TWI275641B - Cold-drawn lubricating oil, lubrication film and method of producing cold-drawn steel tube - Google Patents

Abstract

The invented first lubricating oil has an S content of <=3 mass% and a viscosity of 5x10<-4> to 1x10<-3> m<2>/s (400 to 1,000 cSt) and the second lubricating oil has an S content of 10-30 mass% and a viscosity of 5x10<-5> to 2x10<-4> m<2>/s (50 to 200 cSt). The lubrication film made from the invented two kinds of lubricating oils can ensure lubrication performance during cold-drawing and reduce annealing sludge to be below 3 g/m<2>. Therefore, the most adequate cold-drawn steel tube for use as various mechanical structure parts in automotive industry can be obtained.

Description

1275641 (2) 的各種方法。 舉例來說’在日本特開平1 0-2 8 6 6 1 6號公報中，揭示 一種在拉伸加工過程中經由中空心軸將潤滑油塗佈於管內 面的裝置’該管內面塗佈潤滑油的裝置，在供殘留於前述 中空心軸內之油料回流至儲槽的配管流路設有安全閥。 此外，在日本特開昭6 2 - 2 3 6 8 9 6號公報中揭示一種潤 滑方法’該潤滑方法是當冷拉加工使截面減少率爲3 〇 % 以上時，採用由1 〇〜60重量％的基礎油（base oil )、和 10〜60重量％的硫磺系耐高壓添加劑、及35重量％的增 黏劑混合而成，且4(TC時黏度爲100〜5000百分泊（ centi-P〇ise )的潤滑油。 同樣地，在日本特公平4-4 8 8 3 9號公報中也揭示一種 潤滑處理方法，該潤滑處理方法是在對碳鋼或合金鋼的線 材、棒材或管材進行酸洗處理之後，在材料的表面塗佈： 在2 0 °C時黏度爲1 〇 〇〜3 〇 〇 〇百分泊的潤滑油。 上述所揭示的潤滑油成分，是由：硫磺成分占3 0 % 以上的二烷基具硫化合物5〜4〇% ;和2〇〜7〇%之油脂與烯 煙的化合物’該化合物是由含有1 5 %以上之硫磺成分的 化合物中所選出；和由油脂、合成油、礦物油及高級脂肪 酸中選出1種或2種以上的基礎油；及至少由聚異丁烯、 ^ @共聚合物系增黏劑與聚酯系增黏劑中選出1種以上的 增黏劑所構成。 另外在日本特開2002- 1 92220號公報中揭示一種冷拉 銅I管的製造方法，該冷拉鋼管的製造方法是將管材浸漬於 1275641 (3) 含有金屬鹽的水溶液中，使該管材的內外面形成硼酸的鹼 性金屬鹽、或硼酸的鹼性金屬鹽與脂肪酸之鹼性金屬鹽的 覆膜，並於該覆膜上塗佈液態潤滑劑。 由結構構件的輕量化觀點來看，近年來，以汽車業爲 首之各種機械結構構件所採用的機械結構用鋼管均要求高 強度。 爲了因應上述的需求，有時會採用於冷拉後以較低溫 度執行退火，使因冷拉加工所造成的加工歪斜（skewness )殘存於成品鋼管中，以確保鋼管之高強度的方法。 此外，退火後的鋼管表面爲了確保其平滑性與表面特 性，最好抑制退火時所產生的銹皮，並降低形成於鋼管表 面之銹皮的厚度。因此，機械結構用鋼管的退火，多半是 採用將爐內氣相環境調整成非氧化性的輝面退火。 除此之外，由降低成本的觀點來看，許多冷拉後之鋼 管的內外面可不經硏磨，而直接當作結構用構件使用。在 上述的狀態下，於形成前述化合覆膜的方法中，部分的磷 酸鋅與有機金屬鹽將燒焦於冷拉後之鋼管的表面，將影響 冷拉鋼管的金屬光澤。 由於上述的狀況，使得冷拉加工的前置處理，也就是 指在鋼管母材的表面形成化合覆膜的處理變得困難。 此外，相較於化合覆膜處理，可淸楚地得知在冷拉前 將潤滑油塗佈鋼管母材之油潤滑處理的處理過程則較爲簡 易，且工序與運轉成本可大幅地降低。因此，冷拉加工的 前置處理多半採用油潤滑處理。 -7- 1275641 (4) 誠如以上所述，用於汽車製造等機械結構用鋼管不僅 要求高強度，更由於表面不經硏磨地直接使用，所以冷拉 後必須在低溫環境下的調整爐內進行退火。 當執行上述退火時’如何藉由促進潤滑油的熱分解， 進而充分地揮發去除潤滑油’以達成退火殘渣的減少便成 爲欲解決的新課題。 倘若採用前述日本特開平1 0-2 8 6 6 1 6號公報所揭示的 裝置，於特定的內面塗佈油料之後，由等待拉伸之中空心 軸前端所洩漏的潤滑油將從擠壓口部流入另一端，進而解 決在稍後熱處理過程中因形成碳化導致內面污染的問題。 但由於並非針對潤滑油本身進行改善，因此並無法解決退 火殘渣的新課題。 此外，在日本特開昭62-23 6 8 96號及日本特公平4-48839號公報中，是意圖藉由採用硫擴（s)系耐高壓添 加劑來確保冷拉時的潤滑性，並防止燒焦及附著的情形產 生，而日本特開2002- 1 92220號公報，其目的則是在鋼管 母材的內外面形成鹼性金屬鹽的覆膜，以抑制冷拉時發生 燒焦的同時，防止冷拉後之熱處理過程中產生滲磷。 因此，倘若採用上述日本特開昭62-236896號公報、 曰本特公平4-4 8 8 3 9號公報及日本特開2002- 1 92220號公 報等3件專利文獻所揭示的方法，雖然可防止在冷拉過程 中燒焦與附著的產生，並抑制不規則震動的形成，並無法 解決上述退火殘渣的新課題。 據此，採用上述3件專利文獻所揭示的方法對冷拉後 -8 - 1275641 (5) 的鋼管進行退火’譬如在65〇t以下實施輝面熱處理，由 於在添加S/IL·細（S )系耐局壓添加劑的狀態下潤滑油無法 充分地揮發，將導致退火殘渣大量地形成。 【發明內容】 本發明的目的是以解決上述新課題，也就是在低溫壤 境的爐內進行低溫退火爲前提，在採取油潤滑處理執行冷 拉加工時’確保潤滑性並防止燒焦與附著產生的同時，不 致在鋼管表面產生「黑化」與「污物附著」等退火殘渣， 並可同時使用潤滑油與潤滑覆膜之冷拉鋼管的製造方法。 爲了因應機械結構用鋼管的高強度需求、及省略鋼管 表面硏磨的需求，本發明團隊經各種討論後，發現了以下 (a )〜（C )的重要技術事項。 (a )烏了獲得良好的外觀，並須抑制退火所產生的 錄皮’以降低鋼管表面之銹皮的厚度。具體來說，是於執 行冷拉且退火之後，將鋼管表面的銹皮厚度控制爲〇 . 5〜】〇 β m 〇 (b )爲了有效率地確保高強度，而採用低溫退火使 冷拉所形成的加工歪斜殘留於鋼管。進行低溫退火之際， 根據後述的理由，加熱的溫度爲6 5 0 °C以下。 (c )爲了確保良好的外觀及表面品質，鋼管表面不 能因附著或殘留退火殘渣而形成髒污。具體的目標，·是將 退火殘渣的附著量訂爲3g/m2以下。 除此之外’在確保潤滑性以防止燒焦的同時，爲了達 冬 1275641 (6) 成退火殘渣的減量，本案的發明團隊更針對潤滑油中之S 系耐高壓添加劑與退火殘渣間的關連性進行硏究。 在一般的潤滑處理中，爲了提高潤滑性多半採用耐高 壓添加劑’即使在管材與工具（栓塞、壓膜）的臨界處形 成沒有油料的狀態，也能確保其潤滑性。 根據以上的硏究，當欲提高潤滑性執行安定的冷拉時 ，潤滑油中將添加大量的S系耐高壓添加劑。但是，s系 耐高壓添加劑本身容易形成退火殘渣而殘留，進而妨礙基 礎油之潤滑油的熱分解，而有損潤滑油的揮發性。 此外’由於機械結構用鋼管要求高強度，而必須在冷 拉過程中執行強度的加工，使得油膜產生剝離，而容易形 成燒焦。爲了防止上述情形的產生，可於進行冷拉加工之 前，在管材的表面形成具有良好潤滑油保持性之硼酸鹼性 金屬鹽覆膜，以實施良好的表面處理。 而上述的表面處理，可採用磷酸的鹼性金屬鹽取代硼 酸的鹼性金屬鹽形成覆膜，可獲得相同的效果。此外，亦 可形成硼酸之鹼性金屬鹽與磷酸之鹼性金屬鹽的覆膜。 本發明團隊，是以上述的硏究結果作爲前提，並根據 不同的著眼點，朝開發出「即使是具有不同潤滑特性的潤 滑油’皆能適用於製造出具有良好表面特性之冷拉鋼管的 製造」的方向前進。 (1 )第1潤滑油 如上所述，在油潤滑處理過程中，爲了提高潤滑性而 -10- (7) 1275641 添加於潤滑油的S系耐高壓添加劑，由於其本身除了容易 形成退火殘渣而殘留之外，更因爲會妨礙基礎油之潤滑油 的熱分解，因此盡量降低S系耐高壓添加劑的使用。Various methods of 1275641 (2). For example, in Japanese Laid-Open Patent Publication No. Hei 1 0-2 8 6 6 16 , a device for applying lubricating oil to the inner surface of a pipe via a hollow shaft during the drawing process is disclosed. The apparatus for lubricating oil is provided with a safety valve in a piping flow path for returning the oil remaining in the hollow shaft to the storage tank. In addition, a lubricating method is disclosed in Japanese Laid-Open Patent Publication No. Sho 62- 2 3 6 8 9.6. The lubricating method is to use a weight of 1 〇 to 60 when the cross-sectional reduction rate is 3 〇% or more. % base oil, mixed with 10~60% by weight of sulfur-based high-pressure additive, and 35% by weight of tackifier, and 4 (TC viscosity is 100~5000% poise (centi- Lubricating oil is also disclosed in Japanese Patent Publication No. 4-4 8 8 3 9 , which is a method for lubricating a carbon steel or alloy steel wire or bar. After the pipe is pickled, it is coated on the surface of the material: a lubricating oil having a viscosity of 1 〇〇~3 〇〇〇% poise at 20 ° C. The lubricating oil component disclosed above is composed of: sulfur component More than 30% of the dialkyl sulfur compounds 5 to 4% by weight; and 2 to 7 % by weight of the compound of the oil and the ene cigarette' which is selected from compounds containing more than 15% of the sulfur component And one or more bases selected from oils, synthetic oils, mineral oils, and higher fatty acids An oil; and at least one or more kinds of tackifiers selected from the group consisting of polyisobutylene, a copolymer of a copolymer of a copolymer of a copolymer and a polyester, and a polyester-based tackifier. A method for producing a cold drawn copper tube, which is obtained by immersing a tube in an aqueous solution containing 1,275,541 (3) metal salt to form an alkali metal salt of boric acid or a base of boric acid in the inner and outer surfaces of the tube. A film of a basic metal salt of a metal salt and a fatty acid, and a liquid lubricant is applied to the film. From the viewpoint of weight reduction of structural members, in recent years, various mechanical structural members including the automobile industry have been used. The steel pipes for mechanical structures are required to have high strength. In order to meet the above requirements, annealing is sometimes performed at a lower temperature after cold drawing, so that the skewness caused by cold drawing is left in the finished steel pipe. In order to ensure the high strength of the steel pipe, in addition, in order to ensure the smoothness and surface characteristics of the steel pipe surface after annealing, it is preferable to suppress the scale generated during annealing and to reduce the formation of the steel pipe table. Therefore, the annealing of the steel pipe for mechanical structure is mostly performed by adjusting the gas phase environment in the furnace to a non-oxidative glow surface annealing. In addition, from the viewpoint of cost reduction, many cold drawing The inner and outer surfaces of the steel pipe can be directly used as a structural member without honing. In the above state, in the method of forming the above-mentioned compound film, part of the zinc phosphate and the organic metal salt are burnt to the cold drawing. The surface of the steel pipe to be affected will affect the metallic luster of the cold drawn steel pipe. Due to the above-mentioned situation, the pretreatment of the cold drawing process, that is, the process of forming the composite film on the surface of the steel pipe base material becomes difficult. Compared with the compound coating treatment, it is understood that the process of lubricating the oil of the steel pipe base material before the cold drawing is simple, and the process and running cost can be greatly reduced. Therefore, most of the pre-treatment of the cold drawing process is oil-lubricated. -7- 1275641 (4) As mentioned above, steel pipes for mechanical structures such as automobile manufacturing require not only high strength, but also direct use of the surface without honing, so the furnace must be adjusted in a low temperature environment after cold drawing. Annealing is performed inside. When the above annealing is performed, "how to promote the thermal decomposition of the lubricating oil, and then sufficiently volatilize and remove the lubricating oil" to achieve a reduction in the annealing residue becomes a new problem to be solved. In the case of the apparatus disclosed in the above-mentioned Japanese Patent Publication No. Hei 1 0-2 8 6 6 16 , after the oil is applied to the specific inner surface, the lubricating oil leaking from the front end of the hollow shaft waiting for stretching will be squeezed. The mouth flows into the other end, thereby solving the problem of internal contamination caused by carbonization during later heat treatment. However, since the improvement of the lubricating oil itself is not carried out, it is impossible to solve the new problem of the remnant residue. In addition, in Japanese Patent Publication No. Sho 62-23 6 8 96 and Japanese Patent Publication No. 4-48839, it is intended to ensure lubricity during cold drawing by using a sulfur-expanding (s) high-pressure-resistant additive, and to prevent In the case of scorching and adhesion, the purpose of the invention is to form a film of an alkali metal salt on the inner and outer surfaces of the steel pipe base material to suppress scorching during cold drawing. Prevents the occurrence of phosphorus infiltration during the heat treatment after cold drawing. Therefore, the method disclosed in the three patent documents, such as the above-mentioned Japanese Patent Publication No. Sho 62-236896, the Japanese Patent Publication No. 4-4 8 8 3 9 and the Japanese Patent Laid-Open Publication No. 2002-92222, may be used. It prevents the occurrence of scorching and adhesion during the cold drawing process, and suppresses the formation of irregular vibrations, and cannot solve the new problem of the above annealing residue. Accordingly, the steel pipe after the cold drawing is -8 - 1275641 (5) is annealed by the method disclosed in the above three patent documents. For example, a glow surface heat treatment is performed below 65 〇t, since S/IL·fine is added (S The lubricating oil is not sufficiently volatilized in the state of being resistant to the local pressure additive, and the annealing residue is formed in a large amount. SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned new problem, that is, to perform low-temperature annealing in a low-temperature soil furnace, and to ensure lubricity and prevent scorching and adhesion when performing oil-lubrication processing to perform cold drawing processing. At the same time, it is possible to produce an annealing residue such as "blackening" or "contamination" on the surface of the steel pipe, and a method of manufacturing a cold drawn steel pipe using a lubricating oil and a lubricating coating at the same time. In response to the high strength requirements of steel pipes for mechanical structures and the need to omit the honing of steel pipes, the team of the present invention discovered the following important technical matters (a) to (C) after various discussions. (a) A good appearance is obtained, and the skin produced by the annealing is suppressed to reduce the thickness of the scale on the surface of the steel pipe. Specifically, after performing cold drawing and annealing, the thickness of the surface of the steel pipe is controlled to be 〇. 5~] 〇β m 〇 (b) in order to efficiently ensure high strength, low temperature annealing is used to make the cold drawing The resulting processing skew remains in the steel tube. When the low temperature annealing is performed, the heating temperature is 650 ° C or lower for the reason described later. (c) In order to ensure good appearance and surface quality, the surface of the steel pipe cannot be contaminated by adhesion or residual annealing residue. The specific target is to set the amount of adhesion of the annealing residue to 3 g/m2 or less. In addition, in order to ensure lubricity to prevent scorching, in order to reduce the amount of annealing residue in Dadong 1275561 (6), the invention team of this case is more concerned with the relationship between the S-type high-pressure additive and the annealing residue in the lubricating oil. Sexual research. In the general lubrication treatment, in order to improve the lubricity, the high-pressure-resistant additive is often used to ensure the lubricity even in the state where the oil is not formed at the critical point of the pipe and the tool (plug or film). According to the above research, when it is desired to improve the lubricity and perform a stable cold drawing, a large amount of S-based high-pressure additive is added to the lubricating oil. However, the s-based high-pressure-resistant additive itself tends to form an annealing residue and remains, thereby preventing thermal decomposition of the lubricating oil of the base oil and impairing the volatility of the lubricating oil. Further, since the steel pipe for mechanical structure requires high strength, it is necessary to perform strength processing in the cold drawing process, so that the oil film is peeled off, and it is easy to form charring. In order to prevent the above, a boric acid alkaline metal salt film having good lubricating oil retaining property may be formed on the surface of the pipe before the cold drawing process to perform a good surface treatment. On the surface treatment described above, a basic metal salt of phosphoric acid can be used instead of the basic metal salt of boric acid to form a film, and the same effect can be obtained. Further, a film of an alkali metal salt of boric acid and an alkali metal salt of phosphoric acid may be formed. The team of the present invention presupposes the above-mentioned research results, and according to different points of view, the development of "even lubricating oils with different lubricating properties" can be applied to the manufacture of cold drawn steel pipes with good surface characteristics. The direction of manufacturing is moving forward. (1) First lubricating oil As described above, in order to improve lubricity during the oil lubrication treatment, -10 (7) 1275641 is added to the S-based high-pressure-resistant additive of the lubricating oil, and it is easy to form an annealing residue by itself. In addition to the residue, the use of the S-based high-pressure resistant additive is minimized because it hinders the thermal decomposition of the lubricating oil of the base oil.

