A7 B7 發明所屬的技術領域 本發明係有關對含鎂金屬材料之非鉻系的化成處理液 組成物，該含鎂金屬材料之表面處理方法及其表面處理物 習知技藝 鎂係較鋁質輕且用作與其他金屬之合金時，以至大多 被利用作較強力的構成材，然而此含鎂金屬材料，由於與 含氧化成分之水接觸，具有容易腐蝕的性質。進行淸淨處 理後，於其表面上形成化學被膜之化成處理，再予塗布等 的處理即有必要。 因此而對含鎂金屬材料進行的表面處理，係利用脫脂 處理、水洗、化成處理水洗及乾燥處理予以實行，其後， 再施以塗布等處理係較通常的。又，於上述的化成處理前 亦有在鹼浴內予以處理。 於對此含鎂金屬材料之表面處理，由於構成前述的化 成處理浴液之化學處理劑的組成不同，於該處理表面之耐 蝕性或防銹性，再者塗布附著性等的性能會生成較大的不 同，以至對此化成處理劑乃有各種研究、開發出。 至於向來上述的化成處理劑之主要成分的鉻系者，係 對人體及地球環境有害性者。在最近對非鉻系之化成處理 劑乃有各種硏究，以至實用化。 此非鉻系化成處理劑之習知技術，例如有於含鎂金屬 材料之表面上，使與高溫的氫氧化鈉溶液接觸的方法（曰 (請先閲讀背面之注意事項再氣寫本頁) -裝· 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -4 - 經濟部中央標準局員工消費合作社印製 A' 5 9 Ο 6 5 A7 --—____B7_ 五、發明説明（2 ) 本特願昭61—90776號），以焦磷酸鹽溶液及氫氧 化鹼處理的方法（日本特開平6 一 1 1 6740號），酸 性’ P Η値下’使磷酸、含錳離子及胺化合物之水性液接 觸的方法（日本特開平7— 126858號），使磷酸， 與含15離子或鋁離子及胺化合物之水性液在酸性ρ Η値下 接觸的方法（曰本特開平8 - 1 7 6 8 42號）等被開發 出。 發明欲解決的課頴 於上述的習知例，第一及第二方法，含有氫氧化鎂之 被膜’及弟二方法爲含有碟-鑑化合物及猛_氮化合物之 被膜，又第四方法爲含有磷-鈣化合物及磷一鋁化合物之 被膜，係各自形成於含有鎂之金屬材料的表面上。因此， 若依此等被膜構成，對含有鎂之金屬材料，乃可有效的謀 求耐蝕性，防銹性及塗布附著性。 然而，在由此等習用方法而得的含有鎂之金屬材料表 面的形成被膜，對上述的耐蝕性等之性能仍是不足的。例 如，耐蝕性方面，鹽水噴霧時間係在1 0 0〜2 0 0小時 之短期間內，該性能在可予有效的保持者之該鹽水噴霧時 間以上的時間之長期的情形，係該性能並不足所致。此爲 因與含有鎂之金屬材料有關的製品，對實用性上並不適當 〇 因此，本發明之目的係提供與習用的鉻處理可匹敵或 其以上的性能在長期間經過耐蝕性、防銹性及塗布附著性 本紙張尺度適用中國國家標準（CNS ) Α4规格（210 X 297公釐） 7^~. (請先閲讀背面之注^^項再填寫本頁) -裝· 訂 •'459 0 6 5 A7 B7 五、發明説明（3 ) 仍可保持的同時，在比較低的溫度條件且短時間內可處理 的非鉻系之含鎂之金屬用化成處理液組成物，該含鎂金屬 材料之表面處理方法及其表面處理物。 爲解決課顕而採的手段 的，在本 請 先 閱 讀 經濟部中央標準局員工消費合作社印製 爲達成 含鎂之金屬 亦即， 氧化促進劑 在本發 、M g、Z 合金之外， 又，含 含有其壓鑄 又，鈣 ，硫代硝酸 之配合予以 又 > 錳 、硫酸錳、 種的配合予 又，磷 磷酸、亞磷 上述目 用化成 以含有 之水性 明中， η合金 亦包含 鎂之金 等的製 離子， 鈣、醋 供給。 離子， 磷酸氫 以供給 酸離子 酸、次 處理液組 鈣離子、 液劑而成 含鎂之金 、M g -鎂本身。 屬材料， 品材料。 係在前述 酸鈣、磷 發明，首先係以下述構成作爲 成物。 錳離子及磷酸離子，再者含有 者爲特徵。 屬係除Mg — A 1 — Ζ η合金 A 1 —Ζ η —Μη合金等之鎂 除此金屬材料本身之外，尙包 的水性液由硝酸鈣、亞硝酸鈣 酸二氫鈣等的一種或二種以上 係在前述的水性液，由碳酸錳、硝酸錳 錳、重磷酸錳、硼氟化錳等的一種或二 〇 ，係在前述的水性液，由正磷酸、縮合 亞磷酸等之一種或二種的配合予以供給 又，氧化促進劑，係可使用氯酸鈉、次亞氯酸鈉等氧 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） _ 6 _ 之 注A7 B7 Technical field to which the invention belongs The present invention relates to a non-chromium-based chemical conversion treatment liquid composition for a magnesium-containing metal material, a surface treatment method for the magnesium-containing metal material, and a surface treatment material When it is used as an alloy with other metals, it is often used as a strong constituent material. However, this magnesium-containing metal material has the property of being easily corroded due to contact with water containing an oxidizing component. After the cleaning treatment, a chemical conversion treatment to form a chemical film on the surface, and then a treatment such as coating is necessary. Therefore, the surface treatment of the magnesium-containing metal material is performed by degreasing treatment, water washing, chemical treatment, water washing, and drying treatment, and thereafter, treatments such as coating are more common. It is also treated in an alkaline bath before the aforementioned chemical conversion treatment. In the surface treatment of this magnesium-containing metal material, due to the difference in the composition of the chemical treatment agents constituting the aforementioned chemical conversion treatment bath, the performance of corrosion resistance or rust prevention on the treated surface, and coating adhesion and other properties will be relatively small. It is so different that various researches and developments have been made on this chemical conversion treatment agent. The chromium-based ones that have been the main components of the chemical conversion treatment agents mentioned above are those that are harmful to the human body and the global environment. Recently, various non-chromium-based chemical conversion treatments have been studied and put into practical use. The conventional technology of this non-chromium-based chemical conversion treatment agent is, for example, a method of contacting a high-temperature sodium hydroxide solution on the surface of a magnesium-containing metal material (say (please read the precautions on the back before writing this page) -Assembled and printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). -4-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5 A7 --- ____B7_ V. Description of the invention (2) Bento Sho 61-90776), treatment with pyrophosphate solution and alkali hydroxide (Japanese Unexamined Patent Publication No. 6-1 1 6740), acidic 'P Majesty's method of contacting an aqueous solution of phosphoric acid, manganese ions and amine compounds (Japanese Patent Application Laid-Open No. 7-126858), in which phosphoric acid is mixed with an aqueous solution containing 15 ions or aluminum ions and amine compounds at an acidic pH Η 値 Η 値The method of lower contact (said Japanese Patent Publication No. 8-1 7 6 8 42) has been developed. The lesson to be solved by the invention is based on the above-mentioned conventional examples. The first and second methods include a film containing magnesium hydroxide, and the second method is a film containing a disc compound and a nitrogen compound, and the fourth method is Films containing a phosphorus-calcium compound and a phosphorus-aluminum compound are each formed on the surface of a metal material containing magnesium. Therefore, if such a film is constituted, corrosion resistance, rust prevention, and coating adhesion can be effectively achieved for metallic materials containing magnesium. However, the formation of a film on the surface of a magnesium-containing metal material obtained by such conventional methods is still insufficient for the above-mentioned properties such as corrosion resistance. For example, in terms of corrosion resistance, the salt spray time is within a short period of 100 to 2000 hours, and the performance is a long-term situation in which the effective holder is longer than the salt spray time. Insufficient. This is a product related to a metal material containing magnesium, which is not suitable for practical use. Therefore, the object of the present invention is to provide a performance comparable to or better than the conventional chromium treatment. Corrosion resistance and rust prevention over a long period of time. And coating adhesion This paper size applies Chinese National Standard (CNS) Α4 specification (210 X 297 mm) 7 ^ ~. (Please read the note on the back ^^ before filling out this page)-Binding · Order • '459 0 6 5 A7 B7 V. Description of the invention (3) While being able to be maintained, it can be processed in a relatively low temperature condition and within a short period of time, and is a composition of a chemical treatment liquid for a non-chromium magnesium-containing metal, the magnesium-containing metal Surface treatment