TW201606129A - Replenisher, surface-treated metal material, and method for producing the same - Google Patents
Replenisher, surface-treated metal material, and method for producing the same Download PDFInfo
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本發明係關於一種補給劑、表面處理金屬材料及其製造方法。 The present invention relates to a replenisher, a surface treated metal material, and a method of manufacturing the same.
關於金屬材料製品,為了賦予塗料密合性、塗裝後耐蝕性、裸耐蝕性等功能,一般會對其表面實施根據用途之化學處理,例如磷酸鹽處理或鉻酸鹽處理等。 In the case of a metal material product, in order to impart functions such as adhesion of the coating, corrosion resistance after coating, and corrosion resistance to the bare metal, the surface is generally subjected to chemical treatment according to the use, such as phosphate treatment or chromate treatment.
然而,近年來,對減輕環境負荷之關注較高,研究減少磷酸鹽污泥等產業廢棄物或針對限制使用六價鉻之規定而採取相關應對措施,提出有利用鋯化合物等之化學處理皮膜作為代替磷酸鹽或鉻酸鹽處理之新的皮膜處理(專利文獻1、專利文獻2)。更具體而言,藉由在含有鋯(以下亦記為Zr)離子及氟(以下亦稱為F)離子之金屬材料用表面處理液中進行金屬材料之化學處理及/或電解處理(例如陰極電解等),可於金屬材料表面上獲得鋯系之化學處理皮膜(以下亦簡稱為皮膜),藉此可賦予金屬材料表面優異之性能。 However, in recent years, there has been a high level of concern for reducing environmental impact, and research has been conducted to reduce industrial waste such as phosphate sludge or to take measures to limit the use of hexavalent chromium. A new film treatment in place of phosphate or chromate treatment (Patent Document 1 and Patent Document 2). More specifically, chemical treatment and/or electrolytic treatment (for example, cathode) of a metal material is performed in a surface treatment liquid containing a metal material of zirconium (hereinafter also referred to as Zr) ion and fluorine (hereinafter also referred to as F) ion. Electrolyzed, etc., a zirconium-based chemical treatment film (hereinafter also referred to as a film) can be obtained on the surface of the metal material, whereby the surface of the metal material can be excellent in performance.
上述金屬材料用表面處理中,若連續地進行皮膜之製造,則金屬材料用表面處理液中之鋯離子會變為氧化物等而以皮膜之形態附著被消耗,因此金屬材料用表面處理液中之鋯離子濃度會逐漸降低。另一方面,氟離子向皮膜之摻入少於鋯離子,金屬材料用表面處理液中之每單位面積之氟離子濃度的下降量小於鋯離子。 In the surface treatment of the metal material, when the film is continuously produced, the zirconium ions in the surface treatment liquid for the metal material become oxides and the like, and are deposited in the form of a film. Therefore, the surface treatment liquid for the metal material is used. The zirconium ion concentration will gradually decrease. On the other hand, the fluorine ion is incorporated into the film to be less than zirconium ions, and the amount of decrease in the concentration of the fluoride ion per unit area in the surface treatment liquid for the metal material is smaller than that of the zirconium ion.
更具體而言,含有鋯離子之金屬材料用表面處理液於多數情況下使用H2ZrF6,其反應式如下。 More specifically, a surface treatment liquid for a metal material containing zirconium ions uses H 2 ZrF 6 in many cases, and the reaction formula is as follows.
H2ZrF6+2H2O → ZrO2↓+6HF 式(1) H 2 ZrF 6 +2H 2 O → ZrO 2 ↓+6HF (1)
於金屬材料與金屬材料用表面處理液之界面,因由蝕刻引起之酸的消耗、陰極電極附近之氫離子的還原等,金屬材料附近之pH值上升,如式(1)所示般產生H2ZrF6之水解,而於金屬材料表面形成鋯氧化物等鋯系皮膜。 At the interface between the metal material and the surface treatment liquid for the metal material, the pH of the vicinity of the metal material rises due to the consumption of acid by etching and the reduction of hydrogen ions in the vicinity of the cathode electrode, and H 2 is generated as shown in the formula (1). ZrF 6 is hydrolyzed to form a zirconium film such as zirconium oxide on the surface of the metal material.
另一方面,關於氟離子,如式(1)所示,隨著1莫耳之ZrO2產生,而於金屬材料用表面處理液中理論上產生作為副產物之6莫耳之HF。與作為皮膜主成分之Zr相比,皮膜中所含之HF非常少量,因此若連續地進行金屬表面處理,則HF於金屬材料用表面處理液中累積,其濃度上升。於式(1)中,HF在右邊,因此若HF濃度上升,則皮膜產生反應受到抑制,逐漸難以產生適當的鋯化合物之皮膜。又,若鋯離子濃度下降,則必須補給鋯離子,於該情形時,一般會補給H2ZrF6,於該鋯離子與氟離子之比率的補給中並未避免HF之累積。因此,先前為了避免HF之累積,多採用一面連續作業一面自動地部分廢棄(自動排放)金屬材料用表面處理液而將HF之濃度保持為一定的方法。然而,儘管提出減輕環境負荷之皮膜,但自動排放大量含有鋯離子或HF等之液體而使之流向排水管道,就環境及經濟之觀點而 言並不佳,而被要求改善。 On the other hand, regarding the fluorine ion, as shown in the formula (1), 6 mol of HF as a by-product is theoretically produced in the surface treatment liquid for a metal material as 1 mol of ZrO 2 is generated. Since HF contained in the film is very small compared with Zr which is a main component of the film, HF is accumulated in the surface treatment liquid for metal materials and the concentration thereof is increased when the metal surface treatment is continuously performed. In the formula (1), since HF is on the right side, if the HF concentration is increased, the film formation reaction is suppressed, and it is difficult to form a suitable film of the zirconium compound. Further, when the concentration of zirconium ions is lowered, it is necessary to supply zirconium ions. In this case, H 2 ZrF 6 is generally supplied, and accumulation of HF is not prevented in the supply of the ratio of zirconium ions to fluoride ions. Therefore, in order to avoid the accumulation of HF, a method of automatically partially disposing (automatically discharging) the surface treatment liquid for metal materials while maintaining the concentration of HF constant is employed. However, although a film for reducing environmental load is proposed, it is required to automatically discharge a large amount of liquid containing zirconium ions or HF to flow to a drain pipe, which is not preferable from the viewpoint of environment and economy.
因此,於專利文獻3中提出使用含有含氟之鋯化合物與不含氟之鋯化合物的補給劑,對金屬材料用表面處理液進行考慮到與氟離子補給量之平衡量的鋯離子補給,藉此可解決上述問題。更具體而言於專利文獻3之段落0033中揭示利用Zr離子濃度17g/L之鋯氫氟酸與硝酸鋯混合溶液(以重量比計,鋯氫氟酸:硝酸鋯=55:45)進行Zr離子之補給。 Therefore, Patent Document 3 proposes to use a replenishing agent containing a fluorine-containing zirconium compound and a fluorine-free zirconium compound, and to supply a surface treatment liquid for a metal material with zirconium ion replenishment in consideration of a balance with a fluoride ion replenishing amount. This solves the above problem. More specifically, in paragraph 0033 of Patent Document 3, it is disclosed that a zirconium hydrofluoric acid and zirconium nitrate mixed solution (zirconium hydrofluoric acid: zirconium nitrate = 55:45 by weight ratio) of Zr ion concentration of 17 g/L is used for Zr. Replenishment of ions.
[專利文獻1]日本特開2008-202149號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-202149
[專利文獻2]日本特開2010-90407號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-90407
[專利文獻3]日本第4996409號公報 [Patent Document 3] Japanese Patent No. 4996409
另一方面,用於對金屬材料用表面處理液補給鋯離子補給劑於多數情況下通常在購入後一面長期保管於倉庫等一面使用。因此,要求即便於長期保管後亦可使用,尤其是於將補給劑長期在高溫環境下保管時,補給劑中必須不會產生沈澱等。 On the other hand, the zirconium ion replenishing agent for replenishing the surface treatment liquid for metal materials is usually used for a long period of time in the warehouse or the like after being purchased. Therefore, it is required to be used even after long-term storage, and in particular, when the replenisher is stored in a high-temperature environment for a long period of time, precipitation or the like must not occur in the replenisher.
本發明者等人對專利文獻3中具體記載之補給劑進行了保存穩定性之研究,結果其保存穩定性並不滿足近來之要求程度,必須作進一步改良。 The inventors of the present invention conducted studies on the storage stability of the replenisher specifically described in Patent Document 3. As a result, the storage stability did not satisfy the recent requirements, and further improvement was required.
