201213536 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用於供於冷加工或溫加工之各種 被加工用金屬材料的金屬材料塑性加工用潤滑劑組成物、 由该組成物所形成之潤滑被膜及被覆有談皮膜之被覆金屬 材料、以及被覆金屬材料之製造方法。 【先前技術】 先前，不鏽鋼或鈦、鎳基合金等特殊金屬材料與其他 普通金屬相比，具有耐腐蝕性、耐熱性及機械特性等多種 優異特性’係當今技術進步不可或缺者。言亥等特殊金屬材 料廣泛應用於例如螺針、螺栓、螺母、針、繩索、轴承或 彈簧等機械元件製品或备種機械構成材料。 一 但是，上述特殊金屬材料由於高強度、硬質且缺乏韌 r故屬於難加工材料。例如該等難加工性之金屬材料於 進行用於製成上述各種製品之加工時，易產生材料之破 裂、斷線或折損等加工問題。因此，為了抑制該等問題， :且=模具、親及衝頭（punch)等加工用工具之長壽命 ^業界正謀求最佳之潤滑技術。 工、：如：供t「將上述特殊金屬材料細徑化之拉線加 或者彈菩㈣ f^(hCader)^« heading) 次者彈簧成形」之情形時，先 Γη、ΚΓ; +社，. 、主屬材料之表面鍍敷201213536 VI. Description of the Invention: [Technical Field] The present invention relates to a lubricant composition for plastic working of a metal material used for various cold-working or warm-working metal materials for processing, which is formed by the composition The lubricating film and the coated metal material coated with the film and the method for producing the coated metal material. [Prior Art] Previously, special metal materials such as stainless steel or titanium and nickel-based alloys have various excellent properties such as corrosion resistance, heat resistance and mechanical properties, which are indispensable for today's technological advancement. Special metal materials such as Yanhai are widely used in mechanical component products such as screws, bolts, nuts, needles, ropes, bearings or springs, or for preparing mechanical materials. However, the above special metal materials are difficult to process materials due to their high strength, hardness and lack of toughness. For example, when such a difficult-to-process metal material is subjected to processing for producing the above various products, processing problems such as breakage, breakage, or breakage of the material are liable to occur. Therefore, in order to suppress these problems, the long life of the processing tool such as the mold and the punch is required. The industry is seeking the best lubrication technology. Work, for example: for the case where t is used to reduce the diameter of the above-mentioned special metal material or to play the ball (four) f^(hCader)^«heading), when the spring is formed, first Γ, ΚΓ; +, . Surface plating of the main material
Cu Ν!或其他金屬，或施予樹脂 ^ Μ ^ M h： 人、草知·鹽、或 嶙馱麗孚有機、無機之各種 覆之方、> W π 反犋又，除形成此種被 覆之方去以外，亦已知如下併 土〈濶滑方法：於即將進 201213536 行加工之前，並行使用例如金屬息、二硫化翻、石墨、硼 砂、石灰等輔助潤滑劑、或含有進一步視需要添加之各種 添加劑等之輔助潤滑劑。 上述併用型之潤滑方法，對於形成利用上述難加工性 之金屬材料之螺釘或螺检、螺母等的強程度之鍛粗加工， 或使用硬質線材之彈簣成形等之類的嚴格加工處理尤其有 效。然而’該等潤滑被膜.除上述加工潤滑性能以外，亦需 要研究考慮到近年來之地球環境的組成。 /列如下述專利文獻1中提出有：含有「藉由高級脂肪 族單缓酸與二胺、《高級脂肪族單m酸與多元酸之混合物 與二胺之反應所獲得之羧酸醯胺系蠟（carboxyHC amides wax )」的金屬材料之拉伸加工（drawing )用潤滑劑。 又’下述專利文獻2中提出有：對不鏽鋼線鑛敷厚度 為1…上5…下之Ni，進—步於其表面被覆含㈣ 素之合成樹脂並施加剖面減少率& 6〇%以上之拉線加工， 製成表面粗链度調整為〇.8s〜12s之自動捲繞用鋼線，藉此 改善湖滑性能，謀求拉線時之模具壽命之提昇或捲繞速度 之提昇。 又’下述專利文獻3中提出有：施有由「含有K2S〇4 及Ναβ〇4中之任一者或該等之混合物75〜9〇重量 N a 2 Β 4.0 7 3〜2 5重量％、及非離子系界面活性劑2〜i 〇重量 %者」所構成之硫酸鹽皮膜來作為環 巧衣保型加工被膜的不鏽鋼 線。 進一步，專利文獻4中提出.. I *為了 k供捲繞特性優 201213536 異之彈簧用不鏽鋼線，而藉由氮化處理 〜上a +鏽鋼線之 設置氮化層，並對其拉線，而於表面形成特 衣面 裂引起的氮化層之島狀物，#此提高所賦予之輔 之收容。 w [專利文獻1]日本特開平4 — 2〇2396號公報 [專利文獻2]曰本特開平6 一 226330號公報 [專利文獻3]曰本特開平1〇— 88 179號公報 [專利文獻4]曰本特開平9 — 85332號公報 【發明内容】 但是’利用草酸鹽或碟酸鹽進行化成被膜處理而得 者、或進-步於其上附著有金屬皂等固體滑劑之潤滑被 膜，於金屬材料之塑性加卫後，& 了去除潤滑被膜，需要 進行酸洗、水洗等處理，因而於環保方面存在問題。 又，專利文獻1中所提出之潤滑劑存在耐熱性差之問 題。 進一步，於專利文獻2中，由於該構成被膜含有含鹵 素之合成樹脂’具體而言為四氟乙烯樹脂等氟系樹脂或氯 系樹脂，故難以將其去除，或為其去除需要使用有機溶劑。 因此，專利文獻2之技術亦於環保方面存在問題。 專利文獻3雖然顧慮到環境保護，但硫酸鹽、硼酸鹽 本身缺乏潤滑性，採用該等潤滑被膜未充分解決問題。 進一步，專利文獻4之不鏽鋼線存在如下問題〔由於 形成於其表面之上述氮化層之島狀物直接殘留，故使金屬 材料之表面狀態下降，從而降低製品價值。 201213536 因此’本發明係為了解決先前之潤滑被膜之問題而提 出者，其目的在於提供一種潤滑性能優異，可提高金屬材 料之加工性能，並且可不使金屬材料之表面狀態下降而容 易地去除，於環境保護方面有效且可生產線化（in_nne)之 通用性问之潤滑被膜及被覆有該被膜之被覆金屬材料、及 被覆金屬材料之製造方法。 進一步，本發明之目的在於提供一種可形成此種潤滑 被膜，且於固體滑劑之分散穩定性及環境保護方面優異之 金屬材料塑性加工用潤滑劑組成物。 本案申請專利範圍第1項之發明係一種金屬材料塑性 加工用潤滑劑組成物，其特徵在於：含有（A)選自由硫酸 鹽、硼酸鹽、矽酸鹽、磷酸鹽、鉬酸鹽及鎢酸鹽所組成之 群中至少1種無機鹽，（B )平均粒徑為2〇" m以下之滑物 質’（C)平均分子量為5000〜1〇〇〇〇〇之水溶性樹脂材料， 以及⑼水；上述成分（A):⑻：（c)之重量比為i : 0.01 〜20 : 0.01 〜2〇。 本案申請專利範圍第1項之潤滑劑組成物，由於用作 固體滑物質之分散劑的樹脂材料（C)為水溶性，故容易製 備，並且由於分散固體滑物質之能力優異，故分散穩定性 優異。並且，本發明中所形成之被膜無需有機溶劑，可利 用水而容易地去除。進一步，由於無機鹽（A)及滑物質⑻ 利用水溶性樹脂材料（C)而牢固地保持於金屬材料表面， 故無須進行利料酸鹽或鱗冑鹽等之化成被膜處理等基底 處理，藉由將該組成物直接塗佈於金屬材料表面並將其乾 6 201213536 )可令易地提供〉閏滑性能優異m'骨被膜。 作為上述樹脂材料（c )，較佳為選自由丙稀酸系樹脂 及其他合有羧酸基之樹脂、磺酸系樹脂、以及聚乙烯醇所 組成之群中至少丄種具有電氣性質之水溶性樹脂，且平均 分子量為8000〜50000者。 又，上述樹脂材料（c )更佳為以丙烯酸烷基酯為主成 分之含有陰離子性基之丙烯酸烷基酯共聚物。 本案申請專利範圍第4項之發明係一種潤滑被臈，其 特徵在於.其係含有以下（A )〜（C )之固化物：（a )選 自由硫酸鹽、硼酸鹽、矽酸鹽、磷酸鹽、鉬酸鹽及鎢酸鹽 所組成之群中至少i種無機鹽，（B)平均粒徑為2〇"爪以 下之滑物質，以及（C )固持上述無機鹽（A )及滑物質（B : 之平均分子量為5000〜looooo之水溶性樹脂材料；該固化 ‘:〖物中，具有上述無機鹽（A )之至少一部分結晶化而成之結 晶部。 本案申請專利範圍第4項之潤滑被膜係由無機鹽（A)、 粒徑為20 μ m以下之滑物質（B )、及將該等結合保持於金 屬材料上之水溶性樹脂材料（C )所構成，於環保方面獲得 改善。又，潤滑皮膜中，無機鹽（A )及滑物質（b )係藉 由上述樹脂材料（C )而牢固地保持於金屬材料表面，並且 具備上述無機鹽（A )之至少一部分結晶化而成 叫<吉晶部， 因此具有進一步提昇之潤滑性能，尤其適合作為強力工戋 難加工性之金屬材料之潤滑被膜。 上述潤滑皮膜中之上述構成原料（A ) : ( b、· , ^、 厂（C )之重 7 201213536 量比較佳為i : 0.01〜2{) ιυ · 0·0 1 〜20 〇 又上述結晶部較伟_ 中任-種以上… 為具有粒狀、短纖維狀及葉脈狀 上的突出部。…且形成為凸設於潤滑皮膜之外表面 述結晶部之面積率較 又’觀察调滑皮膜之表面時，上 佳為20〜80%。 者 又，上述結晶部較佳為構成尺寸為0.5_ 以下之微細 又’上述樹脂材料（# /土认 ^ )更佳為選自由丙烯酸系樹脂及 其他含有缓酸基之嫩日t 冥酸系樹脂以及聚乙烯醇所組成 之·群中至少1種水溶料組 性树知，並且具有電氣性質且分子量 為8000〜50000較理想。 又’較佳為於被加工用金屈 备屬材枓之表面上以0.3〜122 m之附著量形成上述潤滑 破膜而成之被覆金屬材料。 此種具有潤滑被膜之被覆 汉设鱼屬材枓，於利用塑性變 之成形加工中，亦可併用金屬 _ .. —石瓜化鉬、石墨、硼砂 或石灰等上述輔助潤滑劑作為第_ 勺乐—潤滑物質，於該情形時 箪二潤滑物質有效地保持於 日 扎，0日日之間，而可謀求潤 '月性能之進一步提昇。又，由妹曰 田、，口日日部之突出所形成 四凸係形成於潤滑被膜上，盔須特 ^匕a …肩特地设置上述專利文獻4 令之氣化層之類的異相’即可具有提高淵滑劑之收容效率 之效果。因此’去除了該表面调滑劑之金屬材料，可抑 表面性之下降，亦於簡化加工處理牛 „ 处理步驟專降低成本方面有 8 201213536 η又’較理想為：上述被加工用金屬材枓係配合冷卜 用袞鍛用或彈簣用之最 狀、帶狀、片狀或塊狀中之任__形狀。 的線狀棒 又車父理想為·上·述被加工用今凰44» , | 鋼、鈦、献入…• 材料係選自由不鏽 之難力、…鎳、鎳合金、鈮及鈮合金所組成之群中 之難加工性金屬線材。 τ 進一步，本案申請專利範圍第13項之發明係一種被霜 枓之“方法，其特徵在於具備：⑴配合最終製 -之形態而預先成形之被加工用素材金屬材料； =係準備含有以下（Α)〜（D)之潤滑劑組成物：選 二由硫酸鹽、删酸鹽、石夕酸鹽、鱗酸鹽、姻酸鹽及鶴酸鹽 所上成之群中之至少1種無機鹽（A)’粒徑為以下 之滑物質（B)，平均分子量為5000〜1_〇〇之水溶性樹脂 材料（C)’以及水（D);⑴於加熱至預先設^之溫度之 上述潤滑劑組成物令浸潰上述素材金屬材料，並對該素材 金屬材料進行加溫之階段；（4)造膜階段，係於上述素材 也屬材料上使上述無機鹽（A )、滑物質（B )及樹脂材料（C ) 曰曰化或膜化，（5 )乾躁階段，係將具有結晶部而獲得之 潤滑被膜乾燥固化而使該結晶部固定。 又，較佳為··於上述乾燥階段後，進一步包含進行上 述素材金屬材料之塑性加工的中間加工階段，並且於該中 對上述素材金屬材料賦予與上述潤滑被膜 不同種類之第二潤滑物質而進行加工。 又軚佳為.上述被覆金屬材料為鍛粗加工用被覆金 201213536 屬線且上述中間加工為加工率3 0 %以下之輕程度之拉線 或壓延加工。 又’較佳為：上述被覆金屬材料為彈簧加工用被覆金 屬線且上述中間加工為加工帛6 〇 %以上之強程度之拉線 或壓延加工。 根據本發明之被覆金屬材料之製造方法，可與先前之 潤滑被膜之形成同樣地，將均勻且穩定之被覆處理設定為 連續系’先而貫現藉由生產線化減輕作業負擔之連續作業。 【實施方式】 以下，基於圖式對本發明之一實施形·態進行說明。 々圖1所7F ’被覆金屬材料1具有長條狀之金屬線2、Cu Ν! or other metals, or the application of resin ^ Μ ^ M h: human, grass know, salt, or 嶙驮 Lifu organic, inorganic, various kinds of covering, > W π 犋 犋, in addition to forming In addition to the covered side, it is also known as the following method: the use of auxiliary lubricants such as metal, disulfide, graphite, borax, lime, etc., or further as needed, before processing into 201213536 An auxiliary lubricant such as various additives added. The above-described combined-type lubricating method is particularly effective for forming a strong degree of forging roughing using a screw or a threaded metal material using the above-mentioned difficult-to-machine metal material, or a strict processing such as a bullet forming using a hard wire material. . However, in addition to the above-mentioned processing lubrication properties, it is necessary to study the composition of the global environment in consideration of recent years. The following Patent Document 1 proposes a carboxylic acid amide group obtained by a reaction of a higher aliphatic mono-acid and a diamine, a mixture of a higher aliphatic mono-m-acid and a polybasic acid, and a diamine. A lubricant for drawing of a metal material of carboxyHC amides wax. Further, in the following Patent Document 2, it is proposed that the thickness of the stainless steel wire is 1 to 5, and the surface of the synthetic resin containing the (tetra) is coated on the surface thereof and the profile reduction rate & According to the above-mentioned drawing processing, the steel wire for automatic winding whose surface roughness is adjusted to 〇.8s to 12s is improved, thereby improving the lake slip performance and improving the life of the mold or the winding speed when the wire is pulled. Further, in the following Patent Document 3, it is proposed to apply "any one of K2S〇4 and Ναβ〇4 or a mixture of such a mixture of 75 to 9 〇N a 2 Β 4.0 7 3 to 25% by weight. And a non-ionic surfactant 2~i 〇% by weight of the sulfate film formed by the sulphate film as a ring-shaped protective film. Further, Patent Document 4 proposes: I * for the k-winding characteristic of the 201213536 different spring stainless steel wire, and by nitriding treatment - the upper a + rust steel wire is provided with a nitride layer, and the wire is pulled On the surface, the island of the nitride layer caused by the surface crack of the special clothing is formed, and this is added to the accommodation. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 9-85332 [Summary of the Invention] However, a lubricant film obtained by chemical conversion using an oxalate or a disc acid salt or a solid lubricant to which a metal soap or the like adheres is attached. After the plastic material is added to the plastic material, the lubricating film is removed and needs to be subjected to pickling, water washing, etc., and thus there is a problem in environmental protection. Further, the lubricant proposed in Patent Document 1 has a problem of poor heat resistance. Further, in Patent Document 2, the constituent film contains a halogen-containing synthetic resin, specifically, a fluorine-based resin such as a tetrafluoroethylene resin or a chlorine-based resin, so that it is difficult to remove it or remove an organic solvent for the removal thereof. . Therefore, the technique of Patent Document 2 also has problems in environmental protection. Although the patent document 3 is concerned about environmental protection, the sulfate and the borate itself are not lubricious, and the use of such a lubricating film does not sufficiently solve the problem. Further, the stainless steel wire of Patent Document 4 has the following problem [because the island of the nitride layer formed on the surface thereof directly remains, the surface state of the metal material is lowered, thereby reducing the value of the product. 201213536 Therefore, the present invention has been made in order to solve the problem of the conventional lubricating film, and an object thereof is to provide an excellent lubricating property, improve the processing property of a metal material, and can be easily removed without lowering the surface state of the metal material. A lubricating film which is effective in environmental protection and which can be used for the production of a lubricating film, a coated metal material coated with the film, and a method for producing a coated metal material. Further, an object of the present invention is to provide a lubricant composition for plastic working of a metal material which is capable of forming such a lubricating film and which is excellent in dispersion stability and environmental protection of a solid lubricant. The invention of claim 1 is a lubricant composition for plastic working of a metal material, characterized in that (A) is selected from the group consisting of sulfates, borates, silicates, phosphates, molybdates and tungstic acids. At least one inorganic salt in the group consisting of salts, (B) a water-soluble resin material having an average particle diameter of 2 〇 " m or less, and a water-soluble resin material having an average molecular weight of 5000 to 1 Å, and (9) Water; the weight ratio of the above component (A): (8): (c) is i: 0.01 to 20: 0.01 to 2 〇. The lubricant composition of the first application of the patent application of the present invention is easy to prepare because the resin material (C) used as a dispersing agent for the solid slip substance is water-soluble, and the dispersion stability is excellent due to the ability to disperse the solid slip substance. Excellent. Further, the film formed in the present invention does not require an organic solvent and can be easily removed by water. Further, since the inorganic salt (A) and the slippery substance (8) are firmly held on the surface of the metal material by the water-soluble resin material (C), it is not necessary to perform a substrate treatment such as treatment with a salt or a salt of a salt or the like. The composition can be directly applied to the surface of the metal material and dried (201213536) to provide an excellent m' bone film with excellent slip properties. The resin material (c) is preferably selected from the group consisting of acrylic acid resins and other carboxylic acid group-containing resins, sulfonic acid resins, and polyvinyl alcohols, and at least one of them has electrical properties. A resin having an average molecular weight of 8,000 to 50,000. Further, the resin material (c) is more preferably an alkyl acrylate copolymer containing an anionic group containing an alkyl acrylate as a main component. The invention of claim 4 is a lubricating bedding characterized by comprising the following cured products of (A) to (C): (a) selected from the group consisting of sulfates, borates, silicates, phosphoric acids At least i inorganic salts of the group consisting of salts, molybdates and tungstates, (B) slippery substances having an average particle size of 2 〇" below the claws, and (C) retaining the above inorganic salts (A) and slippery The material (B: a water-soluble resin material having an average molecular weight of 5000 to looooo; and the solidified portion: a crystal portion obtained by crystallizing at least a part of the inorganic salt (A). The lubricating film is composed of an inorganic salt (A), a slip material (B) having a particle diameter of 20 μm or less, and a water-soluble resin material (C) which is bonded to the metal material, and is obtained in an environmentally friendly manner. Further, in the lubricating film, the inorganic salt (A) and the sliding substance (b) are firmly held on the surface of the metal material by the resin material (C), and at least a part of the inorganic salt (A) is crystallized. It’s called <Ji Jing, so it’s one The lubricating property of the step-up is especially suitable as a lubricating film for a metal material which is difficult to process. The above-mentioned constituent raw materials in the above lubricating film (A): (b, ·, ^, the weight of the factory (C) 7 201213536 Preferably, it is i: 0.01~2{) ιυ · 0·0 1 〜20 〇 and the above crystal part is more _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The area ratio of the crystal portion formed on the outer surface of the lubricating film is preferably 20 to 80% when the surface of the smoothing film is observed. Further, the crystal portion preferably has a constituent size of 0.5 or less. It is more preferable that the above-mentioned resin material (# / 土认^) is at least one water-soluble one selected from the group consisting of acrylic resin and other slow-acid-containing tau t-acid resin and polyvinyl alcohol. It is known that it has electrical properties and has a molecular weight of 8000 to 50,000. It is preferable to form the above-mentioned lubricating rupture film on the surface of the ruthenium material to be processed with a deposition amount of 0.3 to 122 m. Made of coated metal material. This kind of lubrication is The coated Han dynasty genus is used in the forming process of plastic deformation, and the above-mentioned auxiliary lubricant such as molybdenum molybdenum, graphite, borax or lime may be used as the _ spoon-lubricating substance. In this case, the second lubricating material is effectively maintained in the day, between the 0th and the day, and the performance of the month can be further improved. In addition, the four convexity formed by the sisters of the field, the mouth and the Japanese department It is formed on the lubricating film, and the helmet is provided with a heterogeneous phase such as a gasification layer of the above-mentioned Patent Document 4, which has an effect of improving the storage efficiency of the smoothing agent. Therefore, 'the metal material of the surface slip agent is removed, the surface property can be suppressed, and the processing is simplified. The processing step is specifically designed to reduce the cost. 8 201213536 η and 'ideal: the above-mentioned metal for processing 枓It is used in the most shape, strip shape, sheet shape or block shape used for forging or impeachment. It is also a line rod and a car owner's ideal for the above-mentioned processing. » , | Steel, titanium, contribution...