method of materials and surface treatment products thereof. In order to solve the problem, please read this article first printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to achieve the magnesium-containing metal, that is, the oxidation accelerator is outside the Benfa, Mg, Z alloy, and Contains the combination of die-casting, calcium, thionitrate, and manganese, manganese sulfate, and the combination of phosphorus, phosphorous, and phosphorous acid. The η alloy also contains magnesium. Gold and other ions, calcium, vinegar supply. Ions and hydrogen phosphate are formed by supplying acid ions, acid, secondary treatment liquid group, calcium ions, and liquid agent. Magnesium-containing gold, Mg-magnesium itself. Material, product materials. The invention is based on the above-mentioned calcium and phosphorus inventions. Manganese ions and phosphate ions are characterized by their inclusion. In addition to the magnesium of Mg — A 1 — Zn η alloy A 1 — Zn η — Mn alloy, in addition to the metal material itself, the aqueous solution of the package is one of calcium nitrate, calcium nitrite, calcium dihydrogen or the like Two or more of the above-mentioned aqueous liquids are composed of one or two of manganese carbonate, manganese nitrate, manganese biphosphate, manganese borofluoride, etc., and are of the aforementioned aqueous liquids, consisting of one of orthophosphoric acid and condensed phosphorous acid Or the two kinds are supplied together. The oxidation accelerator can use oxygen such as sodium chlorite and sodium hypochlorite. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _ 6 _ Note
I 裝 訂 Μ 經濟部中央橾準局貝工消費合作社印製 ^590-65 A7 ______ B7 五、發明説明（4 ) 化劑。 與本發明有關的含鎂之金屬用化成處理液組成物，係 在常溫下水中使上述的各原料劑混合溶解以水性液劑方式 而得。 又，本發明之含鎂之金屬用化成處理液組成物之各成 分離子之含有量，係於對象之含鎂之金屬材料之表面上以 使形成後述的指定之化成被膜之量爲要件，惟對耐鈾性、 防銹性、塗布附著性等的性能，爲於比較短的時間以內在 含鎂之金屬材料表面上而得特別優越的化成被膜，於前述 的水性液劑中，以含有鈣離子1〜2 0重量份、錳離子1 〜4重量份及磷酸離子2 0重量份以上，及氧化促進劑 0 _ 02〜2重量份之比率而成者爲宜。 如此若依各成分離子等以上述的比率含有的組成物時 ，可容易且較經濟的製得於含鎂之金屬材料之表面上使能 安定的形成具有優越的性能之化成處理膜之化成處理浴液 0 如上述般構成的含鎂之金屬用化成處理液組成物，係 可適用於下示之與本發明有關的含鎂之金屬材料之表面處 理方法。 與本發明有關的含鎂之金屬材料之表面處理方法，係 混合含有鈣離子、錳離子及磷酸離子再者含有氧化促進劑 之水性液劑並予調整成Ρ Η 1 _ 〇〜3 . 0之浴液，使與 已施予脫脂處理之鎂金屬材之表面接觸，於前述的含鎂之 金屬材料之表面上形成鈣、錳及磷之混合被膜爲特徵。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） (請先聞讀背面之注意事項#,填窝本頁) -裝- 訂 經濟部中央操準局員工消費合作社印— άiS〇65 Α7 ______ Β7 五、發明説明（S ) 於此一本發明之表面處理法，含有脫脂處理後之水洗 步驟，又與混合含有前述鈣離子等之水性液劑的而成之浴 液之化成處理浴液的接觸之化成處理後的水洗步驟，依情 況再有其後的純水洗步驟。又，其後，本發明之方法並不 必須含有’惟依一般的方法，可依乾燥、塗布等處理步驟 。又，對此種情形之塗布方法，係利用噴塗方式將環氧樹 脂劑系之電著（E D )塗布或環氧樹脂劑予以底塗，再於 其上利用三聚氰胺樹脂劑予以上塗等一般的方法係適合於 本發明之方法。 於前述的化成處理步驟，以含有前述的鈣離子等的水 性液劑，作爲例如以約6重量％溶解於水中的化成處理浴 液，如前述般，於此浴液中，以使含有以鈣離子〇 . 5〜 10g/l ，錳離子05〜2·Og/Ι及磷酸離子 10g/l以上，及氧化促進劑0 . 01〜1 . lg/1 之範圍之比率爲宜。 以此範圍之量使於化學處理浴液中含有各成分離子等 的情形，可在短時間內對含有鎂之金屬表面上實施化成處 理，同時可得耐蝕性、防銹性、塗布附著性等之性能優越 的鈣、錳及磷之混合被膜。 且，於前述的化成處理浴液，對鈣離子濃度不足或完 全不含有的情形，耐蝕性或塗布附著性等降低，又錳離子 或磷酸離子不足或完全不含有的情形，尤其加上塗布附著 性顯著降低，由於與含有氯離子之水接觸而成爲發生白銹 等外觀不良的原因。 I n ^ I ~ (請先聞讀背面之注項再填寫本頁) 本紙浪尺度適用中國國家樣準（CNS ) A4規格（210X297公釐） _ 8 _ 459065 A7 B7 經濟部中央標準局貝工消費合作社印製 五、發明説明（6 ) 又，氧化促進劑之含有，係於化成處理時提高前述各 離子對含鎂之金屬材之表面的反應性，有助於耐蝕性等性 能優越的化成被膜之形成。因此，於前述的化成處理浴液 中，此氧化促進劑之含有量不足或完全不含有的情形，未 能製得上述性能之化成被膜。 又，於前述的化成處理浴液經予調整Ρ Η 1 · 〇〜 3 · 0之情形，將上述的化成被膜有效的且無障礙的形成 於含鎂之金屬材料的表面上即成爲可能。 於此浴液Ρ Η未滿1 . 〇之情形，蝕刻量變成過大， 對象材之尺度精度上生成問題，同時會導致該面之耐蝕性 的降低，又對ρ Η超過3 . 0之情形，卻未能製得具有充 分性能之化成被膜。 又，前述的化成處理浴液，以予以保持在3 0 °C以上 7 5 °C以下的溫度爲宜。此浴液之溫度若未滿3 0°C時， 則對前述的化成被膜之形成變成需要長時間，又對所得的 化成被膜，其性能變成不足夠，又若變成超過7 5 °C之溫 度時，則由於過度反應反而所得的化成被膜會招致性能之 降低。 又，此化成處理浴液之溫度條件，則與被處理材表面 間之接觸時間有相關關係。亦即，對浴液溫度較低的情形 ，以此接觸時間較長者爲宜，又浴液溫度較高的情形，以 此接觸時間較短者爲宜的關係乃予形成者。 具體而言，浴液溫度經予保持在5 0 °C以下的情形， 以有1 0〜2 0分鐘之接觸時間爲宜，又浴溫溫度經予保 {諳先聞讀背面之注意事項再填寫本頁) .裝· 訂_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9 - 經濟部中央標準局員工消費合作社印製 459065 A7 _____B7 五、發明説明（7 ) 持在5 0 °C次的情形，以在5〜1 0分鐘之接觸時間爲宜 。且’在浴液溫度超過5 0 °C之溫度若接觸時間變長時， 則以形成被膜會再溶出爲原因而有導致耐蝕性等的性能之 降低的情形’又在浴液溫度未滿5 0 t之溫度若接觸時間 較短時’則未能製得具有足夠性能之化成被膜。 又’於本發明之表面處理方法，以可包含在脫脂處理 後利用酸性浴液之蝕刻處理步驟作爲前處理。至於此酸性 浴液’可作成磷酸系、硝酸系、氟酸系等者。若依此蝕刻 處理時，對象係如鎂合金鑄模般，於其對象物表面上若存 在有某種的脫模劑之情形，亦依下一步驟之化成處理，於 其表面上可順利的製得耐蝕性等之性能優越的化成皮膜。 此蝕刻處理，係在污物（smut )不發生的領域可予 設定。在較此設定濃度高的情形，蝕刻量變成過量，污物 發生的情形變多，又對較此設定濃度低的情形即成爲蝕刻 不足。 又，於本發明之表面處理方法，包括有在供脫脂處理 用的浴液以在ρ Η 1 3以上進行的方法。若依此方法，則 在該不動作狀態區域藉由對含鎂之金屬材料進行脫脂處理 ，在下一步驟之化成處理可得較安定的化成被膜。尤其， 以對象物即使爲壓鑄製品等件有脫模劑者，在無前述的蝕 刻步驟，耐蝕性等性能優越的處理亦成爲可能。且對此脫 脂浴液，提高Ρ Η至1 3以上時，再增加氫氧化鉀等的配 合量可予達成。 於藉由前述的表面處理方法而得的含鎂之金屬材內， (請先闊讀背面之注意事項再填寫本頁) 裝· 訂 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -10- 經濟部中央標準局員工消費合作社印製 4 5 9 Ο ο 〇 Α7 ____Β7 五、發明説明（8 ) 於其表面上鈣，錳及磷之混合化成皮膜可得層狀，利用此 化成被膜，對含鎂之金屬材料，對具有耐蝕性、防銹性及 塗布附著性等的性能者，成爲未發生起泡等，外觀上有良 好性狀者。 此種性能係對上述的化成皮膜，以鈣爲1至5 0 0 mg/m2，錳爲1至500mg/m2及磷爲1至 1 0 0 0 m g /m 2之範圍含有的情形，係較宜製得的。 實施例 實施例1 製作由J I SH5 3 0 3MC2之合金而成的鑄件.（ 10 cmx5 cmX2mm)，以此鑄件爲試片。 利用脫脂處理—水洗—化成處理—水洗—純水洗^瀝 乾之過程對此試片進行表面處理。且，處理過程之詳情如 下如述。 (1)脫脂處理係在pHll 5〜12，溫度40 〜4 5 °C，將試片浸漬於由氫氧化鈉1 〇〜1 5 g / 1 ’ 界面活性劑2〜3 g/ 1而成的浸漬液中3分鐘處理。 (2 )化成處理係由下表1所示的試驗號碼1〜2 3 之組成而成的各化成處理浴液設爲6 0〜7 0°C之溫度’ 在此浴液中浸漬2分鐘各自進行。 (請先閱讀背面之注意事項再填寫本頁) 裝· -訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X2.97公釐） -11- 459065 A7 B7 五、發明説明（9 ) 〔表 1 — ( 1 )〕I Binding Μ Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 590-65 A7 ______ B7 5. Description of the invention (4) Chemical agents. The magnesium-containing metal chemical conversion treatment liquid composition according to the present invention is obtained by mixing and dissolving each of the above-mentioned raw material agents in water at normal temperature and using an aqueous solution. In addition, the content of each component ion of the magnesium-containing metal chemical conversion treatment liquid composition of the present invention is based on the surface of the target magnesium-containing metal material so that a specified amount of a chemical conversion film to be described later is required, but The properties of uranium resistance, rust resistance, coating adhesion, etc., are particularly excellent for forming a coating on the surface of a magnesium-containing metal material within a relatively short period of time. A ratio of 1 to 20 parts by weight of ions, 1 to 4 parts by weight of manganese ions, 20 parts by weight of phosphate ions or more, and a ratio of 0 to 02 to 2 parts by weight of the oxidation accelerator is preferred. In this way, if the composition is contained in the above ratio according to the ion of each component, the chemical conversion treatment of the chemical conversion treatment film having superior performance can be easily and economically produced on the surface of the magnesium-containing metal material. Bath Solution 0 The composition of a magnesium-containing metal chemical conversion treatment composition configured as described above is applicable to a surface treatment method of a magnesium-containing metal material related to the present invention shown below. The surface treatment method of the magnesium-containing metal material related to the present invention is to mix an aqueous liquid agent containing calcium ion, manganese ion and phosphate ion, and an oxidation accelerator, and adjust it to P Η 1 _ 〇 ~ 3. 