect of improving corrosion resistance and the like is remarkable. Here, the steel material refers to a block or a molded article containing iron (including an alloy), a plate shape, or a rod shape, and the steel plate is formed by forming iron (including an alloy) into a plate shape 18 200934888. The method of applying the composition for metal surface treatment to the substrate is not a method of coating, and can be carried out according to the coating method. The coating method may, for example, be a dip coating or a spray coating treatment film, and the conditions for the drying (drying) are usually (four) = the table is dry to fine under the condition of 峨 to about torn, and the second is for the metal surface treatment. The treatment medium thickness of the composition is usually preferably a dry film thickness of 〇.001 to 10 g/m2, more preferably 〇.〇5 to 3 g/nf. If the film thickness is too thin, the properties such as corrosion resistance and water resistance tend to be low. If the film thickness is too thick, the surface treatment film may be cracked or the processability may be lowered.
本發明之表面處理鋼板的用途,於建材用、家電用、 八車用冑用、預塗式鋼板用等使用習知表面處理鋼板的 用途上可使用而不受特別限制。又,可因應需要以底塗塗 15料、外塗塗料等適宜塗裝。該塗裝方法係依用途、被塗物 Q 之形狀等來適宜選定即可,例如喷塗裝、刷塗裝、電沉積 塗裝、輥塗裝、淋幕式塗裝等適合使用。亦可以薄片積層 之方法替代塗裝。 t貧施方式】 20實施發明之最佳形態 接著將舉出製造例、實施例及比較例,並更具體地說 明本發明。但本發明並非受以下之例所限定者。各例所揭 不之「部」及「%」皆為以質量基準而得者。 皇造例1 (金屬表面處理用組成物之製造) 200934888 於容器中加入去離子水100質量部,於其中加入3〇%過 氧化氫水3 0質量部並加以攪拌後呈液溫2 5充之溶液中再加 、 入偏釩酸銨15質量部,經30分鐘攪拌而得到過氧釩酸水溶 液。 5 f施例1〜13及比較例1〜2 按照下述表1、2所示配方製作了各金屬表面處理用組 成物。表1、2的各原料之配方量係以水性液之金屬表面處 理用組成物中的固形分質量比來表示。 關於金屬表面處理用組成物,係以去離子水調製使固 〇 10 形分成為15%。 針對由實施例及比較例所獲得之各金屬表面處理用組 成物進行了下述試驗。結果合併於表1、2表示之。 表1中’(※丨)〜(※彳)之原料係下述内容之物。 (※丨)AdekaBontiterUX206:商品名,由ADEKA公 15 司製造,水性聚胺酯樹脂。 (※之)AquabridCC234.商品名,由DainipponInk&The use of the surface-treated steel sheet of the present invention can be used for the purpose of using a conventional surface-treated steel sheet for building materials, household appliances, eight-vehicle use, and pre-coated steel sheets, and is not particularly limited. In addition, it is possible to apply a suitable coating such as primer coating or exterior coating as needed. The coating method may be appropriately selected depending on the application, the shape of the object to be coated Q, and the like, and may be suitably used, for example, spray coating, brush coating, electrodeposition coating, roll coating, and curtain coating. It is also possible to replace the coating by a lamination method. BEST MODE FOR CARRYING OUT THE INVENTION Next, the production examples, examples, and comparative examples will be described, and the present invention will be more specifically described. However, the invention is not limited by the following examples. The "parts" and "%" that are not disclosed in the examples are those based on quality.