TW200406505A - Surface treatment composition, surface treatment liquid, surface treatment method and metallic article - Google Patents

Surface treatment composition, surface treatment liquid, surface treatment method and metallic article Download PDF

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TW200406505A
TW200406505A TW092124439A TW92124439A TW200406505A TW 200406505 A TW200406505 A TW 200406505A TW 092124439 A TW092124439 A TW 092124439A TW 92124439 A TW92124439 A TW 92124439A TW 200406505 A TW200406505 A TW 200406505A
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Taiwan
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surface treatment
concentration
film
zinc
treatment
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TW092124439A
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Chinese (zh)
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Takaomi Nakayama
Toshiyuki Aishima
Masato Washizu
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Nihon Parkerizing
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

Abstract

This invention provides a very fine zinc phosphate conversion film with excellent corrosion resistance under uncoated state or coated state, which can be applied onto the surface of iron, zinc, and metallic material plated with zinc, aluminum and aluminum alloy, magnesium and magnesium alloy. Moreover, the very fine zinc phosphate film with excellent corrosion resistance can be provided without modifying current treatment apparatus in a conventional phosphate treatment process. Furthermore, due to the very fine phosphate film having excellent corrosion resistance and low film weight, a zinc phosphate conversion film which is low in chemical consumption and cheap in price can be provided. The invented method uses a surface treatment composition contains zinc, phosphoric acid, and aromatic nitro compound, which satisfies the relationship: 100≤{[Zn]/[PO4]}/[NO2]≤700, in which [Zn] is the concentration of zinc (unit: mol/L), [PO4] is the concentration of phosphoric acid (unit: mol/L), and [NO2] is the concentration of aromatic nitro compound (unit: mol/L).

Description

200406505 ........ ι 、 五、發明說明（1) · [發明所屬之技術領域] 本發明係有關於提供一種在未塗裝狀態或塗裝狀態都 具有優良耐蝕性之極微細的磷酸鋅化成皮膜之技術，其被 形成於例如鐵、辞以及鍍有鋅、鋁和鋁合金、鎂和鎂合金 專的金屬材料的表面上。 [先前技術] 專利文獻1(特開平2-1 9 7581號公報） 專利文獻2(特公昭46-1 7047號公報） 專利文獻3(特開昭5 4- 1 1 834 9號公報） 專利文獻4(特公昭6 1 -3 6 588號公報） 專利文獻5 (特公昭5 8 - 1 1 5 1 3號公報） 專利文獻6 (特開昭5 6 -1 4 2 8 7 2號公報） 專利文獻7(特表平9-502224號公報） 攸别以來’為了要提升壓製（press)加工時的金屬模 具與被成形金屬之間的耐凝著性，以及提升塗膜和金屬材 料之間的密著性，所以在金屬材料表面進行磷酸鹽處理。 還有’為了提升壓製加工性，所以最好是採用形成結 晶尺寸大而且皮膜重量大的磷酸鹽處理皮膜。還有，為了 提升塗裝後的耐蝕性和塗膜密著性，所以最好是採用形成 結晶尺寸小而且皮膜重量小的磷酸鹽處理皮膜。因此，為 因應各種不同目的而有不同的使用分類。 因此’在進行磷酸鹽處理時會使用促進劑，例如，眾200406505 ........ Ⅴ. V. Description of the invention (1) · [Technical field to which the invention belongs] The present invention relates to providing an extremely fine corrosion resistance in an unpainted state or a painted state. The zinc phosphate formation technology is formed on the surface of metal materials such as iron, zinc, and zinc, aluminum and aluminum alloys, and magnesium and magnesium alloys. [Prior Art] Patent Document 1 (Japanese Patent Application Laid-Open No. 2-1 9 7581) Patent Document 2 (Japanese Patent Publication No. 46-1 7047) Patent Literature 3 (Japanese Patent Publication No. 5 4- 1 1 834 9) Patent Literature 4 (Japanese Patent Publication No. 6 1 -3 6 588) Patent Literature 5 (Japanese Patent Publication No. 5 8-1 1 5 1 3) Patent Literature 6 (Japanese Patent Publication No. 5 6 -1 4 2 8 7 2) Patent Document 7 (Japanese Patent Application Publication No. 9-502224) In order to improve the resistance between the metal mold and the formed metal during press processing, and to improve the Adhesiveness, so phosphate treatment on the surface of metal materials. Furthermore, in order to improve the press workability, it is preferable to use a phosphate-treated film having a large crystal size and a large film weight. Further, in order to improve the corrosion resistance and the adhesion of the coating film after coating, it is preferable to form a phosphate-treated film having a small crystal size and a small film weight. Therefore, there are different classifications for different purposes. So ‘promoters are used in phosphate treatments, such as

200406505 五、發明說明（2) 所皆知的亞硝酸鹽、過氧化氫、羥胺（hydroxy lam ine)類 或是硝基笨績酸鹽（nitrobenzene sulfonic acid salt)。 然而’幾乎所有的場合僅採用亞瑣酸鹽。 其理由是亞硝酸鹽對磷酸鹽化成處理反應有非常大的 促進效果。而且，磷酸鹽化成處理浴中的濃度測定方法已 經被確立，所以容易進行濃度管理。 還有’使用亞硝酸鹽以外的促進劑的例子，例如揭示 於特開平2 -1 9 7 5 81號公報。 在該公報中，係揭示鋼鐵的冷間塑性加工用潤滑處理 方法’其採用含有〇· 〇2〜〇· 25%水溶性芳香族化合物的磷酸 鋅處理液’該水溶性芳香族化合物具有特定濃度的辞離 子、第1鐵離子、磷酸離子、硝酸離子、硝基（nitr〇 base)以及項基（suif0I1 base)。 該公報之技術宣稱沉澱物（s 1 udge)的發生量少。而且 可以得到當作是冷間加工基底的高品質磷酸鹽處理皮膜。 然而’該技術係以冷間鍛造用潤滑處理為目的而被發 明。 因此，若磷酸鹽化成處理浴中的鋅離子濃度是〇. 3〜2. 5%的話則可說是非常的咼’而且所得的皮膜的皮膜重量是 7〜1 2g/m2，雖然作為塑性加工用途是緻密的程度，但是作 為塗裝基底是不能夠被使用的。 為了能夠得到適用於塗裝基底所使用之微細的麟酸鹽 皮膜，所以有磷酸鹽化成處理浴的改良方法係被提出著。200406505 V. Description of the invention (2) Nitrite, hydrogen peroxide, hydroxy lam ine or nitrobenzene sulfonic acid salt are all known. However, 'almost all cases use only acyl salts. The reason for this is that nitrite has a very large promotion effect on the reaction of phosphate formation. In addition, since a method for measuring the concentration in a phosphate conversion treatment bath has been established, it is easy to perform concentration management. An example of using an accelerator other than nitrite is disclosed in, for example, Japanese Patent Application Laid-Open No. 2-1 9 7 5 81. In this bulletin, a method for lubricating cold plastic working of steel is disclosed. It uses a zinc phosphate treatment solution containing 0.25% to 25% of a water-soluble aromatic compound. The water-soluble aromatic compound has a specific concentration. Ions, first iron ions, phosphate ions, nitrate ions, nitrobase and suif0I1 base. The technique of this bulletin claims that the amount of s 1 udge is small. Moreover, a high-quality phosphate-treated film can be obtained as a substrate for cold processing. However, this technology has been invented for the purpose of lubrication treatment for cold forging. Therefore, if the zinc ion concentration in the phosphate conversion treatment bath is 0.3 to 2.5%, it can be said to be very high. Also, the film weight of the obtained film is 7 to 1 2 g / m2, although it is used as plastic processing. The application is dense, but it cannot be used as a coating substrate. In order to obtain a fine linate film suitable for use in a coating substrate, an improved method having a phosphate conversion treatment bath has been proposed.

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例如’在特公昭46- 1 7047號公報中，有揭示在酸性磷 酸鋅被覆，理液中，添加有^“〜丨重量％的經由澱粉或其 介電體或是該等的酸分解所生成的一連的多糖類之一種或 兩種以上的方法。 還有，、在特開昭54- 1 1 8 349號公報中，揭示一種磷酸 鋅皮膜化成法，該方法係使用添加具有〇· 5〜2· 5%重量結合 磷酸的澱粉或是該澱粉的酸分解生成物的磷酸酯化物之磷 酸鋅皮膜化成浴。 …、/無論前述的哪一個技術，其目的皆是在於提子For example, in Japanese Patent Publication No. 46-1 7047, it is disclosed that an acidic zinc phosphate coating is added to a physical solution, and ^ "~ 丨 wt% is generated by starch or its dielectric or by acid decomposition of these. One or two or more methods of continuous polysaccharides. Also, Japanese Patent Application Laid-Open No. Sho 54- 1 1 8 349 discloses a method for forming a zinc phosphate film, which method uses the addition of 2. · 5% by weight phosphate-bound starch or zinc phosphate coating of phosphate esterified product of the acid decomposition product of the starch to form a bath.... / No matter which of the foregoing techniques, the purpose is to raise

使用於預塗（precoat)鋼板的磷酸辞處理皮膜的塗裝密著 性，當作實際對象的金屬材料僅限於鍍鋅鋼板。^ i丄厂付到、目的效果，有必要在預塗用填酸鋅處理線使戶 喷塗（spray)式的磷酸辞處理。 谨点：ΐ姑！述技術對於例如是汽車的車身，僅適用於多 包含冷延鋼板等的鐵系材料，而且… :直接噴塗的具有袋狀構造之被處理對象物。 性能，士種升具有袋狀構造之汽車車身的防彭 鹽化成處理係被；Cull-dip)方法之浸潰處理的碟，The coating adhesion of phosphate coatings used on precoat steel sheets is limited to galvanized steel sheets. ^ It is necessary for the factory to achieve the desired effect. It is necessary to spray zinc phosphate treatment on the pre-coating zinc-filled processing line. Sincerely, Auntie! The above-mentioned technology is applicable to, for example, a car body only for iron-based materials including cold-rolled steel plates and the like, and is a direct-sprayed object having a bag-like structure. Performance, Shizhongsheng has anti-salinization chemical treatment system for automobile body with bag-like structure; Cull-dip method,

例如在特公昭6 1 - 3 6 5 8 8號公報中，右据-子（Cn)型電鑛塗裝用 =离 子，更者從特定濃度的亞罐酸離子、“肖“ 及過氧化氣之中至少選擇-種的皮膜化成；：：：二For example, in Japanese Patent Publication No. 6 1-3 6 5 8 8, the right-type (Cn) type electric ore coating is used for ions, and more specifically, sub-tank acid ions, "Xiao" and peroxide gas with specific concentrations. Select at least-species of membrane formation; ::: two

200406505 五、發明說明（4) 成分。 根據前述技術，在浸潰處理後進行喷塗處理，而能夠 使構酸鋅化成處理皮膜析出於袋部構造内部。 然而’前述技術並沒有控制對應磷酸捶化成處理浴中 的鋅離子濃度和填酸離子濃度的m -硝基苯磺酸離子濃度。 因此，不容易得到低皮膜重量的均一緻密的結晶。 例如，在該公報中的實施例中所使用的皮膜化成促進 劑係限定於亞硝酸離子。而且，也未揭示硝基苯磺酸離 子的適當範圍。更者，也未提及m-硝基苯磺酸離子的簡便 測定方法。因此，在實際的使用狀況中，是不容易將m 一硝 基苯磺酸離子的濃度維持在一定範圍。 還有’將硝基苯磺酸等的有機硝基化合物當作是磷酸 鹽處理的促進劑來使用是眾所皆知的，在前述公報的其他 文獻中有著各式各樣的提案。 例如’在特公昭58- 11 5 1 3號公報中，有揭示一種電鍍 塗裝用金屬的表面處理方法，該方法之特徵係選用特定濃 度的辞離子、璘酸離子、亞硝酸離子以及/或m_硝基苯磺 酸離子當作是主成分，更者包含硝酸離子以及/或氣酸離 子0200406505 V. Description of the Invention (4) Ingredients. According to the aforementioned technique, the spray treatment is performed after the dipping treatment, and the zinc acid formation chemical conversion treatment film can be deposited inside the bag structure. However, the aforementioned technique does not control the m-nitrobenzenesulfonic acid ion concentration corresponding to the zinc ion concentration and the acid filling ion concentration in the phosphorylation formation treatment bath. Therefore, it is not easy to obtain uniform dense crystals with a low film weight. For example, the film formation promoter used in the examples in this publication is limited to nitrite ions. Moreover, a suitable range of nitrobenzenesulfonic acid ions is not disclosed. Furthermore, no convenient method for measuring m-nitrobenzenesulfonic acid ion is mentioned. Therefore, in actual use conditions, it is not easy to maintain the concentration of m-nitrobenzenesulfonic acid ions in a certain range. It is also known to use an organic nitro compound such as nitrobenzenesulfonic acid as a phosphate treatment accelerator, and various proposals have been made in other documents of the aforementioned publication. For example, in Japanese Patent Publication No. 58- 11 5 1 3, there is disclosed a surface treatment method for a metal for electroplating and coating. The method is characterized in that a specific concentration of ion ions, osmic acid ions, nitrite ions, and / or m_nitrobenzenesulfonic acid ion is taken as the main component, and further contains nitrate ion and / or gas acid ion.

還有’在特開昭56- 1 42 872號公報中，有揭示一種由 辞離子、碟酸離子、特定濃度的錳離子、氣酸鹽與硝基苯 % S文二所構成之磷酸鹽被覆（c〇at丨^)溶液。 # ·、一 引述所有提案中的實施例中的钦述，皆沒有研 九I由氣酸的添加而有皮膜重量減低的效果。也就是說，Also, in Japanese Patent Application Laid-Open No. 56-1 42 872, there is disclosed a phosphate coating composed of a ions ion, a disc acid ion, a specific concentration of manganese ion, a gas acid salt, and a nitrobenzene% Swenji. (Coat) ^ solution. # · 1. All the examples in the proposed examples are cited, and none of them has been studied. The effect of reducing the weight of the film due to the addition of gas acid. In other words,

200406505 五、發明說明（5) 皆未揭示關於硝基苯磺酸鹽所具有之效果。更者，經由在 含有氣酸離子的磷酸鹽處理液中處理而得的磷酸鹽處理皮 膜，係具有耐孔蝕性差的問題。 還有，在特表平9-502224號公報中，有揭示一種使用 填酸鹽處理水溶液的磷酸鹽處理方法，該磷酸鹽處理水溶 液含有特定濃度的辞、錳、磷酸離子以及羥胺 (hydroxylamine)及/ 或m -石肖基苯績酸 g旨（m-nitrobenzene sul f onate)，而不含鎳、鈷、銅、亞硝酸鹽以及_素的含 乳陰離子（oxoanion)。200406505 V. Description of Invention (5) None of the effects of nitrobenzene sulfonate have been disclosed. Furthermore, the phosphate-treated film obtained by processing in a phosphate-treatment solution containing gas acid ions has a problem of poor pitting corrosion resistance. In addition, Japanese Patent Publication No. 9-502224 discloses a phosphate treatment method using a salt-filling aqueous solution containing a specific concentration of rhenium, manganese, phosphate ion, and hydroxylamine and / Or m-nitrobenzene sul fonate, and does not contain nickel, cobalt, copper, nitrite and milk-containing anion (oxoanion).