• The material is selected from difficult-to-process metal wires made of stainless steel, nickel, nickel alloy, niobium and tantalum alloys. τ Further, the patent application scope of this case The invention of claim 13 is a "method of frost", which is characterized in that: (1) a metal material for processing to be formed in advance in the form of a final system; the system is prepared to contain the following (Α) to (D) Lubricant composition: at least one inorganic salt (A) of the group formed by the sulfate, the acid salt, the sulphate, the sulphate, the sulphate and the sulphate The following slip material (B), water-soluble tree with an average molecular weight of 5000~1_〇〇 a fat material (C)' and water (D); (1) a lubricant composition heated to a temperature set in advance to impregnate the material metal material and to heat the material metal material; (4) In the film forming stage, the inorganic salt (A), the slip material (B) and the resin material (C) are deuterated or filmed on the material, and (5) the dry phase, which has a crystal portion. The obtained lubricating film is dried and solidified to fix the crystal portion. Moreover, it is preferable that the intermediate processing stage of performing the plastic working of the material metal material is further performed after the drying step, and the second metal material different from the lubricating film is provided to the material metal material. Processing. Further, the coated metal material is a coated gold 201213536 ray forging and rough processing, and the intermediate processing is a light drawing or rolling process with a processing ratio of 30% or less. Further, it is preferable that the coated metal material is a coated metal wire for spring processing and the intermediate processing is a wire drawing or a rolling process which is a strong degree of processing 帛6 〇% or more. According to the method for producing a coated metal material of the present invention, in the same manner as the formation of the conventional lubricating film, the uniform and stable coating treatment can be set as a continuous operation in which the work load is reduced by the production line. [Embodiment] Hereinafter, an embodiment of the present invention will be described based on the drawings. The 7F' coated metal material 1 of Fig. 1 has a long strip of metal wire 2
與幾乎均勻地霜i 1 A ,、 ，、i個外表面之潤滑被膜3，金屬線2與 潤滑被膜3形成為—辦 、 ’’ 體，並且該潤滑被膜3具有由其一部 分組成之結晶化所形成之結晶部κ。 ㈣：述金屬、線2係根據其目的或用途而選定之金屬材料 的線材》作為該金屬材 。你A 萄材科，可使用先前以來應用於塑性加 工者。作為此種金Μ好制_ . ..厲材枓，適宜為例如不鏽鋼、鈦或鈦合 金、鎳或鎳合金、鉬 3 4 5金等難加工性之金屬材料，其 中較理心為加工硬化特 . X » I- '+· 強之上述不鏽鋼或鈥合金。 又，上述塑性加工包j 方Μ ^ 3鍛杻加工、壓製加工、彎曲加工、 滾鍛加工或彈簧加工等各種加工。 進行瞬間: = 或壓製加工，由於係對金屬材料 膜對抑制材料之變形：：=變形，故本發明之潤滑皮 裂或工具類之缺損甚為有效。又， 10 201213536 即便於彈簧成形中，本發明之潤滑皮膜對於使「且有特 定彈簧彈性之高強度之金屬細線」的塑性加工亦有效。 又’作為冷鍛粗加工用之金屬線2,適宜為例如線徑為 2〇職左右、較佳為〇 5〜1Gmm，且其拉伸強度為 _MPa以下之經軟質加工之金屬線材。另一方面，作為彈 簧用之金屬線2 ’適宜使用例如線徑為Q 左右， 且具有拉伸強度為_〜細Mpa左右之高強度特性的經 、拉線加工之金屬線材。於金屬材料為不鏽鋼之情形時， X得A上述之同強度特性，前者之鍛粗加工用金屬線較 佳為例如經固溶化熱處理精加工，或進—步藉由加卫率3〇% 以下（較佳為3〜20%)之輕程度之拉線加卫或壓延加工對 其進行了調質（Skinpass)精加工。又，後者之彈簧用金屬 線車乂佳為最終精加工係藉由例如加工$ 6〇%以上之冷間拉 線加工而進行了加工硬化者。 金屬線2之剖面形狀可為圓形或非圓形中之任一者。 金I線2之長邊方向之表面粗糖度或形狀亦可任意設 疋。例如’金屬線2亦可為沿長邊方向使外徑週期性地變 :之帶有波浪形狀者。進—# ’覆蓋有潤滑皮膜之金屬材 :，除長條之線材以外，亦可廣泛採用棒狀、帶狀、片狀 ’塊狀等各種形狀品，本發明亦包含該等形狀者。 被覆此種金屬材料% + 、於本形態中為金屬線2)之潤滑被 膜· 3，於本發明中係由冬古， 3有如下3種構成材之金屬材料塑性 加工用潤滑劑組成物所形. ^ ^ ^ 〜成 第一構成材係使用選自由硫 酉夂鹽、硼酸鹽、矽酸鹽、4 Μ酸鹽、鉬酸鹽及鎢酸鹽所組成 201213536 之群中之至少1種無機鹽（A )。又’第二構成材係使用平 均粒徑為20 /z m以下之微粒子狀之滑物質（B )。進一步， 第三構成材係使用水溶性樹脂材料（C )，其具有固持上述 ，機鹽（A)及滑物質（B)之作用。潤滑被膜3係藉由將 以特疋比率摻合該等構成材（A )〜（c )而成之水性潤 月齊]且成物」塗佈於上述金屬材料並乾燥固化而獲得。並 且，本發明之特徵在於：於由該等構成材所構成之潤滑被 膜2中’具有上述無傳鹽（A)之至少一部分結晶化而成之 結晶部K。 上述第一構成材之無機鹽（A )係提昇潤滑被膜之承載 f生、耐壓性者’且為水溶性，藉由將其與併用之樹脂材料 (c ) 一併加熱至特定溫度而容易溶解於水。無機鹽（A ) 適宜為伴隨塗膜之乾燥可將其之至少一部分結晶化者。 作為上述無機鹽（A)，可列舉例如：硫酸鈉、硫酸鉀 等硫酸鹽，硼酸鈉、硼酸鉀、硼酸銨等硼酸鹽，矽酸鈉、 矽酸鉀等矽酸鹽，磷酸鋅、磷酸鈣等磷酸鹽，鉬酸銨、鉬 酸鈉等鉬酸鹽，或鎢酸鈉等鎢酸鹽等。該等可單獨使用， 亦可組合使用2種以上。尤其是硫酸鉀或硼酸鈉藉由拉線 會發揮出優異之承載效果，並且為水溶性且結晶於耐壓性 方面優異’故於本發明中較為適宜。 第二構成材係與上述無機鹽（A) 一併構成潤滑被膜3 之滑物質（B )，於潤滑被膜中發揮使摩擦阻力下降之功能。 作為滑物質⑻，適宜使用例如石墨、二硫仙、氮化侧、 一硫化鎢、氟化石墨或PTFE等。該等滑物質可單獨使用其 12 201213536 中任：種’或組合使用任意兩種以上。滑 粒徑為2°一下，其下限較佳為一以上。滑物二) 之形狀並無特別限定，鱼六社Α “ ^ 疋佳為例如微粒子狀者。 推測上述滑物質（Β )合隨 ^ s丨现者其被覆處理或其後之加工 而發生形狀變化。但是，1 俊之加工 /、十均粒把超過20 " m之粗大者， 於將其作為潤滑劑而混合 夜Τ時，易於堆積在底部而難 以獲得均勻之被覆肢離。v ’粗大粒子會使被膜表面性狀 下降、。就該觀點而言’滑物質（B)之更佳之平均粒徑為Η 以下。再者’所謂上述平均粒徑係指對自該群中任意 提取之複數個粒子進彳干測^ 卞運仃冽疋而獲得之各粒子之最大尺寸的 平均值。 石土之/月動性尤其優異而會帶來良好潤滑性能，並且 可藉由輕程度之衝擊而容易地進行細粒化’又，耐熱性及 導電性亦優異。因此，；f；罢从&丄* ‘土作為本發明之上述滑物質（B ) 尤，、適i因此’含有其之潤滑皮膜在使用於例如「鍛粗 加工之類的目舜間承受較大厭·/!々J； 又杈大楗力之加工」之情形時，可吸收 其負荷壓力而防止由發埶引走已之擠 ,、、、Ή起之現附。又，含有石墨之潤 滑皮膜於直接通電而進杆夕、、w 4 γ η > 士 、电阳進仃之/皿加工時容易加熱，有助於增 加工具哥命或減輕加工破裂等問題。 又’作為第二構成材之水溶性樹脂材料（。），其在作 為潤滑被膜而固化之狀能下恭你土 心狀心、下，發揮使上述無機鹽（Α)及滑 物質（Β )牢固地固著於全屬好粗〇 百i屬材枓2上之固著性。該樹脂材 料（C )須具有如下特性：於、、交、波业 竹丨王於岭液狀怨下對滑物質（B )產 生引力’或使水溶液之黏度上升而防止滑物質⑻之沈殿， 13 201213536 或作為界面活性劑使滑物質⑻成為親水性而使分散穩定 化之特性《又，上述潤滑被膜於該加工後經常會去除。該 月形夺為了不使用特殊之溶劑等而以水或熱水即可容易 地，解，上述樹脂材料（c)設為：由產生水溶性之平均分 子量為5000〜looooo之具有電氣性質的樹脂材料所形成 者。 即，若上述平均分子量未達5〇〇〇，則潤滑劑組成物之 黏度下降’進一步其附著量減少，並且固著強度下降，而 難以獲得良好之被膜（即適當之潤滑狀態）。相反，若為上 述平均分子量超過100000之高分子者，則會超過水溶性之 範圍故不適合本發明。又’於提高黏性而降低上述滑物質 (B )之潤濕性、或於内部產生微細空孔等結構方面亦欠 佳上述樹脂材料（C )之平均分子量更佳為8〇〇〇〜50000， 尤佳為10000〜35000。 作為更佳之上述水溶性樹脂材料（C )，例如可列舉： 丙烯醯胺系樹脂或丙烯酸酯系樹脂等丙烯酸系樹脂及其他 含有羧酸基之樹脂、磺酸系樹脂、聚乙烯醇等之聚乙烯系 樹脂等具有親水性官能基者。該等樹脂材料尤佳為具備下 文所說明之電氣性質者，其比介電係數更佳為2〜12，更理 想為2_0〜8.0，藉此可謀求促進該電氣性質，故較佳。上述 丙烯酸系樹脂中，亦存在藉由熱硬化而形成牢固之臈者。 例如於塑性加工後無須脫膜之情形時，亦可藉由加熱乾燥 或熱處理而形成無機鹽（A )及/或滑物質（B )不易脫落 之被膜。尤佳之樹脂材料（C )，可列舉以丙烯酸烷基酯為 14 201213536 ‘主成分之含有陰離子性基的丙烯酸烧基醋共聚物。 再者，所謂上述樹脂材料（c)具有電氣性質，係指具 有電荷及/或極性之樹脂U^ 树知材枓，其之驗證可根據藉由例如 層析儀或FT-IR等所求得之結構式而進行4 ,如此之特 性尤其可由該分子結構中具有含有〇及Η之親水性之官能 基者而實現，藉此可形成水溶性樹脂材料。同樣地，比介 電係數亦如m —Κ6911所示，提出有例如形成電容器並利 用’、電合之平仃平板法、發射電波並測定反射之自由空間 法等各種方法。此種樹脂材料（c)纏繞上述粒子狀之滑物 質⑻，產生導致凝聚之引力、及導致分離之由電荷引起 之斥力，使水溶性之黏度上升而防止滑物質⑻之沈殿， 或者作為界面活性劑而使滑物f (Β)成為親水性從而使分 散穩定化，亦可生成穩定且均勾性良好之潤滑劑組成物。 本發明所使用之上述樹脂材料（c)為水溶性，易溶解 於水或溫水等中。因此，於被覆處理階段或最終加工後， 具有可於去除皮膜時抑制有機溶劑等有害化學藥品之使用 的優點，於環境方面亦較佳。 本發明之金屬材料塑性加工用之潤滑劑組成物係藉由 将上述構成材（A )〜r Γ 3 & π + \ ^ )(c)冷角午或分散至水中而製備，該 :塗佈後之乾燥手奴而最終去除，藉此形成由構成材 〜（C)構成之潤滑被膜。各構成材（A)〜（c)之 摻合比以其固化狀態之重量換算計，為1:〇〇ι〜2〇:〇〇ι 〜匕〇(固體成分重量比)’較佳為設為1:〇卜匕:。」〜心 更佳為，於例如冷鍛粗用途中設為丨：〇 5〜3 : 〇 . β ’ 又’ 15 201213536 於彈蒉用途t以成為1: Η :1〜10之方式進行換合，又， 其附著量例如以固體成分成為Q 3〜12g/m2左右之方式調 、’ β Μ ”’且成物之濃度.或黏度而使用。通常潤滑劑組成物 係以固體成分濃度成為3〜3〇重量％之方式製備。 若上述附著量未達〇.3g/m2,則無法充分發揮潤滑性 能，即使料超過12g/m、量亦無法獲得與其相稱之潤 滑性能，反而會產生加工時之堵塞等弊病。又，若上述固 體成分濃度未達3重量％，則難以藉由i次塗佈操作而獲得 充：之附者量，若超過30重量％，則會產生溶液黏度變得 過高等塗佈操作方面之問題。 本發明之被覆金屬材料係藉由將上述潤滑劑組成物塗 佈於金屬線2上並將塗膜乾燥而獲得。潤滑劑組成物之塗 佈可藉由浸潰塗佈或噴霧塗佈等任意方法進行。於乾.燥階 奴’發生無機鹽（A )之結晶析出及水溶性樹脂材料（C ) 之造膜，藉由完全蒸發水而形成密接於金屬材料表面之潤 滑被膜。潤滑劑組成物較佳為預先加溫至例如4〇〜i〇〇t、 較佳為60〜1()(rC，藉此可具備滑物f(B)，促進無機鹽（A) 之結晶化。 上述乾燥階段中之溫度及時間並無特別限制，通常於 室溫〜150t下加熱例如卜⑽。秒左右。為了使乾燥在短 時間内結束’適宜進行例如80。〇以上，較佳為i〇(rc以上 之熱風乾燥。如此而獲得之潤滑被膜以上述摻合比含有無 機鹽（A )、滑物質（B )及水溶性樹脂材料（c )。若滑物質 (B)及樹脂材料（C)之摻合比分別未達〇 〇1，則結晶部 16 201213536 κ之面積率變得過大，或難以貼附牢固之被膜。另—方 若該等摻合比分別超過20,則結晶Μ之面積率減小面並 月& 且樹脂材料（C)之比例過大’因而無法發揮充分之、潤滑性 〇 )之製造製 圖3係上述被覆金屬線材（被覆金屬材剩 程之一例。該製程具備： 丨)準備階段，係準備上述被加工用之素材金屬線(辛 材金屬材料⑴及上述潤滑劑組成物12;(2)於加 =之上述潤靡成物12中浸潰素材金屬線1;:塗: 1月劑組錢12並且對該素材金I線11之表面進行加溫的 階段；〇)造膜階段，係於上述辛 皿、 :材（Α)〜⑻結晶化或膜化；(4)乾燥階段，係將見 有結晶部之满滑被膜乾燥固化而使該結晶部固定。- 於本貫施悲樣中，素材今属始彳 目的、用途而調整之尺寸=Γ備將具有根據其 丁 形狀、特性之長條材料捲绝5 轴或承載軸10上而成者，將該素材金屬線—面經由 =輥幻、R2、R3連續地抽出，_面導入至 水性潤滑劑組成物12之槽13内。藉此，^積存 之表面上塗佈特定量之上述潤滑劑組成物Κ。屬線U 潤滑劑組成物12係「於上述構成材（a)及 :液中分散有滑物質⑻之水性分散液」，較佳為藉二 二不之適宜加熱手段加熱至特定溫度。加熱溫度係; 含右：， 員“曰分置而適宜設定，例如若為 有上迷丙烯酸烧基嶋物者，藉由設定為6。〜1〇〇;為 17 201213536 可使Jl述無機鹽（A )之結晶有效地析出至被膜固化後之潤 滑被臈。 士又，例如若為含有磺酸系樹脂或具有醯胺基之丙烯酸 系樹月曰作為上述構成材（C )者，藉由將上述乾燥或其後之 加熱處理中之設定溫度設為例如樹脂材料之玻璃轉移溫度 、上之加熱溫度，亦可增加熱硬化性而提高作為潤滑被 膜之固著牢固性。 处谲槽13具有具備與該金屬線11之供給速度 I併獲得調整之股線長度」的充分容積，以使上述長條金 線II成為特；t之溫度。並且，從儲槽13之液面出來之金 :線U藉由潤滑劑組成物12之熱，於其外面上生成上述結 摄、並利用乾你益15獲得乾燥。其後，將金屬線11 捲取至捲取卷轴]4 i 再者，於本形態令，於預先設定之 供藉由溫度1(^以上之熱風 之狀雄下：“彳固定’以於潤滑劑之附著量達到特定範圍 义狀慼下進行固定。 無機：!!)驟？述浸潰、加溫階段係於儲槽13内進行， _tbi/L 之結晶化及樹脂材料（c)之膜化之上述造膜 白又’係於自儲槽13之液面至乾燥器、 因此，莊I ^ 乾圍進行。 藉由-系列之步驟，謀求連續處理， 化。再者，金屬線u之供給速 缺 4 12之組成;足復田然了依照潤滑劑組成物 ''' 八乾燥條件而適宜地調節。 又’於潤滑被膜3之成形後進一步 形時，亦可脾作化/丄 疋仃1f7間加工之情 、，、所形成之潤滑被膜3所含之滑物 201213536 同種類之滑物質作為第二潤滑物質而賦予被覆金屬材料。 作為此第二潤滑物f，例如可列舉m、二硫化翻、 :墨：氮化硼、二硫化鎢、氟化石墨、硼砂、石灰或刪 叙末等。作為中間加卫，例如可列舉：加卫率鄕以下之 奉工程度之拉線或廢延加工、或者加工_ 以上之強程度 之拉線或壓延加工。本發明之被覆金屬材料由於如上所述 於潤滑被膜表©具有微細心’故所使用之第二潤滑物質 之保持性能較高，發揮出優異之潤滑性能。 於圖2A及2B中，表示形成於潤滑被膜3之上述結晶 部κ之分佈狀態之一例，言亥等係放大至35〜8〇倍之顯微鏡 照片。上述結晶部K會因潤滑被膜之構成材之種類或分量 比率而具有不同之結晶狀態，圖2A者係藉由使用硫酸鹽等 作為無.機鹽而形成有點狀或短纖維狀之突出部。又，圖2b 之狀態..係藉由使用硼酸鹽等而形成有葉脈狀之突出部。 如上述各圖所見，於潤滑被膜之外表面，各結晶部κ 係以自其面上凸設之突出狀態均勻地分佈，結晶部κ間具 備平面之凹部。因此，被覆金屬材料之外表面係形成為具 有由結晶部Κ形成之凸部及上述凹部的微小凹凸面，而有 助於提昇潤滑性。 上述結晶部Κ不僅可於該潤滑被膜3中形成為單層， 亦可以於厚度方向以複數之積層分佈狀態而形成。進_ 步’關於結晶部Κ之方向性，無須使所有結晶部均成為與 該潤滑被膜之平面方向並行之狀態，例如包含於傾斜方向 交又之情形。 19 201213536 又’上述結晶部K係由該構成要素之無機鹽（A 者，此情況係藉由使用掃描式電子顯微鏡或χ射線分 圖像繞射，根據各元素之構成圖案與該結晶部κ之符 確認。藉由此種圖案之圖像分析， ， >二址* 竹J谷易地求出該結晶部Κ 之面積率。結晶部K之面猜率传中乾从 之面積羊係疋義為俯視下之潤滑被膜 之母早位面積内之結晶部κ之合 、 〇Λ〇/ 之。汁面積的比例，較佳為20 〜80/。。於該情形，該面積率 思選擇之數點之測定相 野之結果的平均值表示。 』疋現 根據上述圖像繞射之觀察，結晶部κ以外之部 上㈣出滑物質⑻，且可確認該部分為凹部。因此”質 種楗小凹凸面可效率良好地收容例如其後之加工 之上述輔助潤滑劑，而摇古利，典ω 阿予 ^丨而閏滑性。即，藉由結晶部 面積率之最佳化，可於難加 龆认。-故Λ 材之俶粗加工或彈簧成形之 類的嚴格加工處理中具有優 ^ 率與潤滑性之間存在關聯性。 檟 圖4 A其結果之一例，橫轴表示結晶部κ之面 (%)，縱軸表示於上述鍛粗加工令之加工壽命（加。 於本實施態樣中，面積率較佳為設定為20〜80%。由 可知、’採用面⑽低於鳩者時，於適宜進行之 中對被覆金屬材料所賦予、^ ^ σ工 降，使工具壽命τ降。相：：助广劑之收容保持力下 相反，知用面積率超過80%者 無法獲得辅助濁滑劍之右八 、 非常堅硬，因而若過多含有， ^ 表面性下降，又，導使用金屬村料之 ¥致加工工具之壽命下降等。因 ^ fin 20 201213536 曰曰。ρ κ之面積率更佳為設定為3〇〜8〇%，再更佳為設定為 40〜70%，尤佳為設定為4〇〜6〇%。 、再者，結晶部Κ之大小或形態係根據其處理條件或構 成材之種類等而適宜變化。結晶部〖之形狀並無特別限定， 較佳為具備如圖2Α及2Β所示之粉末狀或短纖維狀或葉脈 狀中任「種以上之形狀’其大小（構成尺寸）較佳為〇·5随 以下之微細者。此處，關於結晶部Κ之構成尺寸，粉末狀 之結晶係以其最大直徑之平均值表示，纖維狀或葉脈狀之 結晶係以構成其單-單元（element)(各單—線）之最大粗 度之平均值表示。 若結晶部K之尺寸超過〇.5mm於其後之成形加工中會 f生表面之粗糙化，又，上述短纖維狀或葉脈狀者會因結 阳部間之凹部之小空間化，而使辅助潤滑劑之收容效率下 降。結、，晶部K之尺寸更佳為〇· lmni以下。 