TWI628314B - Mold, forming roll and peeled electroformed product - Google Patents
Mold, forming roll and peeled electroformed product Download PDFInfo
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Abstract
本發明提供一種對樹脂或薄膜之轉印性高、以及該樹脂或薄膜之離型性高的模具、成形輥及剝離電鑄品。 The present invention provides a mold, a forming roll, and a peel-off electroforming product which have high transferability to a resin or a film and high release property of the resin or film.
本發明係形成以鎳為主成分、含有10至20重量%之磷、且含有0.3至3.0原子%之氫、並且包含不可避免之雜質的非晶質之20μm至10mm厚度的電性鎳-磷合金鍍覆被膜，對該被膜表面施行高精密彫刻加工後，復在其表面被覆10μm以下厚度之Cr、DLC或TiN而成者。 The present invention forms an amorphous nickel-phosphorus having a thickness of 20 μm to 10 mm which contains nickel as a main component, contains 10 to 20% by weight of phosphorus, and contains 0.3 to 3.0 atomic % of hydrogen, and contains unavoidable impurities. The alloy is coated with a film, and the surface of the film is subjected to high-precision engraving, and then the surface is covered with Cr, DLC or TiN having a thickness of 10 μm or less.
Description
本發明係關於一種模具、成形輥、及僅由鍍覆被膜與其表面之被覆層所構成的剝離電鑄品(以下，稱為剝離電鑄品)，係作為使用於聚光型太陽光發電之菲涅爾透鏡(Fresnel lens)用模具、光學用微透鏡用模具、液晶用偏光濾鏡加工用，於其表面具有形成高精密彫刻等高精密度超微細形狀之鍍覆被膜的模具或成形輥等中，為了達成提升轉印於設置在該表面之形成精密形狀之樹脂或薄膜的精密度、及所成形之樹脂或薄膜等從模具或成形輥的離型性之目的，藉由在鍍覆被膜表面積層化學性穩定之被覆層，結果可實現長壽命化。 The present invention relates to a mold, a forming roll, and a peeled electroformed product (hereinafter referred to as a peeled electroformed product) composed only of a plating film and a coating layer on the surface thereof, and is used for concentrating solar power generation. A mold for a Fresnel lens, a mold for optical microlenses, and a polarizing filter for liquid crystal, and a mold or a forming roll for forming a high-precision ultra-fine-shaped plating film such as high-precision engraving on the surface thereof. In order to achieve the purpose of improving the precision of the resin or film formed on the surface and forming a precise shape, and the release property of the formed resin or film from the mold or the forming roll, by plating. The coating layer which is chemically stabilized by the surface area of the film has a long life.
在前述光學透鏡用模具或偏光濾鏡加工用模具輥等需要超精密加工的構件中，必須進行寬度或切入量為10μm以下之溝加工等非常精密之彫刻切削加工。在該等超精密加工中，要求欲加工之金屬素材之結晶粒徑以下之嚴格加工精密度。並且，在加工時，由於模材端部之缺口或在切削加工面產生之金屬毛邊最後會轉印在成形品 之表面，因此完全不被容許。再者，經超精密加工之由鍍覆被膜所構成之模具或成形輥本身，由於其加工費而難免成為高成本，因此亦要求形狀精密度之長壽命(耐久性)。亦即，由前述鍍覆被膜所構成之模具或成形輥必須具備超精密加工性、耐摩耗性及耐腐蝕性等特性。此外，具有前述鍍覆被膜之構件的超精密加工，一般係利用金鋼石之車削刀具(turning tool)。 In the member requiring ultra-precision machining such as the optical lens mold or the polarizing filter processing mold roll, it is necessary to perform a very precise engraving and cutting process such as groove processing having a width or a cutting amount of 10 μm or less. In such ultra-precision machining, strict processing precision below the crystal grain size of the metal material to be processed is required. Moreover, at the time of processing, the metal burrs generated at the ends of the molding material or the metal burrs generated on the machined surface are finally transferred to the molded article. The surface is therefore not allowed at all. Further, the mold or the forming roll itself, which is formed of a plated film by ultra-precision processing, is inevitably expensive because of its processing cost, and therefore long life (durability) of shape precision is required. In other words, the mold or the forming roll formed of the plating film must have characteristics such as ultra-precision workability, abrasion resistance, and corrosion resistance. Further, the ultra-precision machining of the member having the plating film described above is generally a turning tool using a diamond.