雖然抑制潤滑油中硫磺的低含有量，將導致油膜剝離 極並容易產生燒焦，爲了防止該情形的產生，可於執行冷 拉之前’在管材的表面形成具有優良潤滑油保持性之硼酸 的鹼性金屬鹽皮膜，並進一步提高潤滑油的黏度。而採用 磷酸的鹼性金屬鹽來取代硼酸的鹼性金屬鹽形成皮膜亦可 獲得相同的效果。 換言之，第1著眼點的前提爲：實施「可在管材表面 塗佈具有良好高黏度潤滑油之潤滑油保持性的覆膜」的表 面處理，並且爲了減少鋼管表面的退火殘渣，選擇盡量減 少S系耐高壓添加劑。Although suppressing the low content of sulfur in the lubricating oil, the oil film is peeled off and the scorch is easily generated, and in order to prevent this, it is possible to form a boric acid having excellent lubricating oil retaining property on the surface of the pipe before performing the cold drawing. An alkaline metal salt film and further increase the viscosity of the lubricating oil. The same effect can be obtained by using an alkaline metal salt of phosphoric acid instead of the basic metal salt of boric acid to form a film. In other words, the premise of the first point of view is to carry out the surface treatment of "coating a lubricant having a good high-viscosity lubricating oil on the surface of the pipe", and to minimize the annealing residue on the surface of the steel pipe, to minimize the S It is a high pressure resistant additive.

本發明的第1潤滑油，是基於上述第i著眼點所完成 的潤滑油，其特徵爲：S含量爲3質量％以下，黏度爲5 XlO 4 〜lXl〇-3m2/s ( 4〇〇 〜i〇〇〇cst) 0 (2 )第2潤滑油 爲了確保潤滑性，而被添加於潤滑油的s系耐高壓添 加劑’會在執行冷拉的管材表面形成低剪斷力的Fes、 F e 2 S等’進而抑制燒焦的情形產生。如上所述地，雖然 潤滑油中的s本身將形成退火殘渣，並將妨礙潤滑油的揮 發性，卻發現形成F e S、F e2 S的S不會妨礙潤滑油的熱分 解及揮發。 -11 - 1275641 (8) 因此，第2著眼點爲：爲了確保潤滑性，積極地使管 材表面含有可形成低剪斷力之FeS、Fe2S等的S。 第1圖爲顯示冷拉後鋼管表面之殘餘油量與S檢測強 度間的關係圖。由於冷拉過程中的油量及膜厚與潤滑油的 黏度成一定比例，因此調整潤滑油的黏度使冷拉後之殘存 油量（g/m2 )產生變化，並藉由螢光X射線分析來檢測鋼 管表面的S量（Kcps )。所使用的潤滑油中S的含量形成 5質重％ 、20質量％及30質量％ 3種。The first lubricating oil of the present invention is a lubricating oil which is completed based on the i-th point of the eye, and has a S content of 3% by mass or less and a viscosity of 5 X10 4 to 1×10 〇 -3 m 2 /s ( 4 〇〇 〜 I〇〇〇cst) 0 (2) The second oil-based s-based high-pressure additive added to the lubricating oil to ensure lubricity will form a low shearing force Fes, F e on the surface of the cold drawn pipe. 2 S, etc., which in turn suppresses scorching. As described above, although s itself in the lubricating oil forms an annealing residue and will hinder the volatility of the lubricating oil, it is found that S forming F e S and F e2 S does not interfere with thermal decomposition and volatilization of the lubricating oil. -11 - 1275641 (8) Therefore, the second point of view is: To ensure the lubricity, the surface of the pipe is actively provided with S such as FeS or Fe2S which can form a low shear force. Fig. 1 is a graph showing the relationship between the residual oil amount on the surface of the steel pipe after cold drawing and the S detection intensity. Since the amount of oil and the thickness of the film during the cold drawing are proportional to the viscosity of the lubricating oil, the viscosity of the lubricating oil is adjusted to change the amount of residual oil (g/m2) after cold drawing, and is analyzed by fluorescent X-ray. To detect the amount of S (Kcps) on the surface of the steel pipe. The content of S in the lubricating oil to be used is three kinds of weight percent, 20 mass%, and 30 mass%.

