200415242 玖、發明說明： (一） 發明所屬之技術領域 本發明係關於鋁管及其製造方法，更詳細的，例如關於 具有作爲使用氟氯烷（Freon)系冷媒的車輛空氣調節器或蒸 發器’使用C〇2冷媒的車輛空氣調節器的氣冷器或蒸發器 、汽車用冷油器、汽車用水箱等所使用熱交換器之入口管 及出口管、或具壓縮機、凝結器及蒸發器且由使用氟氯烷 系冷媒的冷凍循環所成車輛空氣調節器的壓縮機、凝結器 及蒸發器間配管使用、或具壓縮機、氣冷器、中間熱交換 鲁 器、膨脹閥及蒸發器且由使用C02冷媒的冷凍循環所成車 輛空氣調節器的壓縮機、氣冷器、中間熱交換器、膨脹閥 及蒸發器間之配管使用的鋁管及其製造方法。 於本說明書及申請專利範圍，所稱呼「鋁」的用語係純 鋁之外包含鋁合金者。又，當然以元素記號表現的金屬， 並不包含其合金。 (二） 先前技術 0 技術背景 例如作爲.由使用氟氯烷系冷媒的冷凍循環所成車輛空氣 調節器用之凝結器具有··一對鋁製集管箱，互相隔以間隔 配置成平行；鋁製扁平狀熱交換管，將兩端以並排狀分別 連接在兩集管箱；鋁製波形散熱片，配置於相鄰熱交換管 間的通風間隙，同時硬焊在兩熱交換管；鋁製入口管，連 接於一側的集管箱；及鋁製出口管，連接在另一側之集管 -5- 200415242 箱者爲眾所周知。 先前，作爲該凝結器的入口管及出□管，係JIS AL100 、或JIS A3003、或含有Μη 1.0〜1.5質量％，同時含有Mg 〇·2質量％以上且0.6質量％以下，由剩餘部分A1及無法避 免不純物所成合金等形成（參照日本國特公平3 - 2 2 4 5 9號公 報）。 可是於上述凝結器，爲了提高耐鈾性的目的，先前在表 面作鉻酸鹽液處理，但其處理作業麻煩。又Cr6 +爲有害物 0 質其廢液處理麻煩。因而，有製造凝結器全體之作業麻煩 的問題。而且，於歐洲，不久將禁止使用Cr6+。 於是對於上述凝結器之冷媒流通管，對代替使用有害 Cr6+的鉻酸鹽液處理之耐孔蝕性處理，或具有耐孔鈾性者 有作種種的檢討。 然而對於出入口管，在現狀並未找出可簡單且價廉的製 造，而且具有充分的耐孔蝕性者。當然，於記載在上述公 報的熱交換器用出入口管，未施予鉻酸鹽液處理時並不能 ® 期待耐孔蝕性。 本發明之目的係在於提供一種解決上述問題，可簡單且 價廉的製造，而且具有充分的耐孔蝕性之鋁管及其製造方 法。 (三）發明內容 發明之啓示 依本發明的鋁管，由包含Μ η 0.9〜1 . 5質量％，剩餘部分 -6- 200415242 A1及無法避免不純物所成合金形成，自外周面之最表面至 涂度6 Ο μ m以上的表層部予以擴散ζ η，同時此表層部之Ζ η 濃度爲0.2〜0.70質量％者。 於依本發明的鋁管，Μη係發揮了提高耐孔蝕性，同時提 高熱交換器用出入口管強度的效果，但其含有量爲0.9質 量％以下時不能獲得上述效果，超過1 .5質量％時提高強度 之效果會飽和，另一方面增大熱加工時的變形阻力，成形 熱交換器用出入口管之際的加工性，例如降低推出加工性 。因而出入口管的Μη含有量係應作爲〇.9〜1.5質量％，但 馨 以1.0〜1.2質量％爲理想。 又，在本發明的鋁管，Ζη自外周面之最表面至深度60μιη 以上之表層部所擴散，使此表層部之電位爲低，對除了表 層部的部分予以犧牲腐蝕表層部，防止在鋁管產生孔蝕者 ，但上述表層部之Ζ η濃度爲0 · 2 0之質量％以下時不能獲得 上述效果。相反地，超過〇 · 7 〇質量％時對銘管本身之耐倉虫 性雖無問題，但欲作成爲超過〇 . 7 〇質量％者，例如將製造 鋁管以如後述，於熱交換器同時實行熱交換管與散熱片的 Φ 硬焊時，有必要熔射多量的Ζη在熱交換管表面，不能確保 於所製造熱交換器的熱交換管，或熱交換管與散熱片的硬 焊部耐蝕性。因而上述表層部之Ζ η濃度應作爲〇 . 2 〇〜〇 . 7 0 質量％。又自鋁管外周面之最表面的Ζη擴散距離係最大爲 1 0 0 μ m程度。 依本發明之鋁管，並不施予鉻酸鹽液處理能防止產生孔 蝕。而且含Μη 0.9〜1.5質量％，以剩餘部分A1及無法避 200415242 免不純物所成合金形成，自外周面之最表面至深度60μιη 以上之表面層擴散的Ζη，同時此表面層之Ζη濃度僅成爲 0· 20〜〇.70質量％而已，所以能簡單且價廉的製造。 依本發明的鋁管，作爲無法避免不純物的Cu含有量係 〇·〇1質量％以下爲理想。作爲無法避免不純物的Cu由混入 微量亦有降低鋁管耐孔蝕性之慮。 依本發明的鋁管，作爲無法避免不純物的Fe含有量係 〇· 25質量％以下爲理想。作爲無法避免不純物之Fe雖無Cu 程度強的影響者，但有降低鋁管耐孔蝕性之慮者。 · 於依本發明的鋁管，作爲無法避免不純物的Si含有量係 〇 · 2 5質量％以下爲理想。作爲無法避免不純物的S i與Fe 同樣，有降低鋁管耐孔蝕性之慮。 依本發明的鋁管，作爲無法避免不純物的M g含有量係 0 · 3 0質量％以下爲理想。作爲無法避免不純物之M g係硬 焊性及加工性，例如有降低推出性使加工成本上升之慮。 依本發明的鋁管之製造方法，其特徵爲含Μη 0.9〜1.5 質量％，由剩餘部分Α1及無法避免不純物所成合金形成管 φ 素材，及表面形成2.0〜16.0g/m2之Zri熔射層且Ζη熔射層 之合計Zri量爲75〜600g的鋁材，放入惰性氣體環境之爐 中，在580〜610 °C加熱3〜15分鐘者。 依本發明鋁管之製造方法，形成在鋁材表面的Ζη熔射層 ，在後製程加熱之際蒸發擴散於管素材外周面之表層部。 而且限定鋁材表面之Ζη熔射層爲2.0〜16.0 g/m2且合計Ζη 量75〜600g，在該下限値以下時，不能使所製造之鋁管之 -8- 200415242 該表層部的Ζη濃度爲0.20質量％以上，超過上限値時於該 表層部的Ζη濃度會超過0.70質量％者。 又，依本發明鋁管之製造方法，加熱溫度及加熱時間爲 下限値以下時，自Ζη熔射層之Ζη蒸發及所蒸發Ζη對管 素材表層部的擴散並不充分，不能製造鋁管之該表層部的 Ζη濃度爲0.20質量％以上，超過上限値則使製造鋁管，例 如如後述，同時實行於熱交換器的熱交換管與散熱片硬焊 時’招來散熱片等鋁材之母材融解，或熔射在熱交換管表 面的Ζη過度的擴散於熱交換管內，有引起腐蝕漏的可能性 · 。又，加熱溫度以5 85〜605 °C爲理想。 依本發明的鋁管之製造方法，可比較簡單的且廣價的製 造上所述鋁管。 依本發明鋁管之製造方法，於形成管材合金的Μη 含有量係1.0〜1.2質量％爲理想。又於形成管材合金作爲 無法避免不純物的Cu含有量係0.01質量％以下爲理想。於 形成管材合金作爲無法避免不純物的Fe含有量係〇·25質量 %以下爲理想。於形成管材合金作爲無法避免不純物的Si # 含有量係0.25質量％以下爲理想。再者，於形成管材合金 作爲無法避免不純物的M g含有量係0.3 0質量％ 以下爲理想。 依本發明鋁管之製造方法，鋁材爲於熱交換器的複數熱 交換管.，各熱交換管之表面形成2.0〜16.0g/m2之Ζη熔射 層，且於所有熱交換管表面的Ζη熔射層之合計Ζη量爲75 〜7 00g，爐爲硬焊熱交換管與鋁製集管箱及鋁製散熱片的 •9- 200415242 爐，於硬焊惰性氣體環境的熱交換管、集管箱及散熱片之 際，有加熱管材的情況。在此狀況，同時與製造熱交換器 可製造鋁管，故不必要特別的設備等，製造成本變低廉。 (四）實施方式 爲了實施發明的較佳形態 以下，參照圖面說明本發明之實施形態。 於第1圖，使用氟氯烷系冷媒用在車輛空氣調節器的凝 結器（1 )具備有：一對鋁製集管箱（2)(3 )，互相隔以間隔配 置成平行；鋁擠出形材製扁平狀冷媒流通管（3)(熱交換管）φ ，並排狀連接兩端在各個兩集管箱（2)(3 );錦硬焊製波形营女 熱片（5 )，配置於相鄰冷媒流通管（4)間之通風間隙，同時硬 焊於兩冷媒流通管（4);鋁擠出形材製入口管（6)，熔接在第 1集管箱（2)之周壁上端部；鋁擠出形材製出口管（7)，熔接 在第2集管箱（3)之周壁下端部；第1隔間板（8)，設於較第 1集管箱（2)中程的上方位置內部；及第2隔間板（9)，設於 較第2集管箱（3)中程的下方位置內部。尙作爲冷媒流通管 (4)亦可以使用由熔接管所成者。 φ 入口管（6)與第1隔間板（8)間的冷媒流通管（4)支數，第1 隔間板（8)與第2隔間板（9)間的冷媒流通管（4)支數，第2 隔間板（9)與出口管（7)間的冷媒流通管（4)支數，分別自上 依順序減少來構成通路群，從入口管（6)流入的氣相之冷媒 ’至由出口管（7)成液相流出，作成爲以各通路群單位在凝 結器內作蛇行狀流。 入口管（6)及出口管（7)，由分別含Μη 0.9〜1.5質量％， -10- 200415242 剩餘部分A1及無法避免不純物所成合金形成，自外周面之 最表面至深度60μιη以上的表層部擴散的Zn，同時作成此 表層部之Zn濃度爲〇· 20〜0.70質量％。 形成入口管（6)及出口管（7)的合金中Μη含有量係1.0〜 1 _ 2質量％爲理想。又上述合金中無法避免不純物之中c u 含有量爲0.01質量％以下，同樣Fe含有量爲0.25質量％ 以下，同樣Si含有量爲0.25質量％以下，同樣g含有量爲 0 · 3 0質量％以下。 