一般而言，用以進行超精密加工之模具或成形輥，以往係使用被覆有鈹銅或無電解鎳鍍覆被膜之不鏽鋼或碳鋼等。然而，鈹銅之硬度比較低，由切削毛邊之產生或其硬度來看，無法期待加工精密度及長壽命。而且，關於無電解鎳鍍覆被膜，就材料特性而言，會有在切削面產生毛邊之問題，無法充分滿足近年來要求越來越高之超精密加工性。另一方面，對應於無電解鎳鍍覆被膜之電性鎳鍍覆被膜，其硬度比無電解鎳被膜更低而容易塑性變形，不僅完全未具有超精密加工性，而且在昴貴之金鋼石車削刀具的壽命方面亦會產生問題。 In general, a mold or a forming roll for performing ultra-precision machining has conventionally used stainless steel or carbon steel coated with a beryllium copper or an electroless nickel plating film. However, the hardness of beryllium copper is relatively low, and processing precision and long life cannot be expected from the viewpoint of the occurrence of cutting burrs or its hardness. Further, regarding the electroless nickel plating film, there is a problem that the material characteristics are burrs on the cutting surface, and the ultra-precision workability which is required to be higher in recent years cannot be sufficiently satisfied. On the other hand, the electro-nickel plating film corresponding to the electroless nickel plating film is lower in hardness than the electroless nickel film and is easily plastically deformed, and not only has no ultra-precision workability, but also has a diamond in the precious steel. There is also a problem with the life of the turning tool.
在非專利文獻1中，關於電性鎳鍍覆膜中之氫的舉動，有以下之記載：使用金屬鹽濃度及pH不同之3種類的瓦特浴(Watts bath，NiSO4：NiCL2=4：1)定量評估電性鎳鍍覆析出時之物質收支。根據該評估結果，記載有「共存於由瓦特浴進行電氣鍍覆之鎳被膜中的氫之量並非取決於電流效率，大部分之氫係成為氣泡而被排出大氣中。然而，存在(吸藏)於鎳鍍覆被膜中之氫的含量為原子 比H/Ni=10-3以下，看起來像是微量，但係為鎳金屬之室溫下之氫的固溶度(H/Ni=3×10-5)的10倍以上」。然而，有關氫之含量對於切削加工性的影響，則完全未見任何記載。 Non-Patent Document 1 relates to the behavior of hydrogen in an electroless nickel plating film, which is described in three types of Watts bath (NiSO 4 : NiCL 2 = 4: metal salt concentration and pH difference). 1) Quantitatively evaluate the material balance during the deposition of electrical nickel plating. According to the evaluation results, it is described that "the amount of hydrogen coexisting in the nickel coating electrically plated by the Watt bath does not depend on the current efficiency, and most of the hydrogen is bubbled out and is discharged into the atmosphere. However, there is (absorption) The content of hydrogen in the nickel-plated coating film is an atomic ratio of H/Ni = 10 -3 or less, which appears to be a trace amount, but is a solid solubility of hydrogen at room temperature of nickel metal (H/Ni = 3) 10 times or more of ×10 -5 ). However, there is no description at all about the effect of the hydrogen content on the machinability.
此外，在非專利文獻2中，係針對電性鎳-磷合金鍍覆被膜之結晶化過程加以說明，有以下等記載：若在被膜中含有約8重量%以上之磷，則成為非晶質，具有良好之耐蝕性或光澤性，若再加熱非晶質物使之結晶化，則具有達到Hv1100之高硬度。然而，在非專利文獻2中，雖記載有於電鎳-磷合金中若含有約8重量%以上之磷則成為非晶質等，但有關其切削加工性，則完全未記載。 Further, Non-Patent Document 2 describes a crystallization process of an electroplated nickel-phosphorus alloy plating film, and it is described that when the film contains about 8 wt% or more of phosphorus, it becomes amorphous. It has good corrosion resistance or luster. If the amorphous material is heated and crystallized, it has a high hardness of Hv1100. However, in the case of the electro-nickel-phosphorus alloy, it is described that it is amorphous or the like when it contains about 8 wt% or more of phosphorus, but the machinability is not described at all.
再者，在專利文獻1中記載有：為了在成形輥表面形成無微裂痕之硬質鉻層，在輥表面施以作為底層之電鎳-磷非晶質合金鍍覆被膜，並將其表面鏡面加工成0.1μmRy以下之表面粗糙度後，在該電鎳-磷非晶質合金鍍覆被膜上形成電鉻鍍覆被膜。然而，有關電鎳-磷非晶質合金鍍覆被膜中之氫含量並未記載，亦未記載對其表面施行高精密彫刻加工。 Further, Patent Document 1 discloses that a hard chromium layer having no microcracks is formed on the surface of a forming roll, and an electro-nickel-phosphorus amorphous alloy plating film as a bottom layer is applied to the surface of the roll, and the surface thereof is mirror-finished. After processing to a surface roughness of 0.1 μm or less, an electrochromic plating film is formed on the electro-nickel-phosphorus amorphous alloy plating film. However, the hydrogen content in the electroless nickel-phosphorus amorphous alloy plating film is not described, and the surface is not subjected to high-precision engraving.