0 of The bath liquid is in contact with the surface of the magnesium metal material that has been subjected to degreasing treatment, and forms a mixed film of calcium, manganese, and phosphorus on the surface of the aforementioned magnesium-containing metal material. This paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back #, fill in this page)-Binding-Order printed by the Staff Consumption Cooperative of the Central Office of the Ministry of Economic Affairs — άiS 〇65 Α7 ______ Β7 V. Description of the invention (S) The surface treatment method of the present invention includes a washing step after degreasing treatment, and a bath solution mixed with an aqueous liquid agent containing the aforementioned calcium ions and the like. The contacting of the treatment bath liquid is converted into a water washing step after the treatment, and a subsequent pure water washing step is provided as the case may be. In addition, the method of the present invention does not necessarily include the following method. However, the method may include a drying step, a coating step, and the like according to a general method. In addition, the coating method in this case is a general method such as spray-coating an epoxy resin (ED) coating or an epoxy resin undercoating, and then applying a melamine resin coating thereon. The method is suitable for the present invention. In the aforementioned chemical conversion treatment step, an aqueous solution containing the aforementioned calcium ions and the like is used as, for example, a chemical conversion treatment bath that is dissolved in water at about 6% by weight, as described above, in this bath, so that The ratio of the range of ions 0.5 to 10 g / l, manganese ions 05 to 2 · Og / 1, and phosphate ions 10 g / l or more, and the oxidation accelerator 0.01 to 1.lg / 1 is suitable. When the chemical treatment bath contains ions of various components in this range, chemical treatment can be performed on the surface of the metal containing magnesium in a short time, and corrosion resistance, rust prevention, and coating adhesion can be obtained. It is a mixed film of calcium, manganese and phosphorus with excellent performance. In addition, in the case of the aforementioned chemical conversion treatment bath, the calcium ion concentration is insufficient or not contained at all, the corrosion resistance or coating adhesion is reduced, and the manganese ion or phosphate ion is insufficient or not contained at all, especially the coating adhesion is added Significantly lowers its properties, and causes contact with water containing chloride ions to cause appearance defects such as white rust. I n ^ I ~ (Please read the notes on the back before filling out this page) This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 8 _ 459065 A7 B7 Printed by a consumer cooperative V. Description of the invention (6) In addition, the content of the oxidation accelerator is used to improve the reactivity of the aforementioned ions to the surface of the magnesium-containing metal material during the chemical conversion treatment, which contributes to the chemical conversion with excellent properties such as corrosion resistance Formation of coatings. Therefore, in the aforementioned chemical conversion treatment bath, when the content of the oxidation accelerator is insufficient or not contained at all, a chemical conversion film having the above-mentioned properties cannot be obtained. Further, in the case where the aforementioned chemical conversion treatment bath liquid is adjusted to ρ 1 · 〇 ~ 3 · 0, it is possible to form the aforementioned chemical conversion film on the surface of the metal material containing magnesium efficiently and without obstacles. In the case where the bath solution PΗ is less than 1.0, the etching amount becomes too large, which causes a problem in the accuracy of the target material. At the same time, the corrosion resistance of the surface will be reduced. In the case where ρΗ exceeds 3.0, However, a chemical conversion film having sufficient performance has not been produced. The chemical conversion treatment bath solution is preferably maintained at a temperature of 30 ° C to 75 ° C. If the temperature of the bath solution is less than 30 ° C, it takes a long time to form the aforementioned chemical conversion film, and the performance of the obtained chemical conversion film becomes insufficient, and if the temperature exceeds 75 ° C In this case, the chemical conversion coating obtained due to excessive reaction may cause a decrease in performance. In addition, the temperature condition of the chemical conversion treatment bath liquid is related to the contact time between the surfaces of the material to be treated. That is, for a case where the temperature of the bath is low, it is appropriate to use a longer contact time, and for a case where the temperature of the bath is high, a relationship with a shorter contact time is suitable. Specifically, when the temperature of the bath liquid is maintained below 50 ° C, it is advisable to have a contact time of 10 to 20 minutes, and the temperature of the bath liquid is guaranteed {谙 first read the precautions on the back then (Fill in this page). Binding and binding_ This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -9-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 459065 A7 _____B7 V. Description of the invention (7) In the case of 50 ° C times, a contact time of 5 to 10 minutes is appropriate. And 'if the temperature of the bath solution exceeds 50 ° C, if the contact time becomes longer, the film may be dissolved again as a cause, and the performance such as corrosion resistance may be reduced.' And the bath temperature is less than 5 If the temperature of 0 t is short, the chemical conversion film with sufficient performance cannot be produced. Further, in the surface treatment method of the present invention, an etching treatment step using an acidic bath solution after degreasing treatment may be used as a pretreatment. As for the acidic bath solution, phosphoric acid-based, nitric acid-based, fluoric acid-based and the like can be used. If the etching process is performed in this way, the object is like a magnesium alloy mold. If there is a