皇造例1 (Manufacture of metal surface treatment composition) 200934888 Add 100 parts of deionized water to the vessel, add 3 质量% of hydrogen peroxide water to the mass part and stir it to a liquid temperature of 2 5 Further, 15 parts by mass of ammonium metavanadate was added to the solution, and the mixture was stirred for 30 minutes to obtain an aqueous solution of peroxovagic acid. 5 f Examples 1 to 13 and Comparative Examples 1 to 2 Each metal surface treatment composition was prepared in accordance with the formulations shown in the following Tables 1 and 2. The formulation amount of each raw material of Tables 1 and 2 is represented by the solid content mass ratio in the metal surface treatment composition of the aqueous liquid. The composition for metal surface treatment was prepared by deionized water to have a solid content of 15%. The following tests were carried out for each of the metal surface treatment compositions obtained in the examples and the comparative examples. The results are combined in Tables 1 and 2. The raw materials of '(※丨)~(※彳) in Table 1 are the following contents. (※丨) AdekaBontiterUX206: trade name, manufactured by ADEKA Corporation, water-based polyurethane resin. (※) AquabridCC234. Trade name, by DainipponInk&
Chemicals, Inc所製造,水性丙稀酸樹脂。 ® (※3) Adeka Resin EM-0718 :商品名,由ADEKA公 司製造,水性環氧樹脂。 20 (※斗)Superflex E-2500 :商品名,由Dai-Ichi KogyoManufactured by Chemicals, Inc., aqueous acrylic resin. ® (*3) Adeka Resin EM-0718 : trade name, manufactured by ADEKA, waterborne epoxy resin. 20 (※ bucket) Superflex E-2500 : trade name, by Dai-Ichi Kogyo
Seiyaku Co·, Ltd所製造,水性聚胺醋樹脂。 試驗例1 (貯藏安定性試驗) 將已調整成固形分10%之各金屬表面處理用組成物裝 入玻璃瓶並密封,放置於2〇°C恆溫室一個月後,以目視觀 20 200934888 察其外觀並以下述基準評價之。 A :看不到有沉降物或明顯增黏 b:有沉降物 式驗例2 (耐腐姑性試驗) 5 c- 試驗板之製作 將板厚0.5麵,單面電鍍附著量60g/m2之熱浸鑛鋅鋼 板’使用溶有驗性脫脂劑(由Japan CB Chemical所製造, 商品名「Chemicleaner 561B」)濃度2%之水溶液脫脂、水 洗之後’將藉上述實施例及比較例獲得之金屬表面處理用 10 組成物塗佈於其上使乾燥外膜重量成為l.〇g/m2,令材料 到達溫度成為l〇〇°C後烘培20秒以形成表面處理膜。 (2)耐腐蝕性試驗 在獲得之試驗塗板的端面部及後面部經密封後之試驗 塗板上進行JIS Z2371所規定之鹽水喷霧試驗直至72小時, 15將生鏽程度以下述基準評價之。 A.觀察不到有生錄。 B:觀察到生鏽程度為未滿塗膜面積5% (實用範圍)。 C :觀察到生鏽程度為塗膜面積5%以上,未滿10%。 D :觀察到生鏽程度為塗膜面積10%以上,未滿50%。 20 E :觀察到生鏽程度為塗膜面積50%以上。 慈(上層塗膜附著性) C- 試驗板之製作 將板厚0.5mm,單面電鍍附著量60g/m2之熱浸鍍鋅鋼 板,使用溶有鹼性脫脂劑(由japan CB Chemical所製造, 21 200934888 * 商品名「Chemicleaner 561B」)濃度2%之水溶液脫脂、水 洗之後,將藉上述實施例及比較例獲得之金屬表面處理用 組成物塗佈於其上使乾燥外膜重量成為0.3g/m2,令材料 到達溫度成為100°C後烘培20秒以形成表面處理膜。在各試 5 驗塗板上塗裝 Amilac #1000 White (由 Kansai Paint Co.,Ltd 製造,熱硬化型酸醇樹脂塗料,白色)使乾燥膜厚成為30 ym,以130°C烘培20分鐘而獲得外塗塗裝板。 (2)上層塗膜附著性 針對獲得之試驗塗板,在塗板面上以小刀製作縱橫各 ® 10 11道深至未塗裝基材部份的痕跡而劃出棋盤格狀100個每 格1臟2的格子。以玻璃紙黏著膠帶貼附棋盤格部分再瞬間 撕起時的上層塗膜剝離程度用下述基準評價之。 · A ·元全觀察不到上層塗膜剝離。 ‘ B :觀察到上層塗膜雖無完全剝離,但格子邊緣有些微 15 剝離(實用範圍)。 C :觀察到上層塗膜剝離1〜9個。 D :觀察到上層塗膜剝離10個以上。 ❹ 22 200934888 i啭 實施例 卜 100 150 700 220 cd cd cd 100 150 600 200 cd cd m 100 150 cd cd X) 寸 100 〇 IT) Η (N cd cd m 100 150 in CN cd cd CN 100 150 cd cd 〇 150 cd cd X) 過氧飢酸 1-羥甲基-1, 1-二膦酸 1-羥乙基-1,1-二膦酸 1-羥丙基-1, 1-二膦酸 Adeka Bontiter UX206 (※ 1 ) Aquabrid CC234 (※之) Adeka Resin EM-0718 (:※ 3) Superflex E-2500 (:※4) 氟化鍅銨 碳酸錯敍 氟化鈦銨 氫氟酸锆 貯藏安定性 耐腐姓性 外塗塗膜附著性 /-"N S—/ PQ Ο 200934888 比較例 (Ν 100 <N Xi X) 150 in (N cd o 實施例 m 100 2500 200 cd cd cd (Ν 100 100 3500 200 cd cd cd 100 2500 200 cd cd cd Ο 100 100 3000 200 cd cd cd Ον 100 ο 600 〇 1—Η cd cd cd ΟΟ 100 150 700 170 cd cd cd 過氧釩酸 1-羥甲基-1,1-二膦酸 1-羥乙基-1, 1-二膦酸 1-羥丙基-1, 1-二膦酸 Adeka Bontiter UX206 (※ 1 ) Aquabrid CC234 (※之) Adeka Resin EM-0718 (:※ 3) Superflex E-2500 (※4) 氟化鍅銨 碳酸錯銨 氟化鈦銨 氫氟酸锆 貯藏安定性 耐腐蝕性 1 外塗塗膜附著性 /—Ν Ν CQ o 200934888 Λ 5 本發明之金屬表面處理用組成物係包含有過氧釩酸及 有機膦酸者。