非專利文獻1：技術雜誌「表面技術」Vol.63, No.4, 2012、222-226頁、鍍覆膜中之氫舉動 Non-Patent Document 1: Technical Journal "Surface Technology" Vol. 63, No. 4, 2012, pp. 222-226, Hydrogen Behavior in a Plated Film
非專利文獻2：技術雜誌「金屬表面技術」Vol.31, No.12, 1980、667-672頁、電析Ni-P非晶質合金之結晶化過程(專利文獻) Non-Patent Document 2: Technical Journal "Metal Surface Technology" Vol.31, No. 12, 1980, 667-672, electrocrystallization of crystallization process of Ni-P amorphous alloy (patent literature)
專利文獻1：日本特開2012-21174號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-21174
本發明係有鑑於習知技術具有之問題點而研創者，其目的係在於，為了提升在其表面具有施行高精密彫刻加工等超微細之切削加工之鎳-磷合金鍍覆被膜的樹脂成形用模具或薄膜成形用成形輥對樹脂或薄膜之轉印性、及該樹脂或薄膜之離型性，提供一種在鎳-磷合金鍍覆被膜上設置由化學性穩定之材料所構成之被覆層的模具及成形輥、以及在鎳-磷合金鍍覆被膜上設置化學性穩定之材料之被覆層的模具、成形輥及剝離電鑄品。 The present invention has been made in view of the problems of the prior art, and is intended to improve the resin molding of a nickel-phosphorus alloy plating film having an ultrafine cutting process such as high-precision engraving on the surface thereof. The transfer property of a mold or a film forming forming roll to a resin or a film, and the release property of the resin or film, providing a coating layer made of a chemically stable material on a nickel-phosphorus alloy plating film. A mold, a forming roll, and a mold, a forming roll, and a peeling electroformed product in which a coating layer of a chemically stable material is provided on a nickel-phosphorus alloy plating film.
為了達成前述目的，本發明之模具、成形輥及剝離電鑄品係以鎳為主成分，含有10至20重量%之磷，且含有0.3至3.0原子%之氫，以在對包含不可避免之雜質的非晶質之電析鍍覆被膜的表面施行高精密彫刻加工後，設置由化學性穩定之材料所構成的被覆層為特徵。本發明係藉由設置在非晶質之電析鍍覆被膜的表面之由化學性穩定之材料所構成的被覆層，而可長期間保持對於樹脂或薄膜之高精密彫刻形狀的轉印性、及樹脂或薄膜之離型性。為了具備該高精密彫刻加工性，非晶質之電析鍍覆被 膜係以鎳為主成分，含有10至20重量%之磷，且必須含有0.3至3.0原子%之氫。 In order to achieve the above object, the mold, the forming roll and the strip electroformed product of the present invention contain nickel as a main component, contain 10 to 20% by weight of phosphorus, and contain 0.3 to 3.0 atomic % of hydrogen, so that the inclusion is unavoidable. After the surface of the amorphous electrodeposited coating film of the impurity is subjected to high-precision engraving, a coating layer composed of a chemically stable material is provided. The present invention is capable of maintaining transferability to a highly precise engraved shape of a resin or a film over a long period of time by providing a coating layer made of a chemically stable material on the surface of an amorphous electrodeposited coating film. And the release property of the resin or film. In order to have this high-precision engraving processability, amorphous electroplating is coated The film is mainly composed of nickel, contains 10 to 20% by weight of phosphorus, and must contain 0.3 to 3.0 atom% of hydrogen.
此外，本發明係在具有前述特徵之電析鍍覆被膜中，由X線繞射所產生之鎳的最大峰值強度較佳為背景強度的2倍以下，鎳之最大峰值強度更佳為無法與背景強度區別之程度。此外，在具有前述特徵之電析鍍覆被膜中，較佳為X線繞射之鎳的最大峰值強度之半值寬度為3°以上之非晶質材料。 Further, in the present invention, in the electrodeposited plating film having the above characteristics, the maximum peak intensity of nickel generated by X-ray diffraction is preferably twice or less the background intensity, and the maximum peak intensity of nickel is more excellent. The degree of difference in background intensity. Further, in the electrodeposited plating film having the above-described characteristics, an amorphous material having a half-value width of the maximum peak intensity of the X-ray diffraction nickel of 3 or more is preferable.