FeS、Fe2S等的形成，由於是在管材界面產生反應， 因此只能與潤滑油中所含的部分S產生反應。由於此一緣 故，如第1圖所示地，即使增加附著於管材表面的油量， 所形成之FeS、Fe2S等的數量也不會有所變化。相對於此 ，S的檢測強度，則與潤滑油中S的含量有著相當大的依 附關係。 也就是說，形成於管材表面之FeS、Fe2S等的數量， 係仰賴潤滑油中的S含量，受油量與油膜厚度的影響甚少 。因此，爲了有效地在管材表面形成用來確保潤滑性的 FeS、Fe2S等，必須採用具有一定S含量的潤滑油。 其次，當形成FeS、Fe2S等之後，爲了降低潤滑油內 所殘留的S量（絕對量），可降低附著於管材的油量，或 者減少油膜的厚度。Since the formation of FeS, Fe2S, or the like occurs at the interface of the pipe, it can only react with the portion S contained in the lubricating oil. For this reason, as shown in Fig. 1, even if the amount of oil adhering to the surface of the pipe is increased, the amount of FeS, Fe2S, and the like formed does not change. In contrast, the detection intensity of S has a considerable dependence on the content of S in the lubricating oil. That is to say, the amount of FeS, Fe2S, etc. formed on the surface of the pipe depends on the S content in the lubricating oil, and the amount of oil received and the thickness of the oil film are little affected. Therefore, in order to effectively form FeS, Fe2S, etc. for ensuring lubricity on the surface of the pipe, it is necessary to use a lubricating oil having a certain S content. Next, after forming FeS, Fe2S, or the like, in order to reduce the amount of S (absolute amount) remaining in the lubricating oil, the amount of oil adhering to the pipe can be reduced, or the thickness of the oil film can be reduced.

冷拉過程中的油量與油膜厚度，由於與潤滑油的黏度 呈一定比例，故可對應潤滑性適當地選擇潤滑油的S含量 ，並藉由選擇適當的黏度，可確保管材表面之FeS、Fe2S -12- 1275641 (9) 等的形成量，並降低殘留於潤滑油內的S量。 如上所述地，藉由積極地使潤滑油內含有S的方式， 可確保潤滑性並將退火殘渣降低爲3g/m2以下。 本發明的第2潤滑油，是基於上述第2著眼點而成的 潤滑油’其特徵爲：S含量爲10〜30質量％以下，黏度爲 5x1 (Γ5 〜2xl〇-4m2/s ( 50 〜200cSt ) 〇 (3 )使用第1、2潤滑油的潤滑覆膜、及冷拉鋼管的製造 方法 誠如以上所述，當於油潤滑處理後進行冷拉加工時， 爲了防止油膜剝離及燒焦的情形產生，乃於進行冷拉加工 之前，在管材的表面形成具有良好潤滑油保持性之硼酸鹼 性金屬鹽覆膜，以實施良好的表面處理。 上述的表面處理，可採用磷酸的鹼性金屬鹽取代硼酸 的鹼性金屬鹽形成覆膜，並能獲得相同的效果。 據此，本發明之潤滑覆膜的特徵爲：是由形成於被浸 漬之管材表面的硼酸之鹼性金屬鹽覆膜；及被塗佈於前述 覆膜表面的第1或第2潤滑油所構成。 而，本發明的潤滑覆膜，亦可在管材的內外面形成磷 酸的鹼性金屬鹽覆膜，或亦可在管材的內外面形成硼酸的 鹼性金屬覆膜及磷酸的鹼性金屬覆膜。 此外，本發明之冷拉鋼管的製造方法，其特徵爲：將 管材浸漬於含有硼酸之鹼性金屬鹽的水溶液中，使前述管 材的內外面形成硼酸的鹼性金屬鹽覆膜，當將第】或第2 -13- 1275641 (10) 潤滑油塗佈於前述覆膜表面經冷拉之後 給含有c 0之氣體，一邊在6 5 0 °C以下 行退火。 此外，在本發明之冷拉鋼管的製造 有磷酸之鹼性金屬鹽的水溶液取代含有 的水溶液，而在管材的內外面形成磷酸 。除此之外，亦可使用含有硼酸之鹼性 性金屬鹽的水溶液來取代含有硼酸之鹼 ，而在管材的內外面形成硼酸之鹼性金屬 金屬鹽的覆膜。 根據本發明的冷拉用潤滑油及潤滑覆 拉的過程中確保潤滑性，並將退火殘渣降 。據此，只要採用本發明的冷拉用潤滑油 油潤滑處理並製造冷拉鋼管，可提供最適 汽車製造業爲首之各種機械結構構件使用 本發明中所謂的「冷拉鋼管」，是指 與鉻鉬鋼之類的合金鋼、及不鏽鋼等管材 的鋼管，也就是指在汽車業與其他產業領 構用構件使用的鋼管。 又，本發明之冷拉鋼管的製造方法中 c 〇的氣體」，是指爲了促進大氣環境內 供應的氣體，譬如體積％爲 CO : 0.1 10·0〜14.0% 、H2 : 0.1〜1.5%而剩餘部分赁 體。 在一邊對爐內供 丨爐內氣相環境進 •法中，可使用含 丨酸之鹼性金屬鹽 鹼性金屬鹽覆膜 屬鹽及磷酸之鹼 金屬鹽的水溶液 鹽及磷酸之鹼性 膜，可於執行冷 低爲3gy^m2以下 及潤滑覆膜實施 當的鋼管作爲以 〇 對碳鋼、和鉻鋼 施以冷拉所獲得 域中作爲機械結 所規定之「含有 的循環、換氣而 〜3 · 0 % 、C 0 2 · 丨N所構成的氣 -14- (11) 1275641 【實施方式】 本發明的製造方法，其特徵爲：於進行冷拉之際，預 先將管材浸潰於水溶液中，而在管材的內外面形成硼酸的 鹼性金屬鹽或/及磷酸的鹼性金屬鹽之覆膜，並在該覆膜 上塗佈潤滑油，形成2層構造的潤滑覆膜後經冷拉加工， 一邊將含有C 〇的氣體供給至爐內氣相環境的低溫環境下 進行退火。The amount of oil in the cold drawing process and the thickness of the oil film are proportional to the viscosity of the lubricating oil. Therefore, the S content of the lubricating oil can be appropriately selected according to the lubricity, and the FeS on the surface of the pipe can be ensured by selecting an appropriate viscosity. The amount of formation of Fe2S -12- 1275641 (9), etc., and the amount of S remaining in the lubricating oil. As described above, by actively providing S in the lubricating oil, lubricity can be ensured and the annealing residue can be reduced to 3 g/m 2 or less. The second lubricating oil of the present invention is characterized in that the lubricating oil is formed based on the second point of view, and the S content is 10 to 30% by mass or less, and the viscosity is 5x1 (Γ5 to 2xl〇-4m2/s (50 〜 200cSt ) 〇 (3) The lubricating film for the first and second lubricating oils and the method for producing the cold drawn steel pipe are as described above, and when the cold drawing process is performed after the oil lubrication treatment, in order to prevent the oil film from peeling off and burning In the case of the cold drawing process, a boric acid alkaline metal salt film having good lubricating oil retaining property is formed on the surface of the pipe to perform a good surface treatment. The metal salt replaces the basic metal salt of boric acid to form a film, and the same effect can be obtained. Accordingly, the lubricating film of the present invention is characterized by being covered with an alkali metal salt of boric acid formed on the surface of the impregnated pipe material. And a first or second lubricating oil coated on the surface of the coating film. The lubricating coating of the present invention may form an alkaline metal salt coating of phosphoric acid on the inner and outer surfaces of the tubular material, or Can be shaped inside and outside the pipe An alkaline metal coating film of boric acid and an alkali metal coating film of phosphoric acid. The method for producing a cold drawn steel pipe according to the present invention is characterized in that the pipe material is immersed in an aqueous solution containing an alkali metal salt of boric acid to make the pipe material An alkaline metal salt coating film of boric acid is formed on the inner and outer sides, and the lubricating oil containing c 0 is applied to the surface of the coating film after the first or second -13 - 1275641 (10) lubricating oil is applied to the surface of the coating film, while the gas is contained at 6 Annealing at 50 ° C. In addition, in the cold-drawn steel pipe of the present invention, an aqueous solution of an alkali metal salt of phosphoric acid is used instead of the aqueous solution contained, and phosphoric acid is formed on the inner and outer surfaces of the pipe. An aqueous solution containing a basic metal salt of boric acid is substituted for a base containing boric acid to form a coating of an alkali metal metal salt of boric acid on the inner and outer sides of the tube. The lubricating oil for cold drawing and the process of lubricating and pulling according to the present invention The lubricating property is ensured and the annealing residue is lowered. Accordingly, as long as the cold drawn lubricating oil is lubricated by the cold drawing lubricating oil of the present invention and the cold drawn steel pipe is manufactured, various mechanical knots which are optimal for the automobile manufacturing industry can be provided. The term "cold-drawn steel pipe" as used in the present invention refers to a steel pipe such as an alloy steel such as chrome-molybdenum steel or a pipe such as stainless steel, that is, a steel pipe used for members in the automobile industry and other industries. Further, in the method for producing a cold-drawn steel pipe according to the present invention, the gas "c" refers to a gas which is supplied in an atmosphere, for example, a volume % of CO: 0.1 10·0 to 14.0%, and H2: 0.1 to 1.5%. The remaining part of the liquefied body. In one side of the furnace gas supply environment in the furnace, the alkali metal salt salt of the bismuth acid and the alkali metal salt of the alkali metal salt can be used. The basic film of phosphoric acid can be used as a mechanical knot in the field obtained by applying a cold lowering of 3 gy^m2 or less and a lubricating coating as a mechanical knot obtained by applying cold rolling to carbon steel and chrome steel. Circulating and ventilating ～3·0%, C 0 2 · 丨N constituting gas-14- (11) 1275641 [Embodiment] The manufacturing method of the present invention is characterized in that, when performing cold drawing, The tube is immersed in an aqueous solution in advance, while in the tube A film of an alkali metal salt of boric acid or an alkali metal salt of phosphoric acid is formed on the outside, and a lubricating oil is applied onto the film to form a lubricating film having a two-layer structure, which is subjected to cold drawing and contains C. The helium gas is supplied to the low temperature environment of the gas phase environment in the furnace for annealing.

接下來’將本發明的內容分成鹼性金屬鹽之覆膜的形 成（表面處理）、潤滑油及低溫退火來加以說明。 1、鹼性金屬鹽之覆膜的形成 潤滑油的表面處理，是將管材浸漬於含有硼酸之鹼性 金屬鹽的水溶液中，於前述管材的內外面形成硼酸之鹼性 金屬鹽的覆膜。Next, the description of the present invention will be described by the formation of a film of an alkali metal salt (surface treatment), lubricating oil, and low-temperature annealing. 1. Formation of a film of an alkali metal salt The surface treatment of a lubricating oil is to form a film of an alkali metal salt of boric acid on the inner and outer surfaces of the pipe by immersing the pipe in an aqueous solution containing an alkali metal salt of boric acid.