certain release agent on the surface of the object, it is also converted to the next step, and it can be smoothly produced on the surface. It is a chemical conversion film with excellent corrosion resistance and other properties. This etching process can be set in an area where smut does not occur. In the case where the concentration is higher than this, the amount of etching becomes excessive, and the number of cases where dirt occurs, and in the case where the concentration is lower than this, the etching is insufficient. The surface treatment method of the present invention includes a method in which a bath for degreasing treatment is performed at ρ Η 13 or more. According to this method, by performing a degreasing treatment on the magnesium-containing metal material in the non-operating state region, a stable chemical conversion film can be obtained in the chemical conversion treatment in the next step. In particular, even if the target is a die-cast product and a mold release agent, it is possible to perform processing with excellent properties such as corrosion resistance without the aforementioned etching step. In addition, when the degreasing bath solution is raised to a pH of 13 or more, the amount of potassium hydroxide and the like can be increased. In the magnesium-containing metal material obtained by the aforementioned surface treatment method, (please read the precautions on the back first and then fill out this page). The size of the binding and binding paper is applicable to the Chinese National Standard (CNS) Α4 specification (210X297). (%) -10- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 5 9 Ο ο 〇Α7 ____ Β7 V. Description of the invention (8) On the surface, a mixture of calcium, manganese, and phosphorus is formed into a film, which can be used as a layer. Formed into a film, for those materials containing magnesium, those with corrosion resistance, rust resistance, and coating adhesion, etc., have no blistering and have good appearance. This kind of performance is for the case of the chemical film mentioned above, which contains calcium in the range of 1 to 500 mg / m2, manganese in the range of 1 to 500 mg / m2, and phosphorus in the range of 1 to 1000 mg / m2. Should be made. EXAMPLES Example 1 A casting made of an alloy of J I SH5 3 0 3MC2 was made. (10 cmx5 cmX2mm), and the casting was used as a test piece. Surface treatment was performed on this test piece using a process of degreasing treatment—water washing—chemical treatment—water washing—pure water washing ^ draining. And, the details of the process are as follows. (1) The degreasing treatment is performed by immersing the test piece with sodium hydroxide 1 0 ~ 1 5 g / 1 'surfactant 2 ~ 3 g / 1 at pH 11 5 ~ 12, temperature 40 ~ 4 5 ° C. Treat in the dipping solution for 3 minutes. (2) The chemical conversion treatment system is composed of test numbers 1 to 2 3 shown in Table 1 below. Each chemical conversion treatment liquid is set to a temperature of 60 to 70 ° C. Each is immersed in this liquid for 2 minutes. get on. (Please read the precautions on the back before filling in this page.) Binding · -The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X2.97 mm) -11- 459065 A7 B7 V. Description of the invention (9) [ Table 1 — (1)]
- IV,—— 批衣 ~I H. 訂 . - J (請先聞讀背面之注意事項再填寫本頁)-IV, —— Approval ~ I H. Order.-J (Please read the notes on the back before filling this page)
經濟部中央標準局員工消費合作社印I 本紙張尺度適用中國國家標率（CNS ) A4規格（210X2.9/7公釐） _ -J2 - 459065 A7 B7 五、發明説明（ι〇 ) 〔表 1 - ( 2 )〕 \\^試驗 '^碼 成分 \\ 13 14 15 ϊ 6 17 18 19 20 2 1 22 23 Ca2* 2.6 2.6 2.6 2.6 2.6 2,6 2.6 2.6 2.6 2.6 2,6 Zn卜 0.6 N广 1.1 1.1 Μη2' 0.3 0.6 0.9 1.2 0.6 0.6 Ρ0.3 13.8 13.8 13.8 13.8 6.9 20.7 27.6 13.8 13.S 13.8 13.8 NaCl〇3 0.42 0.42 0.42 0.42 0.42 0.42 0.42 _ 0.84 0.42 0.42 (表中，數値單位爲g/< ) (請先閱讀背面之注意事項再填寫本頁) -訂. Ί· 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13 - 459065 A7 ____B7_ 五、發明説明（彳1 ) (3 )水洗及利用去離子水之純水洗的步驟，任一者 均在0 . 5分鐘常溫下進行。 (4 )乾燥步驟，係在瀝乾狀態1 〇 〇〜1 2 〇 t：之 溫度條件下進行2 0分鐘。 其次，對如此已施行表面處理之各處理試片，各自進 行陽離子電著塗布環氧樹脂型式。 於此等的表面上依習用方法設置方格切痕（ crosscut )，以此爲試片，各自依〗I S Z 2 3 7 1規定的鹽水噴 霧試驗（s S T )經過4 8 0小時進行。又對相同的試片 ，各自經2 4 0小時進行鹽水浸漬試驗（3 %食鹽水1 5 〜2 5 °C )，對沿切痕的塗膜之膨潤寬度。與對此外的部 分上塗膜之附著性及自銹或發生起泡之有無的外觀予以觀 察，其結果示於下表2。 (請先閲讀背面之注意事項再填寫本頁) .裝. 訂- 經濟部中央標準局男工消費合作社印製 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X2,97公釐） -14- 經濟部中央標準局員工消費合作社印製 4 59 0 65 a7 B7 五、發明説明（12 ) 〔表2〕 目 試 號碼\ S S Τ ( 4 8 0 小時） 鹽水浸漬（2 4 0時間） (備考） 膨潤寬度 剝離寬度 附著性 外 觀 膨潤寬度 剝離寬度 η 1 η 2 η 3 η ί π 5 η 6 η τ η Β 1 2,5 4.5 全面 4.0 X X 無 1.5 1 . 5 1.5 2 2.5 3 . 0 7.0 9.0 X Δ 3.0 2.0 4,0 1,5 3 (1 4 4小時）腐蝕嚴重 〇 _ 1.5 1,0 0. 5 1 .5 4 _ 5,0 7.0 丨9.0 〇 X 1 .0 1.5 1.3 1 . 0 5 (1 4 4小時）腐蝕嚴重 - - 1.5 3.5 全面 全面 發生大量起 泡現象 6 對CED外觀不良不作試驗 7 ft 8 η 9 3.5 3 . 5 2.0 3.0 〇 X 無_ 4,0 1 . 0 4.0 10 2,5 2.5 3.5 1 . 5 〇 X 4βε 氺 1 . 5 * *發生大量 白銹現象 11 ( 24 0小時）腐蝕嚴重 _ _ 0.5 0.5> 2.0 無 浸鈾嚴重 12 (1 4 4小時）腐蝕嚴重 _ X (72小時）全面自銹 13 3.0 5 _ 0 4.0 7.5 〇 X. 0‘ 5> 1.0 1.5 1 . 5 14 2,0 1.5 - 〇 〇 1.0 — 2.0 - 15 3.0 2.5 3.0 2.5 〇 Δ 1 .0 0.5 1.0 0.5 浸蝕嚴重. 16 2.0 3,0 2,0 1.5 〇 Δ 0.5 1.0 2.0 1 . 5 1 7 全面 5,0 全面 5 . 5 〇 X 2.5 1.5 2.0 2 . 0 1 8 2.0 1 . 5 2,0 1 . 0 〇 〇 0.5 0.5 無 1 . 0 19 無 1-0 無 1.5 〇 〇 0.5 1 .0 1.0 1.0 浸蝕嚴重 20 3-0 8 . 5 8.0 8.5 X X 1.0 0.5 1.0 0.5 浸蝕嚴重 2 1 全面 5 . 0 全面 全 面 X X 2.0 0.5 2 . 5 3.0 發生大量起 泡現象 22 (1 4 4小時）腐蝕嚴重 _ _ 0.5 1 .0 2.0 1 . 5 23 對CED外觀不良不作試驗 (表中數値單位係m m) (請先鬩讀背面之注意事項再填寫本頁) 裝. 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15- 經濟部中央標準局員工消費合作社印製 459065 A7 - B7 五、發明説明（13 ) 且，附著性係依J I s K 5 4 0 0之規定，於試料表 面上施行100個棋盤方格眼（10x10mm)，計數 黏貼膠帶並予拉起後的方格殘留數，其數目爲1 0 0時〇 ，此外之時爲〇。又外觀方面，係在試料表面上被發現有 白銹、起泡現象之任一者發生時設爲X，任一者均少量發 生時設爲△，二者之一者僅少量發生時設爲〇，任一者均 未被發現時設爲◎。又，未能進行前述的電著裝布或塗布 後的外觀不良之情形，即設爲c E D外觀不良。 由表2所示的結果，利用試驗號碼5〜8之C a -Zn系，試驗號碼1〇〜12之Ca、Ni系尤其Ni2H_ 濃度較高時，試驗號碼2 2之N i _Mn系及試驗號碼 2 3之Ζ η — N i — Μ η系之化成處理浴液之情形，任何 一者均可知在耐蝕性方面有問題。針對此點，於利用試料 號碼1 3〜1 6之C a — Μ η系的成分而成的浴液之情形 ，可得知任一者均具有優越的耐蝕性及塗布附著性，又對 外觀亦可得知在試料號碼1 4之Μ η 2 +濃度附近可得良好 者。由而，對含鎂之金屬材料採用C a - Μη — Ρ系之浴 液的化成處理，可確認出在提高其耐鈾性等的性能係有效 的。又，由試驗號碼6〜8及2 3之結果可知Ζ η 2 +之存 在係用作塗布基材處理之被膜係不適合的。 實施例1 對由J I S — H5303-MC2之鎂合金材料而成 的壓鑄製品’進行下述的表面處理，且，在進行此種壓鑄 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -16- (請先閱讀背面之注^^項再填寫本頁) :裝· 訂 A7 B7 五、發明説明（14 ) 之際，可採用非矽氧系之脫模劑。 對此種壓鑄製品’雖然可利用與前述試驗例1相同的 處理過程，但是脫脂處理後以追加由浸漬於含有下表3所 示的触刻劑之触刻處理浴液中的独刻處理步驟之處理過程 作爲前處理。且，供化成處理用之化成處理浴液’係製備 硝酸鈣四水合鹽15.2g/l ’碳酸鹽2·lg/1、 75%磷酸19♦2g/l及氯酸鈉0.4g/l之水溶 出，再將此浴液在7〇°C調整PH1 . 65〜1 · 70。 又，化成處理時間設爲3分鐘或5分鐘。