由化學性穩定之材料所構成的被覆層，較佳為具備高精密彫刻形狀之轉印性及離型性佳的特性者，可列舉例如Cr或DLC(類鑽碳，Diamond Like Carbon)或TiN。該被覆層之厚度雖必須為0.01μm以上，但若可確保前述轉印性與離型性，則以較薄者為佳，較佳為1μm以下。另一方面，從耐摩耗性之觀點來看，被覆層之厚度係以較厚者為佳，但若過厚則形狀精密度會降低，因此以10μm以下為佳。 The coating layer made of a chemically stable material preferably has a high-precision engraving shape and has excellent transfer property and release property, and examples thereof include Cr or DLC (Diamond Like Carbon) or TiN. . The thickness of the coating layer must be 0.01 μm or more. However, if the transfer property and the release property are ensured, it is preferably thinner, preferably 1 μm or less. On the other hand, from the viewpoint of abrasion resistance, the thickness of the coating layer is preferably thicker, but if it is too thick, the shape precision is lowered, so that it is preferably 10 μm or less.
被覆層較佳為離型性或轉印性優異，化學性比Ni鍍覆被膜穩定，且為高硬度、耐摩耗性優異者。例如，就被覆層而言，可列舉Cr之鍍覆被膜。並且，亦可使用藉由利用離子鍍覆(Ion Plating)法或電漿法之化學蒸鍍所製作之DLC或TiN的薄膜作為被覆層。就被覆層而言，並非限定於Cr、DLC或TiN之薄膜，只要具備與該等膜同等之化學性及機械性特性者即可，例如亦可使用由物理蒸鍍法所製作之TiA1N或CrAlN之單層膜或多層膜作為被覆 層。再者，亦可使用AL2O3等氧化膜作為被覆層。 The coating layer is preferably excellent in release property or transfer property, chemically stable than the Ni plating film, and excellent in hardness and abrasion resistance. For example, as the coating layer, a plating film of Cr can be cited. Further, as the coating layer, a film of DLC or TiN produced by chemical vapor deposition using an ion plating (Ion Plating) method or a plasma method may be used. The coating layer is not limited to a film of Cr, DLC or TiN, and may have chemical and mechanical properties equivalent to those of the film. For example, TiA1N or CrAlN produced by physical vapor deposition may be used. A single layer film or a multilayer film is used as the coating layer. Further, an oxide film such as AL 2 O 3 may be used as the coating layer.
除了在必須進行高精密彫刻加工等超精密微細加工之模具或成形輥表面被覆本發明之電析鍍覆被膜以外，提供由本發明之電析鍍覆被膜與由化學性穩定之材料形成之被覆層的積層體所構成的剝離電鑄品亦佳。 In addition to coating the surface of the mold or the forming roll of the ultra-precision micro-machining, such as high-precision engraving, with the electrodeposited coating film of the present invention, the coating layer formed of the electrodeposited coating film of the present invention and the chemically stable material is provided. The peeled electroformed product composed of the laminated body is also excellent.
在本發明之電析鍍覆被膜中，由發明者等調査之結果，在磷含量未達10重量%之情形下，鎳之結晶會析出，藉由X線繞射可明確觀察到Ni3P之波峰。該金屬組織之結晶粒界容易因超精密彫刻加工之加工應力而破壞，阻礙經破壞之結晶粒大小達到目的之微細加工粗糙度的同時，會成為切削毛邊，無法進行高精密度之加工。另一方面，亦難以製造磷含量超過20重量%之電析鍍覆被膜。此外，氫含量未達0.3原子%之電析鍍覆被膜作為被膜或材料的強度低，同樣在切削時易產生毛邊或缺口，超精密彫刻加工性差。此外，即使藉由電氣鍍覆法亦無法得到氫含量超過3.0原子%之電析鍍覆被膜。 In the electrodeposited coating film of the present invention, as a result of investigation by the inventors, etc., in the case where the phosphorus content is less than 10% by weight, crystals of nickel are precipitated, and Ni 3 P can be clearly observed by X-ray diffraction. The peak. The crystal grain boundary of the metal structure is easily broken by the processing stress of the ultra-precision engraving process, and the size of the damaged crystal grain is prevented from reaching the intended fine processing roughness, and the cutting edge is formed, and high-precision processing cannot be performed. On the other hand, it is also difficult to produce an electrodeposited plating film having a phosphorus content of more than 20% by weight. Further, the electrodeposited coating film having a hydrogen content of less than 0.3 atom% has low strength as a film or a material, and similarly, burrs or notches are easily generated during cutting, and ultra-precision engraving workability is poor. Further, even in the electroplating method, an electrodeposited plating film having a hydrogen content of more than 3.0 at% cannot be obtained.