硼酸的鹼性金屬鹽，與管材之間的密著性良好，此外 ’當覆膜表面塗佈潤滑油時，具有良好的保持性。 據此，藉由使管材的表面形成硼酸之鹼性金屬鹽的覆 膜’並於該覆膜上塗佈潤滑油的方式，可降低冷拉過程中 管材與拉伸工具（栓塞、壓模）間的摩擦力，可防止管材 與拉伸工具之間的燒焦。 硼酸之鹼性金屬鹽的覆膜厚度，最好是形成〇·4〜20 从111。一旦覆膜厚度超過2 0 // m將變的容易剝離。而且， 潤滑油殘留於鋼管的表面，當退火後有時會變成退火殘渣 而殘留。另外，當覆膜厚度未達0 ·4 ^ m時，將使管材表 -15- (12) 1275641 面與拉伸工具形成直接的接觸，並且由於潤滑油的保持力 下降，而導致潤滑性降低。 所謂硼酸的鹼性金屬鹽，譬如硼酸鋰、硼酸鉀及硼酸 鈉。其中又以硼酸鉀最爲合適。 爲了使管材的內外面形成硼酸之鹼性金屬鹽的覆膜’ 首先，必須將管材浸漬於含有硼酸之鹼性金屬鹽的水溶液 中。覆膜的厚度可根據浸漬時間及水溶液溫度等進行調整 ，處理後的覆膜厚度最好是形成0.4〜2.0// m。 此外，水溶液中硼酸之鹼性金屬鹽的濃度，可依覆膜 的厚度及浸漬的時間等決定，舉例來說’以2〜1 0質量％ 的範圍最爲適當。而水溶液的溫度則以7〇〜1〇〇的範圍最 佳。 接下來，對浸漬後的管材進行乾燥。藉此，可此管材 的內外面形成硼酸之鹼性金屬鹽的覆膜。而經浸漬之管材 的乾燥，可藉由一般放入1 5 0 t左右之乾燥室內的方法進 行。 適用於本發明的其他表面處理，可使用含有磷酸之鹼 性金屬鹽的水溶液取代含有硼酸之鹼性金屬鹽的水溶液’ 使管材的內外面形成磷酸之鹼性金屬鹽的覆膜，可獲得相 同的效果。換言之，由於上述覆膜與管材間的密著性良好 ，並具有絕佳的潤滑油保持性，故可抑制冷拉加工過程中 管材與拉伸工具間的燒焦。 此外，在上述的場合中，硼酸之鹼性金屬鹽與磷酸之 鹼性金屬鹽的作用效果有著若干的差異。前者可提高管材 -16- 1275641 (13) 與覆膜的密著性，進而提高塗佈於覆膜上之潤滑油的保持 性，具有防止管材與拉伸工具間之燒焦得效果。 相對於此，後者除了可提高塗佈於覆膜表面之潤滑油 的保持性之外，其本身就具有可防止管材與拉伸工具間的 直接接觸、及防止燒焦的效果。 當採用含有磷酸之鹼性金屬鹽的水溶液所形成的覆膜 厚度’與硼酸之鹼性金屬鹽所形成的覆膜相同，皆爲 〇 · 4 〜2 · 0 // m。 所謂的磷酸之鹼性金屬鹽，譬如第2磷酸鈉、第3磷 酸鈉、焦磷酸鈉等。其中又以第2磷酸鈉最爲合適。 管材內外面的磷酸之鹼性金屬鹽覆膜的形成，也與硼 酸之鹼性金屬鹽覆膜的形成方式一樣，採用浸漬法即可。 水溶液中磷酸之鹼性金屬鹽的濃度，舉例來說，以 〇 · 1〜5 · 0質量％的範圍最爲合適，水溶液的溫度只要是 60〜100 °C的範圍內即可。而浸漬後的管材乾燥，採用與硼 酸之鹼性金屬鹽相同的方式即可。 除此之外’適用於本發明之其他不同的表面處理，可 採用含有硼酸之鹼性金屬鹽及磷酸之間性金屬鹽的水溶液 取代含有硼酸之鹼性金屬鹽的水溶液，使管材的內外面形 成硼酸之鹼性金屬鹽與磷酸之鹼性金屬鹽的覆膜，獲得相 同的效果。 採用上述方式所獲得的效果，是介於採用硼酸之鹼性 金屬鹽與採用磷酸之鹼性金屬鹽間之中間値的作用效果。 採用含有硼酸之鹼性金屬鹽及磷酸之鹼性金屬鹽的水 -17- 1275641 (14) 溶液所形成的覆膜厚度、覆膜 使用硼酸之鹼性金屬鹽時所採 水溶液中兩種鹼性金屬鹽的濃 度範圍是合計濃度0.1〜3.0 ® 如上所述地，本發明的潤 形成硼酸之鹼性金屬鹽或/及 爲表面處理，並藉由在該覆膜 層結構的方式，無論是碳鋼、 加工，都能發揮良好的潤滑性 2、潤滑油 本發明的第1潤滑油，S 度爲 5xl(T4 〜lxl0*3m2/s ( 400 〜 第1潤滑油中s含量爲3 當潤滑油中添加S系耐高壓添 %時，將導致退火殘渣的數量 解之故。 據此，由抑制退火殘渣產 中的S含量最好是儘可能地降 是，由於含有些許的S，將具 此在實際使用上，S含量最好 第1潤滑油的黏度（動i (400〜lOOOcSt)。的原因，I ，將導致冷拉過程中流入管材 及形成方式及乾燥方式，與 用的方法相同。此外，前述 度，舉例來說，最合適的濃 ΐ量％ 。 滑覆膜，是在管材的內外面 磷酸之鹼性金屬鹽的覆膜作 上圖布後述的潤滑油形成2 合金鋼或者是不鏽鋼的冷拉 含有量爲3質量％以下，黏 ]OOOcSt) ° 質量％以下的理由，是由於 加劑而使S含量超過3質量 大增，並妨礙潤滑油的熱分 生的觀點來看，第1潤滑油 低，即使不含S亦無妨。但 有不易形成燒焦的效果，因 爲1 .5〜3質量％ 。 S 度）爲 5 X 1 0·4〜1 X 1 (T3m2/s I由於一旦黏度低於5 X 1 (Γ4 與拉伸工具間之潤滑油的量 -18- 1275641 (15) 不足’使管材與拉伸工具形成直接接觸而造成管材的瑕疵 ’此外’一旦黏度超過1 X 1 (T3m2/s，將增加附著於管材 之潤滑油的數量，而不利於成本的考量。 其次’本發明所採用的第2潤滑油，S含量爲1 〇〜3 〇 質量 ％ 以下’黏度爲 5χ1〇.5 〜2xl(r4m2/s(5〇 〜2〇〇cSt)。 一旦第2潤滑油的S含量低於1 〇質量％ ，將使管材 表面的F e S、F e 2 S等的形成量減少而無法確保潤滑性。此 外’倘若S含量高於30質量％ ，雖然可確保FeS、Fe2S 等的形成量，卻也使潤滑油中的S量增加而導致退火殘渣 的數里大增’並妨礙潤滑油的熱分解。故，潤滑油的含 量爲10〜30質量％ 。 而第2潤滑油的黏度（動黏度）爲5x 1 (Γ5〜2 X 1 0·4 m2/s ( 5 0〜200cSt )的原因，是爲了在以上述潤滑油之S 含量作爲前提的條件下，藉由調節附著於管材表面的油量 與油膜厚度，確保管材表面之FeS、Fe2S等的形成量，以 降低殘留於潤滑油內之S量的方式，確保潤滑性並降低退 火殘渣的產生。 換言之，一旦黏度低於5xl(T5m2/s時，將使附著於 管材表面的油量減少，以致冷拉過程中流入管材與拉伸工 具間之潤滑油的量不足，使管材與拉伸工具形成直接接觸 而造成燒焦的產生。 此外，一旦第2潤滑油的黏度超過2 X l(T4m2/s，將 增加附著於管材的油量與油膜厚度，以致殘留於潤滑油內 的S量大增，而無法將退火殘渣的數量降低爲3 g/m2以下 -19- (16) 1275641 本發明所採用的潤滑油，並沒有特別限制其基礎油， 除了可採用豬油、牛油、鯨油、棕櫚油、椰子油及菜子油 (rapeSeed οΠ )等動植物油脂，亦可採用合成油或礦物 油。 本發明中用來將潤滑油塗佈於鹼性金屬鹽之覆膜表面 的方法’只需採用傳統的方法即可。譬如由配置於管材外 周的噴嘴將潤滑油供應至管材外面的方法，或利用設成插 入管材內部的中空心軸將潤滑油供給至管材內面的方法均 適用。 本發明的製造方法中，是在管材表面形成2層結構之 潤滑覆膜後執行冷拉。本發明的冷拉加工可採用一般慣用 的方式’沒有特別限定的必要。 3、退火 本發明中的退火，是以確保冷拉鋼管的強度爲目的， 而保留因冷拉所形成的加工歪斜。當退火溫度過高將使加 工歪斜的情形復原，而無法獲得加工硬化的效果。經冷拉 加工後的鋼管，可藉由在65 0 °C以下的溫度進行退火，以 獲得加工硬化的效果。 此外，爲了維持爐內的安定燃燒，退火溫度的下限最 好爲3 5 0 °C。爲了冷拉鋼管的強度一致，冷拉鋼管保持於 爐內的時間最好爲5分鐘以上。 再者，爲了抑制退火所產生的銹皮，以便將冷拉鋼胃 -20- (17) 1275641 表面之銹皮厚度控制爲Ο . 5〜1 Ο // m，因此退 成非氧化性的環境。 退火時所使用的爐，可爲批量式（bat( 閉爐，或者是利用滾子型的爐將被處理材的 部分離的連續爐。在本發明中，最好是採用 退火爐。 本發明的退火，由於是在非氧化性的環 此潤滑油中的炭成分將不會形成氧化，再加 6 5 0 °C以下的低溫，容易使附著於冷拉鋼管 形成黑化或污物（污物附著）而殘留。因此 供應含有CO的氣體並充分地連續換氣以防 的而殘留。 供給至爐內之含有C Ο的氣體量，最好 積的〇 · 5倍以上。倘若低於爐容積的0 · 5倍 分解後的潤滑油產生黑化，容易再次附著於 面。 另外，倘若上述的氣體供應量過多，對 而言將花費過多的成本，由於不具經濟性， 爐容積的4倍以下。 在上述的說明中，所謂的「每小時供應 氣體」，是指對爐內緩緩地供應氣體之外， 數量相同的氣體，而在1小時內所供應之氣 的4倍。 接下來，根據實施例說明本發明的效果 火爐內必須形 :h type )的密 裝入部及裝出 連續型的輝面 境中進行，因 上處理溫度爲 表面的潤滑油 ，必須充分地 止黑化或污物 每小時爲爐容 以下，將使熱 冷拉鋼管的表 所獲得的效果 供給量最好爲 爐容積4倍的 也由爐內排出 體量爲爐容積 。[實施例1 ] -21 - 1275641 (18) 及[實施例2]，是說明採用本案第1潤滑油時所 果，而[實施例3]則是說明採用本案第2潤滑油 效果。 [實施例1 ] 在實施例1中，是以日本JIS G 3 445 (機械 鋼鋼管）所規定的S TKM 1 3 A作爲測試材料，採 第1潤滑油及比較用潤滑油進行冷拉。 具體來說，是採用外徑7〇.〇mm X 厚度4. 材，執行冷拉使其形成外徑6 0.0 m m x 厚度3 對非氧化性氣相環境的爐內，以每小時供給相當 容積的量，供給含有2 · 1體積％之C Ο的氣體 5 6 0 °C或7 0 0 °C的溫度執行2 0分鐘的退火後獲得 〇 接下來對上述退火過程中是否形成燒焦及退 數量進行調查，並測量所製成之冷拉鋼管的拉伸 表1中，詳細顯不出：所採用之潤滑油的s含有 '和塗佈潤滑油前之表面處理所採用的鹼性金屬 及是否進行表面處理等油潤滑處理的條件。 表1的「燒焦」欄中，「4/5」是表示在採 所製成的5支冷拉鋼管中，有4支產生燒焦之意 果爲「0/5」、「1/5」或「2/5」，便可獲得良好 同樣地，在「退火殘渣」的欄中，〇表示退 爲3g/m2以下，△表示退火殘渣量超過3g/m2至 獲得之效 所獲得之 結構用碳 用本案的 0 m m的管 • 4 m m，並 於2倍爐 ，同時以 冷拉鋼管 火殘渣得 強度。在 量與黏度 鹽種類、 相同條件 。只要結 的評價。 火殘渣量 5 g / ηα2 以 -22 ‘ (19) 1275641 下，x則表示退火殘渣量超過5g/m2以上，倘若是〇，便 可獲得良好的評價。 此外，當「拉伸強度」欄中的結果爲5 1 0 MPa以上， 便可獲得良好的評價。 在「綜合評價」欄中，◎表示極佳，〇表示良好，而 △與X雖然有著程度上的差異，但兩者均表示不佳之意。 倘若獲得◎，即表示評價良好之意。The alkaline metal salt of boric acid has good adhesion to the pipe, and has good retention when the surface of the film is coated with a lubricating oil. Accordingly, by forming a film of an alkali metal salt of boric acid on the surface of the pipe and applying a lubricating oil to the film, the pipe and the stretching tool (plug, die) can be reduced during the cold drawing process. The friction between the tubes prevents scorching between the tube and the stretching tool. The film thickness of the basic metal salt of boric acid is preferably formed from 111·4 to 20 from 111. Once the film thickness exceeds 20 // m, it will become easily peeled off. Further, the lubricating oil remains on the surface of the steel pipe and may become an annealing residue and remain after annealing. In addition, when the thickness of the film is less than 0 · 4 ^ m, the surface of the pipe table -15- (12) 1275641 will be in direct contact with the drawing tool, and the lubricating property will be lowered due to the decrease in the retaining force of the lubricating oil. . The basic metal salts of boric acid, such as lithium borate, potassium borate and sodium borate. Among them, potassium borate is most suitable. In order to form a film of an alkali metal salt of boric acid in the inner and outer surfaces of the pipe, first, the pipe must be immersed in an aqueous solution containing an alkali metal salt of boric acid. The thickness of the film can be adjusted according to the immersion time, the temperature of the aqueous solution, etc., and the thickness of the film after the treatment is preferably 0.4 to 2.0//m. Further, the concentration of the basic metal salt of boric acid in the aqueous solution may be determined depending on the thickness of the film, the time of immersion, and the like, and is preferably in the range of 2 to 10% by mass, for example. The temperature of the aqueous solution is preferably in the range of 7 Torr to 1 Torr. Next, the impregnated pipe is dried. Thereby, a film of an alkali metal salt of boric acid can be formed on the inner and outer sides of the tube. The drying of the impregnated pipe can be carried out by a method generally placed in a drying chamber of about 150 tons. For other surface treatments of the present invention, an aqueous solution containing an alkali metal salt of phosphoric acid may be used in place of an aqueous solution containing an alkali metal salt of boric acid to form a film of an alkali metal salt of phosphoric acid on the inner and outer surfaces of the tube. Effect. In other words, since the adhesion between the coating film and the tube material is good and the lubricating oil retaining property is excellent, scorching between the tube material and the stretching tool during the cold drawing process can be suppressed. Further, in the above case, there are some differences in the effects of the basic metal salt of boric acid and the basic metal salt of phosphoric acid. The former can improve the adhesion of the pipe -16-1275641 (13) to the film, thereby improving the retention of the lubricant applied to the film, and preventing the scorching effect between the pipe and the stretching tool. On the other hand, the latter has an effect of preventing direct contact between the tube and the stretching tool and preventing scorching, in addition to improving the retainability of the lubricating oil applied to the surface of the coating film. When the thickness of the film formed by using an aqueous solution containing an alkali metal phosphate is the same as that of the basic metal salt of boric acid, it is 〇 · 4 〜 2 · 0 // m. The basic metal salt of phosphoric acid is, for example, sodium diphosphate, sodium phosphate, sodium pyrophosphate or the like. Among them, sodium diphosphate is most suitable. The formation of the alkaline metal salt coating of phosphoric acid on the inner and outer sides of the tube is also the same as the formation of the alkaline metal salt coating of boric acid by the dipping method. The concentration of the basic metal salt of phosphoric acid in the aqueous solution is, for example, most preferably in the range of 〇 1 to 5 · 0% by mass, and the temperature of the aqueous solution may be in the range of 60 to 100 °C. The impregnated tube is dried in the same manner as the alkaline metal salt of boric acid. In addition to the other different surface treatments applicable to the present invention, an aqueous solution containing an alkali metal salt of boric acid and an intermetallic metal salt of phosphoric acid may be used in place of an aqueous solution containing an alkali metal salt of boric acid to make the inside and outside of the tube. The same effect is obtained by forming a film of an alkali metal salt of boric acid and an alkali metal salt of phosphoric acid. The effect obtained by the above method is an effect of the intermediate enthalpy between the basic metal salt of boric acid and the basic metal salt of phosphoric acid. The thickness of the film formed by the solution of water 177-127541 (14) containing an alkali metal salt of boric acid and an alkali metal salt of phosphoric acid, and the alkalinity of the aqueous solution in the aqueous solution when the coating is made of an alkaline metal salt of boric acid The concentration of the metal salt ranges from 0.1 to 3.0 in total. As described above, the alkaline metal salt of the boric acid of the present invention is or is surface-treated, and by means of the structure of the coating layer, whether carbon or not Steel and processing can exert good lubricity. 