入口管（6)及出口管（7)例如以如次製造。 首先’使用如上所述的合金擠出成形入口管材及出口管 素材。又準備形成第1圖所示凝結器（1)的1對鋁製集管箱 (2)(3)、複數鋁擠出形材製冷媒流通管（4)及複數鋁硬焊片 製波形散熱片（5)。在兩集管箱（2) (3)分別予以形成複數之 管插入孔。又各冷媒流通管（4)之表面，形成2.0〜16.0g/m2 ，理想爲2.0〜8.0 g/m2的Zn熔射層，且作成所有冷媒流通 管（4)表面的Zn熔射層之合計Zn量爲75〜600g，理想爲 75〜300g ° 而且，隔以間隔配置1對集管箱（2)(3)，同時互相配置複 數冷媒流通管（4)與複數波形散熱片（5)，將冷媒流通管（4) 兩端部插入兩集管箱（2) (3)之管插入孔形成爲組合體。接著 對該等組合體塗布氟化物系助熔劑（氟化鉀及氟化鋁的共 晶組成近旁者），放入作成惰性氣體環境的爐中，同時放入 所有之入口管材及出口管材於上述爐中。其後，以58〇〜 6 l〇°C加熱3〜15分鐘。如此利用設在集管箱（2) (3)的硬焊 200415242 材層硬焊冷媒流通管（4 )及集管箱（2 ) ( 3 )，同時利用波形散 熱片（5)的硬焊材一起硬焊冷媒流通管（4)及集管箱（2)( 3)製 造凝結器（1)，同時製造入口管（6)及出口管（7)。 凝結器（1 )，係壓縮機及蒸發器一起構成使用氟氯烷系冷 媒的冷凍循環，作爲車輛空氣調節器的車輛，例如搭載於 汽車。 於上所述實施形態，依本發明的銘管係由使用氟氯院系 冷媒的冷凍循環所成，雖作爲車輛空氣調節器的凝結器入 口管及出口管，但亦有使用作爲該車輛空氣調節器之蒸發 鲁 器入口管及出口管。再者，依本發明的鋁管，亦有使用於 作汽車用油冷器、汽車用水箱等用熱交換器的出入口管。 又依本發明的鋁管亦有使用於作爲具壓縮機、凝結器及 蒸發器且由使用氟氯烷系冷媒的冷凍循環所成車輛空氣調 節器之壓縮機、凝結器及蒸發器間的配管，或具壓縮機、 氣冷器、中間熱交換器、膨脹閥及蒸發器且由使用 C〇2 冷媒的冷凍循環所成車輛空氣調節器的壓縮機、氣冷器、 中間熱交換器、膨脹閥及蒸發器間的配管。 Φ 再者，依本發明的鋁管亦有使用於作爲，具壓縮機、氣 冷器、中間熱交換器、膨脹閥及蒸發器，且由使用C 02冷 媒的冷凍循環所成車輛空氣調節器之氣冷器或蒸發器間的 入口管及出口管。 實施例1 使用由含Μη 1.08質量％、Cu 0.01質量％以下、Si 0.06 質量％、？6 0.12質量％、1^0.01質量％、（：1*0.01質量％、 -12- 200415242200415242 (1) Description of the invention: (1) The technical field to which the invention belongs The present invention relates to an aluminum pipe and a method for manufacturing the same, and more specifically, for example, to a vehicle air conditioner or evaporator having a Freon-based refrigerant 'Air coolers or evaporators of vehicle air conditioners using CO2 refrigerants, inlet and outlet pipes of heat exchangers used in automotive oil coolers, automotive water tanks, etc., or compressors, condensers, and evaporation Compressors, compressors, condensers and evaporator piping for vehicle air conditioners made of a refrigeration cycle using a chlorochlorohydrin-based refrigerant, or compressors, air coolers, intermediate heat exchangers, expansion valves, and evaporation Aluminum tubes used in compressors, air coolers, intermediate heat exchangers, expansion valves, and evaporator pipes of vehicle air conditioners formed by a refrigeration cycle using C02 refrigerant, and a method for manufacturing the same. In the scope of this specification and the patent application, the term "aluminum" refers to those that contain aluminum alloys in addition to pure aluminum. Of course, metals represented by element symbols do not include their alloys. (2) Prior art 0 Technical background For example, a condenser for a vehicle air conditioner formed by a refrigeration cycle using a chlorochlorohydrin-based refrigerant has a pair of aluminum header boxes arranged parallel to each other at intervals; aluminum Flat heat exchange tube, two ends are connected side by side to the two header boxes respectively; aluminum wave fins are arranged in the ventilation gap between adjacent heat exchange tubes, and are brazed to the two heat exchange tubes at the same time; aluminum The inlet pipe is connected to the header box on one side; and the aluminum outlet pipe is connected to the header -5- 200415242 box on the other side. Previously, the inlet pipe and outlet pipe of the condenser were JIS AL100 or JIS A3003, or contained 1.0 to 1.5% by mass of Mη, and contained 0.2 to 2% by mass of Mg and not more than 0.6% by mass. And the formation of alloys made of impurities cannot be avoided (refer to Japanese National Fair Publication No. 3-2 2 4 5 9). However, in the above-mentioned condenser, for the purpose of improving the uranium resistance, the surface was previously treated with a chromate solution, but the operation was troublesome. Cr6 + is a harmful substance and its waste liquid is troublesome to handle. Therefore, there is a problem that the operation of manufacturing the entire condenser is troublesome. Moreover, in Europe, the use of Cr6 + will soon be banned. Therefore, the