本發明之電析鍍覆被膜係以鎳為主成分，含有10至20重量%之磷，且含有0.3至3.0原子%之氫，因此具有非晶質之特性及具高硬度，亦具備強靭且高度之精密彫刻加工性。 The electrodeposition plating film of the present invention contains nickel as a main component, contains 10 to 20% by weight of phosphorus, and contains 0.3 to 3.0 atomic % of hydrogen, and thus has an amorphous property and a high hardness, and is also strong and High precision engraving and processing.
以鎳為主成分，含有10至20重量%之磷，且含有0.3至3.0原子%之氫的電析鍍覆被膜，雖如上所述為非晶質但為高硬度且具備延展性，然而因活性略高，因 此在使用作為樹脂成形用模具或薄膜成形用成形輥等時，在其成形壓力或成形溫度較高之情形下，有樹脂或薄膜之轉印性或離型性產生缺失之情形。因此，對以鎳為主成分，含有10至20重量%之磷，且含有0.3至3.0原子%之氫，並且包含不可避免之雜質的非晶質之電析鍍覆被膜的表面施行高精密彫刻加工後，藉由設置由化學性穩定之材料所構成的被覆層，即可大幅改善轉印性或離型性、耐久性。 An electrodeposited coating film containing nickel as a main component and containing 10 to 20% by weight of phosphorus and containing 0.3 to 3.0 atomic % of hydrogen is amorphous as described above, but has high hardness and ductility. The activity is slightly higher, because When a molding roll or a film forming forming roll or the like is used, when the molding pressure or the molding temperature is high, the transfer property or the release property of the resin or the film may be lost. Therefore, high-precision engraving is performed on the surface of an amorphous electrodeposited coating film containing nickel as a main component, containing 10 to 20% by weight of phosphorus, and containing 0.3 to 3.0 atomic % of hydrogen, and containing unavoidable impurities. After the processing, by providing a coating layer composed of a chemically stable material, transferability, release property, and durability can be greatly improved.
第1圖係對已施加本發明之電析鍍覆被膜之物品進行切削加工時產生之切削屑的掃描電子顯微鏡照片(300倍)。 Fig. 1 is a scanning electron micrograph (300 magnifications) of the chips generated when the article of the electrodeposited coating film of the present invention was subjected to cutting.
(1)電析鍍覆被膜之製造方法 (1) Method of Producing Electrodeposition Coating Film
本發明之鎳-磷合金鍍覆被膜，當鍍覆被膜中之磷含量超過約8重量%(約15原子%)時，會成為非晶質構造。非晶質構造之合金係在耐蝕性、耐氧化性或耐變色性等方面優異，作為對耐蝕性差之鋼鐵材料表面賦予該等性質的表面處理法之一，一般而言係廣泛利用鎳-磷合金鍍覆法。就鎳-磷合金鍍覆液而言，添加作為鎳供給源之鎳鹽及作為還原劑之次亜磷酸鹽之無電解鎳-磷合金浴被實用化。然而，在無電解鎳-磷合金鍍覆被膜中，具有以下諸多問題：「(1)在合金鍍覆被膜內部存在多數凹陷(缺陷部)；(2)在超過0.1mm厚度的鍍覆被膜之情形，外觀有問題；(3)由於次亜磷酸離子及鎳離子之浴中濃度隨著合金鍍覆被膜 之成長而隨時變化，因此難以進行還原速度之控制；(4)隨著液體之老化而難以獲得磷之含量為一定之鍍覆被膜」。 The nickel-phosphorus alloy plating film of the present invention has an amorphous structure when the phosphorus content in the plating film exceeds about 8% by weight (about 15 atom%). An alloy having an amorphous structure is excellent in corrosion resistance, oxidation resistance, and discoloration resistance, and is one of surface treatment methods that imparts such properties to the surface of a steel material having poor corrosion resistance. Generally, nickel-phosphorus is widely used. Alloy plating method. In the nickel-phosphorus alloy plating solution, an electroless nickel-phosphorus alloy bath in which a nickel salt as a nickel supply source and a hypophosphorus phosphate as a reducing agent are added is put into practical use. However, in the electroless nickel-phosphorus alloy plating film, there are many problems as follows: "(1) There are many depressions (defect portions) inside the alloy plating film; (2) plating film having a thickness exceeding 0.1 mm In case of appearance, there is a problem; (3) due to the concentration of phosphoric acid ions and nickel ions in the bath, the alloy is coated with the film. Since it grows and changes at any time, it is difficult to control the reduction rate; (4) It is difficult to obtain a plated film having a constant phosphorus content as the liquid ages.