2. Lubricating oil The first lubricating oil of the present invention has a S degree of 5xl (T4 ~ lxl0*3m2 / s (400 ~ the first lubricating oil has an s content of 3 when lubricating oil) When S is added to the high pressure-added %, the amount of annealing residue will be solved. Accordingly, it is preferable to suppress the content of S in the production of the annealing residue as much as possible, because it contains a small amount of S. In actual use, the S content is preferably the viscosity of the first lubricating oil (moving i (400 〜 lOOOcSt). The reason, I, will result in the flow of the pipe during the cold drawing, the formation method and the drying method, which are the same as the method used. In addition, the aforementioned degree, for example, the most suitable concentration %. The slip film is a film of an alkali metal salt of phosphoric acid on the inner and outer sides of the pipe. The lubricating oil is formed as follows. 2 The alloy steel or the stainless steel has a cold draw content of 3% by mass or less, and the viscosity is OOOCSt. The reason for the mass % or less is that the S content is more than 3 masses due to the addition, and the first lubricating oil is low from the viewpoint of hindering the heat separation of the lubricating oil, and it is not necessary to contain S. It is difficult to form a scorch effect because 1.5 to 3 mass%. S degree) is 5 X 1 0·4 to 1 X 1 (T3m2/s I because once the viscosity is lower than 5 X 1 (Γ4 and the stretching tool The amount of lubricating oil -18- 1275641 (15) Insufficient 'The direct contact between the pipe and the drawing tool causes the pipe to be 瑕疵 'In addition, once the viscosity exceeds 1 X 1 (T3m2/s, it will increase the lubricating oil attached to the pipe) The quantity is not conducive to the cost. Secondly, the second lubricating oil used in the present invention has an S content of 1 〇~3 〇 mass% or less and a viscosity of 5χ1〇.5 〜2xl (r4m2/s (5〇~ 2〇〇cSt). Once the S content of the second lubricant is less than 1 〇 mass%, the surface of the pipe will be F e The amount of formation of S, F e 2 S, etc. is reduced, and the lubricity cannot be ensured. Further, if the S content is more than 30% by mass, the amount of S in the lubricating oil can be increased while ensuring the formation amount of FeS, Fe2S, or the like. The number of annealing residues is greatly increased, and the thermal decomposition of the lubricating oil is hindered. Therefore, the lubricating oil content is 10 to 30% by mass. The viscosity (dynamic viscosity) of the second lubricating oil is 5x 1 (Γ5 to 2 X 1 The reason of 0·4 m2/s (50 to 200 cSt) is to ensure the FeS on the surface of the pipe by adjusting the amount of oil adhering to the surface of the pipe and the thickness of the oil film under the premise of the S content of the above-mentioned lubricating oil. The amount of formation of Fe2S or the like is such that the amount of S remaining in the lubricating oil is reduced to ensure lubricity and reduce the occurrence of annealing residue. In other words, once the viscosity is less than 5xl (T5m2/s, the amount of oil adhering to the surface of the pipe will be reduced, so that the amount of lubricating oil flowing between the pipe and the drawing tool during the cold drawing is insufficient, so that the pipe and the stretching tool are formed. In addition, if the viscosity of the second lubricating oil exceeds 2 X l (T4m2/s, the amount of oil adhering to the pipe and the thickness of the oil film will increase, so that the amount of S remaining in the lubricating oil is greatly increased. The amount of annealing residue cannot be reduced to 3 g/m2 or less -19- (16) 1275641 The lubricating oil used in the present invention is not particularly limited to the base oil, except that lard, butter, whale oil, palm can be used. Oils such as oil, coconut oil and rapeseed oil (rapeSeed οΠ) can also be used as synthetic oils or mineral oils. The method for applying lubricating oil to the surface of a coating film of an alkali metal salt in the present invention requires only a conventional The method may be such as a method of supplying lubricating oil to the outside of the pipe by a nozzle disposed on the outer circumference of the pipe, or a method of supplying the lubricating oil to the inner surface of the pipe by using a hollow hollow shaft disposed inside the pipe. In the manufacturing method of the invention, cold drawing is performed after forming a lubricating coating of a two-layer structure on the surface of the pipe. The cold drawing process of the present invention can be carried out in a conventional manner, which is not particularly limited. 3. Annealing in the present invention For the purpose of ensuring the strength of the cold drawn steel pipe, the machining skew formed by the cold drawing is retained. When the annealing temperature is too high, the processing is relieved, and the work hardening effect cannot be obtained. After the cold drawing process The steel pipe can be annealed at a temperature below 65 ° C to obtain the work hardening effect. In addition, in order to maintain stable combustion in the furnace, the lower limit of the annealing temperature is preferably 305 ° C. The strength of the cold drawn steel pipe is preferably kept in the furnace for more than 5 minutes. Furthermore, in order to suppress the scale generated by the annealing, the thickness of the scale of the cold-drawn steel stomach -20-(17) 1275641 surface is obtained. The control is Ο. 5~1 Ο // m, so it is decomposed into a non-oxidizing environment. The furnace used for annealing can be batch type (bat (closed furnace, or the furnace to be treated with a roller type) Department The continuous furnace is separated. In the present invention, it is preferred to use an annealing furnace. The annealing of the present invention is because the carbon component in the lubricating oil in the non-oxidizing ring will not form oxidation, and further 60 ° C In the following low temperature, it is easy to cause blackening or dirt (contamination) to adhere to the cold-drawn steel pipe, and it remains. Therefore, a gas containing CO is supplied and sufficiently continuously ventilated to prevent it from remaining. The amount of gas in the crucible is preferably more than 5 times. If the lubricating oil decomposed below 0.5 times the volume of the furnace is blackened, it is easy to adhere to the surface again. It will cost too much, and because it is not economical, it is less than 4 times the volume of the furnace. In the above description, the term "supply gas per hour" refers to a gas of the same amount in addition to the gas supplied slowly in the furnace, and is four times as large as that supplied in one hour. Next, according to the embodiment, the effect of the present invention will be described in the case where the heat-receiving portion of the furnace must be shaped like h type and the surface of the continuous type is used. The lubricating oil having a surface treatment temperature must be sufficiently stopped. The blackening or dirt is below the furnace capacity per hour, and the effect of the heat-drawn steel pipe is preferably 4 times the volume of the furnace and the volume discharged from the furnace is the furnace volume. [Embodiment 1] -21 - 1275641 (18) and [Example 2] are illustrative of the results of the first lubricating oil of the present invention, and [Example 3] illustrates the effect of the second lubricating oil of the present invention. [Example 1] In Example 1, S TKM 1 3 A specified by JIS G 3 445 (Mechanical Steel Pipe) of Japan was used as a test material, and the first lubricating oil and the comparative lubricating oil were subjected to cold drawing. Specifically, the outer diameter is 7〇.〇mm X thickness 4. The material is subjected to cold drawing to form an outer diameter of 6 0.0 mmx and a thickness of 3 in a non-oxidizing gas phase environment, which supplies a considerable volume per hour. Amount, supply a gas containing 2 · 1% by volume of C 5 at a temperature of 560 ° C or 700 ° C to perform annealing for 20 minutes to obtain 〇. Next, whether or not charring and retreating amount are formed during the above annealing process. Investigating and measuring the drawn tensile drawing of the cold drawn steel pipe, it is shown in detail that the s of the lubricating oil used contains 'the basic metal used in the surface treatment before the coating of the lubricating oil and whether Conditions for oil lubrication treatment such as surface treatment. In the "scorch" column of Table 1, "4/5" means that among the five cold-drawn steel pipes produced by the mining, 4 of them are burnt, and the result is "0/5" and "1/5". Or "2/5", in the same column, in the column of "annealing residue", 〇 indicates that the retreat is 3 g/m2 or less, and Δ indicates that the amount of annealing residue exceeds 3 g/m2 to obtain the structure obtained. Use carbon to use the 0 mm tube of this case • 4 mm, and in 2 times the furnace, while taking the strength of the cold-drawn steel tube fire residue. The amount and viscosity of the salt type, the same conditions. As long as the evaluation of the knot. The amount of fire residue is 5 g / ηα2 at -22 ‘ (19) 1275641, and x indicates that the amount of annealing residue exceeds 5 g/m 2 , and if it is 〇, a good evaluation can be obtained. In addition, when the result in the "tensile strength" column is 5 1 0 MPa or more, a good evaluation can be obtained. In the "Comprehensive Evaluation" column, ◎ indicates excellent, 〇 indicates good, and △ and X have a degree of difference, but both indicate poor. If ◎ is obtained, it means that the evaluation is good.