又,近年來,伴隨期望皮膜處理費用之低成本化,期望生產效率之進一步提高。作為提高生產效率之手段,可列舉:儘量抑制自動排放之方法、及較先前進一步增大累計之處理負荷並進行皮膜處理之方法。再者,所謂累計之處理負荷,係指實施皮膜處理之連續運轉後,金屬材料 之累計處理面積(Sm2)除以金屬材料用表面處理液體積(VL)所得者(S/V(m2/L)),作為金屬材料之皮膜處理技術,必須對於更大之累計處理負荷,金屬材料用表面處理液之成分平衡之變化小或處理性不變差。在對於累計之處理負荷,金屬材料用表面處理液之成分平衡的變化大或處理性易變差的情形時,必須部分地或全量更新金屬材料用表面處理液,確保穩定之處理性。該情形就生產效率、成本或環境之方面而言欠佳。 Moreover, in recent years, with the reduction in the cost of the film processing cost, it is desired to further improve the production efficiency. As means for improving the production efficiency, there are a method of suppressing automatic discharge as much as possible, and a method of further increasing the cumulative processing load and performing a film treatment. In addition, the cumulative processing load refers to the cumulative processing area (Sm 2 ) of the metal material divided by the surface treatment liquid volume (VL) for the metal material after the continuous operation of the film treatment (S/V (m 2 ) /L)), as a coating treatment technique for a metal material, it is necessary to have a small change in the composition balance of the surface treatment liquid for the metal material for a larger cumulative treatment load or a poor processability. When the change in the balance of the composition of the surface treatment liquid for the metal material is large or the handleability is liable to be deteriorated for the cumulative processing load, it is necessary to partially or completely renew the surface treatment liquid for the metal material to ensure the stability of the stability. This situation is not good in terms of production efficiency, cost or environment.
本發明者等人使用專利文獻3中具體記載之補給劑,實施皮膜處理之連續運轉,驗證於更大之累計處理負荷之時間點的皮膜處理性,結果發現皮膜向金屬材料上之附著量降低。 The inventors of the present invention performed the continuous operation of the film treatment using the replenishing agent specifically described in Patent Document 3, and verified the film treatment property at the time point of the larger cumulative processing load, and found that the adhesion amount of the film to the metal material was lowered. .
本發明鑒於上述實際情況,其目的在於提供一種補給劑,可避免金屬材料用表面處理液中之HF濃度上升且同時可對金屬材料用表面處理液以更高濃度補給鋯離子,以可對金屬材料連續地進行化學處理及/或電解處理,且該補給劑之長期保存穩定性優異。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a replenishing agent which can prevent an increase in HF concentration in a surface treatment liquid for a metal material and at the same time supply a zirconium ion at a higher concentration to a surface treatment liquid for a metal material, so that the metal can be applied to the metal. The material is continuously subjected to chemical treatment and/or electrolytic treatment, and the long-term storage stability of the replenisher is excellent.
又,本發明之目的亦在於提供一種使用該補給劑之表面處理金屬材料的製造方法。 Further, it is an object of the present invention to provide a method for producing a surface-treated metal material using the replenisher.
本發明人等經潛心研究,結果發現藉由採用使用特定化合物獲得之鋯離子濃度高的補給劑可解決上述課題。 As a result of intensive studies, the present inventors have found that the above problems can be solved by using a replenishing agent having a high zirconium ion concentration obtained by using a specific compound.
即,用以解決上述課題之本發明的構成如下所述。 That is, the configuration of the present invention for solving the above problems is as follows.
(1)一種補給劑,其用於對含有鋯離子及氟離子的金屬材料用表面處理液補給鋯離子,該金屬材料用表面處理液用於藉由化學處理及/或電解處理將含有鋯之化學處理皮膜形成於金屬材料;該補給劑含有:不含氟之鋯化合物(A),包含選自由鹼性碳酸鋯、碳 酸鋯、氫氧化鋯及碳酸鋯銨組成之群中的至少一種;含氟物(B),包含選自由氫氟酸、氫氟酸之鹽、鋯氫氟酸(zirconium hydrofluoric acid)及鋯氫氟酸之鹽組成之群中的至少一種;以及酸成分(C),包含選自由硝酸、鹽酸、硫酸及乙酸組成之群中的至少一種;並滿足以下之(I)~(III):(I)源自酸成分(C)之陰離子合計莫耳量(MAC)與源自含氟物(B)之氟離子合計莫耳量(MF)的比(MAC/MF)為0.35以上,未達2.00,(II)源自不含氟之鋯化合物(A)及含氟物(B)的鋯離子之合計濃度(g/L)為25以上,(III)源自含氟物(B)之氟離子合計莫耳量(MF)與源自不含氟之鋯化合物(A)及含氟物(B)的鋯離子合計莫耳量(MZr)的比(MF/MZr)為2.00以上,未達6.00。 (1) A replenishing agent for replenishing zirconium ions with a surface treatment liquid for a metal material containing zirconium ions and fluorine ions, the surface material for which the surface treatment liquid is used for chemical treatment and/or electrolytic treatment to contain zirconium a chemical treatment film formed on the metal material; the replenisher comprising: a fluorine-free zirconium compound (A) comprising at least one selected from the group consisting of basic zirconium carbonate, zirconium carbonate, zirconium hydroxide, and ammonium zirconium carbonate; Fluorine (B) comprising at least one selected from the group consisting of salts of hydrofluoric acid, hydrofluoric acid, zirconium hydrofluoric acid and zirconium hydrofluoric acid; and acid component (C), And comprising at least one selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid; and satisfying the following (I) to (III): (I) anion total molar amount (M AC ) derived from the acid component (C) The ratio (M AC /M F ) to the molar amount (M F ) of the fluorine ion derived from the fluorine-containing substance (B) is 0.35 or more, less than 2.00, and (II) is derived from a fluorine-free zirconium compound (A). And the total concentration (g/L) of the zirconium ions of the fluorine-containing substance (B) is 25 or more, and (III) the total amount of fluorine ions (M F ) derived from the fluorine-containing substance (B) and The ratio (M F /M Zr ) of the zirconium ion total molar amount (M Zr ) derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) was 2.00 or more and was less than 6.00.
(2)如(1)記載之補給劑,其中,比(MAC/MF)超過0.50,未達2.00。 (2) The replenisher according to (1), wherein the ratio (M AC / M F ) exceeds 0.50 and does not reach 2.00.
(3)如(1)或(2)記載之補給劑,其中,比(MAC/MF)超過0.50且在1.60以下。 (3) The replenisher according to (1) or (2), wherein the ratio (M AC / M F ) exceeds 0.50 and is 1.60 or less.
(4)一種表面處理金屬材料之製造方法,係於含有鋯離子及氟離子之金屬材料用表面處理液中對金屬材料連續地實施化學處理及/或電解處理,而於金屬材料上形成含有鋯之化學處理皮膜,於金屬材料用表面處理液添加(1)至(3)中任一項記載之補給劑而進行鋯離子之補給。 (4) A method for producing a surface-treated metal material, which is characterized in that a metal material is continuously subjected to chemical treatment and/or electrolytic treatment in a surface treatment liquid for a metal material containing zirconium ions and fluorine ions, and zirconium is formed on the metal material. The film is chemically treated, and the replenishing agent described in any one of (1) to (3) is added to the surface treatment liquid for metal materials to supply zirconium ions.
(5)一種表面處理金屬材料,其係藉由(4)記載之表面處理金屬材料的製造方法而獲得。 (5) A surface-treated metal material obtained by the method for producing a surface-treated metal material according to (4).
根據本發明,可提供一種補給劑,可避免金屬材料用表面處理液中之HF濃度上升且同時可對金屬材料用表面處理液以更高濃度補給鋯離子,以可對金屬材料連續地進行化學處理及/或電解處理,且該補給劑之長期保存穩定性優異。 According to the present invention, it is possible to provide a replenishing agent which can prevent the HF concentration in the surface treatment liquid for the metal material from rising and at the same time, can supply the zirconium ion at a higher concentration to the surface treatment liquid for the metal material, so that the metal material can be continuously chemically oxidized. Treatment and/or electrolytic treatment, and the long-term storage stability of the replenisher is excellent.
又,根據本發明,可提供一種使用該補給劑之表面處理金屬材料的製造方法。 Further, according to the present invention, a method of producing a surface-treated metal material using the replenishing agent can be provided.
以下對本發明之補給劑及表面處理金屬材料之製造方法進行說明。 Hereinafter, the method of producing the replenisher and the surface-treated metal material of the present invention will be described.