(2)用以獲得本發明之電析鍍覆被膜的鍍覆浴 (2) A plating bath for obtaining the electrodeposition plating film of the present invention
作為獲得本發明之電析鍍覆被膜的鍍覆浴之一例，係將鎳鹽、亜磷酸及/或亜磷酸鹽、羧酸及/或硼酸等調配所需量而成為電鍍覆浴。在此，就羧酸而言，可使用檸檬酸、丙二酸、草酸、醋酸、乳酸、羥基丁二酸、酪酸、酒石酸、蟻酸、丙酸、戊酸、琥珀酸、馬來酸之任一種/或將該等予以混合者。鍍覆浴之pH係以設在1.6至3.5之範圍為佳。在pH未達1.6時，電流效率會因氫之產生而降低，電析速度變慢，欠缺實用性。另一方面，當pH超過3.5時，因為在陽極被氧化之磷酸離子及鎳離子產生沈殿，因此難以在長時間之電解作業中獲得光澤鍍覆。此外，可依據構成浴之成分的量，藉由氫氧化鈉、氫氧化鉀、氫氧化胺等鹼性成分或硫酸、鹽酸等礦酸而適當調整。 As an example of the plating bath for obtaining the electrodeposited coating film of the present invention, a nickel salt, a bismuth phosphoric acid and/or a phosphonium phosphate, a carboxylic acid, and/or a boric acid are blended in a desired amount to form a plating bath. Here, as the carboxylic acid, any of citric acid, malonic acid, oxalic acid, acetic acid, lactic acid, hydroxysuccinic acid, butyric acid, tartaric acid, formic acid, propionic acid, valeric acid, succinic acid, and maleic acid can be used. / or mix them. The pH of the plating bath is preferably in the range of 1.6 to 3.5. When the pH is less than 1.6, the current efficiency is lowered by the generation of hydrogen, and the electrolysis rate is slow, which is not practical. On the other hand, when the pH exceeds 3.5, since the phosphate ions and nickel ions which are oxidized at the anode are used, it is difficult to obtain gloss plating in a long-time electrolysis operation. Further, it may be appropriately adjusted by an alkaline component such as sodium hydroxide, potassium hydroxide or ammonium hydroxide or a mineral acid such as sulfuric acid or hydrochloric acid depending on the amount of the components constituting the bath.
〔本發明之重要特徵(非晶質、包含適量之氫、離型性佳)〕 [Important features of the invention (amorphous, containing an appropriate amount of hydrogen, good release properties)]
《非晶質》 Amorphous
本發明之電析鍍覆被膜係非晶質合金，其重要特徵之一係以鎳為主成分且含有10至20重量%之磷而成為非晶質。該非晶質合金之其他特徵為：由其特有之原子構造所帶來在電氣性質、磁氣性質、化學性質、機械性質廣泛顯現之特性，關於化學性質，具備優異之耐蝕性。此外，關 於機械性質，為高硬度、高強度，但亦具有靭性。 In the electrodeposition plating film-based amorphous alloy of the present invention, one of the important features is that nickel is contained as a main component and contains 10 to 20% by weight of phosphorus to be amorphous. The amorphous alloy has other characteristics such that it is widely exhibited in electrical properties, magnetic properties, chemical properties, and mechanical properties due to its unique atomic structure, and has excellent corrosion resistance with respect to chemical properties. In addition, off Due to mechanical properties, it is high hardness and high strength, but it also has toughness.
《包含適量之氫》 "Contains the right amount of hydrogen"
由於本發明之電析鍍覆被膜為非晶質合金，因此雖具備前述之各種特性，但僅為非晶質並無法具備不會產生金屬毛邊之良好的切削加工性。因此，本發明之電析鍍覆被膜包含適量之氫(0.3至3.0原子%)亦為其特徵。 Since the electrodeposited coating film of the present invention is an amorphous alloy, it has various characteristics as described above, but is amorphous only and does not have good machinability without causing metal burrs. Therefore, the electroplating coating film of the present invention is also characterized by containing an appropriate amount of hydrogen (0.3 to 3.0 atom%).