過氧鈒酸的财腐姓性優異,但單獨在水中之 安定性差,容易產生沉澱因而實用化有困難。然而,藉著 組合有機膦酸,處理液的貯藏安定性顯著提升,又,藉著 與水性有機樹脂的組合也使之能廣泛地使用,使處理膜的 性能平衡(例如财腐餘性與加工性、材料附著性等的平衡) 變得容易達成,可獲得能與鉻酸鹽處理劑及磷酸鹽處理劑 相匹敵的性能,因此取代該等處理劑成為無鉻型表面處理 m 劑在金屬表面處理用途上是非常有用的。 10 « 又,本發明之表面處理金屬材在加工性、财腐姓性、 外塗塗裝性等方面是優異的。 【圖式簡單說明3 (無) 【主要元件符號說明】 (無) 參 25Water-based polyurethane resin manufactured by Seiyaku Co., Ltd. Test Example 1 (Storage Stability Test) Each of the metal surface treatment compositions adjusted to have a solid content of 10% was placed in a glass bottle and sealed, and placed in a thermostatic chamber at 2 ° C for one month, to visually observe 20 200934888 The appearance was evaluated on the basis of the following criteria. A: There is no sediment or obvious viscosity. b: There is a sediment type test example 2 (resistance to corrosion resistance) 5 c- The test plate is made with a thickness of 0.5, and the plating amount of one side is 60g/m2. The hot-dip galvanized steel sheet is degreased with an aqueous solution having a concentration of 2% dissolved in an organic degreaser (manufactured by Japan CB Chemical Co., Ltd., trade name "Chemicleaner 561B"), and after washing with water, the metal surface obtained by the above examples and comparative examples will be used. The treatment 10 composition was applied thereon so that the weight of the dried outer film became 1. 〇g/m2, and the material reached a temperature of 10 ° C and baked for 20 seconds to form a surface treatment film. (2) Corrosion resistance test The salt spray test prescribed in JIS Z2371 was carried out on the test plate after the end face and the rear portion of the obtained test plate were sealed until 72 hours, and the degree of rust was evaluated on the following basis. A. There is no record of birth. B: The degree of rust was observed to be 5% of the film area (practical range). C: The degree of rust was observed to be 5% or more of the coating area, and less than 10%. D: The degree of rust was observed to be 10% or more of the coating area, and less than 50%. 20 E : The degree of rust was observed to be 50% or more of the coating area. Ci (adhesive film adhesion) C-test plate was prepared by hot-dip galvanized steel sheet with a thickness of 0.5 mm and a single-sided plating adhesion of 60 g/m2, using an alkaline degreasing agent (manufactured by japan CB Chemical). 21 200934888 * Product name "Chemicleaner 561B") After degreasing and washing with an aqueous solution having a concentration of 2%, the metal surface treatment composition obtained by the above examples and comparative examples was applied thereon to make the dry outer film weight 0.3 g/ M2, the material was allowed to reach a temperature of 100 ° C and baked for 20 seconds to form a surface treatment film. Amilac #1000 White (manufactured by Kansai Paint Co., Ltd., thermosetting acid alcohol resin paint, white) was applied to each test plate to make the dried film thickness 30 μm and baked at 130 ° C for 20 minutes. Obtain an outer coated plate. (2) Adhesiveness of the upper coating film For the obtained test coating plate, the traces of the vertical and horizontal sides of each of the 10 11 deep to uncoated substrate portions were made with a knife on the coated surface, and a checkerboard pattern was drawn. 