本發明之補給劑含有特定的不含氟之鋯化合物(A)、特定的含氟物(B)及特定的酸成分(C),且含有高濃度鋯離子(Zr離子)。又,本發明之補給劑中,源自酸成分(C)之陰離子合計莫耳量(MAC)與氟離子(F離子)合計莫耳量(MF)的比(MAC/MF)、及鋯離子合計莫耳量(MZr)與氟離子合計莫耳量(MF)的比(MF/MZr)為特定範圍內。藉由滿足上述成分與其成分量比而達成該補給劑之長期保存穩定性。又,於該補給劑中,與氟離子相比,含有高濃度鋯離子。因此,於連續之化學處理皮膜製造中,對金屬材料用表面處理液連續補給該補給劑之情形時,可避免HF之增加且連續地供給大量鋯離子,因此結果可抑制自動排放量且連續進行金屬材料之化學 處理及/或電解處理。尤其是藉由將比(MAC/MF)調整為特定範圍,可提供一種長期保存穩定性更優異,可連續進行金屬材料之化學處理及/或電解處理的補給劑。 The replenisher of the present invention contains a specific fluorine-free zirconium compound (A), a specific fluorine-containing compound (B), and a specific acid component (C), and contains a high concentration of zirconium ions (Zr ions). Further, in the replenisher of the present invention, the ratio of the total amount of the anion derived from the acid component (C) (M AC ) to the total amount of the fluoride ion (F ion) (M F ) (M AC /M F ) The ratio of the total amount of zirconium ion (M Zr ) to the total amount of fluorine ion (M F ) (M F /M Zr ) is within a specific range. The long-term storage stability of the replenisher is achieved by satisfying the ratio of the above components to their component amounts. Further, in the replenisher, a high concentration of zirconium ions is contained as compared with the fluorine ions. Therefore, in the case of continuous chemical treatment film production, when the surface treatment liquid for metal materials is continuously supplied with the replenishing agent, an increase in HF can be avoided and a large amount of zirconium ions can be continuously supplied, so that the automatic emission amount can be suppressed and continuously performed. Chemical treatment and/or electrolytic treatment of metallic materials. In particular, by adjusting the ratio (M AC /M F ) to a specific range, it is possible to provide a replenisher which is more excellent in long-term storage stability and which can continuously perform chemical treatment and/or electrolytic treatment of a metal material.
首先,於以下說明本發明之補給劑的態樣,其後說明使用該補給劑之表面處理金屬材料的製造方法。 First, the aspect of the replenisher of the present invention will be described below, and a method of producing the surface-treated metal material using the replenisher will be described later.
[補給劑] [Supply agent]
本發明之補給劑主要用於對含有鋯離子及氟離子的金屬材料用表面處理液補給鋯離子,該金屬材料用表面處理液用於藉由化學處理及/或電解處理將含有鋯作為主成分之化學處理皮膜形成於金屬材料表面。再者,於連續之化學處理皮膜製造中並非不允許實施自動排放。 The replenishing agent of the present invention is mainly used for replenishing zirconium ions with a surface treatment liquid for a metal material containing zirconium ions and fluoride ions, and the surface treatment liquid for the metal material is used for chemical treatment and/or electrolytic treatment to contain zirconium as a main component. The chemical treatment film is formed on the surface of the metal material. Furthermore, automatic discharge is not allowed in continuous chemical processing film manufacturing.
首先,詳細說明該補給劑所含之各種材料,其後詳細說明該補給劑之製造方法。 First, various materials contained in the replenisher will be described in detail, and a method of producing the replenisher will be described in detail later.
(不含氟之鋯化合物(A)) (No fluorine-containing zirconium compound (A))
本發明之補給劑中所含之不含氟之鋯化合物(A)為不含氟原子且含有Zr原子之化合物。 The fluorine-free zirconium compound (A) contained in the replenisher of the present invention is a compound which does not contain a fluorine atom and contains a Zr atom.
作為不含氟之鋯化合物(A),可列舉選自由鹼性碳酸鋯、碳酸鋯、氫氧化鋯及碳酸鋯銨組成之群中的至少一種。其中,就補給劑之保存穩定性更優異、可更連續地實施表面處理之方面(以下亦簡稱為「本發明的效果更優異之方面」)而言,更佳為鹼性碳酸鋯或碳酸鋯。 The fluorine-free zirconium compound (A) may be at least one selected from the group consisting of basic zirconium carbonate, zirconium carbonate, zirconium hydroxide, and ammonium zirconium carbonate. Among them, in the case where the storage stability of the replenishing agent is more excellent and the surface treatment can be carried out more continuously (hereinafter also referred to as "the aspect in which the effect of the present invention is more excellent"), it is more preferable that it is basic zirconium carbonate or zirconium carbonate. .
再者,作為不含氟之鋯化合物(A),亦可混合2種以上之上述化合物來使用。 Further, as the fluorine-free zirconium compound (A), two or more kinds of the above compounds may be used in combination.
(含氟物(B)) (fluorine (B))
本發明之補給劑中所含之含氟物(B)為含有氟原子之化合物,藉由該化合物向補給劑中供給F離子。再者,於使用鋯氫氟酸或其鹽作為含氟物(B)之情形時,亦向補給劑中一併供給Zr離子。 The fluorine-containing substance (B) contained in the replenisher of the present invention is a compound containing a fluorine atom, and the compound supplies F ions to the replenisher. Further, when zirconium hydrofluoric acid or a salt thereof is used as the fluorine-containing compound (B), Zr ions are also supplied to the replenisher.
作為含氟物(B),可列舉選自由氫氟酸、氫氟酸之鹽、鋯氫氟酸及鋯氫氟酸之鹽組成之群中的至少一種。其中,就本發明的效果更優異之方面而言,更佳為氫氟酸或鋯氫氟酸。 The fluorine-containing compound (B) may be at least one selected from the group consisting of salts of hydrofluoric acid, hydrofluoric acid, zirconium hydrofluoric acid, and zirconium hydrofluoric acid. Among them, hydrofluoric acid or zirconium hydrofluoric acid is more preferable in terms of the effect of the present invention being more excellent.
再者,作為氫氟酸之鹽,例如可列舉氫氟酸與鹼(例如胺化合物)、較佳為銨鹽等不含金屬之鹼的鹽。又,作為鋯氫氟酸之鹽,例如可列舉K2ZrF6等金屬酸鹽(例如鈉鹽、鉀鹽、鋰鹽、銨鹽等)。 Further, examples of the hydrofluoric acid salt include salts of a metal-free base such as hydrofluoric acid and a base (for example, an amine compound), preferably an ammonium salt. Further, examples of the salt of zirconium hydrofluoric acid include metal acid salts (for example, sodium salt, potassium salt, lithium salt, ammonium salt, etc.) such as K 2 ZrF 6 .
又,作為含氟物(B),亦可混合2種以上之上述化合物來使用。 Further, as the fluorine-containing compound (B), two or more kinds of the above compounds may be used in combination.
(酸成分(C)) (acid component (C))
本發明之補給劑中所含之酸成分(C)發揮調整補給劑之pH值的作用,及促進其他成分(不含氟之鋯化合物(A)及/或含氟物(B))之溶解性的作用。 The acid component (C) contained in the replenishing agent of the present invention functions to adjust the pH of the replenishing agent, and promotes dissolution of other components (zirconium-free compound (A) and/or fluorine-containing compound (B)). The role of sex.
作為酸成分(C),可列舉選自由硝酸、鹽酸、硫酸及乙酸組成之群中的至少一種。其中,就本發明的效果更優異之方面而言,更佳為硝酸或硫酸。 The acid component (C) may be at least one selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid. Among them, nitric acid or sulfuric acid is more preferable in terms of the effect of the present invention being more excellent.
再者,作為酸成分(C),亦可混合2種以上之上述酸成分來使用。 Further, as the acid component (C), two or more kinds of the above acid components may be mixed and used.
(各種含量) (various content)
本發明之補給劑中的各種成分滿足以下(I)~(III)之關係。 The various components in the replenisher of the present invention satisfy the relationship of the following (I) to (III).
(I)源自酸成分(C)之陰離子合計莫耳量(MAC)與源自含氟物(B)之氟離子合計莫耳量(MF)的比(MAC/MF)為0.35以上,未達2.00。 (I) The ratio (M AC /M F ) of the molar amount of the anion total amount (M AC ) derived from the acid component (C) to the total amount of fluorine ion (M F ) derived from the fluorine-containing compound (B) is Above 0.35, it is less than 2.00.
(II)源自不含氟之鋯化合物(A)及含氟物(B)之鋯離子合計濃度(g/L)為25以上。 (II) The total zirconium ion concentration (g/L) derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 25 or more.