-23- (20) 1275641-23- (20) 1275641

評價 潤滑油的S含量 潤滑油黏度 表面處理 退火溫度 拉伸強度 綜合 (質量％ ) [m2/s (cSt)] (°C) 燒焦 退火殘渣 (MPa) 評價 本 1 0 6χ]〇-4 ( 600) 硼酸鹽 560 0/5 〇 595 ◎ 2 2 6x1 Ο*4 ( 600) 硼酸鹽 560 0/5 〇 583 ◎ 1 氺5 6x10.4 ( 600) 硼酸鹽 560 0/5 △ 588 △ 比 較 例 2 氺】0 6x1 Ο*4 ( 600) 硼酸鹽 氺700 0/5 〇 442 X 3 氺20 6x1 Ο·4 ( 600) 硼酸鹽 560 0/5 X 592 X 本 3 0 6x1 Ο·4 ( 600) 磷酸鹽 560 0/5 〇 590 〇 4 0 6χ]〇·4 ( 600) 氺無 560 5/5 〇 583 X it 較 例 5 2 6x1 Ο*4 ( 600) 氺無 氺700 4/5 〇 449 X 6 氺5 6χ1〇·4 ( 600) 氺無 560 1/5 △ 594 △ 7 氺]0 6χ]〇'4 ( 600) 氺無 560 0/5 X 591 X (注）本：表示本實施例 「表面處理」中，硼酸鹽：硼酸鉀，磷酸鹽：第2磷酸鈉 *:代表脫出本發明所規定的範圍 -24- 1275641 (21) 由表1的結果可淸楚地得知，當潤滑油之S含量在本 發明所規定之「第1潤滑油」的範圍內，形成硼酸或磷酸 之鹼性金屬鹽覆腠時（本發明例1〜3 )，可獲得良好的結 果。 相對於此’當潤滑油的S含量超出本發明所規定之Γ 第1潤滑油」的範圍時，即使形成鹼性金屬鹽的覆膜，雖 然未發現燒焦的情形’卻產生大量的退火殘渣（比較例 1〜3 )，倘若沒有形成鹼性金屬鹽的覆膜，有時會產生燒 焦的狀況（比較例6〜7 )。 此外’退火溫度高於本案所規定之溫度的比較例2， 其拉伸強度不彰。 再者，即使潤滑油的S含量符合本發明所規定之「第 1潤滑油」的範圍’倘若沒有鹼性金屬鹽的覆膜，雖然退 火殘渣的量不多’卻會產生燒焦的情形（比較例4〜5 )。 最後’退火溫度高於本案所規定之溫度的比較例2， 其拉伸強度不彰。 [實施例2] 在貫5也例2中’是以含有質量％爲c:〇.、si: 0·2 0% 、Μη=(Κ71% 、Cr : 〇〇6% (其餘爲以及雜質） 的碳鋼鋼管作爲測試材料，採用本案的第1潤滑油及比較 用潤滑油進行冷拉。 與實施例1相同’利用冷拉使外徑70 0mm χ厚度 4.0mm的管材形成外徑60.0mm χ厚度3.4mm，並採用 -25- 1275641 (22) 與實施例1相同的條件在非氧化性氣相環境的爐內進行退 火，以獲得冷拉鋼管。 接下來對上述退火過程中是否形成燒焦及退火殘渣得 數量進行調查，並測量所製成之冷拉鋼管的拉伸強度。詳 細的結果如下頁的表2所示。Evaluation of S content of lubricating oil Lubricating oil surface treatment Annealing temperature Tensile strength synthesis (% by mass) [m2/s (cSt)] (°C) Charging annealing residue (MPa) Evaluation of this 10 6χ]〇-4 ( 600) Borate 560 0/5 〇 595 ◎ 2 2 6x1 Ο*4 ( 600) Borate 560 0/5 〇 583 ◎ 1 氺 5 6x10.4 ( 600) Borate 560 0/5 △ 588 △ Comparative Example 2氺] 0 6x1 Ο*4 (600) Borate 氺700 0/5 〇442 X 3 氺20 6x1 Ο·4 ( 600) Borate 560 0/5 X 592 X Ben 3 0 6x1 Ο·4 ( 600) Phosphoric acid Salt 560 0/5 〇590 〇4 0 6χ]〇·4 ( 600) 氺 no 560 5/5 〇 583 X it Comparative example 5 2 6x1 Ο*4 ( 600) 氺 no 氺 700 4/5 〇 449 X 6氺5 6χ1〇·4 (600) 氺无560 1/5 △ 594 △ 7 氺]0 6χ]〇'4 (600) 氺No 560 0/5 X 591 X (Note) This: This example shows the surface In the treatment, borate: potassium borate, phosphate: sodium diphosphate *: represents the range specified in the present invention -24 - 1275641 (21) From the results of Table 1, it can be clearly known that when lubricating oil The S content is within the range of the "first lubricating oil" specified in the present invention. When an alkaline metal salt of boric acid or phosphoric acid was formed to cover the present invention (Inventive Examples 1 to 3), good results were obtained. In contrast, when the S content of the lubricating oil exceeds the range of the first lubricating oil specified in the present invention, even if a film of an alkali metal salt is formed, although a case where scorch is not found, a large amount of annealing residue is generated. (Comparative Examples 1 to 3), in the case where the film of the basic metal salt was not formed, scorching may occur (Comparative Examples 6 to 7). Further, in Comparative Example 2 in which the annealing temperature was higher than the temperature specified in the present case, the tensile strength was not observed. Further, even if the S content of the lubricating oil conforms to the range of the "first lubricating oil" defined by the present invention, "if there is no coating of the alkali metal salt, although the amount of the annealing residue is small", scorching may occur ( Comparative Examples 4 to 5). In the second comparative example 2 in which the annealing temperature was higher than the temperature specified in the present case, the tensile strength was not good. [Example 2] In the fifth example 2, 'the mass% is c: 〇., si: 0·2 0%, Μη=(Κ71%, Cr: 〇〇6% (the rest and impurities) The carbon steel pipe was used as the test material, and the first lubricating oil and the comparative lubricating oil of the present invention were used for cold drawing. The same as in the first embodiment, the outer diameter of the pipe having an outer diameter of 70 mm and a thickness of 4.0 mm was formed by cold drawing to an outer diameter of 60.0 mm. The thickness is 3.4 mm, and annealing is performed in a furnace of a non-oxidizing gas phase environment under the same conditions as in Example 1 to obtain a cold drawn steel pipe. Next, whether or not charring is formed during the above annealing process The amount of the annealing residue was investigated, and the tensile strength of the cold drawn steel pipe produced was measured. The detailed results are shown in Table 2 on the following page.