又，此處理後’ 對製品噴塗環氧樹脂劑作爲底塗’再施塗以利用三聚氰胺 樹脂劑之塗布作爲上塗’惟其他點則與實施例之情形相同 (請先閱讀背面之注意事項再填寫本頁) ’裝' 訂 經濟部中央標準局員工消費合作社印紫 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） _ f 7 - 459065 A7 __B7 五、發明説明（15 ) 〔表3〕 經濟部中央標準局員工消費合作社印製 \翻 實例\ 號碼\ 蝕刻 處理劑 化成處 理時間 (分） S S Τ時間（小時） 120 200 312 312 312 膨潤寬度（mm) 剝離寬 度（mm) 外觀 1 Μ yi 3 無 2.5 3.0 7.0 X 2 5 1.0 1.0 1.0 0.5 〇 3 硝酸 3 0.5> 0.5 1.0 1.0 〇 4 (0.6%) 5 0.5 0.5 1.0 1.0 ◎ 5 磷酸 3 0.5 1.0 1.0 1.0 〇 6 (0.5%) 5 0.5 0.5 0.5 1.0 〇 7 氫氟酸 3 1.0 1.0 2.0 2.0 〇 8 (0.2%) 5 1.0 1.5 2.5 2.5 Δ +硫酸 (0.7%) ---------------1T------λ „ r .r (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） _ 1 g - 經濟部中央橾準局員工消費合作社印製 Α7 ___ Β7 五、發明説明（16 ) 在上述的條件下’以已施行含有表面塗布之表面處理 者作爲各別的試料，對各試料進行鹽水噴霧試驗之結果示 於表3。且，此試之評估方法係與試驗例1相同，如表3 之結果可得知，對壓鑄製品之時，對前處理不經蝕刻處理 步驟之情形，如實施例1及2般，S S T耐蝕性能係受化 成處理時間所左右，尤其如實施例1之結果般，若其時間 較短時，則發現有耐蝕性等降低之情況，因此，此情形貝IJ 有處理狀態變成不安定之顧慮。針對此點，由實施例3〜 8之結果，可知包含有蝕刻處理時，任一者均S S T耐齡 性能優越且時間上亦可安定的處理。 實施例2 由實施例1之結果，就對鎂合金壓鑄製品之表面處理 而言，於施行以蝕刻處理爲前處理之情形，利用C a -Μ η - P混合被膜之情形，即使利用比較短時間之處理， 亦可得耐蝕性等良好的塗膜性能者，但在追加以蝕刻處理 則反而在技術上，經濟上並不利。 因此，在此試驗例，參閱表3之實施例2之結果，在 不包含蝕刻處理步驟，利用與實施例1相同的化成處理溶 液之化成處理步驟，以對鎂合金壓鑄製品之表面處理進行 化成處理時間5分鐘以上，此情形時，處理時間及化成處 理浴液之溫度對處理後的塗膜性能之影響，以實施例9〜 1 8之結果示於下表4 ^且，對其他處理條件係與試驗例 1者相同。 ---------裝-- - - (請先閲讀背面之注意事項异填寫本頁) 、訂 本尺度逋用中國國家標準（CNS ) Λ4规格（210X 297公釐） __19 - A7 459065 B7 五、發明説明（17 ) 〔表4〕 實施例 號碼 化成處理 SST(時間） 處理溫 度（°C ) 處理時 間（分） 100 200 300 300 膨潤寬度（mm) 剝離寬 度（mm) 9 30 5 0.5> 1.0 1.0 1.0 10 20 0.5> 0.5 1.0 1.0 11 40 5 0.5 1.5 3.0 2.0 12 15 0.5> 0.5 0.5 0.5 13 50 5 0.5 1.0 2.5 2.0 14 15 0.5 1.0 1.5 1.0 15 60 5 0.5 1.5 1.5 1.5 16 15 0.5 1.5 2.0 3.0 17 70 10 0.5 0.5 0.5 0.5 18 15 0.5 2.0 3.0 1.5 (讀先間讀背面之注意事項再填寫本頁) 裝· 訂· 經濟部中央標準局員工消費合作社印掣 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 2.97公釐） -20 - 經濟部中央標準局員工消費合作社印製 4 59 0 So A7 ___ B7_ 五、發明説明（Μ ) 若依表4之結果，可得知化成處理之浴液溫度在3 Ο 〜7 0 °C之範圍內任一者均可得S s Τ耐蝕性能優越的塗 膜。且，實施例1及實施例13，與試驗號碼16及18 ，各自對S S T性能方面被認爲較其他試驗有若干降低， 然而前者方面，可視作反應不足，又後者方面係過度反應 而引起者。亦即，在5 0°C以下之處理溫度若有5分鐘以 上的處理時間，又超過5 0°C之處理溫度若有1 5分鐘以 下的處理時間時，可被視作對處理性能可予較提高所致。 實施例3 其次，於對鎂合金壓鑄製品之表面處理，就塗膜之耐 鈾性等的性能而言，在較嚴苛的條件下之耐久性應予提高 ，利用下述的處理過程進行表面處理。 亦即，表面處理之過程，係與前述試驗例1相同，惟 對構成化成處理浴液之化成處理劑，各組成成分而言 > 係 採下表5之實施例1 9〜2 6之配合量。且實施例2 6係 對化成處理浴液，在表面處理之過程有由鎂合金壓鑄製品 生成的鎂離子含有1.Og/Ι之濃度的情形。 本紙張尺度適用中國國家襟率（CNS ) Α4规格（2〗0X297公釐} - 21 - ---------Μ裝------訂------> •ί - (請先閲讀背面之注意事項再填寫本頁) 4Ε Α7 Β7 五、發明説明（/?) 〔表5〕 經濟部中央標準局貝工消費^^i.fl 化成處理劑:^ 組成¥實施例 / 號碼 實施例 —1 比較例 19 20 21 22 23 24 25 26 1 2 3 4 5 硝酸鈣(Ca、 15.2 21.2 2.2 34.7 15.2 15.2 0.6 34.7 15.2 - 15.2 21.2 - (2*6) (16) (0.4) (5-9) (2.6) (2.6) (0.1) (5.7) (2.6) (2.6) (3.6) 碳酸錳(ΜιΛ 2,1 2.9 2.1 2.1 0.5 9.1 0Λ 2.1 2.1 11 一 2.1 - (1.0) (1.3) (1.0) ⑽ (0.2) (4.3) (0.05) (1.0) (1.0) (1-0) (1.0) (75%)Κ 酸 <Ρ〇Λ) 19.2 26.7 19.2 38.4 19.2 38.4 0,7 48.8 19.2 28.3 19.2 21.0 一 (14.0) (19.4) (14.0) ¢23.0} (14.0) (2S.0) (0.5) (35.6) (H.0) (20.6) (14.0) (15.3) 氫酸鈉 0.4 0,4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Mg1' 1.0 1.0 水 殘 殘 殘 殘 殘 殘 殘 殘 殘 殘 殘 殘 (表中，數値單位爲g / 1 ) 本紙張尺度適用中國國家標準（CNS > A4说格（210 X 297公釐）一ϋ 一 (請先閲讀背面之注意事項再填寫本頁) 訂 S. A7 B7 五、發明説明（20 ) 又，於此等的實施例，如下表6所示，將處理過程的 脫脂處理之洛液pH各自製備成1 3〜1 4。且，其他的 處理條件，係塗布方法包含陽離子電著塗布，與試驗例1 相同。對利用此種處理過程進行表面處理，施以塗布的處 理物，進行經1 0 0 0小時之鹽水噴霧試驗的結果示於下 表6 。 裝 訂 I 妹 -- (請先聞讀背面之注意事項#.填寫本頁) 經濟部中央標準局員工消費合作社印製Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economics I The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X2.9 / 7 mm) _ -J2-459065 A7 B7 V. Description of the invention (ι〇) [Table 1 -(2)] \\ ^ Test '^ Code composition \\ 13 14 15 ϊ 6 17 18 19 20 2 1 22 23 Ca2 * 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 Zn BU 0.6 N 1.1 1.1 Μη2 '0.3 0.6 0.9 1.2 0.6 0.6 P0.3 13.8 13.8 13.8 13.8 6.9 20.7 27.6 13.8 13.S 13.8 13.8 NaCl〇3 0.42 0.42 0.42 0.42 0.42 0.42 0.42 0.42 _ 0.84 0.42 0.42 (In the table, the unit of number is g / <) (Please read the precautions on the back before filling out this page)-Order. 印 · Printed on the paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -13 -459065 A7 ____B7_ V. Description of the Invention (彳 1) (3) The steps of water washing and pure water washing with deionized water are performed at 0.5 minutes at normal temperature. (4) The drying step is performed in a drained state at a temperature of 100 to 12 t for 20 minutes. Next, each of the test pieces which have been subjected to the surface treatment in this way is subjected to a cationic electrodeposition epoxy resin type. On these surfaces, crosscuts are set according to customary methods, and as a test piece, the salt spray test (s S T) according to I S Z 2 3 71 is performed over 480 hours. The same test piece was subjected to a salt water immersion test (3% saline 1 5 to 25 ° C) over 240 hours each to swell the coating film along the cut. The adhesion of the coating film and the appearance of self-rusting or blistering on the other parts were observed. The results are shown in Table 2 below. (Please read the precautions on the back before filling this page). Packing. Order-Printed on paper scales printed by the Men ’s Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, applicable to China National Standard (CNS) A4 (210X2, 97mm) -14 -Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 59 0 65 a7 B7 V. Description of the invention (12) [Table 2] Test number \ SS Τ (480 hours) Salt water immersion (240 hours) (Remarks ) Swelling width Peeling width Adhesive appearance Swelling width Peeling width η 1 η 2 η 3 η ί π 5 η 6 η τ η Β 1 2,5 4.5 Overall 4.0 XX No 1.5 1. 5 1.5 2 2.5 3. 0 7.0 9.0 X Δ 3.0 2.0 4,0 1,5 3 (1 4 4 hours) severe corrosion 〇_ 1.5 1,0 0. 5 1 .5 4 _ 5,0 7.0 丨 9.0 〇X 1 .0 1.5 1.3 1. 0 5 ( 1 4 4 hours) Corrosion is severe--1.5 3.5 A large number of blistering occurred throughout the whole 6 No test on the appearance of CED 7 ft 8 η 9 3.5 3.5. 5 2.0 3.0 〇X None _ 4, 0 1. 0 4.0 10 2, 5 2.5 3.5 1. 5 〇X 4βε 氺 1.5 * * A large amount of white rust occurred 11 (24 0 hours) severe corrosion _ _ 0.5 0.5 > 2.0 no immersion Severe 12 (1 4 4 hours) Corrosion severe _ X (72 hours) Fully self-rusting 13 3.0 5 _ 0 4.0 7.5 〇X. 0 '5 > 1.0 1.5 1.. 5 14 2,0 1.5-〇〇1.0 — 2.0- 15 3.0 2.5 3.0 2.5 〇Δ 1.0 0.5 1.0 0.5 Etching is serious. 16 2.0 3,0 2,0 1.5 〇Δ 0.5 1.0 2.0 1. 5 1 7 Overall 5,0 Overall 5.5 5.0 2.0 2.5 2.0 2. 0 1 8 2.0 1. .5 2,0 1. 0 〇〇0.5 0.5 No 1. 0 19 No 1-0 No 1.5 〇0.5 0.5 1.0 1.0 1.0 Serious erosion 20 3-0 8. 5 8.0 8.5 XX 1.0 0.5 1.0 0.5 Severe erosion 2 1 Full 5.0 0 Full XX 2.0 0.5 2. 5 3.0 A large number of blistering occurred 22 (1 4 4 hours) Serious corrosion _ _ 0.5 1 .0 2.0 1. 5 23 No test for poor appearance of CED (The unit of number in the table is mm) (Please read the precautions on the back before filling in this page.) Binding. The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) -15- Central Standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 459065 A7-B7 V. Description of the Invention (13) In addition, the adhesion is implemented on the surface of the sample according to JI s K 5 4 0 0 Eye grid plate (10x10mm), adhesive tape and to count the number of squares remaining after pulling, the number thereof is 1. 