(III)源自含氟物(B)之氟離子合計莫耳量(MF)與源自不含氟之鋯化合物(A)及含氟物(B)之鋯離子合計莫耳量(MZr)的比(MF/MZr)為2.00以上,未達6.00。 (III) Total amount of fluorine ion derived from fluorine-containing substance (B) (M F ) and total amount of zirconium ion derived from zirconium-free compound (A) and fluorine-containing compound (B) (M) Zr) ratio (M F / M Zr) is 2.00 or more and less than 6.00.
以下對各關係進行說明。 The following describes each relationship.
(關於(I)) (About (I))
本發明之補給劑中源自酸成分(C)之陰離子合計莫耳量(MAC)與源自含氟物(B)之氟離子合計莫耳量(MF)的比(MAC/MF)為0.35以上,未達2.00。若為上述範圍內,則該補給劑之保存穩定性優異,且金屬材料用表面處理液之HF不會累積而可連續穩定地進行化學處理皮膜之製造。其中,作為本發明之效果更優異的範圍,比(MAC/MF)較佳超過0.40,未達2.00,更佳超過0.50,未達2.00,進而較佳超過0.50且在1.60以下,尤佳為1.00以上且在1.60以下。 The ratio of the total molar amount of the anion derived from the acid component (C) (M AC ) to the total amount of fluorine ion derived from the fluorine-containing compound (B) (M F /M) in the replenisher of the present invention (M AC /M F ) is 0.35 or more and less than 2.00. When it is in the above range, the storage stability of the replenishing agent is excellent, and the HF of the surface treatment liquid for metal materials does not accumulate, and the chemical treatment film can be continuously and stably produced. Among them, as a more excellent range of the effect of the present invention, the ratio (M AC / M F ) is preferably more than 0.40, less than 2.00, more preferably more than 0.50, less than 2.00, further preferably more than 0.50 and less than 1.60. It is 1.00 or more and 1.60 or less.
於比(MAC/MF)未達0.35之情形時,該補給劑之長期保存穩定性差。 When the ratio (M AC / M F ) is less than 0.35, the long-term storage stability of the replenisher is poor.
又,於比(MAC/MF)為2.00以上之情形時,若繼續使用該補給劑,則皮膜之附著量減少,無法形成所需之皮膜。 Further, when the ratio (M AC / M F ) is 2.00 or more, when the replenisher is continuously used, the adhesion amount of the film is reduced, and the desired film cannot be formed.
再者,所謂源自酸成分(C)(硝酸、鹽酸、硫酸及乙酸)之陰離子,意指NO3 -、Cl-、SO4 2-、CH3COO-。 Further, the anion derived from the acid component (C) (nitric acid, hydrochloric acid, sulfuric acid, and acetic acid) means NO 3 - , Cl - , SO 4 2- , and CH 3 COO - .
(關於(II)) (About (II))
本發明之補給劑中源自不含氟之鋯化合物(A)及含氟物(B)之鋯離子合計濃度(g/L)為25以上。若為上述範圍內,則可更經濟地製造化學 處理皮膜。其中,就補給劑使用量少而操作經濟性更優異之方面而言,鋯離子之合計濃度(g/L)較佳為30以上,更佳為35以上。上限並無特別限制,就不含氟之鋯化合物(A)及含氟物(B)的溶解性之方面而言,多為70以下。 In the replenisher of the present invention, the total zirconium ion concentration (g/L) derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 25 or more. If it is within the above range, it can be more economically manufactured. Treat the film. In particular, the total concentration of zirconium ions (g/L) is preferably 30 or more, and more preferably 35 or more, in terms of a small amount of the replenishing agent and a more excellent economical operation. The upper limit is not particularly limited, and it is usually 70 or less in terms of solubility of the fluorine-containing zirconium compound (A) and the fluorine-containing compound (B).
再者,於鋯離子之合計濃度(g/L)未達25之情形時,該補給劑濃度稀薄,因此必須向金屬材料用表面處理液大量補充該補給劑,伴隨於此,過量地供水而使金屬材料用表面處理液體積增加,結果為了連續地進行皮膜處理而必須增大金屬材料用表面處理液之自動排放量,就環境及經濟之方面而言欠佳。 In addition, when the total concentration (g/L) of zirconium ions is less than 25, the concentration of the replenishing agent is thin, so it is necessary to replenish the replenishing agent in a large amount to the surface treatment liquid for the metal material, and accordingly, the water supply is excessively supplied. When the volume of the surface treatment liquid for the metal material is increased, it is necessary to increase the automatic discharge amount of the surface treatment liquid for the metal material in order to continuously perform the film treatment, which is not preferable in terms of environment and economy.
又,於使用鋯氫氟酸或其鹽作為含氟物(B)之情形時,供給源自含氟物(B)之鋯離子。 Further, when zirconium hydrofluoric acid or a salt thereof is used as the fluorine-containing compound (B), zirconium ions derived from the fluorine-containing compound (B) are supplied.
(關於(III)) (About (III))
本發明之補給劑中源自不含氟之鋯化合物(A)及含氟物(B)之鋯離子合計莫耳量(MZr)與源自含氟物(B)之氟離子合計莫耳量(MF)的比(MF/MZr)為2.00以上,未達6.00。若為上述範圍內,則金屬材料用表面處理液之HF不會累積而可連續穩定地進行化學處理皮膜之製造。其中,作為本發明的效果更優異之範圍,比(MF/MZr)較佳為2.50~5.50,更佳為3.00~5.00。 In the replenishing agent of the present invention, the zirconium ion total molar amount (M Zr ) derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) and the fluorine ion derived from the fluorine-containing compound (B) are combined. The ratio (M F /M Zr ) of the amount (M F ) was 2.00 or more and was less than 6.00. When it is in the above range, the HF of the surface treatment liquid for metal materials does not accumulate, and the chemical treatment film can be continuously and stably produced. Among them, the range of the effect of the present invention is more excellent, and the ratio (M F /M Zr ) is preferably 2.50 to 5.50, more preferably 3.00 to 5.00.
於比(MF/MZr)未達2.00之情形時,難以使鋯離子溶解於補給劑中。又,於該比(MF/MZr)為6.00以上之情形時,若連續使用該補給劑,則無法避免金屬材料用表面處理液中HF之累積,因此於穩定地進行化學處理皮膜製造之情形時,必須增加自動排放量,就環境及經濟之方面而言欠佳。 When the ratio (M F /M Zr ) is less than 2.00, it is difficult to dissolve the zirconium ions in the replenishing agent. In addition, when the ratio (M F /M Zr ) is 6.00 or more, if the replenisher is continuously used, accumulation of HF in the surface treatment liquid for metal materials cannot be avoided, so that the chemical treatment film is stably produced. In the case of circumstances, it is necessary to increase the amount of automatic emissions, which is not good in terms of environmental and economic aspects.
上述各種離子之測量可使用公知之測量機器、原子吸光、ICP、離子層析或氟離子測定計進行測量。 The measurement of the above various ions can be carried out using a known measuring machine, atomic absorption, ICP, ion chromatography or a fluoride ion meter.
本發明之補給劑中不含氟之鋯化合物(A)的含量只要滿足上述(I)~(III)之關係則並無特別限制,就化學處理皮膜的析出效率更優異之方面而言,相對於含氟物(B)100質量份,較佳為0.1~500質量份,更佳為10~300質量份。 The content of the fluorine-free zirconium compound (A) in the replenisher of the present invention is not particularly limited as long as the relationship of the above (I) to (III) is satisfied, and the chemical treatment film is more excellent in precipitation efficiency. It is 100 parts by mass of the fluorine-containing compound (B), preferably 0.1 to 500 parts by mass, more preferably 10 to 300 parts by mass.
本發明之補給劑的pH值並無特別限制,就補給劑的穩定性優異之方面而言,較佳為未達4.0,更佳為超過0且在1.5以下。再者,於進行pH值調整之情形時,亦可使用鹼成分。作為鹼成分,可列舉:氫氧化鈉、氫氧化鉀等鹼金屬氧化物,氫氧化鈣、氫氧化鎂等鹼土金屬之氫氧化物,氨、單乙醇胺、二乙醇胺、三乙醇胺等有機胺。其中,就無金屬之污染、不含有機溶劑之方面而言,較佳使用氨。 The pH of the replenishing agent of the present invention is not particularly limited, and is preferably less than 4.0, more preferably more than 0 and not more than 1.5, in terms of excellent stability of the replenishing agent. Further, in the case of pH adjustment, an alkali component can also be used. Examples of the alkali component include alkali metal oxides such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide; and organic amines such as ammonia, monoethanolamine, diethanolamine and triethanolamine. Among them, ammonia is preferably used in terms of no metal contamination and no organic solvent.