於、’、α ΒΘ。卩K為短纖維狀或葉脈狀之情形時，結晶部之 單—單几具有特定長度（L )(例如〇.〇 1〜1 mm )，此長度（L ) 與粗度（D)之縱橫比（L/D)較佳為在平均15〜5〇之範 .圍内。尤其是結晶部K長於所需之情形時，藉由其無規分 佈所確定之網眼會變大，故欠佳。關於結晶部κ，更佳之縱 橫比為2〜20。如此縱橫比之調整’可藉由例如上述乾燥之 條件設定而進行。 於本實施形態中’對「被加工用金屬材料為用於冷鍛 粗成形或彈簧成形用途之潤滑被覆線材」之情形進行了說 明。又，主要對「將潤滑劑組成物均勻地塗佈於金屬材料 21 201213536 之整個面而進行被覆形成處理」 本發明並不限定於該算 /進仃了說明。但是 片材、塊材等各/ 歹1 °作為金屬材料，棒材或帶材 总找 璉擇或其材質之種類及大小 程度之應用’係發明所屬 ά ^ ^ ^ ^ ^ 彳77貝域中具有通常知識者可容 易地7L成者，應作為本於 ^ ^明之一形態而包含在本發明中。 [貫施例] 接著，藉由以下之實施例更詳細地說明本發明。 [實施例1 ] [觉试材料之製作] 於本實施例中，選定鋼種SUS304 ' 316及XM7型之冷 鍛粗用之沃斯田鐵系不鏽鋼《3種作為該被處理材料，進 一步將分別冷拉線加工為線徑3 65mm者作為素材。接著， 於溫度1000〜1 i〇(rc以股線型之熱處理裂置對該等進行固 溶化熱處理，並且使用下述之潤滑劑組成物進行被覆，而 獲得被覆不鏽鋼線。於該處理步驟中，上述熱處理裝置係 於其出口側連接圖3所示之結構之被覆裝置，以固溶化熱 處理與被覆處理同時進行之方式構成一系列之生產線裝 置。潤滑劑組成物係使用如下之組成。 [潤滑劑組成物] (A )硫酸納 1 〇重量％ (B)硼酸鈉 2重量％ (C )氮化硼（平均粒徑5 # m ) 1 0重量％ (D )丙烯酸系樹脂 1 0重量〇/0 (陰離子系丙烯酸烷基酯共聚物/介電係數3.8，有電 22 201213536 荷、極性） ‘比） (E)水 (A):(B):(C):(D) =5: 1: 5: 5 6 8重量％ 固體成分重量 固體成分？辰度32重量％ 將混合該等（A )〜（E )而成之潤滑劑組成物導入寬 度200χ深度600χ高度30〇mm之儲槽内，一面利用外部加熱 器於溫度80〜951：之範圍内加熱一面充分攪拌，而製成水 性分散液。於該狀態下，上述無機鹽及水溶性樹脂材料溶 解於溶劑之水中，氮化硼均勻地分散於該水溶液中。 [被膜形成、結晶化處理] 被膜形成處理係以如下方式進行：基於上述潤滑劑組 成物之組成或加熱溫度及儲槽容積，言周節被處理線材（不 鏽鋼線供給速度，藉此使塗膜附著量成為特定範圍。 於本.實施例中，II由將線材供給速度設為3〜7m/_，可 ::均附著量調整為6〜12g/m2之範圍。蒸發水之補充係 進行之自動調整而進行。·，該调滑劑之被覆 U為良好，可將附著量之不均抑制為較少。 =經浸潰塗佈之被處理線材自該液面送出，利用配 塗佈之液面起約°·8ΐΉ之位置之筒狀之熱風乾燥器，使所 於潤滑劑組成物於峨完全乾燥，而使潤滑被膜固定 到=在:液::r儲槽係加溫至―故可觀察 之結：在自液面至熱風乾燥器之間水分蒸發而析出無機鹽 23 201213536 、* x上述速度進行如此一系列之金屬線材之熱處理 被2膜幵V成處理，於各不鏽鋼線之表面上以附著i 6〜i2g 纯曰4皮覆潤α被膜，而獲得具有具備如圖2A之短纖維狀之 日曰P之/閏滑被膜的軟質不鐵鋼線。藉由利用X射線繞射 裝置、（堀場製作所製造）之圖像分析所求得之結晶部，係 又為10 5 0从m、平均縱橫比為2〜丨5之短纖維狀無規分 佈者，且其面積率平均為49.6〜52.1%。 又藉由結晶部之放大顯微鏡觀察，確認到凸設之突 出狀態，進一步由根據「該被覆鋼線於特定位置有無潤滑 劑」而獲得的表面粗糙度（Rz )之下述測定結果，亦獲得 證明。 .潤滑被膜面上之表面粗糙度 9.6〜10.4 " m .去除潤滑劑之面之表面粗縫度 7.6 # m [比較潤滑劑] 作為比·較潤滑被膜（比較例），分別於上述3種不鏽鋼 線上以附著量6〜12g/ m2形成草酸鹽被膜而用作比較線 材。再者，該草酸鹽被膜先前多用於不鐵鋼之冷加工用途， 其處理過程中存在產生六價Cr或產生含有有害物之薄霧 (mist)等含有有害重金屬之淤渣（sludge)或廢酸之問題， 近年來趨向減少。 [中間加工處理] 對本實施例之被覆軟質不鏽鋼線，進一步以4%之加工 率實施調質拉線加工’而獲得表1中所記載之冷鍛粗用不 鏽鋼線》該調質加工係使用於輔助潤滑劑中併用有金屬息 24 201213536 者，可確認該辅助潤滑劑保持於上述鋼線表面之凹部内 25 201213536 【1<〕 表面粗链度（Rz ；tzm) 〇 rn » _< CN (Ν rn 結晶面積率（％) 50.0 50.9 結晶形態 粉狀+短纖維狀 粉狀+短纖維狀 粉狀+短纖維狀 附著量 (g/m2 ) 00 CN 拉延率 (%) 〇〇 〇〇 培1" 〇〇 CO CO m 拉伸強度 (MPa) 〇〇 VO KT) CO un 宕 線徑 (mm) 3.04 | | 3.04 I | 3.04 | 鋼種 | SUS 304 I j SUS316 1 SUSXM7 受試材料 No 1 < A-3 201213536 [潤滑性試驗] 其次，使用上述實施例之 價其加工性之锻粗試驗 二不鏽鋼線，進行評 加工進行十字皿頭螺針之鍛：:面：力，子油-面以冷 鋼製之十字衝頭.（ 形，加工條件為利用工具 rPUneh)以每分鐘15。個之傳送速 度進行合計2 5 0 0 〇個之锻相士 ^ 粗成形，並觀察工具面數及是否 產生破裂等缺陷》 令 試驗結果良好，本實施例之潤滑被膜係獲得超過比較 例之草酸鹽被膜之15_個之q壽命者。又可於不發 2工破裂或燒附等問題之情況下進行鍛粗加工。該加工 分數係評價鍛粗加工性之加工壽命者，認定本實施例之被 膜具有與作為比較潤滑劑之草酸鹽被膜同等以上之潤滑 性。將所獲得之鍛粗製品（試#N〇 A—2)之表面狀態之一 例不於圖5，未見燒附之痕跡。 [實施例2] 針對上述XM7不鏽鋼線（線徑：3 65mm)之固溶化熱 處理材，-併進行改變了「上述構成材（A)無機鹽、⑻ 滑物質、（C)水溶性樹脂之水準」的如下加工性評價。該 斤偏係與上述同樣地以鍛粗加工所造成之工具壽命而確 認，將結果示於表2。 27 201213536 評價結果 綜合 ◎ ◎ 〇 ◎ ◎ ◎ X X 有無燒附 碟 碟 碟 :工具壽命 丨（個） 13500 16300 1 1 12800 13200 15200 14800 7000 8100 (C)水溶性樹脂 濃度（％) CN 〇〇 »-Η <N cn Ο 種類 B- tO ο 卜 1 &- (B)滑物質 濃度（％) 〇〇 〇 CN cn CN (N 種類 Λ Xi Λ X3 o 1 1 (A)無機鹽 濃度（％) CN 〇〇 CN cn 卜 CN »—Η ON r—i 種類 一：= :s • <-H ·— 被膜序號 組成1 組成2 組成3 組成4 組成5 組成6 組成7 組成8 塚翹ίτΛί 鮏紫ο鉍l· 荽鉍妹溫硪域韶裝«to SS 0 S3 s$y^. « (劑苍)迴！Ti窗资&-IS堪(3) 頌 qrwM q f-9r e 鉍荽骷(《) sf ^ ss ^ 额顰魂(V) 201213536 由s亥專各貫施例確認：本發明之潤滑被膜與先前之潤 滑劑同樣地，可用於不鏽鋼之鍛粗機鍛粗用途，尤其是難 加工性材料之強加工用被膜。 [實施例3] [鈦一錄合金帶材之應用例] 製備下述組成之潤滑劑組成物。 (A)矽酸鈉 (B ) —硫化翻（平均粒徑2 # m ) (D )丙烯酸系樹脂 1 〇重量0/〇 (陰離子系丙烯酸烷基酯共聚物/介電係數2 · 7，具有 電荷、極性） 固體成分重量比（A):(B):(C) = 5: 4: 2 固體成分濃度 22重量％ 已知Ni — Ti合金為金屬間化合物且為難加工材，即便 於拉線中亦易產生由拉線模具引起之瑕疵或斷線。作為其 解決方法，例如會形成氧化被膜，然而，形成氧化被膜雖 難以產生瑕疵或斷線，但最終製品不得不除去氧化被膜 (descale )，此時由於使用酸故表面性狀下降，而存在損害 製品品質之缺點。 因此，為了評價本潤滑被膜對該Ni— Ti合金線之適應 性，對線徑為1.8mm之合金退火材1〇〇kg以2〜6g/m2塗 佈上述潤滑劑組成物，並拉線至線徑為16mm。於拉線中 無瑕疫或斷線，可獲得良好之加：性，對於最終製品，僅 藉由去除上層部之金屬皂所需之鹼洗（alkaline wash )及熱 29 201213536 變得可省略酸洗 ’於品質.方面亦 水清洗’便能完全去除潤滑被膜。藉此， 步驟，降低環境負擔並且提昇作業性，又 成功地縮小線徑公差之範圍。 [實施例4] [彈簧用不鏽鋼線之拉線加工] 製備下述組成之潤滑劑組成物。 (A)硫酸鉀 (B )石墨（平均粒徑3以m ) (C)羧酸鹽系水溶性樹脂（銨鹽，有電荷、極性 固體成分重量比（A ) : ( B ) : ( C ) = i : i 5 : 2 固體成分濃度1 8重量％ 對線徑1.5mm之SUSliMMi 丁协a丄 w〇4N1不鏽鋼線之退火材200kg 以〇.3〜2g/m2塗佈上述潤滑劑組成物，並拉線至線徑為 〇·?_。確認拉線後之材料無瑕疮，表面狀態良好，且未見 破=剝離或瑕疯等表面缺陷。繼而，確認彈簧之捲繞性。 先刖’降菁材之捲繞加工係以供禮士士或+ 诉Λ锻鎳材為主流，故以鍍鎳材 為比較材進行比較試驗。 巩嫩你針對 。 -”,从六掩現成形τ之 彈簧自由長度之偏差3σ進行評價’實施例材為〇 25，比較 例材為0.24,結果幾乎相同，又，若使㈣㈣，例如除 了所謂活體過敏之對健康之影響以外，於將其去除時亦存 在廢液處理㈣境負擔，或難以避免去除後之表面狀態下 降等問題，相對於此，本發明品可改善此種問題。 彈簧規格 30 201213536 整縮彈簧D/ d= 20.0 自由長度15.5mm 自由長度公差士〇.3mm 總卷數1 0 速度5 0個/分鐘 [產業上之可利用性] 如以上所說明，本發明之潤滑被膜可使用於要求潤滑 性之各種用途。尤其可用作不鏽鋼或鈦或鈦合金、鎳或$ 合金、鈮或鈮合金等難加工性之金屬材料之鍛粗加工或壓 製加工、f曲加丄、滚鍛加h彈菁加工等嚴格之塑性加 工之潤滑手段，進一步提供一種潤滑性優異及消除環境保 護問題且可生產線化之技術。 【圖式簡單說明】 圖' 1係表示本實施形態之被膜金屬材料之—例的放大 斜視圖。 圖2A係將潤滑被膜之外面放大之顯微鏡照片，表示結 晶部形成為點狀與短纖維狀混合存在之突出部的结晶部之 分佈狀態。 圖係將潤滑被膜之外面放 晶部形成為葉脈狀之突出部的分佈狀態之—例。 圖3係例示被覆金屬材料之製造 圖4係夹千社曰^ mm '、表不〜日日。卩之面積率與鍛粗加工 a 之關係的關係圖。 甲之加工可〒 圖5係表示去除潤滑被膜後之金屬材料之加工製品之 31 201213536 表面狀態的放大照片。 【主要元件符號說明】 1 被覆金屬材料 2 金屬線 3 潤滑皮膜 10 承載軸 11 金屬線 12 潤滑劑組成物 13 儲槽 14 捲取卷軸 15 乾燥器 R1 導輥 R2 導輥 R3 導輥 K 結晶部 32With the lubricating film 3 of the outer surface of the frost i 1 A , , , i, the metal wire 2 and the lubricating film 3 are formed into a body, and the lubricating film 3 has a crystallization consisting of a part thereof. The formed crystal portion κ. (4): The metal material of the metal material selected according to the purpose or use of the metal or wire 2 is used as the metal material. You A material, can be used in plastics processors. As such a good metal system, it is suitable for metal materials such as stainless steel, titanium or titanium alloy, nickel or nickel alloy, molybdenum 345 gold, etc. Special. X » I- '+· Strong above stainless steel or tantalum alloy. Further, the above-mentioned plastic working package includes various processing such as forging processing, press working, bending processing, roll forging processing, or spring processing. At the moment: = or press processing, the deformation of the metal material film against the suppression material: : = deformation, the lubrication crack of the present invention or the defect of the tool is very effective. Further, 10 201213536, that is, in the spring molding, the lubricating film of the present invention is effective for plastic working of "a high-strength metal thin wire having a specific spring elasticity". Further, as the metal wire 2 for cold forging rough processing, for example, a soft-processed metal wire having a wire diameter of about 2 〇, preferably 〇 5 to 1 Gmm and a tensile strength of _MPa or less is suitable. On the other hand, as the metal wire 2' for the spring, for example, a wire having a wire diameter of about Q and having a high strength characteristic of a tensile strength of about _ to a fine Mpa is preferably used. In the case where the metal material is stainless steel, X has the same strength characteristics as described above, and the forging roughing metal wire is preferably, for example, solidified by solution heat treatment, or further increased by a curing rate of 3% or less. A light wire drawing or calendering process (preferably 3 to 20%) is subjected to skin pass finishing. Further, the latter spring is made of a metal wire rudder which is subjected to work hardening by, for example, processing a cold drawing process of $6 〇% or more. The cross-sectional shape of the metal wire 2 may be either a circular shape or a non-circular shape. The surface roughness or shape of the long side of the gold I line 2 can also be arbitrarily set. For example, the metal wire 2 may be such that the outer diameter is periodically changed in the longitudinal direction: it has a wave shape. The metal material of the lubricating film is covered by the ##'; in addition to the long wire, various shapes such as a rod shape, a belt shape, and a sheet shape are also widely used, and the present invention also includes such shapes. In the present invention, the lubricating film of the metal material 2 + and the metal material 2) in the present invention are 3, and in the present invention, the lubricant composition for plastic working of the metal material having the following three kinds of constituent materials is Form . ^ ^ ^ ~ into the first constituent material using at least one inorganic selected from the group consisting of sulfonium salts, borate, silicate, tetradecanoate, molybdate and tungstate 201213536 Salt (A). Further, the second constituent material is a fine particle-like slip material (B) having an average particle diameter of 20 / z m or less. Further, the third constituent material is a water-soluble resin material (C) which has a function of holding the above-mentioned organic salt (A) and slipping substance (B). The lubricating film 3 is obtained by applying the water-repellent resin obtained by blending the constituent materials (A) to (c) at a specific ratio and applying