一般而言，當金屬材料含有(吸藏)氫時，依金屬材料種類，有因吸藏氫之影響而脆化之現象、即所謂之氫脆性，部分之不鏽鋼或高碳鋼等有氫脆性破壞之問題亦為一般所知者。因氫所致之脆性破壞的形態，係在使用中之構造體引起突然破壞，亦稱為延遅破壞。金屬材料脆化之機制已提出各種說法，其原因可列舉例如結合力或表面能量之降低、氣泡內氣壓、氫化物形成等。然而，關於氫脆性破壞，至今依然沒有統一之機制闡明。就其原因而言，可列舉由於氫之原子序最小，容易侵入金屬中，非常快速地擴散且在破壞後立刻從材料放出，因此難以進行實證。除了已知氫侵入金屬材料中使金屬材料之強度明顯變弱以外，為了防止氫脆性破壞，使氫不侵入金屬材料中、或開發即使氫侵入所造成之影響亦少之金屬材料，可謂一般之技術常識。 In general, when a metal material contains (storing) hydrogen, depending on the type of metal material, there is a phenomenon of embrittlement due to the influence of hydrogen absorption, so-called hydrogen embrittlement, and some of the stainless steel or high carbon steel has hydrogen embrittlement. The problem of destruction is also known to the general public. The form of brittle failure due to hydrogen causes sudden damage caused by the structure in use, also known as delayed failure. Various mechanisms have been proposed for the mechanism of embrittlement of metal materials, and the reasons thereof include, for example, reduction in bonding force or surface energy, gas pressure in bubbles, formation of hydride, and the like. However, there is still no unified mechanism for clarifying the destruction of hydrogen brittleness. The reason for this is that since hydrogen has the smallest atomic order and easily intrudes into the metal, it diffuses very rapidly and is released from the material immediately after the destruction, so that it is difficult to carry out the demonstration. In addition to the fact that hydrogen is intruded into the metal material to significantly weaken the strength of the metal material, in order to prevent hydrogen brittle fracture, hydrogen is not intruded into the metal material, or a metal material which has little influence even if hydrogen intrusion is developed is generally described. Technical common sense.
然而，本案發明者係獲致推翻該技術常識之驚人發現者。亦即，與在金屬材料中含有多量氫時材料強度顯著降低而容易破壞之一般常識相反，而得知能在保持靭性之狀態下顯現優異之切削加工特性。亦即，本發明 之電析鍍覆被膜為非晶質且高硬度，雖然具有含有比一般預測更多之異常多量的氫之事實，但係為在切削試驗中切削加工性極佳之材料，且具備高強度並顯現可撓性之特性。這是顯示本發明之電析鍍覆被膜因包含0.3至3.0原子%之氫而具備適當之材料強度與切削加工性。第1圖係以掃描電子顯微鏡照片(300倍)觀察藉由金鋼石車削刀具對本發明之電析鍍覆被膜進行切削加工時產生之切削片者。第1圖所示之切削片雖為極薄之切削屑，但在切削途中不破碎而連續，顯示為柔軟且延展性大、具可撓性之材料。 However, the inventor of the case was the amazing discoverer who overturned the common sense of the technology. In other words, contrary to the general knowledge that the strength of the material is remarkably lowered when the metal material contains a large amount of hydrogen, it is known that the excellent machinability can be exhibited while maintaining the toughness. That is, the present invention The electroplating coating film is amorphous and has high hardness. Although it has a large amount of hydrogen which is more abnormal than the general prediction, it is a material excellent in machinability in a cutting test and has high strength. The characteristics of flexibility are revealed. This indicates that the electrodeposited plating film of the present invention has appropriate material strength and machinability because it contains 0.3 to 3.0 atomic % of hydrogen. Fig. 1 is a view showing a cutting piece produced when a plating film of the present invention is cut by a diamond turning tool by a scanning electron microscope photograph (300 times). Although the cutting piece shown in Fig. 1 is extremely thin chips, it is continuous without being broken during cutting, and is a material that is soft and has high ductility and flexibility.