refrigerant circulation pipe of the above-mentioned condenser has been reviewed variously for the pitting corrosion resistance treatment instead of the chromate solution treatment using harmful Cr6 +, or for those with uranium resistance. However, for the inlet and outlet pipes, no simple and inexpensive manufacturing has been found in the current situation, and those with sufficient pitting resistance. Of course, in the inlet and outlet pipes for heat exchangers described in the above-mentioned publication, pitting resistance cannot be expected when the chromate solution is not applied. An object of the present invention is to provide an aluminum pipe which can solve the above-mentioned problems, can be manufactured simply and inexpensively, and has sufficient pitting resistance, and a method for manufacturing the same. (3) Summary of the invention The aluminum tube according to the present invention is formed from an alloy of Mn η 0.9 to 1.5 mass%, the remainder -6-200415242 A1 and unavoidable impurities, from the outermost surface to The surface layer portion having a coating degree of 60 μm or more is diffused by ζ η, and the Zn η concentration of the surface layer portion is 0.2 to 0.70% by mass. In the aluminum tube according to the present invention, the Mn series exhibits the effect of improving the pitting resistance and the strength of the inlet and outlet pipes for heat exchangers, but the above effects cannot be obtained when the content is 0.9% by mass or less, exceeding 1.5% by mass. When the effect of increasing the strength is saturated, the deformation resistance during hot working is increased, and the workability when forming the inlet and outlet pipes for the heat exchanger is reduced, for example, the workability is reduced. Therefore, the Mη content of the inlet and outlet pipes should be 0.9 to 1.5% by mass, but Xin is preferably 1.0 to 1.2% by mass. Also, in the aluminum tube of the present invention, Zn is diffused from the outermost surface to a surface layer portion having a depth of 60 μm or more, so that the potential of this surface layer portion is low, and the portion other than the surface layer portion is sacrificed to corrode the surface layer portion to prevent the If the tube has pitting corrosion, the above-mentioned effect cannot be obtained when the Z η concentration of the surface layer portion is 0% by mass or less. On the contrary, if it exceeds 0.7 mass%, there is no problem with the worm resistance to the tube itself, but if it is intended to exceed 0.7 mass%, for example, an aluminum pipe is manufactured to be used in a heat exchanger as described later. When performing Φ brazing of heat exchange tubes and fins at the same time, it is necessary to spray a large amount of Zn on the surface of the heat exchange tubes, which cannot ensure the heat exchange tubes of the manufactured heat exchanger, or the brazing of heat exchange tubes and fins. Department of corrosion resistance. Therefore, the concentration of Z η in the surface layer portion should be 0.2 to 0.70% by mass. The maximum Zn diffusion distance from the outermost surface of the aluminum tube is about 100 μm. The aluminum tube according to the present invention can be prevented from generating pitting corrosion without being treated with a chromate solution. In addition, it contains 0.9 to 1.5% by mass of Mn, which is formed by the remainder of A1 and alloys made of impurities that cannot be avoided by 200415242. Zη diffuses from the outermost surface to a surface layer with a depth of 60 μιη or more. At the same time, the Zn concentration of this surface layer becomes only Only 0.20 to 0.70% by mass, so it can be manufactured simply and inexpensively. The aluminum tube according to the present invention is preferably a Cu content of 0.001% by mass or