2 grid. The degree of peeling of the upper coating film when the portion of the checkerboard was attached to the checkerboard portion by the cellophane adhesive tape was evaluated by the following criteria. · A · Yuan did not observe the peeling of the upper coating film. ‘ B : Although the upper coating film was not completely peeled off, the edge of the lattice was slightly peeled off (practical range). C: 1 to 9 peeling of the upper coating film was observed. D: It was observed that the upper coating film was peeled off by 10 or more. ❹ 22 200934888 i啭Examples 100 150 700 220 cd cd cd 100 150 600 200 cd cd m 100 150 cd cd X) inch 100 〇IT) Η (N cd cd m 100 150 in CN cd cd CN 100 150 cd cd 〇150 cd cd X) peroxyl oxalate 1-hydroxymethyl-1, 1-diphosphonic acid 1-hydroxyethyl-1,1-diphosphonic acid 1-hydroxypropyl-1, 1-diphosphonic acid Adeka Bontiter UX206 (※ 1 ) Aquabrid CC234 (※) Adeka Resin EM-0718 (:* 3) Superflex E-2500 (:*4) Ammonium lanthanum fluoride carbonate misunderstanding titanium fluoride hydrofluoric acid zirconium storage stability resistance Corrosive surfacing film adhesion /-"NS-/PQ Ο 200934888 Comparative Example (Ν 100 <N Xi X) 150 in (N cd o Example m 100 2500 200 cd cd cd (Ν 100 100 3500 200 cd cd cd 100 2500 200 cd cd cd Ο 100 100 3000 200 cd cd cd Ον 100 ο 600 〇1—Η cd cd cd ΟΟ 100 150 700 170 cd cd cd Peroxyvanadate 1-hydroxymethyl-1,1 -Diphosphonic acid 1-hydroxyethyl-1, 1-diphosphonic acid 1-hydroxypropyl-1, 1- Phosphonic acid Adeka Bontiter UX206 (※ 1 ) Aquabrid CC234 (※) Adeka Resin EM-0718 (:* 3) Superflex E-2500 (*4) Ammonium lanthanum ammonium carbonate arsenic fluoride titanium ammonium hydroxide hydrofluoric acid storage stability Corrosion resistance 1 External coating film adhesion / - Ν Ν CQ o 200934888 Λ 5 The metal surface treatment composition of the present invention contains peroxovanaic acid and organic phosphonic acid. Permanganic acid It is excellent in its properties, but its stability in water alone is poor, and precipitation is likely to occur, which makes it difficult to use it practically. However, by combining organic phosphonic acid, the storage stability of the treatment liquid is remarkably improved, and the combination with the aqueous organic resin also enables it to be widely used, so that the performance of the treatment membrane is balanced (for example, the sulphur residue and processing) Equilibrium of properties, material adhesion, etc.) It is easy to achieve, and performance comparable to chromate treatment agent and phosphate treatment agent can be obtained. Therefore, instead of these treatment agents, it becomes a chromium-free surface treatment m agent on the metal surface. It is very useful for handling purposes. 10 « Further, the surface-treated metal material of the present invention is excellent in terms of workability, prosperousness, and coatability. [Simple description of the figure 3 (none) [Description of main component symbols] (none) Reference 25