•26- (23) 1275641•26- (23) 1275641

潤滑油的S含量 (質量％ ) 潤滑油黏度 [nr/s ( cSt)] 表面處理 退火溫度 (°C) 評價 燒焦 退火殘渣 拉伸強度 (MPa) 綜合 評價 本 4 0 6x10'4 ( 600) 磷酸鹽 560 2/5 〇 590 〇 5 2 6χ]〇*4 ( 600) 磷酸鹽 560 1/5 〇 585 〇 比 較 例 8 氺5 6x10'4 ( 600) 磷酸鹽 560 0/5 X 580 X 9 氺]0 6x10'4 ( 600) 磷酸鹽 氺700 0/5 〇 452 X 10 氺】0 όχΙΟ*4 (600) 磷酸鹽 560 0/5 X 593 X 本 6 0 6x10'4 ( 600) 硼酸鹽 560 1/5 〇 595 〇 7 2 6xl〇-4 ( 600) 硼酸鹽 560 0/5 〇 583 ◎ 比 較 例 11 2 6x1 Ο*4 ( 600) 硼酸鹽 氺700 0/5 〇 440 X 12 2 6x10'4 ( 600) 硼酸鹽 560 4/5 〇 590 X 】3 氺5 *2xlO*J (200) 硼酸鹽 560 0/5 △ 588 △ 14 氺10 6x1 Ο·4 ( 600) 硼酸鹽 560 0/5 X 591 X 15 氺10 6xl〇·4 ( 600) 硼酸鹽 氺700 0/5 〇 442 X 本 8 2 4.5χ10*4 (450) 磷酸鹽 560 1/5 〇 591 〇 比 16 2 *3χ1〇·4 ( 300) 磷酸鹽 560 4/5 〇 588 X 本 9 2 4·5χ10·4 ( 450) 硼酸鹽 560 0/5 〇 589 ◎ 10 2 8χ]0·4 ( 800) 硼酸鹽 560 0/5 〇 591 ◎ 比 】7 2 *3χ]Ο·4 ( 300) 硼酸鹽 560 4/5 〇 580 X 本 Π 0 6x1 Ο·4 ( 600) 硼酸鹽+ 磷酸鹽 560 2/5 〇 580 〇 12 2 6x1 (Τ4 ( 600) 硼酸鹽+ 磷酸鹽 560 0/5 〇 584 ◎ 比 18 氺5 6χ】0·4 ( 600) 硼酸鹽+ 磷酸鹽 560 0/5 Δ 584 Δ (注）本：表示本實施例，比：表示比較例 「表面處理」中，硼酸鹽：硼酸鉀，磷酸鹽：第2磷酸鈉 *:代表脫出本發明所規定的範圍 -27- 1275641 (24) 表2「燒焦」與「退火殘渣」欄中之結果的表示方法 與實施例1相同。「拉伸強度」倘若爲5 1 Ο Μ P a以上’則 可獲得良好的評價。 此外，「綜合評價」欄中之記號的涵義與實施例1相 同，倘若是◎或◦，則表示爲良好的評價。 由表2的結果可淸楚地得知，當潤滑油之S含量及黏 度符合本發明所規定「第1潤滑油」的範圍，且形成硼酸 或/及磷酸之鹼性金屬鹽覆膜時（本發明例4〜1 2 )，可獲 得良好的結果。 相對於此’當潤滑油之S含量脫離本發明所規定「第 1潤滑油」的範圍時，即使形成有鹼性金屬鹽的覆膜，也 將形成大量的退火殘渣（比較例8、1 〇、1 3、14及18) ’倘右退火溫度局於本發明所規定的溫度時（比較例 4〜1 2 )，雖然可減少退火殘渣的數量，卻導致拉伸強度的 下降（比較例9及1 5 )。 此外，即使潤滑油之S含量符合本發明「第1潤滑油 」所規定之範圍，且形成有鹼性金屬覆膜，但只要退火溫 度高於本發明所規定的溫度時，將導致拉伸強度下降（比 較例1〇 ’當黏度低於本發明所規定的範圍時，將產生 燒焦（比較例1 2、1 6及1 7 )。 [實施例3] 在實施例3中，是以日本：nS G 3 44 5 (機械結構用碳 鋼鋼it )所規定的S TKM 1 3 A作爲測試材料，並採用本案 -28- 1275641 (25) 的第2潤滑油及比較用潤滑油進行冷拉。 而作爲冷拉之前置處理的油潤滑處理，是利用形成鹼 性金屬鹽覆膜的表面處理（包含不進行處理）及藉由塗佈 潤滑油形成2層結構。 具體來說，與實施例1相同，利用冷拉使外徑 70.0mm χ 厚度 4.0mm的管材形成外徑 60.0mm x 厚 度 3 · 4 m m。Lubricating oil S content (% by mass) Lubricating oil viscosity [nr/s (cSt)] Surface treatment annealing temperature (°C) Evaluation of scoring annealing residue tensile strength (MPa) Comprehensive evaluation of this 4 0 6x10'4 (600) Phosphate 560 2/5 〇590 〇5 2 6χ]〇*4 (600) Phosphate 560 1/5 〇585 〇Comparative Example 8 氺5 6x10'4 (600) Phosphate 560 0/5 X 580 X 9 氺]0 6x10'4 ( 600) Phosphate 氺700 0/5 〇452 X 10 氺]0 όχΙΟ*4 (600) Phosphate 560 0/5 X 593 X Ben 6 0 6x10'4 ( 600) Borate 560 1 /5 〇595 〇7 2 6xl〇-4 (600) Borate 560 0/5 〇583 ◎ Comparative Example 11 2 6x1 Ο*4 (600) Borate 氺700 0/5 〇440 X 12 2 6x10'4 ( 600) Borate 560 4/5 〇590 X 】3 氺5 *2xlO*J (200) Borate 560 0/5 △ 588 △ 14 氺10 6x1 Ο·4 ( 600) Borate 560 0/5 X 591 X 15 氺10 6xl〇·4 (600) Borate 氺700 0/5 〇442 X Ben 8 2 4.5χ10*4 (450) Phosphate 560 1/5 〇591 〇 16 16 2 *3χ1〇·4 ( 300) Phosphate 560 4/5 〇 588 X Ben 9 2 4·5χ10·4 ( 450) Borate 560 0/5 〇 589 ◎ 10 2 8 χ] 0·4 ( 800) Borate 560 0/5 〇591 ◎ Ratio] 7 2 *3χ]Ο·4 (300) Borate 560 4/5 〇580 X 本Π 0 6x1 Ο·4 ( 600) Borate + Phosphate 560 2 /5 〇 580 〇 12 2 6x1 (Τ4 (600) borate + phosphate 560 0/5 〇 584 ◎ than 18 氺 5 6 χ] 0·4 (600) borate + phosphate 560 0/5 Δ 584 Δ ( Note: This example shows the present embodiment. Ratio: indicates that in the comparative example "surface treatment", borate: potassium borate, phosphate: sodium diphosphate *: represents the range specified in the present invention -27 - 1275641 (24) The results of the results in the column of "scorch" and "annealing residue" in Table 2 are the same as in the first embodiment. If the "tensile strength" is 5 1 Ο Μ P a or more, a good evaluation can be obtained. Further, the symbol in the column of "comprehensive evaluation" has the same meaning as in the first embodiment, and if it is ◎ or ◦, it indicates a good evaluation. From the results of Table 2, it can be clearly understood that when the S content and viscosity of the lubricating oil conform to the range of the "first lubricating oil" specified in the present invention, and the alkaline metal salt film of boric acid or/and phosphoric acid is formed ( Inventive Examples 4 to 1 2), good results were obtained. In contrast, when the S content of the lubricating oil deviates from the range of the "first lubricating oil" defined in the present invention, even if a film of an alkali metal salt is formed, a large amount of annealing residue is formed (Comparative Example 8, 1 〇) 1, 3, 14 and 18) 'If the right annealing temperature is at the temperature specified in the present invention (Comparative Examples 4 to 12), although the amount of annealing residue can be reduced, the tensile strength is lowered (Comparative Example 9) And 1 5). Further, even if the S content of the lubricating oil conforms to the range specified by the "first lubricating oil" of the present invention and the alkaline metal coating is formed, the tensile strength is caused as long as the annealing temperature is higher than the temperature specified in the present invention. Decrease (Comparative Example 1 〇 'When the viscosity is lower than the range specified by the present invention, scorching will occur (Comparative Examples 1, 2, 16 and 17). [Example 3] In Example 3, it was Japan. : nS G 3 44 5 (carbon steel steel for mechanical structure it) S TKM 1 3 A as the test material, and use the second lubricating oil of the case -28- 1275641 (25) and the comparative lubricating oil for cold drawing The oil lubrication treatment as the cold drawing pretreatment is a surface treatment (including no treatment) for forming an alkali metal salt coating and a two-layer structure by coating the lubricating oil. Specifically, In the same manner as in Example 1, a tube having an outer diameter of 70.0 mm and a thickness of 4.0 mm was formed by cold drawing to have an outer diameter of 60.0 mm x a thickness of 3 · 4 mm.

於冷拉之後，對非氧化性氣相環境的爐內，以每小時 供給相當於2倍爐容積的量，供給含有2. 1體積％之CO 的氣體，同時以560°C或7〇〇°C的溫度執行20分鐘的退火 後獲得冷拉鋼管。 接下來對上述退火過程中是否形成燒焦及退火殘渣得 數量進行調查，並測量所製成之冷拉鋼管的拉伸強度。詳 細的結果如下頁的表3所示。After the cold drawing, in a furnace in a non-oxidizing gas phase environment, a gas equivalent to 2 times the volume of the furnace is supplied per hour, and a gas containing 2.1% by volume of CO is supplied while being 560 ° C or 7 〇〇. A cold drawn steel pipe was obtained after performing a 20 minute annealing at a temperature of °C. Next, the amount of scorch and annealing residue formed during the above annealing process was investigated, and the tensile strength of the produced cold drawn steel pipe was measured. The detailed results are shown in Table 3 on the next page.

此外，所謂油潤滑處理的條件，是指所採用之潤滑油 S含量與黏度、塗佈潤滑油前之表面處理所採用的鹼性金 屬鹽種類、及是否形成鹼性金屬鹽覆膜。 表3「燒焦」與「退火殘渣」欄中之結果的表示方法 與實施例I相同。「拉伸強度」倘若爲5 1 OMPa以上，則 可獲得良好的評價。 此外’ 「合評價」欄中之記號的涵義與貫施例1相 同，倘若是◎或〇，則表示爲良好的評價。 -29- 1275641 (26) 表3Further, the conditions of the oil lubrication treatment refer to the amount and viscosity of the lubricating oil to be used, the type of the basic metal salt used for the surface treatment before the application of the lubricating oil, and whether or not the alkaline metal salt film is formed. Table 3 shows the results of the results in the column of "burning" and "annealing residue" in the same manner as in the first embodiment. If the "tensile strength" is 5 1 OMPa or more, a good evaluation can be obtained. In addition, the mark in the column of 'combined evaluation' has the same meaning as in the case of Example 1, and if it is ◎ or 〇, it means a good evaluation. -29- 1275641 (26) Table 3