the product to the metal material, followed by drying and solidifying. Further, the present invention is characterized in that the lubricating film 2 composed of the constituent materials has a crystal portion K in which at least a part of the salt-free (A) is crystallized. The inorganic salt (A) of the first constituent material is used to improve the bearing capacity and pressure resistance of the lubricating coating, and is water-soluble, and is easily heated to a specific temperature together with the resin material (c) used in combination. Dissolved in water. The inorganic salt (A) is preferably one which crystallizes at least a part of the coating film as it is dried. Examples of the inorganic salt (A) include sulfates such as sodium sulfate and potassium sulfate; borate salts such as sodium borate, potassium borate, and ammonium borate; citrates such as sodium citrate and potassium citrate; and zinc phosphate and calcium phosphate. Such as phosphate, molybdate such as ammonium molybdate or sodium molybdate, or tungstate such as sodium tungstate. These may be used alone or in combination of two or more. In particular, potassium sulfate or sodium borate is preferred in the present invention because it exhibits an excellent load-bearing effect by pulling a wire and is excellent in water solubility and crystallinity in pressure resistance. The second constituent material together with the inorganic salt (A) constitutes the slippery substance (B) of the lubricating coating 3, and exhibits a function of lowering the frictional resistance in the lubricating coating. As the slip material (8), for example, graphite, dithizone, nitriding side, tungsten monosulfide, fluorinated graphite or PTFE or the like is suitably used. These slip substances can be used alone in any of the 12 201213536: species or in combination of any two or more. The sliding particle diameter is 2°, and the lower limit thereof is preferably one or more. The shape of the sliding material 2) is not particularly limited, and the fish is "for example, a particle-like shape. It is presumed that the above-mentioned sliding substance (Β) is shaped according to the coating treatment of the present or the subsequent processing. Change. However, when 1 Jun's processing/, 10 granules are more than 20 " m thick, when they are mixed as a lubricant, they tend to accumulate at the bottom and it is difficult to obtain a uniform coated limb. v 'Coarse The particles cause a decrease in the surface properties of the film. From this point of view, the preferred average particle size of the slip material (B) is Η or less. Further, the above-mentioned average particle size means a plurality of arbitrary extracts from the group. The average value of the maximum size of each particle obtained by the particle enthalpy test. The earth/moon movability is particularly excellent and brings good lubrication performance, and can be easily performed by a slight impact. "fine granulation" is also excellent in heat resistance and electrical conductivity. Therefore, f; sever & 丄 * ' soil as the above-mentioned slippery substance (B) of the present invention is particularly suitable for the lubricating film containing Used in, for example, "forging roughing When the eyes of the class are subjected to a large disgusting /·/!々J; and the processing of the 楗 楗 楗 」 , 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可Attached. In addition, the graphite-containing lubricating film is easily energized when it is directly energized, and w 4 γ η > 士, 阳阳进仃 / 皿/process is easy to heat, which helps to increase the tool life or reduce the problem of processing cracking. In addition, as a water-soluble resin material (.) which is a second constituent material, it can be used as a lubricating film to solidify the core and the inorganic salt (Α) and the sliding substance (Β). Firmly fixed to the sturdiness of the whole genus. The resin material (C) shall have the following characteristics: the gravitational force of the slippery substance (B) in the liquid, and the liquidity of the aqueous solution, or the sedimentation of the slipping substance (8), 13 201213536 Or as a surfactant, the slippery substance (8) is made hydrophilic and stabilizes the dispersion. Further, the above-mentioned lubricating film is often removed after the processing. The resin material (c) is preferably made of a resin having an electrical property of an average molecular weight of 5000 tolooooo which is water-soluble and which is water-soluble or hot water, without using a special solvent or the like. The material formed by the person. That is, when the average molecular weight is less than 5 Å, the viscosity of the lubricant composition is lowered. Further, the amount of adhesion is decreased, and the anchor strength is lowered, so that it is difficult to obtain a good film (i.e., an appropriate lubricating state). On the other hand, in the case of a polymer having an average molecular weight of more than 100,000, the range of water solubility is exceeded, which is not suitable for the present invention. Further, it is also inferior in improving the wettability of the sliding material (B) or the structure in which fine pores are generated inside. The average molecular weight of the above resin material (C) is preferably from 8 〇〇〇 to 50,000. , especially good for 10000~35000. More preferably, the water-soluble resin material (C) is exemplified by an acrylic resin such as a acrylamide resin or an acrylate resin, and a polymer containing a carboxylic acid group, a sulfonic acid resin, or a polyvinyl alcohol. A hydrophilic functional group such as a vinyl resin. It is preferable that the resin material is preferably one having the electrical properties described below, and the dielectric constant is preferably from 2 to 12, more preferably from 2 to 8.0, whereby the electrical property can be promoted. Among the above acrylic resins, there is also a strong bond formed by thermal curing. For example, when it is not necessary to remove the film after plastic working, a film in which the inorganic salt (A) and/or the slip substance (B) are not easily peeled off may be formed by heat drying or heat treatment. The resin material (C) which is particularly preferred is an acrylic acid-based vinegar copolymer containing an anionic group which is an alkyl acrylate of 14 201213536. Further, the above-mentioned resin material (c) has electrical properties and refers to a resin having a charge and/or a polarity, and the verification thereof can be obtained by, for example, a chromatograph or FT-IR. The structural formula is carried out 4, and such characteristics can be realized, in particular, by a functional group having a hydrophilicity containing ruthenium and osmium in the molecular structure, whereby a water-soluble resin material can be formed. Similarly, as for the specific dielectric constant, as shown by m - Κ 6911, various methods such as forming a capacitor and using ', a flat plate method for electrical connection, a free space method for transmitting electric waves, and measuring reflection are proposed. The resin material (c) is wound around the particulate slip material (8) to cause a gravitational force causing agglomeration and a repulsive force caused by electric charge to cause separation, to increase the viscosity of water solubility, to prevent the sliding of the sliding substance (8), or as an interface activity. The lubricant f is a hydrophilic agent to stabilize the dispersion, and a lubricant composition which is stable and has good uniformity can be produced. The above resin material (c) used in the present invention is water-soluble and easily soluble in water or warm water. Therefore, it is advantageous in terms of environment to suppress the use of harmful chemicals such as organic solvents at the time of coating treatment or after final processing. The lubricant composition for plastic working of the metal material of the present invention is prepared by cooling the above-mentioned constituent materials (A)~r Γ 3 & π + \ ^ ) (c) into water or by dispersing into water. The dry hand slave after the cloth is finally removed, thereby forming a lubricating film composed of the constituent materials - (C). The blending ratio of each of the constituent materials (A) to (c) is preferably 1: 〇〇ι 2 〇: 〇〇ι 匕〇 (solid content by weight) in terms of the weight of the cured state. For 1: 〇 匕:. For example, in the case of cold forging and roughing, it is set to 丨: 〇5~3 : 〇. β '又' 15 201213536 For use in magazines, it