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TW201129717A (en) * | 2009-12-04 | 2011-09-01 | Kansai Paint Co Ltd | Composition for treating metal surface and metal substrate with surface treatment film |
CN103540920A (en) * | 2013-09-27 | 2014-01-29 | 宁波英科特精工机械股份有限公司 | Metal surface anti-corrosion treatment agent |
FR3026412B1 (en) * | 2014-09-26 | 2019-03-29 | Aperam | SURFACE TREATMENT OF METAL SUBSTRATES |
MX2017006133A (en) * | 2014-11-12 | 2017-07-27 | Jfe Steel Corp | Method for manufacturing galvanized steel sheet. |
CN104357848B (en) * | 2014-11-14 | 2017-01-11 | 陈伟 | Environment-friendly steel surface anti-rust agent and preparation method thereof |
CN105088209B (en) * | 2015-09-11 | 2017-06-30 | 南通亿能彩钢板有限公司 | A kind of preparation method of black brown chromium-free passivation liquid |
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US5052421A (en) * | 1988-07-19 | 1991-10-01 | Henkel Corporation | Treatment of aluminum with non-chrome cleaner/deoxidizer system followed by conversion coating |
DE69525475T2 (en) * | 1994-11-11 | 2002-10-02 | Commonwealth Scientific And Industrial Research Organisation, Campbell | METHOD AND SOLUTION TO GUARANTEE A CONVERSION COATING ON A METAL SURFACE |
US6027579A (en) * | 1997-07-07 | 2000-02-22 | Coral Chemical Company | Non-chrome rinse for phosphate coated ferrous metals |
JP2975331B2 (en) * | 1997-07-22 | 1999-11-10 | 関西ペイント株式会社 | Metal surface treatment composition and galvanized steel sheet having a coating formed by the composition |
AU6122499A (en) * | 1998-10-15 | 2000-05-01 | Nihon Parkerizing Company Limited | Hydrophilizing agent for metallic material, hydrophilizing fluid, method of hydrophilizing, metallic material, and heat exchanger |
JP2003277945A (en) * | 2002-03-20 | 2003-10-02 | Nisshin Steel Co Ltd | Nonchromium type surface treated steel sheet |
JP2004068067A (en) * | 2002-08-05 | 2004-03-04 | Nippon Parkerizing Co Ltd | Copper-based alloy material and method for manufacturing the same |
JP2004068068A (en) * | 2002-08-05 | 2004-03-04 | Nippon Parkerizing Co Ltd | Combined material and method for producing the same |
US20040256030A1 (en) * | 2003-06-20 | 2004-12-23 | Xia Tang | Corrosion resistant, chromate-free conversion coating for magnesium alloys |
JP3765814B2 (en) * | 2003-09-26 | 2006-04-12 | 株式会社シミズ | Ground treatment solution for metal coating and coating method |
JP4586349B2 (en) * | 2003-10-21 | 2010-11-24 | 住友金属工業株式会社 | Zinc-based plated steel surface treatment solution, treated steel plate, and treatment method |
JP4573586B2 (en) * | 2004-07-07 | 2010-11-04 | 関西ペイント株式会社 | Surface-treated steel sheet |
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