less as an unavoidable impurity. Cu, which is an unavoidable impurity, may be mixed in a trace amount and may reduce the pitting corrosion resistance of aluminum pipes. The aluminum tube according to the present invention is preferably Fe content of 0.25 mass% or less as an unavoidable impurity. Impurities of Fe are unavoidable, although they have no strong influence of Cu, but there are concerns about reducing the pitting corrosion resistance of aluminum pipes. · In the aluminum tube according to the present invention, the Si content which is unavoidable as impurities is preferably 0. 25% by mass or less. Like Si, which is an unavoidable impurity, there is a concern that the pitting resistance of an aluminum pipe may be reduced. The aluminum tube according to the present invention is preferably an M g content of which impurities are unavoidable, and is preferably 0. to 30% by mass. As Mg, which is an unavoidable impurity, is brazeability and processability, for example, there is a concern that processability may be increased by lowering pushability. The method for manufacturing an aluminum pipe according to the present invention is characterized by containing Mn 0.9 to 1.5% by mass, forming a pipe φ material from the remaining portion A1 and unavoidable impurities, and forming a Zri spray of 2.0 to 16.0 g / m2 on the surface. Aluminum with a total Zri content of 75 to 600 g, and put it in an inert gas atmosphere, and heat it at 580 to 610 ° C for 3 to 15 minutes. According to the method for manufacturing an aluminum pipe according to the present invention, a Zn spray coating layer formed on the surface of an aluminum material is evaporated and diffused on the surface layer portion of the outer peripheral surface of the tube material when it is heated in a subsequent process. In addition, the Zη spray layer on the surface of the aluminum material is limited to 2.0 to 16.0 g / m2 and the total amount of Zη is 75 to 600g. When the lower limit is not more than ，, the Zn concentration of the surface layer portion of the manufactured aluminum tube cannot be reduced. It is 0.20% by mass or more, and when the upper limit is exceeded, the Zη concentration in the surface layer portion exceeds 0.70% by mass. In addition, according to the manufacturing method of the aluminum pipe of the present invention, when the heating temperature and heating time are below the lower limit 値, the evaporation of Zη from the Zη spray layer and the diffusion of the evaporated Zη to the surface layer portion of the tube material are insufficient, and the aluminum tube cannot be manufactured. The Zη concentration of the surface layer portion is 0.20% by mass or more. When the upper limit is exceeded, aluminum tubes are manufactured. For example, as will be described later, when the heat exchange tube and the heat sink are simultaneously brazed to the aluminum material, the aluminum material such as the heat sink is called for. The base material melts, or Zη sprayed on the surface of the heat exchange tube is excessively diffused in the heat exchange tube, which may cause corrosion leakage. The heating temperature is preferably 5 85 to 605 ° C. According to the method for manufacturing an aluminum pipe according to the present invention, the aluminum pipe described above can be manufactured relatively simply and at a high price. According to the method for manufacturing an aluminum pipe according to the present invention, the Mη content of the formed tube alloy is preferably 1.0 to 1.2% by mass. In addition, it is desirable to form a pipe alloy as an Cu unavoidable impurity content of 0.01% by mass or less. The Fe content for forming a pipe alloy as an unavoidable impurity is preferably 0.25 mass% or less. The Si # content for forming a pipe alloy as an unavoidable impurity is preferably 