is to be replaced by 1: Η :1~10 Further, the amount of adhesion is used, for example, such that the solid content is adjusted to about Q 3 to 12 g/m 2 , and the concentration of the product or the viscosity is used. Usually, the lubricant composition is 3 in terms of solid content. It is prepared in a manner of not more than 3% by weight. If the amount of adhesion is less than 33g/m2, the lubricating performance cannot be fully exerted. Even if the amount exceeds 12 g/m, the lubricating property is not commensurate with the amount, and the processing time is generated. Further, if the concentration of the solid component is less than 3% by weight, it is difficult to obtain the amount of charge by the i-coating operation, and if it exceeds 30% by weight, the solution viscosity becomes excessive. Problems in the coating operation of the present invention. The coated metal material of the present invention is obtained by applying the above lubricant composition onto the metal wire 2 and drying the coating film. The coating of the lubricant composition can be performed by dipping It is carried out by any method such as coating or spray coating. The dry granules are formed by precipitation of the inorganic salt (A) and the formation of the water-soluble resin material (C), and the lubricating film is adhered to the surface of the metal material by completely evaporating water. The lubricant composition is preferably The temperature is preliminarily heated to, for example, 4 Torr to 1 Torr, preferably 60 to 1 () (rC, whereby the slipper f(B) can be provided to promote crystallization of the inorganic salt (A). The temperature and time are not particularly limited, and are usually heated at room temperature to 150 t, for example, at about (10) seconds. In order to allow drying to be completed in a short time, it is preferable to carry out, for example, 80 〇 or more, preferably i 〇 (hot air above rc) The lubricating film thus obtained contains the inorganic salt (A), the slip material (B), and the water-soluble resin material (c) in the above blending ratio. If the blending ratio of the slip material (B) and the resin material (C) If the ratio of 结晶1 is not reached, the area ratio of the crystal portion 16 201213536 κ becomes too large, or it is difficult to attach a strong film. If the blend ratio exceeds 20, the area ratio of the crystal Μ is reduced. And the ratio of the resin material (C) is too large, so it cannot be fully utilized. (Manufacturing drawing 3 of the lubricating property) is the preparation of the above-mentioned coated metal wire (an example of the remaining process of the coated metal material: the process includes: 丨), and prepares the metal wire for processing (the SiC material (1) and the above lubrication) a composition 12; (2) impregnating the material metal line 1 in the above-mentioned moisturizing product 12;: coating: a period of heating the surface of the material gold I line 11 by the month 12 ; 〇) film formation stage, in the above-mentioned symmetry, material (Α) ~ (8) crystallization or filming; (4) in the drying stage, the crystallized film is dried and solidified to fix the crystal part - In the sorrowful sample, the size of the material is adjusted for the purpose, use, and the length of the material will be rolled up on the 5-axis or the load-bearing shaft 10 according to its shape and characteristics. The material wire surface was continuously drawn through the roll, R2, and R3, and the surface was introduced into the groove 13 of the aqueous lubricant composition 12. Thereby, a specific amount of the above lubricant composition Κ is applied to the surface of the accumulated material. The urethane U lubricant composition 12 is "an aqueous dispersion in which the slip material (8) is dispersed in the above-mentioned constituent material (a) and liquid), and is preferably heated to a specific temperature by a suitable heating means. Heating temperature system; Contains right:, member "曰 is suitable for setting, for example, if there is a sputum-based sputum, by setting it to 6.~1〇〇; for 17 201213536, Jl can be said to be inorganic salt The crystal of (A) is effectively precipitated to the lubricating layer after the film is cured. For example, if it is a sulfonic acid-based resin or an acrylic tree having a guanamine group, the above-mentioned constituent material (C) is used. The setting temperature in the above-described drying or the subsequent heat treatment may be, for example, the glass transition temperature of the resin material or the upper heating temperature, and the thermosetting property may be increased to improve the fixing property of the lubricating film. A sufficient volume is provided to obtain the adjusted strand length "with the supply speed I of the wire 11" so that the long gold wire II becomes a temperature of t; Further, the gold from the liquid level of the storage tank 13 is formed by the heat of the lubricant composition 12 on the outside of the surface, and is dried by using the dryness. Thereafter, the metal wire 11 is taken up to the take-up reel] 4 i. In the present embodiment, the temperature is set to a temperature of 1 (the hot air of the above: "彳 fixed" for lubrication The amount of the agent adhered to a specific range of the shape of the underarm is fixed. Inorganic:!!) The impregnation and heating stages are carried out in the storage tank 13, the crystallization of _tbi/L and the film of the resin material (c) The above-mentioned film-forming white is also carried out from the liquid level of the storage tank 13 to the dryer, and therefore, the Zhuang I ^ dry circumference is carried out. With the steps of the series, continuous processing is achieved, and further, the metal wire u The composition of the supply shortage 4 12; the foot Fu Tianran is appropriately adjusted according to the lubricant composition ''' eight drying conditions. 'When the shape of the lubricating film 3 is further formed, it can also be spleen/丄疋仃In the case of processing between 1f7, the slip material contained in the lubricating film 3 formed in the same manner, 201213536, the same kind of slip material is applied as the second lubricating material to the coated metal material. Examples of the second lubricating material f include m and Vulcanization, ink: boron nitride, tungsten disulfide, graphite fluoride, borax, lime or For the middle of the reinforcement, for example, the drawing line of the degree of maintenance or the following is the drawing line of the engineering degree or the processing of the processing, or the processing of the above-mentioned strong degree of drawing or calendering. The coated metal material of the present invention. Since the lubricating film surface has a fineness as described above, the second lubricating material used has high retention performance and exhibits excellent lubricating performance. In Figs. 2A and 2B, the above-described crystal formed on the lubricating coating 3 is shown. An example of a distribution state of κ, a microscope photograph magnified to 35 to 8 〇 times, and the crystal portion K has a different crystal state due to the type or component ratio of the constituent material of the lubricating film, and FIG. 2A By using a sulfate or the like as the inorganic salt, a protruding portion having a dot shape or a short fiber shape is formed. Further, the state of Fig. 2b is formed by using a borate or the like to form a protruding portion having a vein shape. As seen from the figure, on the outer surface of the lubricating film, each crystal portion κ is uniformly distributed in a protruding state protruding from the surface thereof, and a flat concave portion is provided between the crystal portions κ. Therefore, the outer surface of the coated metal material is coated. The convex portion formed of the crystal portion 及 and the minute uneven surface of the concave portion are formed to contribute to the improvement of lubricity. The crystal portion Κ can be formed not only as a single layer in the lubricating film 3 but also in the thickness direction. It is formed by a plurality of layers distributed in the state of the layer. Regarding the directivity of the crystal portion, it is not necessary to make all the crystal portions parallel to the plane direction of the lubricating film, and for example, it is included in the oblique direction. 