本發明之補給劑視需要可含有溶劑。使用之溶劑種類並無特別限制,通常使用水及/或有機溶劑。 The replenishing agent of the present invention may contain a solvent as needed. The type of the solvent to be used is not particularly limited, and water and/or an organic solvent is usually used.
作為有機溶劑,例如可列舉醇系溶劑等。關於有機溶劑之含量,只要為無損補給劑之穩定性與使用補給劑所補給之金屬材料用表面處理液之穩定性的範圍即可,就作業環境之觀點而言,較佳為不使用。 Examples of the organic solvent include an alcohol solvent and the like. The content of the organic solvent is preferably in the range of the stability of the non-depleting replenishing agent and the stability of the surface treatment liquid for the metal material supplied by the replenishing agent, and is preferably not used from the viewpoint of the working environment.
於補給劑含有溶劑之情形時,上述不含氟之鋯化合物(A)、含氟物(B)及酸成分(C)之合計質量就化學處理皮膜的析出效率更優異之方面而言,相對於補給劑總量,較佳為2~90質量%,更佳為4~80質量%。 When the solvent contains a solvent, the total mass of the fluorine-free zirconium compound (A), the fluorine-containing compound (B), and the acid component (C) is superior in terms of the precipitation efficiency of the chemical treatment film. The total amount of the replenishing agent is preferably 2 to 90% by mass, more preferably 4 to 80% by mass.
再者,本發明之補給劑的製造方法並無特別限制,可採用公知之方法。例如可列舉於溶劑中添加不含氟之鋯化合物(A)、含氟物(B) 及酸成分(C)而進行混合之方法。 Further, the method for producing the replenisher of the present invention is not particularly limited, and a known method can be employed. For example, a fluorine-free zirconium compound (A) or a fluorine-containing compound (B) may be added to a solvent. A method of mixing with the acid component (C).
[表面處理金屬材料之製造方法] [Method of Manufacturing Surface Treatment Metal Material]
以下說明使用本發明之補給劑的表面處理金屬材料之製造方法。 A method of producing a surface-treated metal material using the replenisher of the present invention will be described below.
本發明之表面處理金屬材料的製造方法係於包含鋯離子及氟離子之金屬材料用表面處理液中對金屬材料連續實施化學處理及/或電解處理,而於金屬材料上形成含有鋯之化學處理皮膜的方法。 The method for producing a surface-treated metal material according to the present invention is to continuously perform chemical treatment and/or electrolytic treatment on a metal material in a surface treatment liquid for a metal material containing zirconium ions and fluoride ions, and form a chemical treatment containing zirconium on the metal material. The method of the membrane.
若連續實施上述表面處理金屬材料之製造方法,則金屬材料用表面處理液中之鋯離子的濃度會隨之下降,難以產生鋯化合物之皮膜。為了補充此種鋯離子之濃度下降部分,而於金屬材料用表面處理液中補給上述該補給劑。 When the method for producing the surface-treated metal material is continuously carried out, the concentration of zirconium ions in the surface treatment liquid for the metal material is lowered, and it is difficult to produce a film of the zirconium compound. In order to supplement the concentration drop portion of the zirconium ions, the above-mentioned supply agent is supplied to the surface treatment liquid for metal materials.
再者,一般而言,為了連續穩定地於金屬材料上獲得特定之化學處理皮膜,較佳以鋯離子濃度未下降20%以上之方式添加該補給劑。關於與鋯同時補給之氟離子總量,較佳補給下述之量:自化學處理皮膜所含氟離子總量與附著於金屬材料而被帶出之金屬材料用表面處理液所含氟離子總量的合計量,減去產生鋯化合物皮膜時副產於金屬材料用表面處理液中HF之氟離子量所得的量。 Further, in general, in order to obtain a specific chemical treatment film continuously and stably on a metal material, it is preferred to add the replenisher so that the zirconium ion concentration does not decrease by 20% or more. Regarding the total amount of fluoride ions replenished simultaneously with zirconium, it is preferable to replenish the following amounts: the total amount of fluorine-containing ions from the chemical treatment film and the total amount of fluorine-containing ions in the surface treatment liquid for metal materials which are carried out by the metal material The total amount of the amount is subtracted from the amount of the fluorine ion of HF which is produced by-product in the surface treatment liquid for metal materials when the zirconium compound film is produced.
再者,於金屬材料用表面處理液中添加本發明之補給劑的方 法並無特別限制,可列舉:將補給劑每次少量分成數次添加的方法(方法A)、或一次添加特定量之補給劑的方法(方法B)。其中,就金屬材料用表面處理液中之成分變動小、可連續穩定地進行表面處理金屬材料之製造的方面而言,較佳為方法A。 Furthermore, the side of the surface treatment liquid for metal materials is added with the replenisher of the present invention. The method is not particularly limited, and examples thereof include a method in which a small amount of a replenishing agent is added in a small amount (method A), or a method in which a specific amount of a replenishing agent is added at a time (method B). Among them, the method A is preferable in that the component of the surface treatment liquid for a metal material is small in variation and the surface-treated metal material can be continuously and stably produced.
又,添加本發明之補給劑於金屬材料用表面處理液時,可採用暫時中 止製造而添加補給劑於金屬材料用表面處理液之方法、及不中止製造而於正在實施表面處理金屬材料之製造方法的過程中向金屬材料用表面處理液添加補給劑之方法的任一者。其中,就高速操作時之生產效率優異、可連續穩定地進行表面處理金屬材料之製造方法的方面而言,較佳為於正在實施表面處理金屬材料之製造方法的過程中向金屬材料用表面處理液添加補給劑之方法。 Further, when the replenishing agent of the present invention is added to the surface treatment liquid for a metal material, it may be temporarily used. A method of adding a replenishing agent to a surface treatment liquid for a metal material, and a method of adding a replenishing agent to a surface treatment liquid for a metal material during the process of manufacturing the surface-treated metal material without stopping the production. . Among them, in terms of high production efficiency at high-speed operation and continuous and stable production of a surface-treated metal material, it is preferable to surface-treat a metal material in a process of manufacturing a surface-treated metal material. A method of adding a replenisher to a liquid.
以下,說明本發明之表面處理金屬材料的製造方法使用之金屬材料用表面處理液。 Hereinafter, the surface treatment liquid for metal materials used in the method for producing a surface-treated metal material of the present invention will be described.
(金屬材料用表面處理液) (surface treatment liquid for metal materials)
上述本發明之表面處理金屬材料的製造方法使用之金屬材料用表面處理液含有Zr離子及氟離子。 The surface treatment liquid for a metal material used in the method for producing a surface-treated metal material according to the present invention contains Zr ions and fluorine ions.
作為金屬材料用表面處理液中之鋯離子的供給源,例如可列舉上述不含氟之鋯化合物(A)、鋯氫氟酸或其鹽等。 Examples of the supply source of zirconium ions in the surface treatment liquid for a metal material include the above-mentioned fluorine-free zirconium compound (A), zirconium hydrofluoric acid or a salt thereof.
再者,作為金屬材料用表面處理液中之Zr離子,係指(1)如ZrFn (4-n)所示般對1莫耳之鋯配位有1~6莫耳之氟的氟化鋯錯離子、及(2)由硝酸鋯或硫酸鋯等無機酸鋯,或者氧鋯或乙酸鋯或乙酸氧鋯等有機酸鋯或是產自氧鋯之鋯離子或氧鋯離子兩者。 Further, the Zr ion in the surface treatment liquid for a metal material means (1) fluorination of 1 to 6 moles of fluorine to 1 mole of zirconium as shown by ZrF n (4-n) The zirconium mision, and (2) zirconium mineral acid such as zirconium nitrate or zirconium sulfate, or zirconium oxychloride or zirconium acetate or zirconium acetate or zirconium ion or zirconium ion.
金屬材料用表面處理液中之鋯離子含量並無特別限制,就金屬材料用表面處理液之穩定性更優異、化學處理皮膜的析出效率亦更優異之方面而言,較佳為0.05~10.00g/L,更佳為0.10~2.00g/L。 The zirconium ion content in the surface treatment liquid for a metal material is not particularly limited, and is preferably 0.05 to 10.00 g in terms of more excellent stability of the surface treatment liquid for the metal material and more excellent precipitation efficiency of the chemical treatment film. /L, more preferably 0.10~2.00g/L.
又,作為金屬材料用表面處理液中氟離子之供給源,係使用公知之含有氟的化合物(含氟化合物)。 Moreover, as a supply source of fluorine ions in the surface treatment liquid for metal materials, a fluorine-containing compound (fluorine-containing compound) is used.