特別是從歐洲的環境規定的點來看，該技術係限定不 含鎳和亞硝酸鹽的處理液，而能夠析出具有在塗裝後的優 良耐餘性的磷酸鹽處理皮膜。 然而， 基苯確酸g旨 最適的緻密 因此， 溫下。 該提案的技術適用於取代亞硝酸鹽而使用m-硝 。但該提案的方法並無法析出作為塗裝基底的 且極微細的磷酸鋅處理結晶。 有必要將磷酸鹽處理時的處理溫度維持在一高 而且’為了要達到耐餘性的目標，在 有必要再施予鉻洗（chr〇me rinse)處理在^鋅處理之後In particular, from the standpoint of European environmental regulations, this technology restricts a treatment liquid that does not contain nickel and nitrite, and is capable of precipitating a phosphate-treated film having excellent residual resistance after coating. However, phenylbenzoic acid is intended to be optimally dense and, therefore, warm. The proposed technique is applicable to the use of m-nitrate instead of nitrite. However, the proposed method cannot precipitate extremely fine zinc phosphate-treated crystals as a coating substrate. It is necessary to maintain the processing temperature during the phosphate treatment at a high level. In order to achieve the target of remaining resistance, it is necessary to apply a chromium washing treatment after the zinc treatment.

[發明所欲解決之課題] 根據上述，可知習知技術並沒有提出 構造之複雜構造的被處理金屬材料，而且不兩/具有袋狀 助製程，而能析出經由磷酸鹽處理浴 而後處理的補 徑制而能得到耐蝕[Problems to be Solved by the Invention] According to the above, it is known that the conventional technology has not proposed a metal structure to be treated with a complicated structure, and it does not have two or have a bag-shaped auxiliary process, but can precipitate a supplement processed through a phosphate treatment bath. Corrosion resistance

200406505 五、發明說明（6) 性優良且又極微細的敏密碟酸鹽皮膜结曰曰曰。 本發月之目的係為解決上述習知技術的問題 是’本發明提供一種在 具有優良耐蝕性之極撒知沾# ^ ^不、η〜X裴狀態都 例如鐵、鋅以及鍍有鋅g u文化成皮膜，其被形成於 屬材料的表面上辞銘和銘合金、鎮和鎂合金等的金 H ^月在習知所採用的磷酸鹽處理製程中，並 的磷酸鹽皮膜。 也此美供耐蝕性優的極微細 特別是，由於是耐蝕性優 酸越皮膜，所以太恭Η日坦I 極^細的低皮膜重量的填 ^ J 本毛月^供一種能夠降低藥劑消耜旦坠又 廉價的磷酸辞化成皮膜。 牛瓜辨^，肖耗里且又 [發明内容] 本發明者係著眼於上述課 法，其係藉由控制磷酸鹽處理浴==:九出解決的方 裝狀態與塗裝狀態都具有優良二出在未塗 成皮膜之目的。 了蝕丨生之極楗細的磷酸鋅化 % 本發明基於下述知識而達成。 於是，解決前述課題之方法 鋅、磷酸、芳香族硝基化合物的用：糸經由將含有 鋅的濃度[Zn](單位m〇i/L)、磷酸处、^物’其中 與芳香族硝基化合物的濃度[N〇 ](單1又4 (單位mol/L) 2』（早位mol/L)，而使其滿 5S02PF(Nl).ptd $ 9頁 200406505 五、發明說明（7) 足100 S{[Zn]/[P〇4]}/[N〇2]蕊 700 的關係式。 特別是’解決前述課題之方法特徵在於：係經由將含 有鋅、磷酸、芳香族硝基化合物的表面處理用組成物，其 中鋅的濃度[Zn](單位m〇i/L)、磷酸的濃度[p〇4](單位 mol/L)，而使其滿足〇· 〇5 $[Ζη]/[ρ〇4] $〇· 2的關係式；還 有其中鋅的濃度[Zn](單位m〇i/L)、磷酸的濃度[p〇4](單位 mol/L)與芳香族硝基化合物的濃度[Ν〇2κ單位m〇i/L)，而 使其滿足100 $ { [Zn]/[P〇4 ] } / [n〇2 ] $ 700 的關係式。 還有’解決前述課題之方法特徵在於··係經由將含有 鋅、填酸、芳香族硝基化合物的表面處理用處理液，其中 鋅的濃度[Zn](單位m〇l/L)、磷酸的濃度[poj(單位mol/L) 與芳香族硝基化合物的濃度[N〇2K單位m〇i/L)，而使其滿 足100 S{[Zn]/[P〇4]}/[N〇2] $7〇〇 的關係式。 特別是’解決前述課題之方法特徵在於：係經由將含 有鋅、填酸、芳香族硝基化合物的表面處理用處理液，其 中辞的濃度[Zn](單位m〇i/L)、磷酸的濃度[Ρ〇4 ](單位 mol/L) ’而使其滿足〇· 05 $[Zn]/[p〇j $〇· 2的關係式；還 有其中鋅的濃度[Zn](單位m〇i/L)、磷酸的濃度[p〇4](單位 mol/L)與芳香族硝基化合物的濃度[n〇2](單位㈣丨/!^)，而 使其滿足100 $ { [Zn] / [P〇4 ] } / [n〇2 ] $ 700 的關係式。 更者’解決前述課題之方法特徵在於：係經由將含有 辞、填酸、芳香族硝基化合物的表面處理用處理液，其中 鋅的濃度[Zn](單位m〇i/L)、磷酸的濃度[p〇4](單位 mol/L) ’而使其滿足〇· 05 $ [Zn]/[p〇4] $〇· 2的關係式；還200406505 V. Description of the invention (6) The finely divided and dense microscopy salt film has excellent properties and is very fine. The purpose of this issue is to solve the problems of the conventional techniques described above. The present invention provides a method that has excellent corrosion resistance. ^ No, η ~ X Pei states such as iron, zinc, and zinc plated gu The culture is formed into a film, which is formed on the surface of the genus material by inscriptions and inscriptions of alloys, towns, magnesium alloys, and the like. In the conventional phosphate treatment process, a phosphate film is formed. It is also used in the United States to provide extremely fine corrosion resistance. In particular, because it is a corrosion-resistant and acid-resistant film, it is too respectful. Ritan I Very thin and low film weight filling ^ J this hair month ^ for a kind that can reduce the consumption of drugs The cheap phosphoric acid is converted into a film. Distinguishing Niu Gua, Xiao Shaili and [Content of the Invention] The inventor focused on the above-mentioned lesson, which is controlled by the phosphate treatment bath ==: Nine out of the square state and painting state are excellent Two out for the purpose of not being coated. The extremely fine zinc phosphate that has been etched% The present invention has been achieved based on the following knowledge. Therefore, the method for solving the aforementioned problems is to use zinc, phosphoric acid, and aromatic nitro compounds: by mixing the concentration of zinc containing [Zn] (unit mOi / L), phosphoric acid, and aromatic compounds, The concentration of the compound [N〇] (single 1 and 4 (unit mol / L) 2 "(early mol / L), so that it is full of 5S02PF (Nl) .ptd $ 9 pages 200406505 V. Description of the invention (7) The relational expression of 100 S {[Zn] / [P〇4]} / [N〇2] is 700. In particular, the method for solving the above-mentioned problem is characterized in that it is obtained by combining zinc, phosphoric acid, and aromatic nitro compounds. A composition for surface treatment, in which the concentration of zinc [Zn] (unit m〇i / L) and the concentration of phosphoric acid [p〇4] (unit mol / L) are satisfied so as to satisfy 0.005 $ [Zη] / [ρ〇4] The relational expression of $ 〇 · 2; and the concentration of zinc [Zn] (unit m〇i / L), the concentration of phosphoric acid [p〇4] (unit mol / L), and the aromatic nitro group The concentration of the compound [NO2κ unit moi / L) satisfies the relationship of 100 $ {[Zn] / [P〇4]} / [n〇2] $ 700. The method for solving the above-mentioned problems is characterized in that: a surface treatment liquid containing zinc, an acid filling agent, and an aromatic nitro compound is used, wherein the concentration of zinc is [Zn] (unit: mol / L), phosphoric acid Concentration [poj (unit mol / L) and the concentration of the aromatic nitro compound [N〇2K unit m〇i / L), so that it satisfies 100 S {[Zn] / [P〇4]} / [N 〇2] The relation of $ 700. In particular, a method for solving the aforementioned problems is characterized in that a surface treatment solution containing zinc, an acid filling agent, and an aromatic nitro compound is used, wherein the concentration of [Zn] (unit mOi / L), Concentration [PO4] (unit mol / L) 'so that it satisfies the relational expression of 0.05 [[Zn] / [p0j $ 0.2]; and the concentration [Zn] (unit m0) of zinc therein i / L), the concentration of phosphoric acid [p〇4] (unit mol / L) and the concentration of aromatic nitro compounds [n〇2] (unit ㈣ 丨 /! ^), so that it satisfies 100 $ {[Zn ] / [P〇4]} / [n〇2] $ 700 relation. Furthermore, the method for solving the aforementioned problems is characterized in that a surface treatment liquid containing a compound, an acid filling agent, and an aromatic nitro compound is used, wherein the concentration of zinc [Zn] (unit m〇i / L), Concentration [p〇4] (unit mol / L) 'so that it satisfies the relationship of 0.05 05 [Zn] / [p〇4] $ 〇 · 2; also

5802PF(N1).ptd 200406505 五、發明說明（8) 有其中鋅的濃度[Zn](單位mol/L)、磷酸的濃度[p〇4](單位 ffl〇l/L)與芳香族喊基化合物的濃度[N〇2](單位m〇i/L)，而 使其滿足100S{[Zn]/[P04]}/[N02]S 700的關係式；其中 磷酸的濃度係50〜2 50m mol/L (註：。 還有，上述的表面處理用組成物（處理液）中，更包含 有選自芳香族氨基（amino)化合物以及芳香族重氮基 (diazo)化合物的群組中的一種或兩種以上的化合物。 前述化合物的合計的摩爾濃度係芳香族硝基化合物的 摩爾濃度的0· 1倍〜10倍的值。 還有，上述的表面處理用組成物（處理液）中，更包含 有選自鎳、錳、鎂、鈣、鐵（II)以及鈷的群組中的一種或 兩種以上，特別是兩種以上的陽離子成分。 還有，上述的表面處理用組成物（處理液）中，更包含 有選自羥胺供給物質、亞硝酸以及亞硝酸鹽的群組中的一 種或兩種以上的化合物。 還有，解決前述課題之表面處理方法之特徵在於：該 表面處理方法具備有一表面調整製程與一表面處理製程， 其中該表面調整製程係在以鈦膠體（titan coll〇id)為主 成分的表面調整液中處理金屬材料；而該表面處理製程係 在該表面調整製程之後，伟田# φ = μ &+ # 便用该表面调整液來處理該金屬 材料。 或者是’解決前述課韻+生 味喊之表面處理方法之特徵在於： 該表面處理方法具備有一表π ^ 程，其中該表面調整製程# 处 表 &狂彳糸在包含有一種或兩種以上的磷5802PF (N1) .ptd 200406505 V. Description of the invention (8) The concentration of zinc [Zn] (unit mol / L), the concentration of phosphoric acid [p〇4] (unit ffl01 / L), and aromatic group Compound concentration [N〇2] (unit m〇i / L) so that it satisfies the relationship of 100S {[Zn] / [P04]} / [N02] S 700; where the concentration of phosphoric acid is 50 ~ 2 50m mol / L (Note: The above-mentioned surface treatment composition (treatment liquid) further includes a compound selected from the group consisting of an aromatic amino compound and an aromatic diazo compound. One or two or more compounds. The total molar concentration of the aforementioned compounds is a value that is 0.1 to 10 times the molar concentration of the aromatic nitro compound. The composition (treatment liquid) for the above-mentioned surface treatment It further contains one or two or more, especially two or more cationic components selected from the group of nickel, manganese, magnesium, calcium, iron (II) and cobalt. In addition, the composition for surface treatment described above The (treatment liquid) further contains one or two or more selected from the group consisting of a hydroxylamine-supplying substance, nitrous acid, and nitrite. In addition, the surface treatment method for solving the foregoing problem is characterized in that the surface treatment method includes a surface adjustment process and a surface treatment process, wherein the surface adjustment process is mainly based on titanium colloid (titan colloid). The metal material is treated in the surface adjustment liquid of the component; and the surface treatment process is after the surface adjustment process, Wei Tian # φ = μ & + # will use the surface adjustment liquid to treat the metal material. Or 'solve the aforementioned The characteristics of the surface treatment method of the lesson rhyme + raw yell are: The surface treatment method has a table π ^ process, wherein the surface adjustment process # 表 & 彳 糸 彳 糸 contains one or two or more kinds of phosphorus

5802PF(Nl).ptd5802PF (Nl) .ptd

第11頁 2UU4U6505 五、發明說明（9) 酸鹽，而該磷酸鹽具有一種或兩藉 A ^ y- a, ^ 上的2價或3價的金屬 的表面調整液中處理金屬材料；而該 矣而纲效制扣衣165嚴理製程係在該 調整製.之後，使用該表面處理用έΒ # ^ 處理該金屬材料。 ^用組成物（處理液）來 右解決前述課題之具有金屬材料的製品之特徵在 ΐ旦”金屬材料，以及設計於該金屬材料表面上的 方二g/m2的皮膜，且該皮膜是經由上述的表面處理 方法所形成。 還有，在該金屬材料是鐵系金屬材料的場合時，形 於該鐵系金屬材料表面上的皮膜重量最好係05〜3g/m2 ^而 在該金屬材料是鋅系金屬材料的場合時，形成於該鋅系金 屬材料表面上的皮膜重量最好係卜4. 5g/m2。 [實施方式] 本發明的表面處理用組成物（處理液）係含有鋅、碟 酸、芳香族硝基化合物的表面處理用組成物，其中辞的遭 度[Zn](單位m〇i/L)、磷酸的濃度[P〇4](單位m〇i/L)與芳香 族硝基化合物的濃度[N02](單位mol/L)，而滿足1〇〇$ {[Zn]/[P〇4]}/[N02] $ 700的關係式（特別是符合150 $ {[Zn]/[P〇4]}/[N02]‘ 650，更者是符合20 0 $ {[Ζη]/[Ρ04]}/[Ν02] $60〇)。 還有，滿足0.05$[^11]/[?〇4]$〇.2的關係式（特別是 符合0.06$[211]/[?〇4]$〇.19，更者是符合0.7$ [Ζη]/[Ρ04] ‘0· 18)。Page 11 2UU4U6505 V. Description of the invention (9) Acid salt, and the phosphate has one or two metals conditioned on the surface adjustment solution of a divalent or trivalent metal on A ^ y-a, ^; and the Then, the rigorous manufacturing process of the outline effect button 165 is based on the adjustment system. After that, the metal material is treated by using the surface treatment with a handle # ^. ^ The composition (treatment liquid) is used to solve the above-mentioned problem. The characteristics of products with metal materials are the "dandan" metal material, and a square g / m2 film designed on the surface of the metal material. It is formed by the above-mentioned surface treatment method. In addition, when the metal material is an iron-based metal material, the weight of the film formed on the surface of the iron-based metal material is preferably from 05 to 3 g / m2. In the case of a zinc-based metal material, the weight of the film formed on the surface of the zinc-based metal material is preferably 4.5 g / m2. [Embodiment] The surface treatment composition (treatment liquid) of the present invention contains zinc , Acetic acid, and aromatic nitro compounds for surface treatment composition, wherein the exposure degree [Zn] (unit m〇i / L), the concentration of phosphoric acid [P〇4] (unit m〇i / L) and The concentration of the aromatic nitro compound [N02] (unit mol / L), while satisfying the relationship of 100 $ {[Zn] / [P〇4]} / [N02] $ 700 (especially 150 150 { [Zn] / [P〇4]} / [N02] '650, or more in line with 20 0 $ {[Zη] / [Ρ04]} / [Ν02] $ 60〇) Also, 0.05 $ [^ 11 ] / [? 〇4] $ 0.2 (especially in line with 0.06 $ [211] / [? 〇4] $ 〇19. Even more, it matches 0.7 $ [Zη] / [P04] ‘0 · 18).