0.25% by mass or less. In addition, the Mg content as an unavoidable impurity in forming a pipe alloy is preferably 0.30% by mass or less. According to the manufacturing method of the aluminum tube of the present invention, the aluminum material is a plurality of heat exchange tubes on the heat exchanger. The surface of each heat exchange tube forms a zeolite spray layer of 2.0 to 16.0 g / m2, and The total amount of Zη of the Znη spray layer is 75 ~ 700g. The furnace is a brazed heat exchange tube, an aluminum header box and an aluminum fin. • 9-200415242 furnace, heat exchange tubes in a brazed inert gas environment, In the case of the header box and the heat sink, the pipe may be heated. In this case, since aluminum tubes can be manufactured together with the manufacturing of the heat exchanger, special equipment and the like are not necessary, and the manufacturing cost becomes low. (4) Embodiments Preferred Embodiments for Implementing the Invention Embodiments of the present invention will be described below with reference to the drawings. As shown in Fig. 1, a condenser (1) used in a vehicle air conditioner using a halothane refrigerant is provided with: a pair of aluminum header boxes (2) (3), which are arranged parallel to each other at intervals; aluminum extrusion A flat-shaped refrigerant circulation pipe (3) (heat exchange pipe) φ made out of material, and connected at two ends in parallel to each of two header boxes (2) (3); a braided wave-shaped female hot film (5), It is arranged in the ventilation gap between the adjacent refrigerant circulation pipes (4), and is brazed to the two refrigerant circulation pipes (4) at the same time. The upper end of the peripheral wall; the outlet pipe (7) made of aluminum extrusion is welded to the lower end of the peripheral wall of the second header box (3); ) Inside the upper position of the middle range; and the second compartment plate (9) is provided inside the lower position than the middle range of the second header box (3).尙 As a refrigerant circulation pipe (4), it is also possible to use a welded pipe. φ The number of refrigerant circulation pipes (4) between the inlet pipe (6) and the first compartment plate (8), and the refrigerant circulation pipes (4) between the first compartment plate (8) and the second compartment plate (9) ), The number of refrigerant circulation pipes (4) between the second compartment plate (9) and the outlet pipe (7) are reduced in order from above to form a channel group, and the gas phase flowing from the inlet pipe (6) Refrigerant 'flows from the outlet pipe (7) into a liquid phase to make a meandering flow in the condenser in each channel group unit. The inlet pipe (6) and the outlet pipe (7) are formed of alloys containing Mn 0.9 to 1.5% by mass, -10- 200415242, and the remaining part A1 and unavoidable impurities, from the outermost surface to the surface with a depth of 60 μm or more. At the same time, the Zn concentration of this surface layer portion was set to be 0.2 to 0.70% by mass. The Mn content in the alloy forming the inlet pipe (6) and the outlet pipe (7) is preferably 1.0 to 1-2 mass%. In the above alloys, it is unavoidable that the cu content in the impurities is 0.01 mass% or less, the Fe content is 0.25 mass% or less, the Si content is 0.25 mass% or less, and the g content is 0. 