再者,作為含氟化合物,可較佳使用具有選自由Ti、Zr、Hf、Si、Al及B組成之群的原子之至少1種元素者。具體而言,例如可列舉:對(TiF6)2-、(ZrF6)2-、(HfF6)2-、(SiF6)2-、(AlF6)3-、(BF4OH)-等在陰離子配位有1~3個氫原子之錯合物,該等陰離子之銨鹽,該等陰離子之金屬鹽等。 Further, as the fluorine-containing compound, at least one element having an atom selected from the group consisting of Ti, Zr, Hf, Si, Al, and B can be preferably used. Specifically, for example, (TiF 6 ) 2- , (ZrF 6 ) 2- , (HfF 6 ) 2- , (SiF 6 ) 2- , (AlF 6 ) 3- , (BF 4 OH) - A complex having 1 to 3 hydrogen atoms in the anion coordination, an ammonium salt of the anions, a metal salt of the anions, and the like.
此外,作為含氟化合物,例如可列舉:氫氟酸、其銨鹽、其鹼金屬鹽、或金屬氟化物(例如氟化鋁、氟化鋅、氟化釩、氟化錫、氟化錳、氟化亞鐵、氟化鐵等)、或酸氟化物(例如氧化氟、乙醯氟、苯甲醯氟等)。 Further, examples of the fluorine-containing compound include hydrofluoric acid, an ammonium salt thereof, an alkali metal salt thereof, or a metal fluoride (for example, aluminum fluoride, zinc fluoride, vanadium fluoride, tin fluoride, manganese fluoride, Ferrous fluoride, iron fluoride, etc., or acid fluoride (such as fluorinated fluorine, acetamidine fluoride, benzamidine fluoride, etc.).
再者,金屬材料用表面處理液中之氟離子係指存在於金屬材料用表面處理液中源自HF之氟離子(F-)、及如上述氟化鋯錯離子般含氟錯離子中的氟離子兩者,上述及後述氟離子總濃度係指該兩者之合計濃度。游離氟離子濃度係指源自HF之氟離子(F-)的濃度。 Further, the fluorine ion in the surface treatment liquid for a metal material refers to a fluorine ion (F - ) derived from HF present in a surface treatment liquid for a metal material, and a fluorine-containing counter ion as in the above-mentioned zirconium fluoride mision. In the case of both fluorine ions, the total concentration of fluoride ions described above and below refers to the total concentration of the two. The free fluoride ion concentration refers to the concentration of fluoride ion (F - ) derived from HF.
金屬材料用表面處理液之全部氟離子含量並無特別限制,就金屬材料用表面處理液之穩定性更優異、化學處理皮膜的析出效率亦更優異的方面而言,作為氟離子總濃度,較佳為0.050~10.000g/L,更佳為0.100~3.000g/L。作為游離氟離子濃度,較佳為5mg/L~400mg/L,更佳為10~250mg/L。 The content of the fluorine ion in the surface treatment liquid for a metal material is not particularly limited, and the total stability of the surface treatment liquid for the metal material is more excellent, and the precipitation efficiency of the chemical treatment film is also more excellent. Preferably, it is 0.050~10.000g/L, more preferably 0.100~3.000g/L. The free fluoride ion concentration is preferably 5 mg/L to 400 mg/L, more preferably 10 to 250 mg/L.
再者,金屬材料用表面處理液中之Zr離子及全部氟離子、游離氟離子之含量(濃度)可使用原子吸光、ICP、離子層析或氟離子測量計進行定量。 Further, the content (concentration) of Zr ions and all fluorine ions and free fluorine ions in the surface treatment liquid for metal materials can be quantified by atomic absorption, ICP, ion chromatography or a fluoride ion meter.
金屬材料用表面處理液之pH值係根據作為對象之金屬材料或化學處理或電解處理之條件等而適當調整,就金屬材料用表面處理液之穩定性更優異、化學處理皮膜之析出性亦更優異的方面而言,較佳為2.5~ 5.0左右,更佳為3.0~5.0。再者,金屬材料用表面處理液之pH值可使用pH測定計進行測量。 The pH of the surface treatment liquid for metal materials is appropriately adjusted depending on the metal material to be used, the conditions of chemical treatment or electrolytic treatment, etc., and the surface treatment liquid for metal materials is more excellent in stability and the precipitation property of the chemical treatment film is also improved. In terms of excellence, it is preferably 2.5~ 5.0 or so, more preferably 3.0 to 5.0. Further, the pH of the surface treatment liquid for the metal material can be measured using a pH meter.
以下說明本發明之表面處理金屬材料的製造方法使用之金屬材料、以及化學處理及電解處理。 The metal material used in the method for producing a surface-treated metal material of the present invention, as well as the chemical treatment and the electrolytic treatment will be described below.
(金屬材料) (metallic material)
使用之金屬材料種類並無特別限制,可使用公知之金屬材料。例如可列舉:鐵系材料、鍍敷系材料、鋅系材料、鋁系材料、鎂系材料等。 The kind of the metal material to be used is not particularly limited, and a known metal material can be used. For example, an iron-based material, a plating-based material, a zinc-based material, an aluminum-based material, and a magnesium-based material may be mentioned.
金屬材料之形狀並無特別限制,可為板狀,亦可為其他形狀。作為其他形狀,例如可列舉:汽車等運輸機器之車體及其零件、農機具及其零件、鋼製傢具、建材等。 The shape of the metal material is not particularly limited and may be a plate shape or other shapes. Examples of other shapes include a body of a transportation machine such as an automobile and parts thereof, agricultural machinery and parts thereof, steel furniture, and building materials.
(化學處理或電解處理) (chemical treatment or electrolytic treatment)
作為使用上述金屬材料用表面處理液之化學處理,可使用公知之處理設備以公知之條件實施。再者,所謂化學處理,係指使特定之金屬材料用表面處理液於常溫下或加熱而接觸(浸漬或塗佈或噴霧)金屬材料,而於金屬材料表面上形成皮膜之處理。 The chemical treatment using the surface treatment liquid for a metal material described above can be carried out under known conditions using a known treatment equipment. In addition, the term "chemical treatment" refers to a treatment in which a specific metal material is contacted (immersed or coated or sprayed) with a surface treatment liquid at a normal temperature or by heating to form a film on the surface of the metal material.
使金屬材料與金屬材料用表面處理液接觸之時間係根據作為對象之金屬材料的材質或形狀或處理方式及用途、目標皮膜附著量而適當調整,就作為化學處理皮膜的特性更優異之方面而言,通常多為0.1~600秒左右。 The time during which the metal material is brought into contact with the surface treatment liquid of the metal material is appropriately adjusted depending on the material or shape of the metal material to be used, the treatment method, the use, and the target film adhesion amount, and the chemical treatment film is more excellent in characteristics. Generally speaking, it is usually about 0.1~600 seconds.
又,作為使用金屬材料用表面處理液之電解處理(陽極電解處理、陰極電解處理),可使用公知之電解處理設備以公知之條件實施。 Further, electrolytic treatment (anode electrolysis treatment, cathodic electrolysis treatment) using a surface treatment liquid for a metal material can be carried out under known conditions using a known electrolytic treatment equipment.
例如就化學處理皮膜的析出效率更優異之方面而言,作為電流密度,較佳為0.1~20.0A/dm2,更佳為0.5~10.0A/dm2。 For example, the current density is preferably from 0.1 to 20.0 A/dm 2 , more preferably from 0.5 to 10.0 A/dm 2 , from the viewpoint of more excellent precipitation efficiency of the chemical treatment film.
形成之化學處理皮膜的鋯附著量係根據作為對象之金屬材料的材質或用途而適當調整,就作為化學處理皮膜的特性更優異之方面而言,於化學處理及電解處理之任一情形時,皆通常多為1~70mg/m2左右。 The zirconium adhesion amount of the chemical treatment film to be formed is appropriately adjusted depending on the material or use of the metal material to be used, and in the case of any of chemical treatment and electrolytic treatment, as the chemical treatment film is more excellent in characteristics. They are usually about 1~70mg/m 2 .
[實施例] [Examples]
以下,列舉具體之實施例說明本發明。本實施例僅為說明本發明之一部分,並不限定本發明。 Hereinafter, the present invention will be described by way of specific examples. This embodiment is merely illustrative of one aspect of the invention and is not intended to limit the invention.
(供試板) (for test panels)
關於實施例與比較例使用之供試板,使用以下之(1)~(3)。 For the test plates used in the examples and the comparative examples, the following (1) to (3) were used.