5802PF(Nl).ptd 第12頁 200406505 五、發明說明（ίο) ------- 特別疋’含有鋅、磷酸、芳香族硝基化合物的表面處 理用處理，，其中鋅的濃度[Zn](單位m〇1/L)、磷酸的濃 度[P〇4](單位mol/L)與芳香族硝基化合物的濃度[N〇2](單 位 m〇l/L)，而滿足 100${[Ζη]/[ρ〇4]}/[Ν〇2]$7〇〇 的關係 式（特別是符合150${[Ζη]/[Ρ〇4]丨/[ν〇2]$65〇，更者是符 合200${[211]/[?〇4]}/[^02]$600)，而且也滿足〇()5‘ [Zn]/[P〇4] $〇· 2 的關係式（特別是符合〇· 〇6 $ [Zn]/[p〇4] $0.19，更者是符合〇.7$[211]/[?〇4]$〇.18)，其中磷酸 的濃度係50〜250m mol/L (特別是8〇〜2〇〇m m〇i/L)。 更者，上述表面處理用組成物（處理液）更包含有選自 芳香族氨基（ami no)化合物以及芳香族重氮基（diaz〇)化合 物的群組中的一種或兩種以上的化合物，且前述一種或兩 種以上的化合物的合計摩爾濃度係芳香族硝基化合物的摩 爾濃度的0· 1倍〜10倍（特別是〇· 2〜5倍）的值。 還有，上述的表面處理用組成物（處理液）中，更包含 有選自鎳、錳、鎂、鈣、鐵（H)以及鈷的群組中的一種或 兩種以上’特別是兩種以上的陽離子成分。而且，上述的 表面處理用組成物（處理液）中，更包含有選自羥胺供給物 質、亞硝酸以及亞硝酸鹽的群組中的一種或兩種以上的化 合物。 本發明的表面處理方法係使用上述的表面處理用組成 物（處理液）來處理金屬材料的表面。 特別是，該表面處理方法具備有一表面調整製程與一 表面處理製程’其中该表面調整製程係在以鈦膠體（tit an5802PF (Nl) .ptd Page 12, 200406505 V. Description of the invention (ί) ------- Special treatment for surface treatment containing zinc, phosphoric acid, and aromatic nitro compounds, in which the concentration of zinc [Zn ] (Unit m〇1 / L), the concentration of phosphoric acid [P〇4] (unit mol / L) and the concentration of the aromatic nitro compound [N〇2] (unit m〇l / L), and 100 $ is satisfied. {[Zη] / [ρ〇4]} / [Ν〇2] $ 7〇〇 (especially in line with 150 $ {[Zη] / [Ρ〇4] 丨 / [ν〇2] $ 65〇, more The one is in accordance with the relationship of 200 $ {[211] / [? 〇4]} / [^ 02] $ 600), and also satisfies the relationship of 〇 () 5 '[Zn] / [P〇4] $ 〇 · 2 (especially It is in accordance with 〇 · 〇6 $ [Zn] / [p〇4] $ 0.19, or more in line with 0.7 $ [211] / [? 〇4] $ 〇.18), where the concentration of phosphoric acid is 50 ~ 250m mol / L (especially 80 to 2000 mmi / L). Furthermore, the surface treatment composition (treatment liquid) further contains one or two or more compounds selected from the group consisting of an aromatic amino (ami no) compound and an aromatic diazo group (diaz0) compound, The total molar concentration of the one or two or more compounds is a value that is 0.1 to 10 times (particularly 0.2 to 5 times) the molar concentration of the aromatic nitro compound. The above-mentioned surface treatment composition (treatment liquid) further contains one or two or more selected from the group consisting of nickel, manganese, magnesium, calcium, iron (H), and cobalt, particularly two kinds. The above cationic components. The surface treatment composition (treatment liquid) further contains one or two or more compounds selected from the group consisting of a hydroxylamine-supplying substance, nitrous acid, and a nitrite. The surface treatment method of the present invention uses the above-mentioned surface treatment composition (treatment liquid) to treat the surface of a metallic material. In particular, the surface treatment method includes a surface adjustment process and a surface treatment process, wherein the surface adjustment process is based on titanium colloid (tit an

5802PF(Nl).ptd5802PF (Nl) .ptd

第13頁 200406505 —一· 一 五、發明說明（11) col loid)為主成合 面處理製程俜在面調整液中處理金屬材料； 决#搜在表面調整製程之後，使用哕矣 該表 法之特徵在於：該表：：疋’解決前述課題之表面處理： 一表面處理製程，Α處理方法具備有一表面調整製斤 兩種以上的碟酸鹽：調整製程係在包含c 價或3價的金馱鹽具有一種或兩種以或 老X®」 屬的表面調整液中處理金屬材枓. 的2 處理製程係在該表面調 ^金屬材枓，而該表面 成物(處理液)來處理該4;;後，使用该表面處理用組 設計的製品”備有-金屬材料… 皮膜是經由上述的2 重里疋〇. 5〜5g/m2的皮祺，且， 系金屬材料的場合時，形成於該u:金屬 面上的皮膜重量最好係0.5〜3g/m2。而在兮1属t屬材料表 金屬材料的場合時，形成 屬材料是鋅系 重量最好係卜4. 5g//。 金屬材料表面上的皮膜 及於^ ^明係以金屬材料為對象。特別是適用於鐵、辞以 的被 1:2和銘合金、鎂和鎂合金等的金屬材料。在此 ::::對象的被處理金屬材料，是各個單獨的前述金屬 »·认,可以，還有即使是從前述金屬材料中任選二種類以 的，，且合也很好。還有，在此所謂的含有 鑛鋅、或是鋅和其他金屬，例如錄、鐵、』的】鍵鉻、 鎂姑錯或録等的至少一種的合金，更者是含有不可避 免之不純物的電鍍。電鍍的方法，例如是溶融電鍍、電解 IHUi 第14頁 5802PF(Nl).ptd 200406505 五、發明說明（12) 電鍍、蒸著電鍍等等都可以。還有，本發明也可採用磷酸 鹽處理製程，且不限定被使用於脫脂處理的脫脂劑種類和 脫脂條件。 以下，更詳細來說明。 本發明的表面處理用組成物（處理液）係含有鋅以及填 酸。 關於鋅和磷酸的供給源，可以使用習知的磷酸辞處理 所用的化合物。 鋅的供給源係可以採用例如從金屬鋅、氧化辞、氮氧 化鋅、鋅酸鹽、硝酸鋅、亞硝酸鋅、碳酸辞、碟酸辞、敗 化鋅、硫酸鋅以及鹽酸鋅等之中選擇一種以上的辞來源物 質。 彳’、 填酸的供給源係可以採用例如從正麟酸、碟酸納等的 磷酸鹼金屬鹽、磷酸氨以及磷酸金屬鹽等之中選擇_種以 上。磷酸的供給源，在使用磷酸金屬鹽的場合時，最好是 採用被包含於本發明的表面處理用處理液中的金屬成分# 磷酸金屬鹽。 本發明的表面處理用組成物（處理液）係亦含有芳香族 硝基化合物。 芳香族喊基化合物最好是採用例如是硝基茴香胺 (nitroanisidin)、硝基苯胺（nitroaniline)、硝基苯胺 績酸（nitroaniline sulfonic acid)及其鹽、硝基替氨某 笨（nitroaminobenzene)、石肖基苯甲酸乙酉旨 (ethylnitrobenzoate) 及其鹽、硕基曱紛Page 13 200406505 — One, One, Five, Description of the invention (11) col loid) is the main surface treatment process of 面 俜 processing metal materials in the surface adjustment solution; #Search after the surface adjustment process, use the table method It is characterized in that the table :: 疋 'Surface treatment to solve the aforementioned problems: A surface treatment process, A treatment method has a surface adjustment of two or more kinds of dish salt: the adjustment process is based on the price of c or 3 The salt has one or two kinds of surface treatment liquids of the same type, which are used to treat metal materials 枓. The 2 treatment process is to adjust the metal materials on the surface, and the surface product (treatment liquid) is used to treat the 4 After that, the product designed using the surface treatment group is provided with "metal material ... The film is made of Pi Qi with a thickness of 0.5 to 5 g / m2, and when it is a metal material, it is formed in 5g //。 The u: The weight of the film on the metal surface is preferably 0.5 ~ 3g / m2. In the case of a metal material of the t genus, the genus material is a zinc-based weight of 4.5 g //. Coatings on the surface of metal materials and metal materials Objects. Especially suitable for metal materials such as iron, quilt 1: 2 and Ming alloys, magnesium and magnesium alloys. Here: ::: The target metal materials to be treated are the individual aforementioned metals »· Yes, yes, there are even two kinds of metals selected from the aforementioned metal materials, and the combination is also very good. In addition, the so-called mineral zinc, or zinc and other metals, such as iron, iron, The alloys of at least one of chromium, magnesium, and the like are electroplating containing unavoidable impurities. The electroplating methods are, for example, molten electroplating and electrolytic IHUi, page 14 5802PF (Nl) .ptd 200406505 V. Explanation of the invention (12) Electroplating, evaporation plating, etc. may be used. In addition, the present invention can also use a phosphate treatment process, and the types of degreasing agents and degreasing conditions used for degreasing treatment are not limited. Hereinafter, more details The surface treatment composition (treatment liquid) of the present invention contains zinc and an acid filling agent. Regarding the supply source of zinc and phosphoric acid, conventional compounds used in phosphate treatment can be used. The supply source system of zinc can be exemplified. Such as metal zinc, zinc oxide, zinc oxynitride, zincate, zinc nitrate, zinc nitrite, carbonic acid, zinc acid, zinc oxide, zinc sulfate and zinc hydrochloride, etc. to select more than one word source substance. For example, the supply source of acid filling can be selected from, for example, alkaline metal salts of phosphoric acid, sodium phosphonate and the like, ammonium phosphate, and metal phosphate salts. The source of phosphoric acid is metal phosphate. In the case of salts, it is preferred to use the metal component # phosphate metal salt contained in the surface treatment liquid of the present invention. The surface treatment composition (treatment liquid) of the present invention also contains an aromatic nitro compound. The aromatic compound is preferably, for example, nitroanisidin, nitroaniline, nitroaniline sulfonic acid and its salt, nitroaminobenzene, Ethyl benzoate ethanoate (ethylnitrobenzoate) and its salts

5802PF(Nl).ptd 第15頁 200406505 五、發明說明（13) (nitrocresol)、硝基水楊酸（nitrosalicylic)及其鹽、 硝基苯硫紛（nitrothiophenol)、硝基對苯二曱酸 (nitroterephthalic acid)及其鹽、石肖基曱苯胺 (nitrotoluidine)、硝基甲苯績酸（nitrotoluene sulfonic acid)及其鹽、硝基萘績酸（nitronaphthalene sulfonic acid)及其鹽、硝基萘胺 % (nitronaphthyamine)、硝基氫酉昆（nitrohydroquinone)、 硝基焦倍酚（nitropyrogallol)、硝基苯讲 (nitrophenylhydrazine)、硝基苯基脲 (nitrophenylurea)、硝基苯酚（nitrophenol)、硝基磷苯 二甲酸（nitrophthalic acid)及其鹽、硝基根皮酚 (nitrophloroglucinol)、硝基〒胺 (nitrobenzylamine)、硝基苄醇（nitrobenzylalcohol)、 頌基苯酰胺（nitrobenzamide)、頌基苯績酸 (nitrobenzene sulfonic acid)及其誘導體和鹽、以及硝 基苄晴（nitrobenzonitrile)等。更好是採用硝基苯磺酸 (nitrobenzene sulfonic acid)、硝基苯胺績酸 (nitroaniline sulfonic acid)、硝基曱苯石黃酸 (nitrotoluene sulfonic acid)、硝基二曱苯石黃酸 (nitroxylene sulfonic acid)及其該等的鹽。 本發明的金屬的表面處理用處理液係將前述表面處理 用組成物用水稀釋或溶解於水中。 用水稀釋或溶解時，為了要調整處理液的全酸度（pt: 用滴管吸取表面處理用處理液1〇礼，然後用〇. 的苛5802PF (Nl) .ptd Page 15 200406505 V. Description of the Invention (13) (nitrocresol), nitrosalicylic and its salts, nitrophenylphenol, nitroparaphenylic acid ( nitroterephthalic acid) and its salts, nitrotoluidine, nitrotoluene sulfonic acid and its salts, nitronaphthalene sulfonic acid and its salts, and nitronaphthyamine , Nitrohydroquinone, nitropyrogallol, nitrophenylhydrazine, nitrophenylurea, nitrophenol, nitrophosphoric acid ( nitrophthalic acid and its salts, nitrophloroglucinol, nitrobenzylamine, nitrobenzylalcohol, nitrobenzamide, nitrobenzene sulfonic acid And its inducers and salts, as well as nitrobenzonitrile. More preferably, nitrobenzene sulfonic acid, nitroaniline sulfonic acid, nitrotoluene sulfonic acid, and nitroxylene sulfonic acid) and their salts. The treatment liquid for surface treatment of a metal of the present invention is a solution for diluting or dissolving the composition for surface treatment in water with water. When diluting or dissolving with water, in order to adjust the total acidity of the treatment solution (pt: use a dropper to suck the surface treatment treatment solution for 10 days, and then use 0.1

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IIH 第16頁 200406505IIH Page 16 200406505