30 mass% or less. . The inlet pipe (6) and the outlet pipe (7) are manufactured, for example, as such. First, the above-mentioned alloy is used to extrude the inlet pipe material and the outlet pipe material. In addition, a pair of aluminum header boxes (2) (3), a plurality of aluminum extruded refrigerant refrigerant circulation tubes (4), and a plurality of aluminum brazed fins are formed to form the condenser (1) shown in Fig. 1. (5). A plurality of tube insertion holes are formed in the two header boxes (2) and (3), respectively. On the surface of each refrigerant circulation tube (4), a Zn spray layer of 2.0 to 16.0 g / m2, ideally 2.0 to 8.0 g / m2 is formed, and the total Zn spray layer on the surface of all refrigerant flow tubes (4) is formed. The amount of Zn is 75 ~ 600g, ideally 75 ~ 300g ° Furthermore, a pair of header boxes (2) (3) are arranged at intervals, and a plurality of refrigerant circulation tubes (4) and a plurality of wave-shaped heat sinks (5) are arranged at the same time, Insert the two ends of the refrigerant circulation pipe (4) into the tube insertion holes of the two header boxes (2) (3) to form a combined body. Then apply a fluoride-based flux to these assemblies (near the eutectic composition of potassium fluoride and aluminum fluoride), and put them into a furnace made of an inert gas environment. At the same time, put all the inlet pipes and outlet pipes in the above. In the furnace. Thereafter, it is heated at 580 to 6 ° C for 3 to 15 minutes. In this way, the brazing material 200415242 provided in the header box (2) (3) is used to braze the refrigerant flow pipe (4) and the header box (2) (3), and the brazing material using the corrugated heat sink (5) is also used. The condenser circulation pipe (4) and the header box (2) (3) are brazed together to manufacture the condenser (1), and the inlet pipe (6) and the outlet pipe (7) are also manufactured. The condenser (1), a compressor and an evaporator together constitute a refrigerating cycle using a chlorochlorohydrin-based refrigerant, and is used as a vehicle air conditioner, for example, in a car. In the embodiment described above, the inscription tube according to the present invention is formed by a refrigerating cycle using a fluorochlorine refrigerant. Although it is used as a condenser inlet pipe and an outlet pipe of a vehicle air conditioner, it is also used as the vehicle air. The inlet and outlet pipes of the evaporator of the regulator. Furthermore, the aluminum pipe according to the present invention is also used as an inlet and outlet pipe for a car oil cooler, a car water tank, and the like. In addition, the aluminum pipe according to the present invention is also used as a pipe between a compressor, a condenser, and an evaporator of a vehicle air conditioner having a compressor, a condenser, and an evaporator and a refrigeration cycle using a chlorochlorohydrin-based refrigerant. , Or compressor, air cooler, intermediate heat exchanger, expansion with compressor, air cooler, intermediate heat exchanger, expansion valve and evaporator and vehicle air conditioner formed by the refrigeration cycle using CO2 refrigerant Piping between valve and evaporator. Φ Furthermore, the aluminum tube according to the present invention is also used as a vehicle air conditioner with a compressor, an air cooler, an intermediate heat exchanger, an expansion valve, and an evaporator, and a refrigeration cycle using a C 02 refrigerant. Inlet and outlet pipes between air coolers or evaporators. Example 1 Mn 1.08% by mass, Cu 0.01% by mass or less, Si 0.06% by mass, and? 6 0.12% by mass, 1 ^ 0.01% by mass, (: 1 * 0.01% by mass, -12-200415242
Ti 0.01質量％以下、ζη 〇·〇1質量％以下，剩餘部分A1及 無法避免不純物所成合金，分別擠出形成外徑1 2 · 7 m m、周 壁之壁厚1.0mm之出口管材各50克。各入口管材之長度 239mm、各出口管材之長度43 9mm，所有入口管材及出口 管材之外周面表面積係總共1 · 7 3 2 m2。 另一方面，準備外周面之表面積爲0.0219 m2的鋁擠出形 材製扁平狀冷媒流動管（4) 1750克，形成8g/m2之Zn熔射 層在各冷媒流通管（4)的外周面。形成於所有冷媒流通管（4) 外周面的Zn熔射層合計Zn量爲306.6g。 φ 再者，準備各個具35個管插入孔的一對鋁製集管箱（2) (3)50組，及兩面具硬焊材層的鋁硬焊片製波形散熱片（5) 1800 fi ° 然後，隔以間隔配置一對集管箱（2)(3)，同時互相以35 支之冷媒流通管（4)及36個波形散熱片（5)，配置使波形散 熱片（5)至兩端側，準備將冷媒流通管（4)之兩端部插入兩集 管箱（2 )( 3 )的管插入孔所成組合體5 0組。接著，對該等組 合體塗布氟化物系助熔劑（氟化鉀及氟化鋁的共晶組成近 β 旁者），放入作成氮氣環境的爐中。又，放入所有入口管材 及出口管材在上述爐中。接著以56°C /min之加熱速度自30°C 加熱至80°C，保持5 80°C 8.5min之後以冷卻速度48°C /min 降溫至300°C，再急冷至30°C。