(1)鋁合金板(6000系鋁合金,板厚:0.8mm) (1) Aluminum alloy plate (6000 series aluminum alloy, plate thickness: 0.8mm)
(2)冷軋鋼板(SPC,板厚:0.8mm) (2) Cold rolled steel sheet (SPC, sheet thickness: 0.8 mm)
(3)合金化熔融鍍鋅鋼板(GA,板厚:0.8mm) (3) Alloyed hot-dip galvanized steel sheet (GA, sheet thickness: 0.8 mm)
(補給劑) (Supply agent)
將表1所示之不含氟之鋯化合物(A)、含氟物(B)及酸成分(C)以成為表1所示之組成方式於水中混合,製備各種補給劑。 The fluorine-free zirconium compound (A), the fluorine-containing compound (B) and the acid component (C) shown in Table 1 were mixed in water in the form shown in Table 1, and various kinds of replenishers were prepared.
(金屬材料之表面處理方法) (surface treatment method of metal materials)
後述實施例及比較例之金屬材料的表面處理方法係依據以下順序進行。 The surface treatment methods of the metal materials of the examples and comparative examples described later were carried out in the following order.
(1)脫脂 (1) Degreasing
(2)水洗(自來水) (2) Washing (tap water)
(3)化學處理 (3) Chemical treatment
(4)水洗(自來水) (4) Washing (tap water)
(5)水洗(離子交換水) (5) Washing (ion exchange water)
(6)除水乾燥 (6) water removal drying
再者,上述脫脂係使用Nihon Parkerizing公司製造之鹼性脫脂劑Fine Cleaner L4460(2.0%,45℃,120秒,噴霧處理)進行。 Further, the above degreasing was carried out using an alkaline degreaser, Fine Cleaner L4460 (2.0%, 45 ° C, 120 seconds, spray treatment) manufactured by Nihon Parkerizing Co., Ltd.
關於化學處理之方法,以下述連續處理試驗方法詳細說明。又,於除水乾燥,係利用輥去除水分後,於100℃環境烘箱中進行乾燥。 The method of chemical treatment is described in detail by the following continuous treatment test method. Further, after drying in water removal, the water was removed by a roller, and then dried in an oven at 100 °C.
(連續處理試驗方法(運轉性試驗) (Continuous processing test method (operability test)
作為上述化學處理,實施以下之連續處理方法1~3中任一者。 As the above chemical treatment, any of the following continuous treatment methods 1 to 3 is carried out.
<連續處理方法1> <Continuous processing method 1>
製備10L之下述成分濃度的處理液,將pH值調為4.0且加熱至40℃者作為金屬材料用表面處理液。攪拌該處理液,浸漬供試板(1)180秒,進行目標Zr附著量13mg/m2之表面處理。將此作為1次處理,其後,使用新的供試板(1)重複進行表面處理(連續處理試驗)。此時,附著於供試板(1)而被帶出之處理液(帶出液)之液量為75mL/m2,因此利用水及表1所示之補給劑,於處理負荷每0.5m2/L進行液面及處理液中之Zr濃度下降部分的補充,調整液面之同時,進行與Zr濃度之調整。關於處理液之pH值,亦對每0.5m2/L視需要以氨水進行調整。上述連續試驗進行至處理液總量之10L被帶出液100%置換為止。即,進行試驗至處理負荷成為13.3m2/L,測量連續試驗初期之Zr附著量與13.3m2/L處理時之Zr附著量。再者,處理材表面上之Zr附著量,係使用XRF(螢光X射線分析法)進行定量。 A treatment liquid having a concentration of the following components of 10 L was prepared, and the pH was adjusted to 4.0 and heated to 40 ° C as a surface treatment liquid for a metal material. The treatment liquid was stirred, and the test plate (1) was immersed for 180 seconds, and the surface treatment of the target Zr adhesion amount of 13 mg/m 2 was performed. This was treated as one treatment, and thereafter, surface treatment (continuous treatment test) was repeated using a new test plate (1). At this time, since the liquid amount of the treatment liquid (without liquid) attached to the test plate (1) is 75 mL/m 2 , the water and the replenishing agent shown in Table 1 are used for the treatment load per 0.5 m. 2 / L is used to supplement the drop in the Zr concentration in the liquid level and the treatment liquid, and the Zr concentration is adjusted while adjusting the liquid level. Regarding the pH of the treatment liquid, it is also adjusted with ammonia water every 0.5 m 2 /L as needed. The above continuous test was carried out until 10 L of the total amount of the treatment liquid was replaced by 100% of the discharge liquid. That is, the test was carried out until the treatment load was 13.3 m 2 /L, and the Zr adhesion amount at the initial stage of the continuous test and the Zr adhesion amount at the time of the 13.3 m 2 /L treatment were measured. Further, the amount of Zr adhesion on the surface of the treated material was quantified by XRF (fluorescence X-ray analysis).
(處理液成分) (treatment liquid component)
各種成分之濃度為Zr離子:100mg/L、所有F離子:150mg/L、游 離F離子:25mg/L、NO3離子:190mg/L。 The concentrations of the various components were Zr ions: 100 mg/L, all F ions: 150 mg/L, free F ions: 25 mg/L, and NO 3 ions: 190 mg/L.
<連續處理方法2> <Continuous processing method 2>
製備下述成分濃度之處理液10L,將pH值調為4.0且加熱至40℃者作為金屬材料用表面處理液。攪拌該處理液,浸漬供試板(2)120秒,進行目標Zr附著量20mg/m2之表面處理。將此作為1次處理,其後,使用新的供試板(2)重複進行表面處理(連續處理試驗)。此時,附著於供試板(2)而被帶出之處理液(帶出液)的液量為60mL/m2,因此利用水及表1所示之補給劑,於處理負荷每0.5m2/L進行液面及處理液中之Zr濃度下降部分的補充,調整液面之同時,進行Zr濃度之調整。關於處理液之pH值,亦對每0.5m2/L視需要以氨水調整。上述連續試驗進行至處理液總量之10L被帶出液100%置換為止。即,進行試驗至處理負荷成為16.7m2/L,測量連續試驗初期之Zr附著量與16.7m2/L處理時之Zr附著量。再者,處理材表面上之Zr附著量,係使用XRF(螢光X射線分析法)進行定量。 10 L of the treatment liquid having the following component concentrations was prepared, and the pH was adjusted to 4.0 and heated to 40 ° C as a surface treatment liquid for a metal material. The treatment liquid was stirred, and the test plate (2) was immersed for 120 seconds, and the surface treatment of the target Zr adhesion amount of 20 mg/m 2 was performed. This was treated as one treatment, and thereafter, the surface treatment (continuous treatment test) was repeated using a new test plate (2). At this time, since the liquid amount of the treatment liquid (without liquid) which is attached to the test plate (2) is 60 mL/m 2 , the water and the replenishing agent shown in Table 1 are used for the treatment load per 0.5 m. 2 / L is used to supplement the drop in the Zr concentration in the liquid level and the treatment liquid, and the Zr concentration is adjusted while adjusting the liquid level. Regarding the pH of the treatment liquid, it is also adjusted with ammonia water every 0.5 m 2 /L as needed. The above continuous test was carried out until 10 L of the total amount of the treatment liquid was replaced by 100% of the discharge liquid. That is, the test was carried out until the treatment load was 16.7 m 2 /L, and the Zr adhesion amount at the initial stage of the continuous test and the Zr adhesion amount at the time of the 16.7 m 2 /L treatment were measured. Further, the amount of Zr adhesion on the surface of the treated material was quantified by XRF (fluorescence X-ray analysis).
(處理液成分) (treatment liquid component)
各種成分之濃度為Zr離子:500mg/L、所有F離子:680mg/L、游離F離子:36mg/L、NO3離子:750mg/L。 The concentrations of the various components were Zr ions: 500 mg/L, all F ions: 680 mg/L, free F ions: 36 mg/L, and NO 3 ions: 750 mg/L.