0 0:00, in addition to the time square. In terms of appearance, it is set to X when any one of white rust and blistering is found on the surface of the sample, △ when any one occurs in small amounts, and △ when either one occurs only in small amounts. ○, when neither was found, it was set to ◎. In addition, if the above-mentioned appearance defect of the electrotextile cloth or coating is not performed, it is assumed that the c E D appearance is defective. From the results shown in Table 2, using the Ca-Zn series of test numbers 5-8, the Ca and Ni series of test numbers 10-12, and especially when the concentration of Ni2H_ is high, test numbers 22 and Ni-Mn series and tests In the case of the Z η — Ni — Μ η-based chemical conversion treatment bath of No. 2 3, any one can know that there is a problem in the corrosion resistance. In view of this point, in the case of a bath liquid using the C a-M η-based components of sample numbers 1 3 to 16, it can be known that any one has excellent corrosion resistance and coating adhesion, and also has an appearance It can also be found that those with good numbers can be obtained near the M η 2 + concentration of sample number 14. Therefore, it has been confirmed that the Ca-Mn-P-based bath chemical conversion treatment is applied to a magnesium-containing metal material to improve its properties such as uranium resistance. Further, from the results of Test Nos. 6 to 8 and 23, it can be seen that the existence of Z η 2 + is not suitable as a coating system for coating substrate treatment. Example 1 The following surface treatment was performed on a die-cast product 'made of a magnesium alloy material of JIS-H5303-MC2, and the paper size of this die-cast was applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) ) -16- (Please read the note ^^ on the back before filling this page): Binding and ordering A7 B7 V. Invention description (14), non-silicone type release agent can be used. Although such a die-cast product 'can use the same processing procedure as in Test Example 1 mentioned above, after the degreasing treatment, a single-etching treatment step immersed in a contact-treatment bath containing the etching agent shown in Table 3 below is added. This process is used as pre-processing. In addition, the chemical conversion treatment bath for chemical conversion treatment was prepared by dissolving calcium nitrate tetrahydrate salt 15.2 g / l 'carbonate 2 · lg / 1, 75% phosphoric acid 19 ♦ 2 g / l, and sodium chlorate 0.4 g / l in water. Out, and then adjust the bath at 70 ° C to pH 1.65 ~ 1.70. The chemical conversion treatment time was 3 minutes or 5 minutes. In addition, after this treatment, the product is sprayed with an epoxy resin agent as a primer, and then applied with a melamine resin agent as an overcoat, but the other points are the same as those in the example (please read the precautions on the back before filling (This page) The binding of the printed purple paper size of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) _ f 7-459065 A7 __B7 V. Description of the invention (15) [Table 3] Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs \ Conversion example \ Number \ Etching agent chemical conversion processing time (minutes) SS T time (hours) 120 200 312 312 312 Swelling width (mm) Peeling width (mm) Appearance 1 Μ yi 3 No 2.5 3.0 7.0 X 2 5 1.0 1.0 1.0 0.5 〇3 Nitric acid 3 0.5 > 0.5 1.0 1.0 〇4 (0.6%) 5 0.5 0.5 1.0 1.0 ◎ 5 Phosphoric acid 3 0.5 1.0 1.0 1.0 〇6 (0.5% ) 5 0.5 0.5 0.5 1.0 〇7 Hydrofluoric acid 3 1.0 1.0 2.0 2.0 〇8 (0.2%) 5 1.0 1.5 2.5 2.5 Δ + sulfuric acid (0.7%) --------------- 1T ------ λ „r .r (Please read the notes on the back before filling this page ) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) _ 1 g-printed by the Consumers' Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs A7 ___ B7 V. Description of the invention (16) Under the above conditions 'The results of the salt spray test performed on each sample with a surface treatment containing a surface coating as a separate sample are shown in Table 3. The evaluation method of this test is the same as that of Test Example 1, and the results are shown in Table 3. It can be known that, in the case of die-casting products, the pre-treatment without the etching treatment step, as in Examples 1 and 2, the SST corrosion resistance is affected by the chemical treatment time, especially as the result of Example 1, if When the time is short, corrosion resistance may be reduced. Therefore, in this case, there is a concern that the processing state may become unstable. In view of this, from the results of Examples 3 to 8, it is known that the etching process is included. Either of them has superior SST ageing resistance and can be treated stably in time. Example 2 From the result of Example 1, as for the surface treatment of magnesium alloy die-casting products, the etching treatment is performed as In the case of treatment, when using a Ca-M η-P mixed film, even if the treatment is relatively short, good coating film properties such as corrosion resistance can be obtained, but the addition of etching treatment is technically Economically bad. Therefore, in this test example, referring to the results of Example 2 in Table 3, without including the etching treatment step, the same chemical conversion treatment step as in Example 1 was used to chemically modify the surface treatment of the magnesium alloy die-casting product. The processing time is more than 5 minutes. In this case, the effect of the processing time and the temperature of the chemical conversion treatment bath liquid on the performance of the coating film after processing. The results of Examples 9 to 18 are shown in Table 4 below. It is the same as that in Test Example 1. --------- Installation---(Please read the precautions on the reverse side and fill in this page first). The revised standard uses the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) __19-A7 459065 B7 V. Description of the invention (17) [Table 4] Example number conversion processing SST (time) Processing temperature (° C) Processing time (minutes) 100 200 300 300 Swelling width (mm) Peeling width (mm) 9 30 5 0.5 > 1.0 1.0 1.0 10 20 0.5 > 0.5 1.0 1.0 11 40 5 0.5 1.5 3.0 2.0 12 15 0.5 > 0.5 0.5 0.5 13 50 5 0.5 1.0 2.5 2.0 14 15 0.5 1.0 1.5 1.0 15 60 5 0.5 1.5 1.5 1.5 16 15 0.5 1.5 2.0 3.0 17 70 10 0.5 0.5 0.5 0.5 18 15 0.5 2.0 3.0 1.5 (Read the precautions on the back and then fill out this page) Binding, binding, and printing by employees