潤滑油的S含量 (質量％ ) 潤滑油黏度 [m2/s ( cSt)] 表面處理 退火溫度 (°C) 評價 燒焦 退火殘渣 拉伸強度 (MPa) 綜合評價 本 發 明 例 21 ]〇 lx]0·4 ( 100) 硼酸鹽 560 0/5 〇 588 〇 22 20 IxlO·4 ( 100) 硼酸鹽 560 0/5 〇 582 ◎ 23 30 lxl〇·4 ( 100) 硼酸鹽 560 0/5 〇 582 〇 24 20 lxl〇·4 ( 100) 磷酸鹽 560 0/5 〇 590 〇 25 20 IxlO'4 ( 100) 硼酸鹽+磷酸鹽 560 0/5 〇 579 〇 26 10 6x1 Ο·5 (60) 硼酸鹽 560 1/5 〇 580 〇 27 20 6x10'5 (60) 硼酸鹽 560 0/5 〇 585 ◎ 28 】0 】.8χ】0·4 ( 180) 硼酸鹽 560 0/5 〇 581 〇 29 20 ].8χ]〇·4 (180) 硼酸鹽 560 0/5 〇 591 〇 30 30 1.8χ1〇·4 (180) 硼酸鹽 560 0/5 〇 588 〇 3】 】0 6x10'5 (60) 磷酸鹽 560 1/5 〇 587 〇 32 30 1.8x1 Ο*4 (180) 磷酸鹽 560 0/5 〇 581 〇 33 10 6x10'5 (60) 硼酸鹽+磷酸鹽 560 1/5 〇 585 〇 34 30 1.8χ1〇·4 (180) 硼酸鹽+磷酸鹽 560 0/5 〇 586 〇 比 較 例 35 10 6x1 Ο*5 (60) *無 560 5/5 〇 588 X 36 30 ].8χ1〇·4 (180) *無 560 4/5 〇 580 X 37 氺5 6x10'5 (60) 硼酸鹽 560 5/5 〇 579 X 38 氺5 2x1 Ο*4 ( 200) 硼酸鹽 560 3/5 〇 582 X 39 氺35 6x10'5 (60) 硼酸鹽 560 0/5 △ 591 △ 40 氺5 *3χ1〇·5 (30) 硼酸鹽 560 5/5 〇 587 X 4] 30 氺 3χ]0·5 (30) 硼酸鹽 560 4/5 〇 583 X 42 10 氺4χ】0·4 ( 400) 砸酸鹽 560 0/5 X 588 X 43 20 1χ】0·4 ( 100) 硼酸鹽 氺700 0/5 〇 455 X (注）「表面處理」中，硼酸鹽：硼酸鉀，磷酸鹽：第2磷酸鈉 「退火殘渣」中，◦表示退火殘渣量爲3g/m2以下，△表示退火殘渣量超過3g/m2〜5g/m2，&gt;(則表示退火殘渣量超過 5g/m2 *:代表脫出本發明所規定的範圍 -30- 1275641 (28) 法可提供一種：即使冷拉後不對表面進行硏磨，也能充分 地降低退火殘渣及燒焦，並進一步確保高強度的冷拉鋼管 【圖式簡單說明】 第1圖：爲顯示冷拉後鋼管表面之殘餘油量與S檢測強 度間的關係圖。 -32-S content of lubricating oil (% by mass) Lubricating oil viscosity [m2/s (cSt)] Surface treatment annealing temperature (°C) Evaluation of tensile strength of scorch annealing residue (MPa) Comprehensive evaluation Example 21 of the present invention] 〇lx]0 · 4 ( 100 ) borate 560 0/5 〇 588 〇 22 20 IxlO · 4 ( 100 ) borate 560 0/5 〇 582 ◎ 23 30 lxl 〇 · 4 ( 100 ) borate 560 0/5 〇 582 〇 24 20 lxl〇·4 ( 100) phosphate 560 0/5 〇 590 〇 25 20 IxlO'4 ( 100) borate + phosphate 560 0/5 〇 579 〇 26 10 6x1 Ο · 5 (60) borate 560 1 /5 〇 580 〇 27 20 6x10'5 (60) Borate 560 0/5 〇 585 ◎ 28 】0 】.8χ]0·4 (180) Borate 560 0/5 〇581 〇29 20 ].8χ] 〇·4 (180) Borate 560 0/5 〇591 〇30 30 1.8χ1〇·4 (180) Borate 560 0/5 〇588 〇3] 】0 6x10'5 (60) Phosphate 560 1/5 〇587 〇32 30 1.8x1 Ο*4 (180) Phosphate 560 0/5 〇581 〇33 10 6x10'5 (60) Borate + Phosphate 560 1/5 〇585 〇34 30 1.8χ1〇·4 ( 180) Borate + Phosphate 560 0/5 〇 586 〇 Comparative Example 35 10 6x1 Ο*5 (60) *No 560 5/5 588 X 36 30 ].8χ1〇·4 (180) *No 560 4/5 〇580 X 37 氺5 6x10'5 (60) Borate 560 5/5 〇579 X 38 氺5 2x1 Ο*4 ( 200) Borate 560 3/5 〇582 X 39 氺35 6x10'5 (60) Borate 560 0/5 △ 591 △ 40 氺5 *3χ1〇·5 (30) Borate 560 5/5 〇587 X 4] 30氺3χ]0·5 (30) Borate 560 4/5 〇583 X 42 10 氺4χ]0·4 (400) citrate 560 0/5 X 588 X 43 20 1χ]0·4 (100) Boric acid Salt 氺 700 0/5 〇 455 X (Note) In the "surface treatment", borate: potassium borate, phosphate: sodium diphosphate "annealing residue", ◦ indicates that the amount of annealing residue is 3g/m2 or less, △ indicates The amount of annealing residue exceeds 3 g/m 2 to 5 g/m 2 , &gt; (the amount of annealing residue exceeds 5 g/m 2 *: represents the range specified by the present invention -30 - 1275641 (28). The method provides one: even cold drawing After the surface is not honed, the annealing residue and charring can be sufficiently reduced, and the high-strength cold-drawn steel pipe is further ensured. [Simple description of the drawing] Fig. 1 shows the residual oil content of the surface of the steel pipe after cold drawing and S A graph of the relationship between the detected intensities. -32-

Claims (1)

1275641 (1) 月0(曰修(齡，替換頁 拾、申請專利範圍 第92 1 3 65 60號專利申請案 中文申請專利範圍修正本 民國95年11月9日修正 1 · 一種冷拉用潤滑油，其特徵爲··爲了抑制利用低溫 環境爐對冷拉後的鋼管執行退火的步驟所產生的退火殘渣 ’硫（S)含量爲3質量％以下，黏度爲5χ1(Γ4〜1χ 1 〇-3m2/s ( 400〜1 OOOcSt ) 〇 2. —種冷拉用潤滑覆膜，其特徵爲：是由形成於經浸 漬之管材內外面的硼酸之鹼性金屬鹽覆膜；及塗佈於該覆 膜表面，硫（S)含量爲3質量％以下，黏度爲5xl(T4〜1χ l(T3m2/S ( 400〜lOOOcSt )的潤滑油所構成。 3 .如申請專利範圍第2項所記載的冷拉用潤滑覆膜， 其中在管材的內外面形成磷酸的鹼性金屬覆膜，來取代上 述的硼酸之鹼性金屬鹽覆膜。 4.如申請專利範圍第2項所記載的冷拉用潤滑覆膜， 其中在管材的內外面形成硼酸的鹼性金屬鹽及磷酸的鹼性 金屬鹽覆膜。 5 · —種冷拉鋼管的製造方法，其特徵爲：將管材浸漬 於含有硼酸之鹼性金屬鹽及/或磷酸之鹼性金屬鹽的水溶 液中，使前述管材的內外面形成硼酸之鹼性金屬鹽及/或 磷酸之鹼性金屬鹽的覆膜，於該覆膜表面塗佈硫（S)含 量爲3質量％以下，黏度爲5x 10_4〜1 X l(T3m2/s ( (2) (2)1275641 400〜lOOOcSt)的潤滑油經冷拉之後，一邊對爐內氣相環 境供給含有C0之氣體，一邊以650°C以下的溫度進行退 火。 6·—種冷拉用潤滑覆膜，其特徵爲：是由形成於經浸 漬之管材內外面的硼酸之鹼性金屬鹽覆膜；及塗佈於該覆 膜表面，硫（S)含量爲10〜30質量％，黏度爲5x 10_5〜2xl0_4m2/s ( 5 0〜200cSt )的潤滑油所構成。 7. 如申請專利範圍第6項所記載的冷拉用潤滑覆膜， 其中在管材的內外面形成硼酸的鹼性金屬鹽及磷酸的鹼性 金屬鹽覆膜。 8. —種冷拉鋼管的製造方法，其特徵爲：將管材浸漬 於含有硼酸之鹼性金屬鹽的水溶液中，使前述管材的內外 面形成硼酸之鹼性金屬鹽的覆膜，於該覆膜表面塗佈硫 (S)含量爲10〜30質量％，黏度爲5xl0·5〜2xl(T4m2/s ( 5 0〜2 00cSt)的潤滑油經冷拉之後，一邊對爐內氣相環境 供給含有CO之氣體，一邊以65(TC以下的溫度進行退火 〇 9. 如申請專利範圍第5或8項所記載的冷拉鋼管的製 造方法，其中於前述熱處理後形成於冷拉鋼管表面的殘渣 爲3 g/m2以下。1275641 (1) Month 0 (曰修 (age, replacement page pick, patent application scope 92 1 3 65 60 patent application Chinese patent application scope revision of the Republic of China November 9, 1995 amendment 1 · a cold drawing lubrication The oil is characterized in that the sulfur residue (S) content of the annealing residue generated by the step of annealing the cold-drawn steel pipe by the low-temperature environment furnace is 3% by mass or less, and the viscosity is 5χ1 (Γ4~1χ 1 〇- 3m2/s (400~1 OOOcSt) 〇2. A lubricating coating for cold drawing, characterized in that it is a film of an alkali metal salt of boric acid formed on the inner and outer sides of the impregnated pipe; and coated thereon The surface of the coating film is composed of a lubricating oil having a sulfur (S) content of 3% by mass or less and a viscosity of 5x1 (T4 to 1 χ l (T3m2/S (400 to 1000 ° CSt). 3. As described in the second item of the patent application. A lubricating film for cold drawing in which an alkaline metal film of phosphoric acid is formed on the inner and outer surfaces of the pipe to replace the above-mentioned alkaline metal salt film of boric acid. 4. For cold drawing as described in claim 2 Lubricating film, wherein an alkaline metal salt of boric acid and phosphoric acid are formed on the inner and outer sides of the pipe An alkali metal salt coating method. The method for producing a cold drawn steel pipe characterized by immersing a pipe material in an aqueous solution containing an alkali metal salt of boric acid and/or an alkali metal salt of phosphoric acid to make the pipe material A film of an alkali metal salt of boric acid and/or an alkali metal salt of phosphoric acid is formed on the inner and outer surfaces, and the surface of the film is coated with a sulfur (S) content of 3% by mass or less and a viscosity of 5×10_4 to 1×1 (T3m2). /s ( (2) (2) 1275441 400 to lOOOcSt) After the cold drawing, the lubricating oil containing C0 is supplied to the gas phase in the furnace, and annealing is performed at a temperature of 650 ° C or lower. The lubricating film for cold drawing is characterized in that it is a film of an alkali metal salt of boric acid formed on the inner and outer surfaces of the impregnated pipe; and is coated on the surface of the film, and the sulfur (S) content is 10 to 30 mass. And a lubricating oil for cold drawing according to the sixth aspect of the invention, wherein boric acid is formed on the inner and outer sides of the pipe. Alkaline metal salt and alkaline metal salt coating of phosphoric acid. 8. Kind of cold drawn steel pipe The method is characterized in that a tube is immersed in an aqueous solution containing an alkali metal salt of boric acid, and a film of an alkali metal salt of boric acid is formed on the inner and outer surfaces of the tube, and sulfur (S) is coated on the surface of the film. The lubricating oil having a content of 10 to 30% by mass and a viscosity of 5xl0·5 to 2xl (T4m2/s (5 0 to 2 00 cSt) is supplied to the gas phase in the furnace while supplying a gas containing CO. The method for producing a cold drawn steel pipe according to the fifth or eighth aspect of the invention, wherein the residue formed on the surface of the cold drawn steel pipe after the heat treatment is 3 g/m 2 or less.