19 201213536 Further, the above-mentioned crystal portion K is an inorganic salt of the constituent element (A. In this case, by using a scanning electron microscope or a krypton ray image, the pattern is formed according to the constituent pattern of each element and the crystal portion κ Confirmation. With the image analysis of such a pattern, the area ratio of the crystal portion 易 is easily obtained by > The area of the crystal portion K is estimated to be in the middle of the dry area. The sheep system is the combination of the crystal parts κ in the early maturity area of the lubricating film in a plan view. The ratio of the area of the juice is preferably 20 to 80/. . In this case, the area ratio is expressed as the average of the results of the measurement of the number of points.疋 根据 According to the observation of the image diffraction described above, the sliding material (8) is emitted from the portion other than the crystal portion κ, and it is confirmed that the portion is a concave portion. Therefore, the quality of the small uneven surface can efficiently accommodate the above-mentioned auxiliary lubricant, for example, and the subsequent processing, and the granules are the most smooth. It is difficult to add acquaintance to the improvement. Therefore, there is a correlation between the excellent rate and the lubricity in the strict processing such as roughing or spring forming of the slab. 之一 Figure 4A, an example of the result, The horizontal axis represents the surface (%) of the crystal portion κ, and the vertical axis represents the processing life of the forging roughing process (addition. In the present embodiment, the area ratio is preferably set to 20 to 80%. When the surface (10) is lower than that of the crucible, it is given to the coated metal material during the appropriate process, and the tool life is reduced by τ. The phase:: the holding capacity of the auxiliary agent is reversed, and the area ratio is known. More than 80% of them cannot obtain the right eight of the auxiliary turbid sword, which is very hard. Therefore, if it is excessively contained, ^ the surface is degraded, and the life of the processing tool using the metal material is reduced. Because of ^ fin 20 201213536 曰曰. The area ratio of ρ κ is better set to 3〇~8〇% Further, it is more preferably set to 40 to 70%, and more preferably set to 4 to 6 %. Further, the size or form of the crystal portion is suitably changed depending on the processing conditions, the type of the constituent material, and the like. The shape of the part is not particularly limited, and it is preferable to have a shape of a powder or a short fiber or a vein as shown in FIGS. 2A and 2A, and the size (constitution size) of the seed is preferably 〇·5. Here, as for the constituent size of the crystal portion, the powder crystals are represented by the average value of the maximum diameters thereof, and the fibrous or vein-like crystals are formed to constitute the single-element (each) The average value of the maximum thickness of the single-line is expressed. If the size of the crystal portion K exceeds 〇.5 mm, the roughening of the surface will occur in the subsequent forming process, and the short fiber or veins may be caused by the above. The space between the concave portions of the yang is reduced, and the storage efficiency of the auxiliary lubricant is lowered. The size of the crystal portion K is preferably 〇· lmni or less. 、, ', α ΒΘ. 卩 K is short fiber Or in the case of veins, the single-single of the crystallized part has a specific Degree (L) (for example, 〇.〇1~1 mm), the aspect ratio (L/D) of the length (L) and the thickness (D) is preferably within an average of 15 to 5 。. When the crystal portion K is longer than necessary, the mesh determined by the random distribution becomes large, which is not preferable. Regarding the crystal portion κ, the aspect ratio is preferably 2 to 20. Thus, the aspect ratio adjustment In the present embodiment, the case where the metal material to be processed is a lubricated coated wire for cold forging rough forming or spring forming is described. The coating forming process is performed by uniformly applying the lubricant composition to the entire surface of the metal material 21 201213536. The present invention is not limited to the description. However, the use of sheets, blocks, etc., as 金属1 ° as a metal material, the choice of the bar or strip, or the type and size of the material, is the invention of the invention. ^ ^ ^ ^ ^ 彳 77 Those who have ordinary knowledge can easily become 7L, and should be included in the present invention as one of the forms. [Examples] Next, the present invention will be described in more detail by way of the following examples. [Example 1] [Production of the test material] In the present embodiment, three types of steel materials, SUS304 '316 and XM7 type, for the cold forging and roughing of the Worstian iron-based stainless steel, were selected as the material to be processed, and further The cold drawn wire is processed as a material with a wire diameter of 3 65 mm. Then, the solution is subjected to a solution heat treatment at a temperature of 1000 to 1 μm (rc is subjected to heat treatment cracking in a strand type, and is coated with the following lubricant composition to obtain a coated stainless steel wire. In this processing step, The above-mentioned heat treatment apparatus is a coating apparatus which is connected to the structure shown in Fig. 3 on the outlet side thereof, and constitutes a series of production line apparatuses in such a manner that the solution heat treatment and the coating treatment are simultaneously performed. The lubricant composition uses the following composition. Composition] (A) sodium sulphate 1 〇 wt% (B) sodium borate 2 wt% (C) boron nitride (average particle size 5 # m ) 10 wt% (D) acrylic resin 10 wt 〇 / 0 (Anionic alkyl acrylate copolymer / dielectric coefficient 3.8, with electricity 22 201213536 charge, polarity) 'ratio' (E) water (A): (B): (C): (D) = 5: 1: 5: 5 6 8 wt% solids weight solids? 32% by weight of the mixture The lubricant composition obtained by mixing the above (A) to (E) is introduced into a storage tank having a width of 200 χ depth of 600 χ and a height of 30 〇 mm, while using an external heater at a temperature of 80 to 951: The inner heating side was thoroughly stirred to prepare an aqueous dispersion. In this state, the inorganic salt and the water-soluble resin material are dissolved in water of a solvent, and boron nitride is uniformly dispersed in the aqueous solution. [Film formation and crystallization treatment] The film formation treatment is carried out in such a manner that the wire is processed (the stainless steel wire supply speed, based on the composition of the lubricant composition, the heating temperature, and the storage tank volume) In the present embodiment, II is obtained by setting the wire supply speed to 3 to 7 m/_, and the total adhesion amount is adjusted to be in the range of 6 to 12 g/m 2 . Automatic adjustment is performed. · The coating U of the smoothing agent is good, and the unevenness of the adhesion amount can be suppressed to a small amount. = The coated wire to be coated by the dipping is sent out from the liquid surface, and the coating is applied by the coating. a cylindrical hot air dryer with a liquid level of about 8 ΐΉ, so that the lubricant composition is completely dried in the crucible, and the lubricating film is fixed to the = liquid::r storage tank is heated to Observable knot: water is evaporated from the liquid surface to the hot air dryer to precipitate inorganic salts. 23 201213536 , * x The above-mentioned speed is processed by a series of metal wires, which are treated by 2 membranes 幵V, in each stainless steel wire. On the surface to attach i 6~i2g pure 曰4 skin The α-film is obtained, and a soft non-ferrous steel wire having a slippery film of the same shape as the short fiber of Fig. 2A is obtained by an image analysis apparatus using an X-ray diffraction device (manufactured by Horiba, Ltd.). The obtained crystal portion is a short fiber-like random distribution of 10 50 from m and an average aspect ratio of 2 to 丨 5, and the area ratio is 49.6 to 52.1% on average. Under the microscope observation, the protruding state of the convexity was confirmed, and the following measurement results of the surface roughness (Rz) obtained based on "the presence or absence of the lubricant at the specific position of the coated steel wire" were also confirmed. Surface roughness 9.6 to 10.4 " m. Surface roughness of the surface on which the lubricant is removed 7.6 # m [Comparative lubricant] As a comparative lubricant film (comparative example), the adhesion amount is respectively applied to the above three types of stainless steel wires. 