of the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, Paper size applicable China National Standard (CNS) A4 specification (210 X 2.97 mm) -20-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 59 0 So A7 ___ B7_ V. Description of the invention (M) It is known that the temperature of the bath liquid for the chemical conversion treatment is in the range of 3 0 to 70 ° C. Both coatings with excellent corrosion resistance can be obtained. In addition, Example 1 and Example 13 and Test Nos. 16 and 18 are considered to have some reductions in SST performance compared to other tests. However, the former aspect can be considered as insufficient response, and the latter aspect is caused by overreaction. . That is, if the processing temperature below 50 ° C has a processing time of more than 5 minutes, and if the processing temperature exceeds 50 ° C has a processing time of 15 minutes or less, it can be regarded as the processing performance. Caused by the increase. Example 3 Secondly, in the surface treatment of magnesium alloy die-casting products, in terms of the uranium resistance and other properties of the coating film, the durability under severe conditions should be improved, and the surface was processed by the following treatment process deal with. That is, the process of surface treatment is the same as that of Test Example 1 above, but for the chemical conversion treatment agent constituting the chemical conversion treatment bath, for each component, it is based on the combination of Examples 1-9 to 6 in Table 5 below. the amount. In addition, in Example 2 and 6, the surface treatment process of the chemical conversion treatment bath may include a concentration of 1.0 g / 1 in the magnesium ion produced from the magnesium alloy die-casting product. This paper size is applicable to China National Standard (CNS) Α4 specification (2〗 0X297 mm)-21---------- M Pack -------- Order ------ > • ί-(Please read the precautions on the back before filling this page) 4Ε Α7 Β7 V. Description of the invention (/?) [Table 5] Consumption of shellfish by the Central Standards Bureau of the Ministry of Economic Affairs ^^ i.fl Chemical treatment agent: ^ Composition ¥ Example / Number Example-1 Comparative Example 19 20 21 22 23 24 25 26 1 2 3 4 5 Calcium nitrate (Ca, 15.2 21.2 2.2 34.7 15.2 15.2 0.6 34.7 15.2-15.2 21.2-(2 * 6) (16) ( 0.4) (5-9) (2.6) (2.6) (0.1) (5.7) (2.6) (2.6) (3.6) Manganese carbonate (ΜιΛ 2,1 2.9 2.1 2.1 0.5 9.1 0Λ 2.1 2.1 11-2.1-(1.0) (1.3) (1.0) ⑽ (0.2) (4.3) (0.05) (1.0) (1.0) (1-0) (1.0) (75%) K acid < P〇Λ) 19.2 26.7 19.2 38.4 19.2 38.4 0, 7 48.8 19.2 28.3 19.2 21.0 one (14.0) (19.4) (14.0) ¢ 23.0) (14.0) (2S.0) (0.5) (35.6) (H.0) (20.6) (14.0) (15.3) sodium hydroxide 0.4 0,4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Mg1 '1.0 1.0 Water residual residual residual residual residual residual residual residual (In the table, the unit of number 値 is g / 1) The paper size applies the Chinese national standard (CNS > A4 scale (210 X 297 mm) 1ϋ1 (Please read the notes on the back before filling out this page) Order S. A7 B7 V. Description of the invention (20) Also, In these examples, as shown in Table 6 below, the pH of the degreasing solution of the treatment process was prepared to 1 3 ~ 1 4. Moreover, other processing conditions, including coating methods including cationic electrode coating, and test Example 1 is the same. The results of the surface treatment using this treatment process, the application of the coating treatment, and the salt spray test after 1000 hours are shown in Table 6 below. Binding I Girl-(Please read first Note on the back #. Fill out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs
經濟部中央標準局員工消費合作社印製 A7 __B7 五、發明説明（2*J ) 〔表6〕 實施 例 號碼 脫脂 條件 CPH) 化成處理 浴液之 PH値 化成皮膜（mg/m1) SST(1000小時） 附著性 Ca Μ η P 膨潤寬度 (mm) 有無 起泡 實 施 例 19 13-14 L.65-1.70 140-130 so~no 580-650 1.0-1.5 無 〇 20 13-14 1.50-1,55 200-250 100-150 &00-900 ◦ ‘5〜1 .0 無 〇 21 13-14 1.65-1.70 5-40 80-110 580-650 1.5-2,0 無 〇 22 13-14 1.40- 1.45 300-400 100-150 800-900 0,5-1,0 無 〇 23 13 〜14 1 ,65-1.70 140-180 5-40 580-650 1 .0-1.5 無 〇 24 13-14 i.15-1.20 140-180 300-450 800-900 0.5- 1.0 無 〇 25 13-14 2.85-2.90 5-40 5-40 5-40 2,5-3,0 無 〇 26 13-14 2.25-2.30 140-180 S0~i 10 580-650 1.0-1.5 無 〇 比 較 例 1 11,5- 12 1.65-1.70 140-180 SO〜1 10 300-500 3.0〜5.0 有（多） 〇 2 13-14 1.55-1.60 — 100-150 580-650 2.0-3.0 (48◦小時） 有 厶 3 13-14 1.65-1.70 140〜180 580-650 1.0-2,0 無 X 4 13-14 3,01-3.05 5-40 5-40 5-40 全面 (480小時） 有 X 5 13-14 — 全面 (480小時） X 6 13- 14 — 2.0-3.0 (48小時） 有 △ ---------：==裝------訂------X .* (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 24 - 經濟部中央標準局員工消費合作社印製 ' .Q D A7 ____ B7五、發明説明（22 ) 且，表6中，對各性能之評估基準係與試驗例1相同 0 於前述之表5及表6，其比較例1之化成處理劑之成 分組成係與實施例1 9相同，惟揭示著脫脂條件係設爲 ρ Η 1 1 . 5〜1 2的情形。 在此比較例1之處理條件下，如表6所示般，在較嚴 苛的環境條件下會招致塗膜性能之降低，尤其起泡現象會 大量發生。針對此點，在實施例1 9〜2 5之處理條件下 ，對塗膜性能，發現任一者均有提高耐久性。 又，於表6，包含於化成處理後所得的化成皮膜內之 鈣、錳及磷之含有率係予各別表示出。由此已揭示的各成 分元素之含有率，利用實施例1 9〜2 6之處理條件的情 形，不論何者均可確出係由鈣、錳及磷之混合被膜而成的 〇 於表5及表6內，至於化成處理劑，對不含鈣離子的 情形表示作比較例2，對不含錳離子的情形表示作比較例 3 ·而不進行化成處理者表示作比較例5。 利用此等的處理條件之情形，任一者在包含附著性之 塗膜的耐蝕性或起泡發生的點上會有問題，未能保持塗膜 性能之耐久性。針對此點，若依前述的鈣、錳及磷之混合 被膜時，可得知實施例1 9〜2 5之任一種情形均對其耐 久性之提高係有效的。又’尤其由實施例2 0、2 2及 2 4之結果，亦可知在所得的化成皮膜中之鈣、錳及磷之 成分元素的任一者的增量，係對其耐久性之提高係較宜的 本紙張尺度適用中國國家標準（CNS ) Α4规格（2丨Ο X 297公釐） -25 - H. II , I - I H I Ί ντΛ n I n I H Ϊ— n n I (請先間讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 459065 A7 _____B7 五、發明説明（23 ) 〇 又，由表6之實施例2 6之結果，係在與比較例4之 對比，依與本發明有關的化成處理浴液時，由處理負荷， 對相同浴液中溶出的鎂離子量變多的情形，亦顯示出可得 有效的處理被膜。 又，表6之比較例，係顯示出習用的鉻處理法之情形 的結果。亦即以化成處理劑爲含有重鉻酸鈉1 5 0 g / 1 及氟化鎂2 . 5 g / 1之液劑組成，並將之作成化成處理 浴液。且，脫脂條件爲浴液ρ Η 1 3〜1 4，浴液溫度 9 0〜1 0 0°C處理時間10分鐘，又化成處理爲浴液溫 度90〜100 °C，處理時間30分鐘，依與前述試驗例 1相同處理過程之規定。若依此比較例5之處理條件時， 由表6所示的結果，可知爲使保持能耐鹽水噴霧1 〇 〇 〇 小時之耐久性的表面處理係有困難的。 發明之功效 如上述般，本發明係由所構成的事實，可發揮下述的 功效。 若依與本發明有關的含有鎂之金屬用化成處理劑，則 由此化成處理劑而得的化成處理浴液係藉由使用於脫脂處 理後的化成處理，可得具有高耐蝕性且防銹性，塗布附著 性等非常優越的鈣、錳及磷之混合皮膜的處理物。 又，此一與本發明有關的處理方法，係非鉻處理，不 致生成起因於鉻離子之公害問題，又不論任何作業環境上 ---；--W----. .¾ 裝-- (請先間讀背面之注$項再填寫本頁) -訂 本紙張尺度適用肀國國家標準（〇师）八4規格（210父297公釐） -26 - 459065 A7 ____ B7五、發明説明（24 ) ，亦可安全的實施。 又’若依包含與本發明有關的前處理之蝕刻步驟的處 理方法，則可實行對已附著有脫模劑之鎂合金壓鑄製品之 表面處理至可有效的保持優越的塗膜性能等，又，若依將 與本發明有關的脫脂處理之條件設成ρ η 1 3以上的處理 方法時，則可在減少包括蝕刻處理下，對上述的壓鑄製品 ，欲得較具耐鈾性等之耐久性優越的表面處理即成可能。 ---.