如此，利用設冷媒流通管（4) 及集管箱（2 )( 3 )於集管箱（2 )( 3 )的硬焊材層作硬焊’同時將 冷媒流通管（4)及波形散熱片（5)利用波形散熱片（5)的硬焊 材，一起作硬焊製造凝結器（1 )，同時製造了凝結器用入口 -13- 200415242 管（6)及出口管（7)。 比較例1 作爲入口管材及出口管材，除使用由JIS A3 003所成者 ’其他與上述實施例同樣製造了凝結器用入口管及同出口 管。 比較例2 作爲入口管材及出口管材，除使用由jIS A1100所成者 ’其他係與上述實施例1同樣製造了凝結器用入口管及同 出口管。 比較例3 使用實施例1之合金擠出成形，其後照無施予任何處理 的原樣者作入口管及出口管。 評價試驗1 從實施例1、比較例1、比較例2及比較例3所製造入口 管中各個抽出各1支，分別對該等施予S WAAT 960hr試驗 調查其腐蝕狀況。其結果，在實施例1之入口管最大腐蝕 深度爲642 μιη，無產生了穿通周壁的孔蝕。對於此，比較 例1〜3之入口管係產生了穿通周壁的孔蝕。 評價試驗2 從實施例1製造的入口管及出口管中分別抽出各2支， 由電子束微分析儀（ΕΡΜΑ)，測定自外周面之最表面的Ζη 最大擴散距離及在最大擴散距離的Ζη濃度。其結果表示於 表1。又對該等之入口管及出口管分別施予SWAAT 960hr 試驗調查了最大腐蝕深度。其結果亦表示在表1。 200415242 [表1] 試料No Zn濃度 最大擴散距離 最大腐蝕深度 1 0.32質量％ 65μηι 206μηι 入口管 2 0.26質量％ 65μηι 23 1 μηι 3 0.43質量％ 70μπι 521μπι 出口管 4 0.43質量％ 75μπι 446μπι 評價試驗3 從實施例1製造的入口管及出口管中分別抽出各2支， 以硝酸洗淨後，由電子束微分析儀（E p M A) ’測定自外周面 馨 之最表面的Zn最大擴散距離及在最大擴散距離的Zri濃度 。其結果表示於表2。又對該等之入口管及出口管分別施 予S W A A T 9 6 0 h r試驗調查了最大腐鈾深度。其結果表示於 表2。 [表2] 試料No Zn濃度 最大擴散距離 最大腐蝕深度 入口管 5 0.21質量％ 70μιη 462μπι 6 0.23質量％ 60μηι 159μπι 出口管 7 0.25質量％ 65 μιη 120μηη 8 0.28質量％ 75μπι 144μηι 產業上之利用可能性Ti 0.01% by mass or less, ζη 〇.〇1% by mass, the remaining part A1 and the alloy formed by unavoidable impurities are extruded to form 50 g of each of the outlet pipes with an outer diameter of 1 2 · 7 mm and a wall thickness of 1.0 mm. . The length of each inlet pipe is 239mm, and the length of each outlet pipe is 43.9mm. The outer peripheral surface area of all inlet pipes and outlet pipes is a total of 1 · 7 3 2 m2. On the other hand, a 1750 g flat refrigerant flow tube (4) made of aluminum extruded material having a surface area of 0.0219 m2 on the outer peripheral surface was prepared, and a Zn spraying layer of 8 g / m2 was formed on the outer peripheral surface of each refrigerant circulation tube (4). . The total Zn content of the Zn spraying layer formed on the outer peripheral surfaces of all the refrigerant circulation tubes (4) was 306.6 g. φ In addition, prepare a pair of aluminum header boxes (2) (3) and 50 sets each with 35 tube insertion holes, and corrugated aluminum heat sinks (5) 1800 fi ° Then, a pair of header boxes (2) and (3) are arranged at intervals, while 35 refrigerant circulation tubes (4) and 36 wave fins (5) are arranged at each other, and the wave fins (5) to At both ends, it is prepared to insert 50 sets of both ends of the refrigerant circulation pipe (4) into the tube insertion holes of the two header boxes (2) and (3). Next, a fluoride-based flux (the eutectic composition of potassium fluoride and aluminum fluoride is near β) is applied to these assemblies, and the mixture is placed in an oven under a nitrogen atmosphere. In addition, all the inlet pipes and outlet pipes are put in the furnace. It is then heated from 30 ° C to 80 ° C at a heating rate of 56 ° C / min, maintained at 5 80 ° C for 8.5min, then cooled to 300 ° C at a cooling rate of 48 ° C / min, and then quenched to 30 ° C. In this way, the brazing material layer provided with the refrigerant circulation pipe (4) and the header box (2) (3) to the header box (2) (3) is used for brazing. At the same time, the refrigerant circulation pipe (4) and the waveform are radiated. The sheet (5) uses the brazing material of the corrugated heat sink (5) to braze together to manufacture the condenser (1), and simultaneously manufactures the inlet-13-200415242 tube (6) and the outlet tube (7) for the condenser. Comparative Example 1 An inlet pipe and an outlet pipe for a condenser were manufactured in the same manner as in the above-mentioned Example except that the inlet pipe and the outlet pipe were made of JIS A3 003. Comparative Example 2 An inlet pipe and an outlet pipe for a condenser were manufactured in the same manner as in Example 1 above except that the product made of jIS A1100 was used as the inlet pipe and the outlet pipe. Comparative Example 3 The alloy of