6~12g/m2 forms an oxalate film and is used as a comparative wire. Moreover, the oxalate film is previously used for cold working of non-ferrous steel, and there is a hexavalent Cr or a thin substance containing harmful substances during the treatment. Mist, etc. contain harmful The problem of heavy metal sludge or waste acid has been decreasing in recent years. [Intermediate processing] For the coated soft stainless steel wire of the present embodiment, the quenching and tempering process is further performed at a processing rate of 4%, and Table 1 is obtained. The cold forging rough stainless steel wire described in the above is used in the auxiliary lubricant and used in the metal coupon 24 201213536, it can be confirmed that the auxiliary lubricant is held in the concave portion of the surface of the steel wire 25 201213536 [1< 】 Surface thick chain (Rz ; tzm) 〇rn » _< CN (Ν rn Crystal area ratio (%) 50.0 50.9 Crystal form powder + short fiber powder + short fiber powder + short fiber adhesion ( g/m2 ) 00 CN drawing rate (%) 〇〇〇〇培1" 〇〇CO CO m tensile strength (MPa) 〇〇VO KT) CO un 宕 wire diameter (mm) 3.04 | | 3.04 I | 3.04 Steel grade | SUS 304 I j SUS316 1 SUSXM7 Test material No 1 < A-3 201213536 [Lubricity test] Next, using the forging rough test two stainless steel wire of the above-mentioned example, the processing is performed for cross Forging of the head screw:: face: force, child The oil-face is made of a cold steel cross punch. (Shape, processing conditions using the tool rPUneh) is 15 per minute. The transfer speed of the total is 2,500, and the forgings are rough, and the number of tool faces and the occurrence of defects such as cracks are observed. The test results are good. The lubricating film of this example is obtained over the grass of the comparative example. The life of the acid film is 15_q. Forging roughing can be carried out without problems such as cracking or burning. The processing fraction was evaluated for the processing life of forging rough workability, and it was confirmed that the film of the present example had lubricity equal to or higher than that of the oxalate film as a comparative lubricant. One of the surface states of the obtained forged rough product (test #N〇 A-2) was not shown in Fig. 5, and no trace of burning was observed. [Example 2] The solid solution heat treatment material of the above-mentioned XM7 stainless steel wire (wire diameter: 3 65 mm) was changed to the level of "the above-mentioned constituent material (A) inorganic salt, (8) slip material, and (C) water-soluble resin. The following processability evaluation. The yoke was confirmed in the same manner as described above by the tool life caused by forging roughing, and the results are shown in Table 2. 27 201213536 Evaluation results comprehensive ◎ ◎ 〇 ◎ ◎ ◎ XX With or without burnt discs: Tool life 丨 (pieces) 13500 16300 1 1 12800 13200 15200 14800 7000 8100 (C) Water-soluble resin concentration (%) CN 〇〇»- Η <N cn 种类 Type B- tO ο 卜 1 &- (B) Slip material concentration (%) 〇〇〇CN cn CN (N type Λ Xi Λ X3 o 1 1 (A) Inorganic salt concentration (%) CN 〇〇CN cn 卜CN »—Η ON r—i Category 1:= :s • <-H ·— Film number composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Composition 6 Composition 7 Composition 8 冢 ί ίτΛί 鮏铋 · · 硪 硪 « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti (") sf ^ ss ^ 额颦魂(V) 201213536 It is confirmed by the specific application of shai: the lubricating film of the present invention can be used for the rough forging of stainless steel for the same purpose as the previous lubricant, especially [Strong Example 3] [Application Example of Titanium Alloy Sheet] A lubricant composition of the following composition was prepared. (A) Sodium (B) - vulcanization (average particle size 2 # m) (D) acrylic resin 1 〇 weight 0 / 〇 (anionic acrylate copolymer / dielectric coefficient 2 · 7, with charge, polarity) Solid component weight ratio (A): (B): (C) = 5: 4: 2 Solid content concentration 22% by weight It is known that Ni-Ti alloy is an intermetallic compound and is difficult to process, and is easily produced even in a wire. The wire is broken or broken by the wire drawing die. As a solution, for example, an oxide film is formed. However, although the oxide film is hard to be formed or broken, the final product has to be removed from the oxide film (descale). When acid is used, the surface properties are degraded, and there is a disadvantage of impairing the quality of the product. Therefore, in order to evaluate the suitability of the lubricating film to the Ni-Ti alloy wire, the alloy annealed material having a wire diameter of 1.8 mm is 1 〇〇kg to 2~ 6g/m2 is applied to the above lubricant composition, and the wire is drawn to a wire diameter of 16 mm. There is no plague or broken wire in the wire, and good addition is obtained. For the final product, only the metal of the upper layer is removed. Alkaline wash and heat required for soap 29 201213536 It is possible to omit pickling. In terms of quality, water cleaning can completely remove the lubricating film. By doing so, steps are taken to reduce the environmental burden and improve workability, and the range of wire diameter tolerances is successfully reduced. [Example 4] [Wire drawing of stainless steel wire for spring] A lubricant composition of the following composition was prepared. (A) Potassium sulphate (B) graphite (average particle diameter 3 m) (C) Carboxylate-based water-soluble resin (ammonium salt, charge, polar solid content weight ratio (A): (B): (C) = i : i 5 : 2 Solid content concentration 18% by weight SUSliMMi Dingxie a丄w〇4N1 stainless steel wire annealed material 200kg with a wire diameter of 1.5mm The above lubricant composition is applied at 〇3~2g/m2, And pull the wire to the wire diameter is 〇·?_. It is confirmed that the material after the wire is pulled without hemorrhoids, the surface condition is good, and no surface defects such as peeling or smashing are observed. Then, the winding property of the spring is confirmed. The winding processing of the crystal material is mainly for the gift of the priest or the + Λ Λ 镍 镍 镍 , , , , , , , , , , , 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀 镀The deviation of the free length is 3σ. The evaluation example is 〇25, and the comparative example is 0.24. The result is almost the same. If (4) (4), for example, in addition to the health effects of the so-called living allergy, it is also present when it is removed. The waste liquid treatment (4) the burden of the environment, or it is difficult to avoid the problem of the surface state after the removal, etc. Ming products can improve this problem. Spring size 30 201213536 Shrinking spring D / d = 20.0 Free length 15.5mm Free length tolerance gentry. 3mm Total volume 1 0 Speed 50 / min [industrial availability] As described above, the lubricating film of the present invention can be used for various applications requiring lubricity, and can be used, for example, as a forging material of a hard-to-machine metal material such as stainless steel or titanium or titanium alloy, nickel or alloy, niobium or tantalum alloy. Lubrication means such as processing or pressing, f-twisting, roll-forging and h-cylinder processing, etc., further providing a technology that is excellent in lubricity and eliminates environmental protection problems and can be produced in line. [Simplified illustration] Fig. 2A is an enlarged perspective view showing an example of a film metal material according to the present embodiment. Fig. 2A is a micrograph showing an enlarged outer surface of a lubricating film, and shows a crystal portion formed into a protruding portion in which a dot shape and a short fiber shape are mixed. The distribution state of the crystallized portion. The figure shows a distribution state in which the crystallizing portion on the outer surface of the lubricating film is formed into a leaf-like protruding portion. FIG. 3 illustrates the manufacture of the coated metal material. Fig. 4 is a diagram showing the relationship between the area ratio of 卩 表 mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmm Product 31 201213536 Magnified photo of surface condition [Description of main component symbols] 1 Covered metal material 2 Metal wire 3 Lubricating film 10 Bearing shaft 11 Metal wire 12 Lubricant composition 13 Storage tank 14 Reel 15 Winder R1 Guide roller R2 guide roller R3 guide roller K crystal portion 32