------裝------訂------— (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標率局男工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -27 -Printed A7 __B7 by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (2 * J) [Table 6] Example No. Degreasing Conditions CPH) PH of chemical conversion bath liquid (mg / m1) SST (1000 hours) ) Adhesive Ca M η P Swelling width (mm) With or without foaming Example 19 13-14 L.65-1.70 140-130 so ~ no 580-650 1.0-1.5 None 020 13-14 1.50-1, 55 200 -250 100-150 & 00-900 ◦ '5 ~ 1.0 0 None〇21 13-14 1.65-1.70 5-40 80-110 580-650 1.5-2,0 None〇22 13-14 1.40- 1.45 300 -400 100-150 800-900 0,5-1,0 None 〇23 13 ～ 14 1, 65-1.70 140-180 5-40 580-650 1 .0-1.5 None 〇24 13-14 i.15- 1.20 140-180 300-450 800-900 0.5- 1.0 None 〇25 13-14 2.85-2.90 5-40 5-40 5-40 2,5-3,0 None 〇26 13-14 2.25-2.30 140-180 S0 ~ i 10 580-650 1.0-1.5 None 〇 Comparative Example 1 11,5- 12 1.65-1.70 140-180 SO ~ 1 10 300-500 3.0 ~ 5.0 Yes (many) 〇 2 13-14 1.55-1.60 — 100 -150 580-650 2.0-3.0 (48◦ hours) Yes 3 13-14 1.65-1.70 140 ~ 180 580-650 1.0-2,0 No X 4 13-14 3,01-3.05 5-40 5-40 5-40 full (480 hours) Yes X 5 13-14 — Full (480 hours) X 6 13- 14 — 2.0-3.0 (48 hours) Yes △ ---------: == Equipment ------ Order ------ X. * (Please read the notes on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) _ 24-Staff Consumption of Central Standards Bureau, Ministry of Economic Affairs Printed by the cooperative '. QD A7 ____ B7 V. Description of the invention (22) In Table 6, the evaluation criteria for each performance are the same as those in Test Example 1 0 in Tables 5 and 6 above, and the formation of Comparative Example 1 The component composition of the treatment agent is the same as that of Example 19, but the case where the degreasing conditions are set to ρ Η 1 1. 5 to 12 is disclosed. Under the processing conditions of this Comparative Example 1, as shown in Table 6, under severe environmental conditions, the performance of the coating film is lowered, and especially the blistering phenomenon occurs in large amounts. In view of this, under the processing conditions of Examples 19 to 25, it was found that the durability of any of the coating film properties was improved. In Table 6, the content rates of calcium, manganese, and phosphorus contained in the chemical conversion film obtained after the chemical conversion treatment are shown individually. The content ratio of each component element thus disclosed, using the processing conditions of Examples 19 to 26, can be confirmed by any combination of calcium, manganese and phosphorus. Table 5 and Table 5 In Table 6, as for the chemical conversion treatment agent, the case where calcium ion is not included is shown as Comparative Example 2, and when the manganese ion is not included, it is shown as Comparative Example 3. The case where no chemical treatment is performed is shown as Comparative Example 5. In the case of using these processing conditions, there is a problem in that the corrosion resistance of the coating film including adhesion and the point where foaming occurs, and the durability of the coating film performance cannot be maintained. In view of this point, if the above-mentioned mixed coating of calcium, manganese, and phosphorus is used, it can be seen that any of Examples 19 to 25 is effective in improving its durability. It is also known from the results of Examples 20, 22, and 24 that the increase of any one of the calcium, manganese, and phosphorus component elements in the obtained chemical conversion film is an improvement of its durability. Appropriate paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 〇 X 297 mm) -25-H. II, I-IHI Ί ντΛ n I n IH Ϊ— nn I (please read the back first) Please pay attention to this page, please fill in this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs Consumer Cooperatives 459065 A7 _____B7 V. Description of Invention (23) 〇 The results of Example 2 and 6 in Table 6 are compared with Comparative Example 4. In the case of the chemical conversion treatment bath according to the present invention, it has been shown that an effective treatment film can be obtained even when the amount of magnesium ions dissolved in the same bath is increased by the treatment load. The comparative example in Table 6 shows the results in the case of a conventional chromium treatment method. That is, the chemical conversion treatment agent is composed of a liquid agent containing sodium dichromate 150 g / 1 and magnesium fluoride 2.5 g / 1, and is formed into a chemical conversion bath. In addition, the degreasing conditions are: bath liquid ρ Η 1 3 ~ 1 4, bath temperature 90 ~ 100 ° C, processing time 10 minutes, and chemical conversion treatment into bath liquid temperature 90 ~ 100 ° C, processing time 30 minutes. Provisions for the same treatment procedure as in the aforementioned Test Example 1. According to the processing conditions of Comparative Example 5, from the results shown in Table 6, it is understood that it is difficult to make the surface treatment capable of maintaining the durability against salt water spray for 1000 hours. Effect of the Invention As described above, the fact that the present invention is constituted can exert the following effects. According to the chemical conversion treatment agent for a metal containing magnesium according to the present invention, the chemical conversion treatment bath liquid obtained from the chemical conversion treatment agent can be used for the chemical conversion treatment after the degreasing treatment to obtain high corrosion resistance and rust prevention. It is a treated product of a mixed film of calcium, manganese and phosphorus which is excellent in coating properties and adhesion. In addition, this treatment method related to the present invention is a non-chromium treatment, which does not generate pollution problems caused by chromium ions, regardless of any operating environment ---; --W ----.. ¾- (Please read the note $ on the back before filling in this page)-The size of the paper is applicable to the national standard (0 division) of the 8th specification (210 father 297 mm) -26-459065 A7 ____ B7 V. Description of the invention (24), can also be implemented safely. If the treatment method including the pre-treatment-related etching step according to the present invention is adopted, the surface treatment of the magnesium alloy die-casting product to which the mold release agent has been attached can be performed to effectively maintain the superior coating film performance, etc., and If the conditions for degreasing treatment related to the present invention are set to ρ η 1 3 or more, the durability of the above-mentioned die-casting products can be reduced to include uranium resistance, etc. under the reduction and etching treatment. Excellent surface treatment is now possible. ---.------ Installation ------ Order -------- (Please read the notes on the back before filling this page) Printed by the Male Workers Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) Α4 size (210X297 mm) -27-