性蘇打水溶液當作是酚酞（phen〇lphthalein)指示劍戶 定時的滴定量）和游離酸度（pt:用滴管吸取表面處理厅滴 理液1 0mL，然後用〇· 1 mo 1 /l的苛性蘇打水溶液當作是、、臭處 藍（bromophenol blue)指示劑所滴定時的滴定量）至所、―齡 之值，而添加硝酸等的酸、苛性蘇打、苛性鉀、氣 ^ 或胺類（amine)等的鹼成分。 匕氨 全酸度的所定的值係經由被包含於表面處理用處理液 中的全部的離子濃度而有必然的限定值，但在本發明中= 未有特別的限定。游離酸度的值，本來係經由以表面處理 用處理液處理被處理物時的處理溫度和處理時間來定，作 在本發明中並未有特別的限定。然而，採用現在日本國内 一般被使用之磷酸鹽處理的處理溫度和處理時間，使用於 本發明時，則游離酸度最好是調整在〇· 3〜2pt的範圍，更 好是0.5〜1.5pt的範圍。 在使用本發明的表面處理用處理液時，用水稀釋或溶 解表面處理用組成物，而使表面處理用處理液中的磷酸濃 度變成50〜250m mol/L。 本發明係將鋅、磷酸、芳香族硝基化合物的摩爾濃度 的比f控制在特定的範圍内。更者，最好是藉由將鋅\二 酸、芳香族硝基化合物的摩爾濃度的比率控制在特定的範 圍内’而能夠析出極微細且緻密的磷酸鹽皮膜的結晶。 曲因此在本發明中’若固定表面處理用處理液中的麟 6^ /辰度必然地’也能將鋅與芳香族确基化合物固定於適 當的沒度範圍。因此，若表面處理用處理液中的磷酸濃度Aqueous soda solution is taken as phenophthalein to indicate the titration of Kendo at regular time) and free acidity (pt: 10 mL of the surface treatment hall titration solution is pipetted with a dropper, and then causticity of 0.1 mo 1 / l Aqueous soda solution is used as the titer of the bromophenol blue indicator at the time of titration) to the value of the age, and acid such as nitric acid, caustic soda, caustic potassium, gas ^ or amines ( amine). The predetermined value of the total acidity of ammonia is necessarily limited by the total ion concentration contained in the treatment liquid for surface treatment, but it is not particularly limited in the present invention. The value of the free acidity is originally determined by the treatment temperature and the treatment time when the object to be treated is treated with the surface treatment treatment liquid, and is not particularly limited in the present invention. However, the treatment temperature and treatment time of phosphate treatment generally used in Japan today are adopted. When used in the present invention, the free acidity is preferably adjusted in the range of 0.3 to 2 pt, more preferably 0.5 to 1.5 pt. Range. When the treatment liquid for surface treatment of the present invention is used, the composition for surface treatment is diluted or dissolved with water, so that the concentration of phosphoric acid in the treatment liquid for surface treatment becomes 50 to 250 m mol / L. In the present invention, the ratio f of the molar concentration of zinc, phosphoric acid, and aromatic nitro compound is controlled within a specific range. Furthermore, it is preferred that crystals of extremely fine and dense phosphate films can be deposited by controlling the ratio of the molar concentration of zinc, diacid and aromatic nitro compounds within a specific range '. Therefore, in the present invention, 'if fixing the lin 6 ^ / Chen degree in the treatment liquid for surface treatment inevitably', zinc and an aromatic compound can be fixed in a suitable range. Therefore, if the concentration of phosphoric acid in the treatment liquid for surface treatment is

200406505 五、發明說明（15) 比5 0m mol/L小時，則皮膜主成分的鋅和磷酸濃度就會 小。因此’就不容易在所定的時間内使磷酸鹽皮膜結晶被 析出。相反地，若表面處理用處理液中的磷酸濃度比250m mo 1 /L大時，雖然析出磷酸鹽皮膜結晶，但是表面處理用 處理液的濃度大。因此，經由被處理金屬材料的處理液成 分的帶出量就會變多，這對經濟上不利。 關於磷酸鋅處理的皮膜結晶的析出機構，被處理金屬 材料若與填酸鋅處理液接觸的話，被處理金屬材料的溶解 (蚀刻）反應就會發生。接著，經由蝕刻反應，被處理金屬 材料表面的pH值就會上升。因此，磷酸鋅處理浴中的皮膜 成分會不安定，而有沉澱析出。 、 在此，以當作是被處理金屬材料的鐵當作例子，從^ 子平衡的觀點而以反應式來表示前述析出機構。200406505 V. Description of the invention (15) When the ratio is less than 50m mol / L, the zinc and phosphoric acid concentration of the main component of the film will be small. Therefore, it is difficult to crystallize the phosphate film within a predetermined time. Conversely, when the concentration of phosphoric acid in the treatment liquid for surface treatment is larger than 250 m 1 / L, the phosphate film crystals are precipitated, but the concentration of the treatment liquid for surface treatment is large. Therefore, the amount of component taken out of the processing liquid through the metal material to be processed is increased, which is economically disadvantageous. Regarding the precipitation mechanism of the zinc phosphate-treated film crystals, if the metal material to be treated comes into contact with the zinc-acid treatment solution, a dissolution (etching) reaction of the metal material to be treated occurs. Subsequently, the pH value of the surface of the metal material to be treated is increased by the etching reaction. Therefore, the components of the film in the zinc phosphate treatment bath are unstable and precipitate out. Here, the iron used as the metal material to be treated is taken as an example, and the aforementioned precipitation mechanism is represented by a reaction formula from the viewpoint of the balance of the ions.

Fe + 2H3P04->Fe(H2P04)2 + H2 式⑴ 3Zn(H2P〇4)2^ Zn3(P04)2 + 4H3P〇4 式（2) 上述式（1 )係被處理金屬材料的鐵的蝕刻反應。Fe + 2H3P04- > Fe (H2P04) 2 + H2 Formula ⑴ 3Zn (H2P〇4) 2 ^ Zn3 (P04) 2+ + 4H3P〇4 Formula (2) The above formula (1) is the etching of iron in the metal material to be treated reaction.

3跋辦上忽述式（2)係顯示在磷酸鋅處理液中的第1磷酸鋅和% 3 %I鋅的平衡反應。 S ⑴：上前述化學式’磷酸鋅處理反應係為了要補充式 出應朝右方進灯…’不溶性的第3磷酸鋅Zn3(p〇4)2析 因此，對於磷酸鋅處理的反應性， 的比率[Zn ] / [ PO4 ]是非常重要的要素。 辞和填酸的濃度比The formula (2), which was omitted from the description of the 3 post, shows the equilibrium reaction between the first zinc phosphate and the% 3% I zinc in the zinc phosphate treatment solution. S ⑴: The above-mentioned chemical formula 'Zinc phosphate treatment reaction is to be turned on to the right to supplement the formula ...' The insoluble third zinc phosphate Zn3 (p04) 2 is analyzed. Therefore, for the reactivity of zinc phosphate treatment, the ratio [ Zn] / [PO4] is a very important element. Ratio

200406505 五、發明說明（16) 在前述[Zn]/[p〇4]是非常大的場合時，磷酸鋅處理液 中的磷酸濃f是非常的低，或是辞濃度非常的高。 在鱗酸濃度是非常的低的場合時，是反應的第1步驟 的被處理金屬材料的蝕刻反應係不容易發生、，因此，就不 谷易析出填酸辞皮膜結晶。在鋅濃度非常的高的場合時， 式（2)的平衡就容易朝右方進行，因此，就容易析出磷酸 鋅皮膜結晶。然而，卻會形成結晶尺寸大而且皮膜重量大 的結晶。 還有’在鋅濃度是極端高的場合時，磷酸鋅處理液中 的式（2 )的平衡係朝右方進行，因此，形成析出的第3磷酸籲 鋅之沉澱物（sludge)。 在前述[Zn ] / [ PO4 ]是非常小的場合時，構酸鋅處理液 中的磷酸濃度是非常的高，或是辞濃度非常的低的狀況。 無論是哪種狀況，都不容易使式（2)的平衡係朝右方 進行，因此，就不容易析出磷酸鋅皮膜結晶。 根據以上的說明，可以知道經由將磷酸的濃度固定在 某一濃度範圍以及控制[Zn ] / [ P04 ]比率，是可以控制填酸 鋅處理反應。 然而，若僅有控制前述磷酸濃度與[Ζη]/[Ρ04]，是無 法得到比現在被使用的填酸鋅皮膜更微細且緻密的結晶。鲁 也就是說，經由本發明者精心的檢討，為了要得到微 細且緻密的磷酸鋅結晶，係要在磷酸鋅處理液中添加芳香 族硝基化合物，而且，經由使用具有特定濃度比率之鋅、 鱗酸以及芳香族硝基化合物’則能夠得到在未塗裝狀態與200406505 V. Description of the invention (16) When the aforementioned [Zn] / [p〇4] is very large, the phosphoric acid concentration f in the zinc phosphate treatment solution is very low or the concentration is very high. When the concentration of scale acid is very low, the etching reaction system of the metal material to be treated, which is the first step of the reaction, does not easily occur. Therefore, crystals of the acid-filled film are not easily precipitated. In the case where the zinc concentration is very high, the balance of the formula (2) is easily performed to the right, and therefore, the crystal of the zinc phosphate film is easily precipitated. However, crystals having a large crystal size and a large film weight are formed. In the case where the zinc concentration is extremely high, the equilibrium of the formula (2) in the zinc phosphate treatment liquid proceeds to the right, so that a precipitated third phosphate sludge is formed. When the aforementioned [Zn] / [PO4] is very small, the phosphoric acid concentration in the zinc acid acid treatment solution is extremely high or the concentration is extremely low. In either case, it is not easy to make the balance of the formula (2) to the right, and therefore, it is difficult to precipitate the zinc phosphate film crystals. According to the above description, it can be known that by fixing the concentration of phosphoric acid in a certain concentration range and controlling the [Zn] / [P04] ratio, it is possible to control the zinc filling treatment. However, if only the aforementioned phosphoric acid concentration and [Zη] / [P04] are controlled, it is impossible to obtain finer and denser crystals than the zinc-filled zinc film currently used. In other words, after careful review by the inventors, in order to obtain fine and dense zinc phosphate crystals, an aromatic nitro compound was added to the zinc phosphate treatment liquid, and by using zinc having a specific concentration ratio, Lepidonic acid and aromatic nitro compounds can be obtained in an unpainted state with

5802PF(Nl).ptd 第 19 頁 200406505 五、發明說明（17) ---- 塗裝狀態都具有優良耐蝕性之極微細的磷酸鋅皮膜結晶。 子於碟酸辞皮膜結晶的微細化的芳香族硝，基化合物的 反應機構’以現在的觀點是不容易明瞭的。 然而’本發明係精心研究出將前述化合物添加至磷酸 鋅處理液時的作用效果。該結果發現，當以添加有前述化 合物之麟酸鋅處理液處理鋼板時，是被處理金屬材料之鋼 板的蚀刻量會增加。還有，發現磷酸鋅化成反應初期所析 出結晶的數目也增加。更者，比較習知所使用亞硝酸鹽和 芳香知硝基化合物的氧化力，則發現從鐵（I丨）到鐵（丨丨工） 的氧化力，係芳香族硝基化合物這一方的氧化力是很小 的0 因此’芳香族硝基化合物係促進被處理金屬材料的蝕 刻反應’而促進磷酸鋅皮膜結晶的非常初期的析出反應。 而且’保持在被處理金屬材料與表面處理用處理液之間介 面的鐵（I I )離子，而抑制已析出的磷酸鋅皮膜結晶的成 長。所以’在磷酸鋅皮膜結晶的成長被抑制時，因為磷酸 鋅皮膜結晶的析出持續，而使得最終所得之磷酸鋅皮膜結 晶變成極微細且緻密。5802PF (Nl) .ptd Page 19 200406505 V. Description of the invention (17) ---- Very fine zinc phosphate film crystal with excellent corrosion resistance in the coating state. It is not easy to understand the reaction mechanism 'of a finely crystalline aromatic nitrate and a base compound crystallized in a crystal film of a dish acid film from the present viewpoint. However, the present invention has carefully studied the effect when the aforementioned compound is added to a zinc phosphate treatment solution. As a result, it was found that when the steel sheet is treated with the zinc inlinate treatment solution to which the aforementioned compound is added, the etching amount of the steel sheet which is a metal material to be treated increases. In addition, it was found that the number of crystals precipitated at the beginning of the zinc phosphate formation reaction also increased. Furthermore, comparing the oxidizing power of conventionally used nitrite and aromatic nitro compounds, it is found that the oxidizing power from iron (I 丨) to iron (丨 丨) is the oxidation of aromatic nitro compounds The force is very small. Therefore, the "aromatic nitro compound promotes the etching reaction of the metal material to be treated" and promotes the very early precipitation reaction of the zinc phosphate film crystal. In addition, iron (I I) ions are held at the interface between the metal material to be treated and the surface treatment liquid, and the growth of the precipitated zinc phosphate film crystals is suppressed. Therefore, when the growth of the zinc phosphate film crystal is inhibited, the precipitation of the zinc phosphate film crystal continues, so that the finally obtained zinc phosphate film crystal becomes extremely fine and dense.

在此’為了要抑制前述雄酸辞皮膜結晶的成長，表面 處理用處理液之反應性，亦即對應表面處理用處理液中的 [Zn ] / [ P04 ]的芳香族硝基化合物的濃度是有必要規定的。 也就是說，在表面處理用處理液中的[Zn]/[P〇4]係大 的場合時’為了要使磷酸鋅皮膜結晶容易析出，則必須提 高芳香族硝基化合物的濃度。但相反地，在[Ζ η ] / [ P〇4 ]係Here, in order to suppress the growth of the crystals of the above-mentioned maleic acid film, the reactivity of the treatment liquid for surface treatment, that is, the concentration of the aromatic nitro compound corresponding to [Zn] / [P04] in the treatment liquid for surface treatment is It is necessary to stipulate. That is, when the [Zn] / [P04] system in the surface treatment liquid is large ', the concentration of the aromatic nitro compound must be increased in order to precipitate the zinc phosphate film easily. But on the contrary, in the [Z η] / [P〇4] system

5802PF(Nl).ptd 第20頁 200406505 五、發明說明US} -------η 小的場合時，則必須降低芳香族硝基化合物的濃度。 、士發明者等係調查表面處理用處理液中的[Zn]/[P〇4] =及芳香族硝基化合物的摩爾濃度和所得的磷酸鋅皮膜結 曰曰之間的關係。本發明係發現在規定的濃度範圍内，能多句， 得到極微細且緻密的磷酸鋅皮膜結晶。 在此，在{ [Zn]/[p〇4] }/[N〇2]小於1〇〇的場合時，對應 於[Zn]/[P〇4]的芳香族硝基化合物的濃度係大。因此，磷 酸鋅皮膜結晶的成長抑制效果就會過大，就容易產生所得 之皮膜外觀上有所謂"透明”的未析出結晶的部位。 相反地’在{[ Zn]/[ P〇4 ] } / [n〇2 ]大於7〇〇的場合時，對 應於[Z n ] / [ P 〇4 ]的芳香族硝基化合物的濃度係小。因此，_ 雖然填酸鋅皮膜結晶係被析出，但卻無法達到本發明目的 之極微細且緻密的填酸辞皮膜結晶。 在本發明的表面處理用處理液中，若添加有是芳香族 硝基化合物的從0· 1倍到1 〇倍的摩爾濃度之芳香族氨基化 合物以及芳香族重氮基化合物的1種以上，則能夠得到更 好的皮膜。5802PF (Nl) .ptd Page 20 200406505 V. Description of the invention US} ------- When the η is small, the concentration of the aromatic nitro compound must be reduced. The inventors and the investigators investigated the relationship between the [Zn] / [P〇4] = and the molar concentration of the aromatic nitro compound in the treatment liquid for surface treatment, and the obtained zinc phosphate film structure. In the present invention, it is found that within a predetermined concentration range, multiple sentences can be obtained to obtain extremely fine and dense zinc phosphate film crystals. Here, when {[Zn] / [p〇4]} / [N〇2] is less than 100, the concentration of the aromatic nitro compound corresponding to [Zn] / [P〇4] is large. . Therefore, the effect of suppressing the growth of the crystals of the zinc phosphate film is too large, and it is easy to produce so-called " transparent " non-precipitated crystals in the appearance of the obtained film. Conversely, '{[Zn] / [P〇4]} / [n〇2] When it is larger than 700, the concentration of the aromatic nitro compound corresponding to [Z n] / [P 〇 4] is small. Therefore, although the crystal system of the zinc-filled zinc film is precipitated, However, the extremely fine and dense acid-filled film crystal of the object of the present invention cannot be achieved. In the surface treatment liquid of the present invention, if it is added from 0.1 times to 10 times the aromatic nitro compound, The molar concentration of one or more kinds of the aromatic amino compound and the aromatic diazo compound can obtain a better film.