<連續處理方法3> <Continuous processing method 3>
製備下述成分濃度之處理液10L,將pH值調為3.7且加熱至40℃者作為金屬材料用表面處理液。攪拌該處理液,浸漬供試板(3)30秒,進行目標Zr附著量10mg/m2之表面處理。將此作為1次處理,其後,使用新的供試板(3)重複進行表面處理(連續處理試驗)。此時,附著於供試板(3)而被帶出之處理液(帶出液)的液量為22mL/m2,因此利用水及表1所示 之補給劑,於處理負荷每0.5m2/L進行液面及處理液中之Zr濃度下降部分的補充,調整液面之同時,進行Zr濃度之調整。關於處理液之pH值,亦對每0.5m2/L視需要以氨水調整。上述連續試驗進行至處理液總量之10L被帶出液100%置換為止。即,進行試驗至處理負荷成為45.5m2/L,測量連續試驗初期之Zr附著量與45.5m2/L處理時之Zr附著量。再者,處理材表面上之Zr附著量,係使用XRF(螢光X射線分析法)進行定量。 10 L of the treatment liquid having the following component concentrations was prepared, and the pH was adjusted to 3.7 and heated to 40 ° C as a surface treatment liquid for a metal material. The treatment liquid was stirred, and the test plate (3) was immersed for 30 seconds, and the surface treatment of the target Zr adhesion amount of 10 mg/m 2 was performed. This was treated as one treatment, and thereafter, the surface treatment (continuous treatment test) was repeated using a new test plate (3). At this time, since the liquid amount of the treatment liquid (without liquid) attached to the test plate (3) is 22 mL/m 2 , the water and the replenishing agent shown in Table 1 are used for the treatment load per 0.5 m. 2 / L is used to supplement the drop in the Zr concentration in the liquid level and the treatment liquid, and the Zr concentration is adjusted while adjusting the liquid level. Regarding the pH of the treatment liquid, it is also adjusted with ammonia water every 0.5 m 2 /L as needed. The above continuous test was carried out until 10 L of the total amount of the treatment liquid was replaced by 100% of the discharge liquid. That is, the test was carried out until the treatment load was 45.5 m 2 /L, and the Zr adhesion amount at the initial stage of the continuous test and the Zr adhesion amount at the time of the 45.5 m 2 /L treatment were measured. Further, the amount of Zr adhesion on the surface of the treated material was quantified by XRF (fluorescence X-ray analysis).
(處理液成分) (treatment liquid component)
各種成分之濃度為Zr離子:1500mg/L、全部F離子:2010mg/L、游離F離子:95mg/L、NO3離子:2190mg/L。 The concentrations of the various components were Zr ions: 1500 mg/L, all F ions: 2010 mg/L, free F ions: 95 mg/L, and NO 3 ions: 2190 mg/L.
(評價試驗) (evaluation test)
使用表1所示之補給劑,進行下述所示(A)、(B)之評價。 The evaluations shown in Table 1 below were used to evaluate the following (A) and (B).
(A)補給劑保管穩定性試驗(長期保管性) (A) Retention agent storage stability test (long-term storage)
將表1所示之補給劑密封於聚合物材質容器內,自剛製造後起於35℃環境保管最長6個月,評價液體外觀。評價基準如下所述。「○」或「◎」於實用上較佳。 The replenishing agent shown in Table 1 was sealed in a polymer material container, and was stored in a 35 ° C environment for up to 6 months from the time of production, and the appearance of the liquid was evaluated. The evaluation criteria are as follows. "○" or "◎" is practically preferred.
◎:6個月後之外觀無變化 ◎: No change in appearance after 6 months
○:自3個月後起至未達6個月間外觀有變化 ○: Appearance changes from 3 months to less than 6 months
△:自2週後起至未達3個月間外觀有變化 △: Appearance changes from 2 weeks later to less than 3 months
×:於2週內確認到沈澱或渾濁或凝膠化 ×: precipitation or turbidity or gelation was confirmed within 2 weeks.
再者,所謂外觀無變化,係表示沈澱物、懸濁及凝膠化均未被確認到,呈無色透明之狀態。 In addition, the appearance was not changed, and it was shown that the precipitate, the suspension, and the gelation were not confirmed, and it was in a state of being colorless and transparent.
(B)運轉性試驗(連續處理性試驗) (B) Runnability test (continuous treatment test)
利用表1所示之處理方法進行連續處理試驗,測量試驗初期(第1次)與處理液之置換率100%時之試片(供試板)的Zr附著量,比較該值。評價基準如下所述。「○」或「◎」於實用上較佳。 The continuous treatment test was carried out by the treatment method shown in Table 1, and the Zr adhesion amount of the test piece (test plate) at the initial stage (first time) of the test and the replacement rate of the treatment liquid was measured, and the value was compared. The evaluation criteria are as follows. "○" or "◎" is practically preferred.
◎:相對於連續處理試驗初期之Zr附著量,100%置換後之Zr附著量為95%以上,未達105% ◎: Compared with the Zr adhesion amount at the initial stage of the continuous treatment test, the Zr adhesion amount after 100% replacement is 95% or more, less than 105%.
○:相對於連續處理試驗初期之Zr附著量,100%置換後之Zr附著量為85%以上,未達95% ○: The Zr adhesion amount after 100% replacement was 85% or more with respect to the Zr adhesion amount at the initial stage of the continuous treatment test, and was less than 95%.
△:相對於連續處理試驗初期之Zr附著量,100%置換後之Zr附著量為50%以上,未達85% △: The Zr adhesion amount after 100% replacement is 50% or more with respect to the Zr adhesion amount at the initial stage of the continuous treatment test, and is less than 85%.
×:相對於連續處理試驗初期之Zr附著量,100%置換後之Zr附著量未達50% ×: The Zr adhesion amount after 100% replacement is less than 50% with respect to the Zr adhesion amount at the initial stage of the continuous treatment test.
表1中,「碳酸Zr」表示碳酸鋯,「鹼性碳酸Zr」表示鹼性 碳酸鋯,「Zr濃度」表示鋯離子濃度(g/L)。 In Table 1, "carbonated Zr" means zirconium carbonate, and "alkaline carbonic acid Zr" means alkaline. Zirconium carbonate, "Zr concentration" means zirconium ion concentration (g/L).
*1)H2ZrF6:HF=4.6:1(重量比) *1) H 2 ZrF 6 : HF = 4.6: 1 (weight ratio)
*2)比較例1~3中,補給劑本身之長期保管性較差,於35℃環境於1週內確認到沈澱,因此視為無法用於實際使用上,未實施運轉性試驗。 *2) In Comparative Examples 1 to 3, the long-term storage property of the replenisher itself was inferior, and precipitation was confirmed within one week at 35 ° C. Therefore, it was considered that it could not be used for actual use, and the running test was not performed.
如表1所示,確認於使用本發明之補給劑的實施例中,補給劑之長期保管性優異,且處理之連續處理性(連續運轉性)亦優異。 As shown in Table 1, in the examples using the replenishing agent of the present invention, the replenishing agent was excellent in long-term storage property and excellent in continuous treatment property (continuous running property).
其中,由實施例2~3與實施例1、4~9之比較得知,確認於MAC/MF超過0.50且未達2.00之情形時,補給劑之長期保管性更優異。 In comparison with Examples 1 to 3 and Examples 1 and 4 to 9, it was confirmed that when the M AC /M F exceeds 0.50 and does not reach 2.00, the long-term storage property of the replenisher is further excellent.
又,由實施例2~3、7~9與實施例1、4~6之比較得知,確認於MAC/MF超過0.50且為1.60以下之情形時,運轉性(連續運轉性)更優異。 Further, in comparison with Examples 1 to 3 and 7 to 9 and Examples 1 and 4 to 6, it was confirmed that when M AC / M F exceeds 0.50 and is 1.60 or less, the operability (continuous operation) is further improved. Excellent.
另一方面,於比(MAC/MF)小於特定範圍內之比較例1~3中,補給劑之保存穩定性差。 On the other hand, in Comparative Examples 1 to 3 in which the ratio (M AC / M F ) was smaller than the specific range, the storage stability of the replenishing agent was poor.
又,專利文獻3(日本專利第4996409號)之段落[0033]中記載之鋯氫氟酸與硝酸鋯混合補給液之MAC/MF=0.33,如表1之比較例1~3所示,若利用該補給劑則無法獲得所需之效果。 Further, M AC / M F = 0.33 of the mixed solution of zirconium hydrofluoric acid and zirconium nitrate described in paragraph [0033] of Patent Document 3 (Japanese Patent No. 4996409), as shown in Comparative Examples 1 to 3 of Table 1. If the replenisher is used, the desired effect cannot be obtained.
比較例4~6中,推測作為使補給劑中之鋯穩定化的陰離子,源自酸成分(C)之陰離子的比率高於源自含氟物(B)之氟,因而向金屬材料用表面處理液中添加比較例4~6之補給劑後,於處理液中鋯與其他陰離子之配位強於Zr-F之配位,成膜反應難以穩定。認為由於利用H2ZrF6之水解作為成膜反應,故鋯離子與F離子之配位狀態對此產生影響。 In Comparative Examples 4 to 6, it is presumed that as an anion which stabilizes zirconium in the replenishing agent, the ratio of the anion derived from the acid component (C) is higher than that derived from the fluorine-containing compound (B), and thus the surface to the metal material is used. When the replenishing agents of Comparative Examples 4 to 6 were added to the treatment liquid, the coordination of zirconium with other anions in the treatment liquid was stronger than that of Zr-F, and the film formation reaction was difficult to stabilize. It is considered that since the hydrolysis by H 2 ZrF 6 is used as a film formation reaction, the coordination state of zirconium ions and F ions affects this.
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