Example 1 was used for extrusion molding, and the inlet pipe and the outlet pipe were used as they were without any treatment thereafter. Evaluation Test 1 Each of the inlet pipes manufactured in Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 was drawn, and each of them was subjected to a SWAAT 960hr test to investigate the corrosion condition. As a result, the maximum corrosion depth of the inlet pipe of Example 1 was 642 μm, and no pitting corrosion was caused to penetrate the peripheral wall. In this regard, pitting through the peripheral wall occurred in the inlet piping systems of Comparative Examples 1 to 3. Evaluation test 2 Each of the inlet pipe and the outlet pipe manufactured in Example 1 was extracted, and an electron beam microanalyzer (EPMA) was used to measure the maximum diffusion distance Zn and the maximum diffusion distance Zn from the outermost surface. concentration. The results are shown in Table 1. The inlet and outlet pipes were respectively subjected to SWAAT 960hr test to investigate the maximum corrosion depth. The results are also shown in Table 1. 200415242 [Table 1] Sample No. Zn concentration maximum diffusion distance maximum corrosion depth 1 0.32 mass% 65μηι 206μηι inlet tube 2 0.26 mass% 65μηι 23 1 μηι 3 0.43 mass% 70μπι 521μπι outlet tube 4 0.43 mass% 75μπι 446 μπι Evaluation test 3 implemented from The two inlet tubes and the outlet tube manufactured in Example 1 were respectively taken out, washed with nitric acid, and then the maximum diffusion distance of Zn from the outermost surface and the maximum distance were measured by an electron beam microanalyzer (E p MA) '. Zri concentration of diffusion distance. The results are shown in Table 2. SW A A T 960 hr tests were performed on these inlet and outlet pipes to investigate the maximum uranium depth. The results are shown in Table 2. [Table 2] Sample No Zn concentration Maximum diffusion distance Maximum corrosion depth Inlet pipe 5 0.21% by mass 70μιη 462μπι 6 0.23% by mass 60μηι 159μπι Outlet tube 7 0.25% by mass 65 μιη 120μηη 8 0.28% by mass 75μπι 144μηι Industrial availability
本發明之鋁管，適於具有作爲氟氯烷系冷媒的車輛空氣 調節器之凝結器或蒸發器，使用C02冷媒的車輛空氣調節 器之氣冷器或蒸發器、汽車用油冷器、汽車用水箱等使用 的熱交換器用出入口管、或具壓縮機、凝結器及蒸發器且 -15- 200415242 使用氟氯烷系冷媒的車輛空氣調節器之壓縮機、凝結器及 蒸發器間的配管使用，或具有壓縮機、氣冷器、中間熱交 換器、膨脹閥及蒸發器且使用c 〇2冷媒的車輛空氣調節器 之壓縮機、氣冷器、中間熱交換器、膨脹閥及蒸發器間的 配管使用。。 (五）圖式簡單說明 第1圖依本發明其鋁管具有作爲入口管及出口管，表示 具使用氟氯烷系冷媒的車輛空氣調節器的凝結器斜視圖。 [主要部分之代表符號說明] φ 1 凝結器 2、3 第i、第2集管箱 4 扁平狀冷媒流動管（熱交換管） 5 波形散熱片 6 鋁擠出形材製入口管 7 鋁擠出形材製出口管 8 第1隔間板 9 第2隔間板 _The aluminum tube of the present invention is suitable for a condenser or an evaporator of a vehicle air conditioner as a chlorochlorohydrin refrigerant, an air cooler or an evaporator of a vehicle air conditioner using a C02 refrigerant, an oil cooler for an automobile, an automobile Inlet and outlet pipes for heat exchangers used for water tanks, etc., or piping between compressors, condensers and evaporators of vehicle air conditioners with compressors, condensers and evaporators and -15-200415242 using halothane refrigerants , Or compressors, air coolers, intermediate heat exchangers, expansion valves, and evaporators with compressors, air coolers, intermediate heat exchangers, expansion valves, and evaporators, and vehicle air conditioners using C02 refrigerant For piping. . (5) Brief Description of Drawings Fig. 1 is an oblique view of a condenser of a vehicle air conditioner using a chlorochlorohydrin refrigerant as an aluminum pipe having an inlet pipe and an outlet pipe according to the present invention. [Description of representative symbols of main parts] φ 1 Condenser 2, 3 i, 2 header box 4 Flat refrigerant flow tube (heat exchange tube) 5 Corrugated fins 6 Aluminum extrusion inlet pipe 7 Aluminum extrusion Outlet pipe made of shaped material 8 1st compartment panel 9 2nd compartment panel _