所採用的芳香族氨基化合物與芳香族重氮基化合物最 好是採用例如是硝基茴香胺（nitroanisidin)、硝基苯胺 (nitroaniline)、石肖基本胺石黃酸（nitroaniline sulfonic acid)及其鹽、硝基替氨基苯（nitroaminobenzene)、硝基 苯曱酸乙酯（ethylnitrobenzoate) 及其鹽、硝基曱紛 (nitrocresol)、喊基水楊酸（nitrosalicylic)及其鹽、 硝基苯硫酚（ni trothiophenol)、硝基對笨二曱酸The aromatic amino compound and the aromatic diazo compound used are preferably nitroanisidin, nitroaniline, nitroaniline sulfonic acid, and salts thereof. , Nitroaminobenzene, ethylnitrobenzoate and its salts, nitrocresol, nitrosalicylic and its salts, nitrothiophenol ( ni trothiophenol), nitroparaben

5802PF(Nl).ptd 第21頁 200406505 五、發明說明（19) (nitroterephthal ic acid)及其鹽、破基甲苯胺 (nitrotoluidine)、硝基甲苯磺酸（nitrotoluene sulfonic acid)及其鹽、硝基萘磺酸（nitronaphthalene sulfonic acid)及其鹽、石肖基萘胺 (nitronaphthyamine)、硝基氫酉昆（nitrohydroquinone) ' 硝基焦倍酚（nitropyrogallol)、硝基苯肼 (nitrophenylhydrazine)、硝基苯基脲 (nitrophenylurea)、硝基苯酚（nitrophenol)、硝基磷苯 二曱酸（nitrophthalic acid)及其鹽、硝基根皮酚 (nitrophloroglucinol)、硝基节胺 (nitrobenzylamine)、石肖基〒醇（nitrobenzylalcohol)、 硝基苯酰胺（nitrobenzamide)、硝基苯績酸 (nitrobenzene sulfonic acid)及其誘導體和鹽、以及硝 基T晴（ni trobenzoni tri le)等的將芳香族硝基化合物的 硝基經過氨基（ami no)化的化合物或是將芳香族硝基化合 物的硝基經過重氮基（d i a ζ 〇 )化的化合物。更好是採用硝 基苯磺酸（nitrobenzene sulfonic acid)、硝基苯胺磺酸 (nitroaniline sulfonic acid)、硝基曱苯磺酸 (ni trotoluene sulfonic acid)、硝基二甲苯石黃酸 (nitroxylene sulfonic acid)及其該等的鹽的將芳香族 硝基化合物的硝基經過氨基（ami no)化的化合物或是將芳 香敎硝基化合物的确基經過重氮基（d i a ζ 〇)化的化合物。 還有，本發明所使用之芳香族氨基化合物與芳香族重 氮基化合物的一種以上，係即使事先地添加至本發明的表5802PF (Nl) .ptd Page 21, 200406505 V. Description of the invention (19) (nitroterephthal ic acid) and its salt, nitrotoluidine, nitrotoluene sulfonic acid and its salt, nitro Nitronaphthalene sulfonic acid and its salts, nitronaphthyamine, nitrohydroquinone, nitropyrogallol, nitrophenylhydrazine, nitrophenylurea (nitrophenylurea), nitrophenol, nitrophthalic acid and its salts, nitrophloroglucinol, nitrobenzylamine, nitrobenzylalcohol, Nitrobenzamide, nitrobenzene sulfonic acid and its inducers and salts, and nitrobenzonitrile pass the amino group of the aromatic nitro compound through the amino group ( ami no) compounds or compounds in which the nitro group of an aromatic nitro compound is diazotized (dia ζ). More preferably, nitrobenzene sulfonic acid, nitroaniline sulfonic acid, ni trotoluene sulfonic acid, and nitroxylene sulfonic acid are used. ) And their salts are compounds in which the nitro group of an aromatic nitro compound has been amino grouped, or a compound in which the aromatic nitro compound has a diazo group (dia ζ). In addition, one or more of the aromatic amino compound and the aromatic diazo compound used in the present invention are added to the table of the present invention in advance.

5802PF(Nl).ptd 第22頁 200406505 五、發明說明（20) 面處理用處理液中也可以，還有’採用經由以本發明的表 面處理方法來處理被處理金屬材料時的芳香族硝基化合物 的氧化還原反應所生成之化合物也可以。 本發明所使用之芳香族氨基化合物與芳香族重氮基化 合物，係具有提高經過表面處理的金屬材料的未塗裝耐姓 性之作用。 本發明的表面處理用處理液係能夠將習知技術無法得 到的極微細且敏密的磷酸處理皮膜析出。因此，能夠提供 具有比習知技術優良的塗裝後耐蝕性以及未塗裝耐蝕性的 金屬材料。在此，將芳香族氨基化合物與芳香族重i基 合物的一種以上添加至表面處理用處理液的場合時，盥 酸鋅處理同時地，前述芳香族氨基化合物與芳香族氣 化合物會吸著於金屬表面上’特別是更能提高未塗裝耐ς 所被含有 的濃度最好是 濃度。所被含 物的濃度，若 時，表面處理 未塗裝耐蝕性 基化合物的1 0 性能上就不會 族氨基化合物 不利的。 的芳香族氨 芳香族硝基 有的芳香族 是比芳香族 用處理液中 的效果就會 倍大的場合 有障礙。但 與芳香族重 化合物 氨基化 硝基化 的絕對 減少。 時，經 是，經 氮基化 的攸0 · 1倍到1 〇倍的摩爾 合物與芳香族重氮基化合 合物的0 · 1倍小的場合 量是小的，因此，更提高 相反地，若是比芳香族5 過表面處理的金屬材料的 由外部的供給來維持芳香 合物的濃度，在經濟上Η5802PF (Nl) .ptd Page 22, 200406505 V. Description of the invention (20) The treatment liquid for surface treatment is also possible, and the aromatic nitro group used when the metal material to be treated is treated by the surface treatment method of the present invention is used. The compound produced by the redox reaction of the compound may be used. The aromatic amino compound and the aromatic diazo compound used in the present invention have the effect of improving the unpainted surname resistance of the surface-treated metal material. The treatment liquid system for surface treatment of the present invention is capable of precipitating extremely fine and dense phosphoric acid-treated films which cannot be obtained by conventional techniques. Therefore, it is possible to provide a metal material having better corrosion resistance after coating and unpainted corrosion resistance than conventional techniques. Here, when one or more of an aromatic amino compound and an aromatic heavy i-base compound are added to the treatment liquid for surface treatment, the zinc-acid treatment simultaneously causes the aforementioned aromatic amino compound and aromatic gas compound to adsorb. On the metal surface, the concentration which is more effective to increase the resistance of the unpainted coating is preferably the concentration. Concentrations of contained substances, if 10%, surface treatment of unpainted corrosion-resistant compounds will not be disadvantageous in the case of amino compounds. Aromatic ammonia, aromatic nitro, and some aromatics are more difficult to use than aromatic treatment solutions. But the absolute reduction with the aromatic heavy compounds amidation and nitration. At this time, the amount of nitrogen compound is 0.1 to 10 times that of moles and aromatic diazo compound is smaller than that of 0.1 times, so the amount is smaller. It is economical to maintain the concentration of aromatic compounds by externally supplying a metal material surface-treated than aromatic 5.

5802PF(Nl).ptd 第23頁 200406505 五、發明說明（21) '— --—^ 本發明的表面處理液係從鎳、錳、鎂、鈣、鐵（u 及=的群組中選擇一種或兩種以上，特別是含有兩種以上 的陽離子（cat ion)成分。例如，從鎳、錳、鎮、約、鐵 (11)以及鈷的群組中所選擇的陽離子（cat i〇n)的總量係〇 (Π〜〇· 0 6mol/L，因此在被包含的陽離子中的最多被包含種 類的陽離子（cat ion)的量最好是50wt%以上、1〇〇wt%以 下。亦即’特別是在包含兩種以上的陽離子（cati〇n)的場 合，可使磷酸鋅皮膜結晶的性能向上提升，特別是提升塗 裝後與未塗裝b的性月b。所以’在採用上述表面處理用處 理液的場合時，能夠將習知技術無法得到的極微細且緻密 的填酸處理皮膜析出。因此’能夠提供具有比習知技術優 良的塗裝後耐蝕性以及未塗裝耐蝕性的金屬材料。 本發明的表面處理用處理液更包含有選自經胺 (hydroxy 1 am i ne )供給物質、亞硝酸以及亞硝酸鹽的群組 中的一種或兩種以上的化合物。 經胺供給物質例如是採用硫酸經胺、碟酸羥胺、硝酸 羥胺、游離羥胺等。亞硝酸鹽例如是採用亞硝酸鈉或亞瑣 酸鋅。因此，該等的磷酸鹽化成皮膜形成的促進劑係例如 在使用羥胺供給物質的場合時’最好是含有3〜10〇m mQl几 的經胺。而在採用亞硝酸鹽的場合時，最好是含有1〜5 m m ο 1 / L的亞硝酸鹽。 本發明的表面處理方法，依照所需，最好在採用碟酸 鋅處理的磷酸鋅處理工程前，事先進行表面調整處理。 所使用的表面調整處理液’例如是以鈦勝體（t i t a η5802PF (Nl) .ptd Page 23, 200406505 V. Description of the invention (21) '---- ^ The surface treatment liquid of the present invention is selected from the group consisting of nickel, manganese, magnesium, calcium, iron (u and =) Or two or more, especially containing two or more cat ion components. For example, cat ions selected from the group of nickel, manganese, sulphur, iron, iron (11), and cobalt Since the total amount is 〇 (Π ~ 〇.06 mol / L), it is preferable that the amount of cations of the most contained species among the contained cations is 50 wt% or more and 100 wt% or less. That is, 'especially when two or more cations are contained, the performance of the zinc phosphate film crystal can be improved upwards, especially the property b after coating and unpainted b. Therefore,' In the use of In the case of the above-mentioned surface treatment liquid, it is possible to precipitate an extremely fine and dense acid-filled film which cannot be obtained by the conventional technique. Therefore, it is possible to provide excellent post-coating corrosion resistance and uncoated corrosion resistance than the conventional technique. Metal material. The surface treatment liquid of the present invention further contains One or two or more compounds selected from the group consisting of amine (hydroxy 1 am in) supply, nitrous acid, and nitrite. The amine supply material is, for example, sulfuric acid, amine diacetate, hydroxylamine diacetate, hydroxylamine nitrate, Free hydroxylamine, etc. Nitrite is, for example, sodium nitrite or zinc oxalate. Therefore, such a promoter for the formation of a phosphate film is, for example, when using a hydroxylamine-supplying substance. 〇m mQl of several amines. When using nitrite, it is best to contain 1 ~ 5 mm ο 1 / L of nitrite. The surface treatment method of the present invention is best used in accordance with needs. Before the zinc phosphate-treated zinc phosphate treatment process, surface adjustment treatment is performed in advance. The surface adjustment treatment liquid used is, for example, titanium titanate (tita η

200406505 五、發明說明（22) col loid)為主成分的斛▲田” ^ 處理液，或是已揭示：：二一…“·鹽之表面調整 2_-96256號公報中^=平1Q-245685號公報與特開 酸鹽具有至少一種的2的二有一種以上的碟酸L而該填 特別是，前述之包含有“』價的金屬的表面調，處理液。 至少-種的2價或3;::，以上的填酸鹽而該填酸鹽具有 以鈦膠體為主成分屬的表面調整處理液，係比採用 得到細緻的皮膜。 面調整處理液的場合，㉟夠容易地 經由本發明^7矣 得到的極微細所得…，係從前以來無法 被處理金屬材料矣鋅結晶。因此，經由磷酸鋅的 的塗裝後耐蝕性ί::;覆率係非常高’而能夠得到優良 料表面進行經由性。在此系金屬材 時，表面處理皮膜；面處理方法的表面處理之場合 〇.5~3g/m2(特別疋一層的皮膜重量係 行經由本發明的^ 2’5g/m2)。對鋅系金屬材料表面進 處理皮膜層最杯:面處理方法的表面處理之場合時，表面 1.0〜4.0g/m2)。疋一層的皮膜重量係L〇〜4.5g/m2(特別是 微細的。因此。因此，本發明所得之磷酸辞皮膜結晶係極 裝後耐蝕性以另2比習知輕的皮膜重量，來發揮優良的塗 前述下限時，ϊίΐ製耐蝕性。然而，若皮膜重量係小於 的未析出磷酸粒t易產生所得之皮膜外觀上有所謂"透明，， 大於前述上限_皮膜結晶的部位。相反地，若皮膜重量係 以下，與盼，就有塗裝後的塗膜密著性下降之傾向。 牛一些具體的實施例來說明本發明。200406505 V. Description of the invention (22) col loid) as the main component ^ Tian "^ treatment liquid, or it has been revealed: two one ..." · Salt surface adjustment 2_-96256 ^ = flat 1Q-245685 The gazette has at least one kind of 2 and two or more kinds of discic acid L, and the filling is in particular, the aforementioned surface treatment solution containing a metal of "" value, a treatment solution. At least-a kind of 2 valence or 3; :: The above salt-filling salt, which has a titanium colloid as the main component of the surface-adjusting treatment liquid, is more suitable to obtain a fine film. When the surface-adjusting treatment liquid is used, it is easy to pass The extremely finely obtained 7 矣 is a metal material that cannot be treated since the zinc crystals. Therefore, the corrosion resistance after coating with zinc phosphate is very high, and excellent materials can be obtained. The surface is transparent. In the case of this metal material, the surface treatment film; the surface treatment of the surface treatment method 0.5 ~ 3g / m2 (the weight of the film of the first layer is based on ^ 2'5g / m2 of the present invention. ). The cup of the zinc-based metal material is treated: surface In the case of the surface treatment of the treatment method, the surface is 1.0 to 4.0 g / m2). The weight of the film of one layer is L0 to 4.5g / m2 (especially fine. Therefore. Therefore, the phosphoric acid film film system obtained by the present invention The corrosion resistance after the extreme load is 2 times lighter than the conventionally lighter film weight to achieve excellent coating resistance when the aforementioned lower limit is applied. However, if the weight of the film is less than the unprecipitated phosphate particles t, the appearance of the resulting film is likely to occur. There are so-called " transparent, parts larger than the aforementioned upper limit_film crystal. Conversely, if the weight of the film is less than that, there is a tendency that the adhesiveness of the coating film after coating will decrease. Some specific examples The present invention will be described.

5802PF(Nl).ptd 第25頁 2004065055802PF (Nl) .ptd Page 25 200406505

實施例 [供試板] CRS (冷延鋼板：ns —g〜3Q4i > g/m2) ί兩面合金化熔融鋅電鍍鋼板：電鍍單位量45 Α1 (無合金板：6 0 0 〇系鋁合金） [磷酸鋅處理] :施例和比較例係依照鹼脫脂—水洗一表面調整—皮 膜化成—水洗—純水洗的處理製程來進行處理。 [驗脫脂] 無論是採用哪一種的脫脂劑，例如Example [Test plate] CRS (Cold-rolled steel plate: ns —g ~ 3Q4i > g / m2) ί Double-side alloyed molten zinc electroplated steel plate: electroplating unit amount 45 Α1 (without alloy plate: 6 0 0 〇 series aluminum alloy ) [Zinc phosphate treatment]: The examples and comparative examples were processed according to the treatment process of alkali degreasing-washing with water-surface adjustment-film formation-washing with water-pure washing. [Examination of degreasing] No matter which degreasing agent is used, for example

Finecleaner-L4460A(登錄商標：日本parkerizing 公司 製、略號 FC-L4460A)2% 或 Finecleaner-L4460B(登錄商標· 日本口&汁61^211^公司製、略號？(：-1446(^)，皆先用自來· 水稀釋而使Finecieaner —L4460A的濃度變成2°/。或使Finecleaner-L4460A (registered trademark: made by Japanese parkerizing company, abbreviated number FC-L4460A) 2% or Finecleaner-L4460B (registered trademark, Japan port & juice 61 ^ 211 ^ company made, abbreviated number? (: -1446 (^) , All first diluted with tap water to make the concentration of Finecieaner —L4460A 2 ° /. Or

Finecleaner-L446 0B的濃度變成1.4%，然後加熱到42。(：。 之後，將其喷灑至被處理金屬材料上。 [水洗] 鹼脫脂後以及皮膜化成處理後的水洗以及純水洗，無 論是哪一種，將其在室溫下喷灑至被處理金屬材料上清洗 3 0秒。 [表面調整] 在實施例1、比較例1以及比較例2中，係用自來水稀 釋而使市面上販賣的表面調整處理劑的SprayZN(登錄商 標··日本parkerizing公司製）的濃度變成〇·1% ’將其在室The concentration of Finecleaner-L446 0B became 1.4%, and then heated to 42. (：. After that, spray it on the metal material to be treated. [Washing] After alkaline degreasing and film-forming treatment, water washing and pure water washing, no matter which one, spray it to the metal to be treated at room temperature. The surface was cleaned for 30 seconds. [Surface adjustment] In Example 1, Comparative Example 1, and Comparative Example 2, SprayZN (registered trademark, manufactured by Japan Parkerizing Co., Ltd.), a commercially available surface adjustment treatment agent, was diluted with tap water. ) The concentration becomes 0.1% 'in the room

5802PF(Nl).ptd 第26頁 2004065055802PF (Nl) .ptd Page 26 200406505

五、發明說明（24) 溫下喷灑至被處理金屬材料上進行表面調整處理3〇 在實施例2、3、4、5中，係以下述方式噴麗霧 整後的表面調整處理液而進行表面調整處理。 $務㉟ 首先先用自來水稀釋而使市面上販賣的丨—羥基乙叉 -1，1-二碟酸四納鹽 (l~hydroxyethylidene-l,1-diphosphonate acid natrium salt)的濃度變成2〇wt%，然後取其lkg添加至 Zri3(P〇4)2 .瑪0試藥lkg中。之後，以使用直徑〇 二的氧 化錯塊的球磨（ba 1 1 mi 1 1 )來粉碎上述混合物中。粉碎 後，以自來水將懸濁液中的Ζη3(Ρ〇4)2 · 4H2〇的濃度^整至 〇· 5g/L，而製作表面調整處理液。 還有’使用雷射回折/散亂式粒度分佈測定裝置 (LA-92 0 :堀場製作所製）來測定經過調整後的表面調整處 理液中的微粒子的平均粒徑。其結果的平均粒徑係q · 6 α m ° [皮膜化成] 第1實施例 為 了要使[Ζη]/[Ρ04]=0·05、{[Zn]/[P〇4]}/[N02] = 100V. Description of the invention (24) Spraying on the metal material to be treated at room temperature for surface adjustment treatment 30. In Examples 2, 3, 4, and 5, spraying the surface adjustment treatment liquid after finishing the mist in the following manner, Perform surface adjustment. $ 务 ㉟ Firstly dilute with tap water to make the concentration of hydroxyethylidene-1,1-diphosphonate acid tetratrile salt on the market become 2wt. %, Then take 1 kg of it and add it to 1 kg of Zri3 (P04) 2. Thereafter, the above mixture was pulverized by a ball mill (ba 1 1 mi 1 1) using an oxidation block having a diameter of 0.2. After pulverization, the concentration of Zη3 (PO4) 2 · 4H2O in the suspension was adjusted to 0.5 g / L with tap water to prepare a surface conditioning treatment liquid. In addition, the average particle diameter of fine particles in the adjusted surface conditioning liquid was measured using a laser fold / scatter type particle size distribution measuring device (LA-92 0: manufactured by Horiba, Ltd.). The average particle size of the results is q · 6 α m ° [film formation] In the first example, [Zη] / [Ρ04] = 0 · 05, {[Zn] / [P〇4]} / [N02 ] = 100

(鋅的濃度[Zn](單位mol / L)、磷酸的濃度[p〇4 ](單位 mol/L)與芳香族硝基化合物的濃度[N02](單位m〇l/L)，以 下皆同），所以配合市面上販賣的氧化鋅試藥、磷酸試藥 與m -確基笨續酸試藥，而調整表面處理用組成物。 添加所定量的硝酸鎳試藥、碳酸錳試藥以及六氟矽酸 (hexafluorosilicic acid)試藥於該表面處理用組成物(Concentration of zinc [Zn] (unit mol / L), concentration of phosphoric acid [p〇4] (unit mol / L), and concentration of aromatic nitro compound [N02] (unit mol / L), the following are all Same), so the zinc oxide test reagent, phosphoric acid test reagent and m-acid stearic acid test reagent that are commercially available are adjusted to adjust the surface treatment composition. Add the specified amount of nickel nitrate reagent, manganese carbonate reagent and hexafluorosilicic acid reagent to the surface treatment composition

5802PF(Nl).ptd 第27頁 200406505 五、發明說明（25) 中。之後，用自來水稀釋而使稀釋後的磷酸濃度變成2i〇m ，鎳濃度變成17m mol/L，錳濃度變成9m mol/L，全 氟素濃度變成53m mol/L。 添加氫氧化納試藥於該稀釋液中，而使稀釋液的磷酸 濃度變成0· 5pt。之後，再添加i80ppm的亞硝酸鈉試藥、 2 0ppm的4, 4’ -重氮胺撐-二苯磺酸2納 (4,4 diazoamino~dibenzene sulfonic acid 2 natrium)試藥而做成表面處理用處理液。 然後’將已進行過脫脂、水洗以及表面調整處理之被 處理金屬材料，浸潰於加溫至4〇 °c的前述表面處理用處理 液中9 0秒而進行表面處理。 第2實施例 為 了要使[Ζη]/[Ρ〇4]=〇· 1、{[Zn]/[p〇4]}/[N〇2]=4〇〇， 所以配合市面上販賣的氧化鋅4水和物試藥、填酸試藥與 m-硝基苯磺酸試藥，而調整表面處理用組成物。 添加所定量的碳酸錳試藥、硝酸鎂試藥以及六氟矽酸 (hexaf luorosi 1 icic acid)試藥於該表面處理用組成物 中。之後’用自來水稀釋而使稀釋後的磷酸濃度變成53[11 mol/L，猛濃度變成9m m〇i/L，鎂濃度變成8〇m mol/L，全 氟素濃度變成53m mol/L。 添加氫氧化納試藥於該稀釋液中，而使稀釋液的磷酸 ✓辰度變成0.5pt。之後，再添加3〇〇ppm的亞硝酸鈉試藥而 做成表面處理用處理液。5802PF (Nl) .ptd Page 27 200406505 V. Description of Invention (25). After that, it was diluted with tap water so that the diluted phosphoric acid concentration became 2 mmol, the nickel concentration became 17 m mol / L, the manganese concentration became 9 m mol / L, and the perfluorinated concentration became 53 m mol / L. Sodium hydroxide reagent was added to the diluted solution so that the phosphoric acid concentration of the diluted solution became 0.5 pt. After that, i80 ppm sodium nitrite reagent and 20 ppm of 4, 4'-diazoamine-dibenzenesulfonic acid 2 sodium (4,4 diazoamino ~ dibenzene sulfonic acid 2 natrium) reagent were added to make a surface treatment. Use treatment fluid. Then, the to-be-treated metal material which has been subjected to degreasing, water washing and surface conditioning treatment is immersed in the above-mentioned surface treatment treatment liquid heated to 40 ° C for 90 seconds for surface treatment. In the second embodiment, in order to make [Zη] / [Ρ〇4] = 〇 · 1, {[Zn] / [p〇4]} / [N〇2] = 4〇〇, in accordance with the commercially available oxidation Zinc 4 water and substance reagents, acid-filling reagents, and m-nitrobenzenesulfonic acid reagents, while adjusting the composition for surface treatment. Manganese carbonate reagent, magnesium nitrate reagent and hexaf luorosi 1 icic acid reagent were added to the surface treatment composition. After that, it was diluted with tap water so that the diluted phosphoric acid concentration became 53 [11 mol / L, the violent concentration became 9 m mol / L, the magnesium concentration became 80 m mol / L, and the perfluorinated concentration became 53 m mol / L. Add the sodium hydroxide reagent to this diluent to make the dilute phosphoric acid of the diluent ✓0.5pt. Thereafter, 300 ppm of a sodium nitrite reagent was added to prepare a surface treatment liquid.

5802PF(Nl).ptd 第28頁 200406505 五、發明說明（26) 一 - 然後’將已進行過脫脂、水洗以及表面調整處理之被 處理金屬材料，浸潰於加溫至5〇 〇c的前述表面處理用處理 液中60秒而進行表面處理。 第3實施你！ 為 了要使[Ζη]/[Ρ〇4]=〇·;ι、{[Zn]/[P〇4]}/[N〇2]=700， 所以配合市面上販賣的氧化鋅4水和物試藥、磷酸試藥與 m-銷基笨續酸試藥，而調整表面處理用組成物。 添加所定量的硝酸鈷試藥、碳酸鈣試藥以及六氟矽酸 Chexafluoro Siiicic acid)試藥於該表面處理用組成物 中。之後’用自來水稀釋而使稀釋後的磷酸濃度變成丨58m mol/L ’銘濃度變成i7m mol/L，鈣濃度變成12m mol/L， 全氟素濃度變成53m mol/L。 添加重碳酸氨試藥於該稀釋液中，而使稀釋液的游離 囊文度變成l.Opt。之後’再添加i20ppm的亞确酸納試藥、 1 OOppm的m-硝基苯磺酸試藥而做成表面處理用處理液。 然後，將已進行過脫脂、水洗以及表面調整處理之被 處理金屬材料，浸潰於加溫至35 °C的前述表面處理用處理 液中6 0秒而進行表面處理。 第4實施例 為 了要使[Ζη]/[Ρ04]=〇· 2、{ [Ζη]/[Ρ04] }/[N02] = 200， 所以配合市面上販賣的氧化鋅試藥、磷酸試藥與4 —硝基苯 胺 -2 -績酸（4 - nitroaniline-2 - sulfonic acid)試藥，而5802PF (Nl) .ptd Page 28, 200,406,505 V. Description of the invention (26) A-Then 'the metal material to be treated which has been degreased, washed, and surface-adjusted is immersed in the aforementioned material heated to 500 ° C The surface treatment was performed in the surface treatment liquid for 60 seconds. 3rd to implement you! In order to make [Zη] / [Ρ〇4] = 〇 ·; ι, {[Zn] / [P〇4]} / [N〇2] = 700, it is necessary to cooperate with commercially available zinc oxide and water. Reagent, phosphoric acid reagent, and m-pin-based stearic acid reagent, and adjust the composition for surface treatment. Cobalt nitrate reagents, calcium carbonate reagents, and Chexafluoro Siiicic acid) reagents were added to the surface treatment composition. After that, it was diluted with tap water so that the diluted phosphoric acid concentration became 58m mol / L, and the concentration of i was changed to i7m mol / L, the calcium concentration was changed to 12m mol / L, and the perfluorinated concentration was changed to 53m mol / L. An ammonium bicarbonate reagent was added to the diluted solution, so that the free capsule resolution of the diluted solution became 1.0 Opt. After that, i20 ppm sodium hypochlorite reagent and 100 ppm m-nitrobenzenesulfonic acid reagent were added to prepare a surface treatment solution. Then, the metal material to be treated which has been degreased, washed with water, and surface-adjusted is immersed in the aforementioned surface-treatment treatment liquid heated to 35 ° C for 60 seconds to perform surface treatment. In the fourth embodiment, in order to make [Zη] / [P04] = 〇 2, 2. [[Zη] / [P04]} / [N02] = 200, it is necessary to cooperate with commercially available zinc oxide reagents, phosphoric acid reagents, and 4 —nitroaniline-2-sulfonic acid, and

5802PF(Nl).ptd 第29頁 200406505 五、發明說明（27) 調整表面處理用組成物。 添加所定量的硝酸鎂試藥、硫酸鐵（Π )試藥、羥胺 (hydroxyl amine)試藥以及六 I矽酸（hexafluorosilicic acid)試藥於該表面處理用組成物中。之後，用自來水稀 釋而使稀釋後的磷酸濃度變成10 5m mol/L，鎂濃度變成 82m mol/L，鐵濃度變成4m mol/L，羥胺濃度變成0.06m mol/L，全氟素濃度變成53m mol/L。 添加重氫氧化鈉試藥於該稀釋液中，而使稀釋液的游 離酸度變成1.5pt。之後，再添加200ppm的m-硝基苯績酸 試藥而做成表面處理用處理液。 然後，將已進行過脫脂、水洗以及表面調整處理之被 處理金屬材料，浸潰於加溫至4 0 °C的前述表面處理用處理 液中9 0秒而進行表面處理。 第5實施例 為 了要使[Ζη]/[Ρ04]=0· 15、 {[Ζη]/[Ρ04]}/[Ν02]=3 0 0，所以配合市面上販賣的氧化鋅 試藥、磷酸試藥與m-硝基苯磺酸試藥，而調整表面處理用 組成物。 添加所定量的硝酸鎳試藥、碳酸錳試藥以及六氟矽酸 (hexafluorosilicic acid)試藥於該表面處理用組成物 中。之後，用自來水稀釋而使稀釋後的磷酸濃度變成1 26m mol/L，鎳濃度變成17m mol/L，猛濃度變成18m mol/L， 全I素濃度變成53m mol / L。5802PF (Nl) .ptd Page 29 200406505 V. Description of the invention (27) Adjust the composition for surface treatment. The specified amount of magnesium nitrate reagent, ferric sulfate (Π) reagent, hydroxyll amine reagent, and hexafluorosilicic acid reagent were added to the surface treatment composition. After that, it was diluted with tap water so that the diluted phosphoric acid concentration became 105 m mol / L, the magnesium concentration became 82 m mol / L, the iron concentration became 4 m mol / L, the hydroxylamine concentration became 0.06 m mol / L, and the perfluorin concentration became 53 m. mol / L. The dilute sodium hydroxide reagent was added to the diluent so that the free acidity of the diluent became 1.5 pt. Then, 200 ppm of m-nitrobenzoic acid reagent was added to prepare a surface treatment liquid. Then, the metal material to be treated which has been subjected to degreasing, water washing and surface conditioning treatment is immersed in the aforementioned surface treatment solution for heating to 40 ° C for 90 seconds for surface treatment. In the fifth embodiment, in order to make [Zη] / [P04] = 0.15, {[Zη] / [Ρ04]} / [N02] = 3 0 0, it is necessary to cooperate with commercially available zinc oxide reagents and phosphoric acid reagents. And m-nitrobenzenesulfonic acid, and adjust the composition for surface treatment. The surface treatment composition is added with a predetermined amount of a nickel nitrate reagent, a manganese carbonate reagent, and a hexafluorosilicic acid reagent. After that, it was diluted with tap water so that the diluted phosphoric acid concentration became 126m mol / L, the nickel concentration became 17m mol / L, the abrupt concentration became 18m mol / L, and the total I concentration became 53m mol / L.

5802PF(Nl).ptd 第30頁 200406505 五、發明說明（28) 添加氫氧化鈉試藥試藥於該稀釋液中，而使稀釋液的 游離酸度變成〇.9pt。之後’再添加1 80ppm的亞硝酸鈉試 藥、50ppm的4, 4’-重氮胺撐-二苯績酸2鈉 (4, 4, -diazoamino-dibenzene sulfonic acid 2 natrium)試藥而做成表面處理用處理液。 然後，將已進行過脫脂、水洗以及表面調整處理之被 處理金屬材料，浸潰於加溫至40 °C的前述表面處理用處理 液中9 0秒而進行表面處理。5802PF (Nl) .ptd Page 30 200406505 V. Description of the invention (28) The sodium hydroxide reagent and reagent are added to the diluted solution so that the free acidity of the diluted solution becomes 0.9 pt. Then, '80 ppm sodium nitrite reagent and 50 ppm of 4, 4'-diazoamino-diphenyl sulfonic acid 2 natrium were added. Surface treatment liquid. Then, the metal material to be treated which has been degreased, washed with water, and surface-adjusted is immersed in the aforementioned surface-treatment treatment liquid heated to 40 ° C for 90 seconds to perform surface treatment.

[比較例1 ] 為 了要使[Ζη]/[Ρ04]=〇·〇5、{[Zn]/[P04]}/[N02]=80， 所以配合市面上販賣的氧化鋅試藥、填酸試藥與m —確基苯 績酸試藥，而調整表面處理用組成物。 添加所定量的硝酸鎳試藥、碳酸錳試藥以及六氟矽酸 (hexaf luorosi 1 icic acid)試藥於該表面處理用組成物 中。之後’用自來水稀釋而使稀釋後的磷酸濃度變成丨5 8m mol/L，鎳濃度變成17m mol/L，錳濃度變成9m mol/L，全 氟素濃度變成53m mol/L。[Comparative Example 1] In order to make [Zη] / [P04] = 〇〇〇5, {[Zn] / [P04]} / [N02] = 80, in combination with commercially available zinc oxide reagents and acid filling The test reagent and the m-acid benzoate test reagent, and the composition for surface treatment was adjusted. The surface treatment composition was added with a predetermined amount of a nickel nitrate reagent, a manganese carbonate reagent, and a hexaf luorosi 1 icic acid reagent. After that, it is diluted with tap water so that the diluted phosphoric acid concentration becomes 5 8 m mol / L, the nickel concentration becomes 17 m mol / L, the manganese concentration becomes 9 m mol / L, and the perfluorinated concentration becomes 53 m mol / L.

添加氫氧化納試藥試藥於該稀釋液中，而使稀釋液的 游離酸度變成〇· 5pt。之後，再添加18〇ppm的亞硝酸鈉試 藥而做成表面處理用處理液。 然後’將已進行過脫脂、水洗以及表面調整處理之被 處理金屬材料，浸潰於加溫至4〇 X的前述表面處理用處理 液中90秒而進行表面處理。A sodium hydroxide reagent and a reagent are added to the diluted solution, so that the free acidity of the diluted solution becomes 0.5 pt. Thereafter, 180 ppm of a sodium nitrite reagent was added to prepare a surface treatment liquid. Then, the to-be-treated metal material which has been subjected to degreasing, water washing and surface conditioning treatment is immersed in the above-mentioned treatment solution for surface treatment for 90 seconds to perform surface treatment.

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[比較例2 ] 為 了要使[Zn]/[P04]=〇 2、i「7 η 所以配合市面上販賣的4i化二{lZn]/t[P0山/[叫^ ’ ^ ^ ^ ^ 虱化鋅试樂、磷酸試藥與m-硝基苯 尹、S夂试樂’而調整表面處理用組成物。 ，加所定量的蝴酸錄試藥、碳酸猛試藥以及六氟石夕酸 (hexaf uorosilicic acid)試藥於該表面處理用組成物 二禮Λ自來水稀釋而使稀釋後㈣酸濃度變成— /痒度變成17m m〇1/L，猛濃度變成9m niol/L ’全 氟素〉辰度變成53m mol/L。 添加氫氧化鈉試藥試藥於該稀釋液中，而使稀釋液的 游離酸度變成h〇pt。之後，再添加18〇ppm的亞硝酸鈉試 藥而做成表面處理用處理液。 然後’將已進行過脫脂、水洗以及表面調整處理之被 處理金屬材料，浸潰於加溫至4〇。。的前述表面處理用處理 液中9 0秒而進行表面處理。 [磷酸新皮膜的評價] (1)外觀： 用目視觀察來評價磷酸辞皮膜有無”透明區”以及”暗 區（或波紋）。其結果如表1所示。其符號代表之意思如下 述。 ◎ 均一良好的外觀 0 具有一部分的暗區 I I S I s Ϊ IRH 5802PF(Nl).ptd ~ _ -------- 200406505 五、發明說明 △ 具有"透明區"以及"暗區，， x 具有很多的"透明區，， XX 沒有化成皮膜 (2) 皮膜重量（c· W·) 、測定化，處理後的處理板的重量（wl[g])。接著，在 化成處理板是冷延鋼板的場合時，將其浸潰於75 t的5〇% 鉻，水浴液中1 5分鐘，而進行皮膜剝離處理。在化成處理 板是，辞鋼板的場合時，將其浸潰於常溫的重鉻酸銨（2%) 以及氨水（1 3 · 7% )水溶液中丨5分鐘，而進行皮膜剝離處 理。在化成處理板是鋁合金板的場合時，將其浸潰於常溫 的重鉻酸銨（50%)水溶液中5分鐘，而進行皮膜剝離處理。 之後’測定皮膜剝離後的重量（w 2 [ g ])。然後，依照下列 式來异出皮膜重量。該結果如表1所示。 皮膜重量[g/m2] = (Wl-W2) /處理板的表面積（m2) (3) 皮膜結晶尺寸（c· s·) 使用掃描式電子顯微鏡（SEM)來觀察影像而調查結晶 粒徑’其影像係被放大丨5 〇 〇倍。該結果如表1所示。 (4) 未塗裝财姓性 將實施例與比較例所製作之CRS的磷酸鋅處理板放入 設定在95%RH、5 0 °C的濕潤試驗機中，然後判定在24小時 後的生鏽面積。該結果如表1所示。 (5 )塗裝性能 (a )評價板的作成 為了要評價經由實施例和比較例所得之鱗酸鋅處理板[Comparative Example 2] In order to make [Zn] / [P04] = 〇2, i "7 η, so as to cooperate with the commercially available 4i ions {lZn] / t [P0 mountain / [called ^ '^ ^ ^ ^ lice Zinc test, phosphoric acid test, m-nitrophenyl Yin, S 夂 test music 'and adjust the composition for surface treatment. Add the amount of butterfly acid test reagent, carbonic acid test reagent and hexafluorite acid (hexaf uorosilicic acid) The test compound was diluted in the surface treatment composition Erli Λ tap water to make the dilute acid concentration after the dilution-/ the itching degree became 17m m〇1 / L, and the fierce concentration became 9m niol / L 'perfluorin 〉 Chen degree becomes 53m mol / L. Sodium hydroxide reagent and reagent are added to the diluted solution, so that the free acidity of the diluted solution becomes hOpt. After that, 180 ppm of sodium nitrite reagent is added to make The surface treatment liquid is prepared. Then, the metal material to be treated which has been degreased, washed with water, and surface conditioning treatment is immersed in the surface treatment liquid heated to 40 ° C for 90 seconds to perform the surface treatment. [Evaluation of a new phosphate film] (1) Appearance: The presence or absence of a "transparent area" and a "dark area" of the phosphate film was evaluated by visual observation. Or corrugated). The results are shown in Table 1. The meaning of the symbols is as follows. ◎ Uniform good appearance 0 Has a part of dark area IISI s Ϊ IRH 5802PF (Nl) .ptd ~ _ -------- 200406505 V. Description of the invention △ It has " transparent area " and " dark area, , X has many " transparent regions, and XX is not formed into a film (2), the film weight (c · W ·), and the weight of the treated board after the measurement and treatment (wl [g]). Next, when the chemically treated sheet is a cold-rolled steel sheet, it is immersed in 75 t of 50% chromium and immersed in a water bath for 15 minutes to perform a film peeling treatment. When the chemical conversion treatment plate is a steel plate, it is immersed in an aqueous solution of ammonium dichromate (2%) and aqueous ammonia (13.7%) at room temperature for 5 minutes, and the film is peeled off. When the chemical conversion treatment plate is an aluminum alloy plate, it is immersed in an aqueous solution of ammonium dichromate (50%) at room temperature for 5 minutes to perform a film peeling treatment. Thereafter, the weight (w 2 [g]) of the peeled film was measured. Then, the weight of the film was varied according to the following formula. The results are shown in Table 1. Film weight [g / m2] = (Wl-W2) / surface area of the treated plate (m2) (3) Film crystal size (c · s ·) Using scanning electron microscope (SEM) to observe the image and investigate the crystal grain size ' Its image is magnified 5,000 times. The results are shown in Table 1. (4) Unpainted property Put the CRS zinc phosphate treated plate made in the examples and comparative examples into a humidity tester set at 95% RH and 50 ° C, and then determine the health after 24 hours. Rust area. The results are shown in Table 1. (5) Coating performance (a) Preparation of evaluation plate In order to evaluate the zinc-scale-acid-treated plate obtained through Examples and Comparative Examples

5802PF(Nl).ptd 第33頁 2004065055802PF (Nl) .ptd Page 33 200406505

的塗裝性能，所以以下述製程來進行塗裝。 陽離子（cat i〇n)電解塗裝—純水洗〜燒結 結—上塗—燒結 陽離子電解塗裝：epoxy系陽離子電解塗料 (工卜夕口〆9400 :關西塗料公司製）、電壓20 0V、膜厚2〇Coating performance, so the following process is used for coating. Cationic cationic coating—pure water washing ~ sintering junction—top coating—sintering cationic electrolytic coating: epoxy-based cationic electrolytic coating (Gongbu Xikou 〆9400: made by Kansai Paint Co., Ltd.), voltage 20 0V, film thickness 2〇

"m、175 °C燒結20分鐘。 、与ZU 中塗塗裝：氨基醇酸（aminoalkyd)系塗料 TP-37夕|一：關西塗料公司製）、喷射塗 膜厚3 5 /z m、1 4 0 °C燒結2 〇分鐘。 、 夕TM-13白：關 140 °C燒結20分" m, 175 ° C for 20 minutes. Coating with ZU: aminoalkyd coating TP-37 (1: made by Kansai Paint Co., Ltd.), spray coating film thickness 35 / z m, sintering at 140 ° C for 20 minutes. , Xi TM-13 White: Off 140 ° C for 20 minutes

上塗塗裝：氨基醇酸系塗料（7 S予 西塗料公司製）、喷射塗裝、膜厚35 Am 鐘0 (b )塗裝性能評價 將上述經過塗裝的表面處理板進行塗裝性能 該結果如表2所示。 、 還有’評價項目、評價方法與略號皆如以下所述。還 有丄電解塗裝完了時點的塗膜係以電解塗膜稱之，上塗塗 裝元了時點的塗膜係以3 c 〇 a t s塗膜稱之。 1 )SST :鹽水噴霧實驗（電解塗膜）Top coating: amino alkyd paint (7 S Yosei Paint Co., Ltd.), spray coating, film thickness 35 Am Zhong 0 (b) Evaluation of coating performance The coating performance of the above-mentioned surface-treated board is The results are shown in Table 2. , And ‘Evaluation items, evaluation methods, and abbreviations are as follows. In addition, the coating film at the time point when electrolytic coating is completed is referred to as an electrolytic coating film, and the coating film at the time point when an upper coating is applied is referred to as a 3 c oat s coating film. 1) SST: salt spray test (electrolytic coating)

對用銳利的刀具而橫切入的電解塗裝板施予5%的“口 水溶液之840小時喷霧（依據JIS-Z-2 37 1 )。噴霧終了後， 測量從橫切部分到一側的最大膨脹寬度。 2)SDT :鹽溫水實驗（電解塗膜）5% of the "mouth solution of 840 hours spray (according to JIS-Z-2 37 1) was applied to the electrolytic coating plate cut into the cross with a sharp knife. Maximum expansion width 2) SDT: salt warm water experiment (electrolytic coating)

200406505 五、發明說明（32) 對用銳利的刀具而橫切入的電解塗裝板施予 。(：之5%的NaCl水溶液之240小時浸潰。浸潰終了後概至bb 來水清洗。然後，進行經過常溫乾燥的電解塗膜用自 的Cello-tape(赛璐玢管）（登錄商標）剝離。之後^ 橫切部分到兩側的最大剝離寬度。 測里從 3) lstADH ·· 1 次密著性（3coats 塗膜） 在3c〇atS塗膜上，以銳利的刀具切出互相間隔“η的 \〇()個棋盤眼，然後進行棋盤眼部分的Cello-tape(赛璐玢 管）（登錄商標）剝離。之後，計算棋盤眼的剝離個數。 4) 2ndADH :耐水2次密著性（3c〇ats塗膜） $主將3coats塗裝板浸潰於4〇。〇的去離子水中24〇小時。 /文/貝後以銳利的刀具切出互相間隔2mm的1 〇 〇個棋盤眼， 然後進行棋盤眼部分的c e丨丨〇 — t a p e (赛璐玢管）（登錄商標） 剝離。之後，計算棋盤眼的剝離個數。200406505 V. Description of the invention (32) Apply to the electrolytic coating board cut in with a sharp knife. (: Immersion for 240 hours in a 5% NaCl aqueous solution. After the immersion is complete, wash it with bb water. Then, perform the electrolytic coating film dried at room temperature using Cello-tape (celluloid tube) (registered trademark) ) Peeling. Afterwards ^ The maximum peeling width from the cross-section to both sides. From 3) lstADH · 1 time adhesion (3coats coating) On the 3c〇atS coating, cut each other with a sharp knife. "\\ () checkerboard eyes, and then the cello-tape (celluloid tube) (registered trademark) peeling of the checkerboard eye is peeled off. After that, the number of peeling off of the checkerboard eye is calculated. 4) 2ndADH: Water-resistant 2 times dense Adhesiveness (3coat coating film) $ Mainly immerse the 3coats coating board in 40% deionized water for 24 hours. After cutting the 100 chessboards with 2mm intervals, use a sharp knife. Then, peel off the ce 丨 丨 〇-tape (registered trademark) of the checkerboard eye part, and then count the number of peeling off the checkerboard eye.

5802PF(Nl).ptd 第35頁 200406505 五、發明說明（33) [表1] 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 比較例 1 比較例 2 皮膜外觀 CRS ◎ ◎ ◎ ◎ ◎ X ◎ GA ◎ ◎ ◎ ◎ ◎ ◎ ◎ A1 〇 ◎ ◎ ◎ ◎ X Δ 皮膜重量 CRS 2.1 0.8 1.7 1.7 1.8 2.8 3.2 GA 3.8 2.5 3.2 3.3 3.1 4.2 5.8 A1 1.5 1.3 1.9 1.8 1.8 0.8 1.8 結晶尺寸 CRS 3> 2> 2> 2> 2> 3 5〜10 GA 5> 5> 3> 3> 3> 5〜10 10-15 A1 5> 3> 3> 3> 3> 5〜10 5~10 耐蝕性 生絲面積 % CRS 5> 10 5> 5> 5> 全面 生絲 30 1HI11 第36頁 5802PF(Nl).ptd 200406505 五、發明說明（34) [表2】 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 比較例 1 比較例 2 SST CRS 1.3 1.9 1.2 1.2 1.1 5.3 4.6 GA 2.6 2.8 2.6 2.7 2.6 5.8 6.3 A1 0.5 0.5 0.6 0.5 0.5 1.5 1.1 SDT CRS 3.5 3.8 3.2 3.4 3.3 10S Ί2 GA 3.8 4.1 3.3 3.5 3.6 6.0 5.9 A1 2.3 2.7 2.2 2.1 2.1 5.1 4.5 1st ADH 剝離個數 CRS 0 0 0 0 0 〇 0 GA 0 0 0 0 0 0 2 A1 0 0 0 0 0 0 0 2nd ADH 剝離個數 CRS 0 0 0 0 0 0 0 GA 0 0 0 0 0 0 5 A1 0 0 0 0 0 0 0 根據上述說明，可知比較例由於沒有滿足〇. 〇5 $ [Ζη]/[Ρ04] $0· 2、100 $ { [Zn]/[P〇4] }/[N02] $ 70 0 (其中 鋅的濃度[Zn](單位m〇l/L)、磷酸的濃度[p〇4](單位mol/L) 與芳香族石肖基化合物的濃度[N 〇2 ](單位m ο 1 / L ))，所以不具 有實施例之皮膜的特長。 例如，[Zn]/[P〇4] }/[N〇2卜80的比較例1，特別是在 CRS上的磷酸鋅皮膜外觀上被認為有所謂”透明區”的金屬 材料的露出部分。也就是說，比較例1的耐蝕性比實施例5802PF (Nl) .ptd Page 35 200406505 V. Description of the invention (33) [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Film appearance CRS ◎ ◎ ◎ ◎ ◎ X ◎ GA ◎ ◎ ◎ ◎ ◎ ◎ A1 〇 ◎ ◎ ◎ ◎ X Δ Film weight CRS 2.1 0.8 1.7 1.7 1.8 2.8 3.2 GA 3.8 2.5 3.2 3.3 3.1 4.2 5.8 A1 1.5 1.3 1.9 1.8 1.8 0.8 1.8 Crystal size CRS 3 > 2 > 2 > 2 > 2 > 3 5 ~ 10 GA 5 > 5 > 3 > 3 > 3 > 5 ~ 10 10-15 A1 5 > 3 > 3 > 3 > 3 > 5 ~ 10 5 ~ 10 Corrosion resistant filament area% CRS 5 > 10 5 > 5 > 5 > Comprehensive raw silk 30 1HI11 Page 36 5802PF (Nl) .ptd 200406505 V. Description of the invention (34) [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 SST CRS 1.3 1.9 1.2 1.2 1.1 5.3 4.6 GA 2.6 2.8 2.6 2.7 2.6 5.8 6.3 A1 0.5 0.5 0.6 0.5 0.5 1.5 1.1 SDT CRS 3.5 3.8 3.2 3.4 3.3 10S Ί2 GA 3.8 4.1 3.3 3.5 3.6 6.0 5.9 A1 2.3 2.7 2.2 2.1 2.1 5.1 4.5 1st ADH stripping number CRS 0 0 0 0 0 〇0 GA 0 0 0 0 0 0 2 A1 0 0 0 0 0 0 0 2nd ADH stripping number CRS 0 0 0 0 0 0 0 GA 0 0 0 0 0 0 5 A1 0 0 0 0 0 0 0 Meet 〇. 〇5 $ [Zη] / [Ρ04] $ 0 · 2, 100 $ {[Zn] / [P〇4]} / [N02] $ 70 0 (wherein the concentration of zinc [Zn] (unit m〇l / L), the concentration of phosphoric acid [p04] (unit mol / L), and the concentration of the aromatic stone shoshyl compound [N 〇2] (unit m ο 1 / L)), so it does not have the features of the film of the example. For example, Comparative Example 1 of [Zn] / [P〇4]} / [N〇2 卜 80, particularly the exposed portion of a metallic material that is considered to have a so-called "transparent zone" in the appearance of the zinc phosphate film on the CRS. That is, the corrosion resistance of Comparative Example 1 is better than that of Examples.

5802PF(Nl).ptd 第37頁 200406505 五、發明說明（35) 差0 還有’ [Ζ η ] / [ P 〇4 ] } / [ n 〇2 ] = 8 〇 〇的比較例2 ’鱗酸鋅皮 膜的結晶並沒有變成微細的結晶。而且，碟酸鋅皮膜重量 重，填酸鋅皮膜的耐蝕性也不好。更者，即使在磷酸鋅皮 膜上設計有塗膜，該塗膜的密著性也不好，因此耐蝕性也 不好。 相對於此，根據本發明的實施例，磷酸鋅皮膜的結晶 是微細的。而且，磷酸鋅皮膜重量輕，磷酸鋅皮膜的耐蝕 性也很好。更者，被設計在磷酸鋅皮膜上的塗膜的密著性 也很好而很難剝落，而且，耐蝕性也很好。 [產業上的利用可能性] 根據本發明，係能在未塗裝狀態與塗裝狀態都具有優 良耐蝕性之極微細的磷酸鋅化成皮膜。特別是，在習知所 採用的磷酸鹽處理製程中，並且即使不改良現有處理裝 置’也能提供耐蝕性優的極微細的磷酸鹽皮膜。於是，能 夠形成皮膜薄且耐蝕性優又極微細的磷酸鹽皮膜。因此， 本發明所能夠降低藥劑消耗量，降低填酸鋅化成皮膜的形 成成本。5802PF (Nl) .ptd Page 37 200406505 V. Description of the invention (35) Difference 0 There is also '[Z η] / [P 〇4]} / [n 〇2] = 8 〇〇 Comparative Example 2 The crystals of the zinc film did not become fine crystals. In addition, the zinc plated acid film has a heavy weight, and the zinc oxide filled film has poor corrosion resistance. Furthermore, even if a coating film is designed on the zinc phosphate film, the adhesion of the coating film is not good, and thus the corrosion resistance is not good. On the other hand, according to the embodiment of the present invention, the crystal of the zinc phosphate film is fine. In addition, the zinc phosphate film is light in weight, and the zinc phosphate film has good corrosion resistance. Furthermore, the coating film designed on the zinc phosphate film has good adhesion and is difficult to peel off, and also has good corrosion resistance. [Industrial Applicability] According to the present invention, an extremely fine zinc phosphate which has excellent corrosion resistance in both an unpainted state and a painted state is formed into a film. In particular, in the conventionally used phosphate treatment process, an extremely fine phosphate film having excellent corrosion resistance can be provided without modifying the existing treatment device '. As a result, it is possible to form a phosphate film having a thin film, excellent corrosion resistance, and extremely fineness. Therefore, the present invention can reduce the consumption amount of the medicament and reduce the formation cost of the zinc-filled acid to form a film.

5802PF(Nl).ptd 第38頁 200406505 圖式簡單說明 5802PF(Nl).ptd 第39頁5802PF (Nl) .ptd page 38 200406505 Schematic description 5802PF (Nl) .ptd page 39

Claims (1)

200406505 六、申請專利範圍 1· 一種表面處理用姐成物，其特徵在於： 該表面處理用組成物含有鋅、磷酸、芳香族硝基 (ni tro)化合物，其中鋅的濃度[Zn](單位㈣丨/!^)、磷酸的 濃度[P04](單位m〇l/L)與芳香族硝基化合物的濃度 [N02](單位m〇i/L)，而滿足 1〇〇${[Ζη]/[Ρ04]}/[Ν02]‘70〇 的關係式。 2 ·如申請專利範圍第1項所述之表面處理用組成物’ 其中更滿足0· 05 $[Ζη]/[Ρ04] $0· 2的關係式。 3 · 一種表面處理用處理液，其特徵在於·· 該表面處理用組成物含有鋅、鱗酸、芳香族硝基化合 物’其中辞的濃度[Zn](單位m〇i /L)、磷酸的濃度[P04 ](單 位mo 1 / L)與芳香族硝基化合物的濃度[nq2 ](單位的1 /L )， 而滿足100 $ ( [Zn]/[P〇4] }/[N02] $ 70 0 的關係式。 4·如申請專利範圍第3項所述之表面處理用處理液， 其中更滿足0· 05 $[Ζη]/[Ρ〇4] $〇· 2的關係式。 5·如申請專利範圍第3或4項所述之表面處理用處理 液’其中該磷酸的濃度範圍係50〜25 0m mol/L。（註： m : m i 1 1 i ) 6·如申請專利範圍第3、4或5項所述之表面處理用處 ^液：更包含有選自芳香族氨基（ami ηο)化合物以及芳香 知重氣基（diazo)化合物的群組中的一種或兩種以上的芳 f族=合物’而且前述芳香族化合物的合計摩爾濃度係該 方香族硝基化合物的摩爾濃度的0· 1倍〜10倍的值。 7·如申清專利範圍第3、4、5或6項所述之表面處理200406505 6. Scope of patent application 1. A surface treatment product for surface treatment, characterized in that: The composition for surface treatment contains zinc, phosphoric acid, and aromatic nitro (ni tro) compounds, in which the concentration of zinc is [Zn] (units) ㈣ 丨 /! ^), The concentration of phosphoric acid [P04] (unit m〇l / L) and the concentration of aromatic nitro compounds [N02] (unit m〇i / L), and satisfying 100 $ {[Zη ] / [Ρ04]} / [Ν02] '70 〇. 2 · The composition for surface treatment as described in item 1 of the scope of the patent application, wherein the relational expression of 0. 05 $ [Zη] / [Ρ04] $ 0 · 2 is more satisfied. 3. A surface treatment liquid, characterized in that the surface treatment composition contains zinc, phosphonic acid, an aromatic nitro compound, and a concentration of [Zn] (unit mOi / L), phosphoric acid Concentration [P04] (unit mo 1 / L) and aromatic nitro compound concentration [nq2] (unit 1 / L), and satisfy 100 $ ([Zn] / [P〇4]} / [N02] $ The relational expression of 70 0. 4. The treatment liquid for surface treatment as described in item 3 of the scope of the patent application, which more satisfies the relational expression of 0. 05 $ [Zη] / [Ρ〇4] $ 〇 · 2. 5. The treatment liquid for surface treatment as described in item 3 or 4 of the scope of patent application, wherein the concentration range of the phosphoric acid is 50 to 250,000 m mol / L. (Note: m: mi 1 1 i) 6. The liquid for surface treatment according to item 3, 4 or 5: further comprising one or two or more aromatic compounds selected from the group consisting of aromatic amino (ami ηο) compounds and aromatic diazo compounds. f group = compound 'and the total molar concentration of the aforementioned aromatic compound is a value of 0.1 to 10 times the molar concentration of the aromatic nitro compound. The surface of the first 4, 5 or 6 treatment 200406505 六.、申請專利範圍 用處理液，更包含有選自鎳、錳、鎮、鈣、鐵（π)以及鈷 的群組中的一種或兩種以上的陽離子成分。 8·如申請專利範圍第3、4、5、6或7項所述之表面 理用處理液，更包含有選自羥胺（hydr〇xylamine)供給物 質、亞硝酸以及亞硝酸鹽的群組中的一種種以 合物。 J 9· 一種表面處理方法，其特徵在於： 使用前述工請專利範圍第3、4、5、6、7或8項所述之 該表面處理用處理液來處理金屬材料的表面。 10. 一種表面處理方法，其特徵在於： 具備有一表面調整製程與一表面處理製程， 面調整製程係在以鈦膠體（titan c〇u〇id)為主分的表 面調整液中處理金屬材料；而該表面處理製程係在該的表 调整製程之後，使用前述申請專利範圍第3、4、5、6广 或8項所述之該表面處理用處理液來處理該金屬材料。 1 1 . 一種表面處理方法，其特徵在於： 具f有該表面處理方法具備有一表面 面處理製程，其中該表面調整 I轾與表 以上的墙酸鹽的表面調整液Ά:有：：或兩種 係在該表面調整製程之後，使々二，由=^亥表面處理製程 屬材料。 項狀之^面處理用處理液來處理該金 特徵在於 種具有金屬材料的製品，其200406505 VI. Scope of patent application The treatment liquid further contains one or two or more cationic components selected from the group consisting of nickel, manganese, town, calcium, iron (π) and cobalt. 8. The surface treatment liquid according to item 3, 4, 5, 6, or 7 of the scope of patent application, further comprising a group selected from the group consisting of a hydroxylamine (hydroxylamine) supply material, nitrous acid, and nitrite All kinds of compounds. J 9 · A surface treatment method, characterized in that the surface of a metal material is treated by using the surface treatment treatment liquid described in the aforementioned application patent scope item 3, 4, 5, 6, 7 or 8. 10. A surface treatment method, comprising: a surface adjustment process and a surface treatment process, the surface adjustment process is to process metal materials in a surface adjustment liquid mainly composed of titanium colloid (titan cuouid); The surface treatment process is to process the metal material by using the surface treatment treatment liquid described in the aforementioned patent application scope Nos. 3, 4, 5, 6, or 8 after the watch adjustment process. 1 1. A surface treatment method, characterized in that: the surface treatment method is provided with a surface surface treatment process, wherein the surface adjustment I 轾 and the surface adjustment liquid of the wall acid salt above the table are: or: two After the seed line is adjusted on the surface, the second material is processed by the surface treatment process material. The treatment solution for treating the gold of the surface of the item is characterized by a product having a metal material, and 5802PF(Nl).ptd 第41頁 2004065055802PF (Nl) .ptd Page 41 200406505 六、申請專利範圍 具備有，金屬材料，以及設計於該金屬材料表面上的 皮膜重量是0· 5~5g/m2的皮膜，且該皮膜是經由前述申請專 利範圍第9項所述之該表面處理方法所形成。 13. —種具有金屬材料的製品，其特徵在於： 具備有一金廣材料’以及設計於該金屬材料表面上的 皮膜重量是0.5〜的皮膜，且該皮膜是經由前述申請專 利範圍第1 0或11頊所述之該表面處理方法所形成。 14. 如申請專利範圍第12或13項所述之具有金屬材料 的製品，其中當该金屬材料是鐵系金屬材料時，形成於該 鐵系:屬材料i面上的該皮膜的皮膜重量係0· 5〜3W。 15. 如申請專利範圍第1 2或1 3項所述之具有金屬材料 的f。，其中合該金屬材料是鋅系金屬材料時，形成於該 鋅ί ϊ屬材料i面上的該皮膜的皮膜重量係卜4. 5 g / #。6. The scope of patent application includes: metal material, and a film with a weight of 0.5 to 5 g / m2 designed on the surface of the metal material, and the film is passed through the surface described in item 9 of the aforementioned patent scope Formed by processing methods. 13. A product with a metal material, characterized in that: it is provided with a Jinguang material 'and a film with a film weight of 0.5 to 5 designed on the surface of the metal material, and the film is passed through the aforementioned patent application No. 10 or It is formed by the surface treatment method as described in (11). 14. The product with a metal material as described in item 12 or 13 of the scope of the patent application, wherein when the metal material is an iron-based metal material, the film weight system of the film formed on the i-based: belongs to material i surface 0 · 5 ~ 3W. 15. f with metallic materials as described in item 12 or 13 of the scope of patent application. 5 g / #。 When the metal material is a zinc-based metal material, the film weight of the film formed on the surface of the zinc metal material i is 4.5 g / #. 5802PF(Nl).ptd 第42頁5802PF (Nl) .ptd Page 42
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