《離型性優異》 "Excellent release"
以鎳為主成分、含有10至20重量%之磷、且含有0.3至3.0原子%之氫的電析鍍覆被膜，其切削加工性優異，對其表面施行高精密度彫刻加工，且使用作為光學用途之樹脂製品、薄膜製品之成形用模具或成形用成形輥材料。光學用途之樹脂製品或薄膜製品的高精密度彫刻係為10nm至100μm之凹凸形狀，且要求極高之尺寸精密度及形狀精密度。以鎳為主成分、含有10至20重量%之磷、且含有0.3至3.0原子%之氫的電析鍍覆被膜雖為非晶質，但為高硬度且具備延展性，然而因活性略高，因此在使用作為樹脂成形用模具或薄膜成形用成形輥等時，不論要成形之樹脂種類或其成形壓力或成形溫度等為何，皆有所成形之樹脂或薄膜之轉印性及離型性產生缺失之情形。因此，對以鎳為主成分，含有10至20重量%之磷，且含有0.3至3.0原子%之氫，並且包含不可避免之雜質的非晶質 之電析鍍覆被膜的表面施行高精密彫刻加工後，藉由設置由化學性穩定之材料所構成的被覆層，即可改善轉印性及離型性。就該被覆層而言，可使用Cr、DLC、TiN等薄膜。並且，若能滿足高精密度彫刻加工、尺寸精密度、或形狀精密度等，則亦可使用奈米金鋼石被覆層。再者，碳化物、氮化物、氧化物及其化合物所構成的陶瓷，比鎳鍍覆被膜更加化學性穩定，且該等物質之薄膜形成法亦廣為人知，因此可使用作為被覆層。 An electrodeposited coating film containing nickel as a main component and containing 10 to 20% by weight of phosphorus and containing 0.3 to 3.0 atomic % of hydrogen is excellent in machinability, and is subjected to high-precision engraving on the surface thereof, and is used as A resin product for optical use, a molding die for a film product, or a forming roll material for molding. High-precision engraving of resin products or film products for optical use is a concave-convex shape of 10 nm to 100 μm, and requires extremely high dimensional precision and shape precision. An electrodeposited coating film containing nickel as a main component, containing 10 to 20% by weight of phosphorus, and containing 0.3 to 3.0 atomic % of hydrogen is amorphous, but has high hardness and ductility, but has a slightly higher activity. Therefore, when a mold for molding a resin or a forming roll for forming a film is used, the transfer property and the release property of the molded resin or film are different regardless of the type of the resin to be molded, the molding pressure, the molding temperature, and the like. Produce a missing situation. Therefore, an amorphous material containing nickel as a main component, containing 10 to 20% by weight of phosphorus, and containing 0.3 to 3.0 atomic % of hydrogen, and containing unavoidable impurities After the surface of the electrodeposited plating film is subjected to high-precision engraving, the transfer layer and the release property can be improved by providing a coating layer made of a chemically stable material. As the coating layer, a film such as Cr, DLC or TiN can be used. Further, if high-precision engraving processing, dimensional precision, or shape precision can be satisfied, a nano-diamond coating layer can also be used. Further, ceramics composed of carbides, nitrides, oxides, and compounds thereof are more chemically stable than nickel-plated coatings, and a film forming method of these materials is also widely known, and thus can be used as a coating layer.
以下，雖說明本發明之實施例，但本發明並非限定於前述實施例，在不脫離本發明之技術範圍內，當然可適當地進行各種變更或修正。 The embodiments of the present invention are described below, but the present invention is not limited to the embodiments described above, and various changes and modifications may be appropriately made without departing from the scope of the invention.
(1)實施例 (1) Example
調製硫酸鎳190g/公升、亜磷酸50g/公升、硼酸35g/公升、檸檬酸15g/公升、氯化鈉1g/公升之組成的鎳-磷合金鍍覆浴，將白金被覆鈦材作為陽極，將浴溫度50℃、電流密度2.5A/m2設為固定之條件，在由作為模具用材料之使用例多之STAVAX鋼(鉻合金不鏽鋼工具鋼、C：Si：Mn：Cr=0.38：0.8：0.5：13.6)所構成的基材表面、形成200μm厚度的電性鎳-磷合金鍍覆被膜。該被膜之氫含量為0.7原子%、磷含量為13重量%(其餘部分為鎳)。再者，為了對該電性鎳-磷合金鍍覆被膜表面施行高精密度彫刻加工，使用4軸控制超精密加工機(日本東芝公司製，商品名ULG-100D(SH3))，利用單結晶金鋼石工具，在 電性鎳-磷合金鍍覆被膜表面之縱方向為100mm、橫方向為100mm的範圍內，施行複數次深度為20μm、寬度為20μm之斷面呈V槽的切削加工。 A nickel-phosphorus alloy plating bath composed of 190 g/liter of nickel sulfate, 50 g/liter of bismuth phosphate, 35 g/liter of boric acid, 15 g/liter of citric acid, and 1 g/liter of sodium chloride is used, and the titanium-coated titanium material is used as an anode. Bath temperature: 50 ° C, current density of 2.5 A / m 2 was set as a fixed condition, and STAVAX steel (chromium alloy stainless steel tool steel, C:Si:Mn:Cr=0.38:0.8: used as a material for the mold) 0.5:13.6) The surface of the substrate to be formed, and an electric nickel-phosphorus alloy plating film having a thickness of 200 μm was formed. The film had a hydrogen content of 0.7 at% and a phosphorus content of 13 wt% (the balance being nickel). In order to perform high-precision engraving on the surface of the electroless nickel-phosphorus alloy plating film, a 4-axis controlled ultra-precision processing machine (manufactured by Toshiba Corporation, trade name ULG-100D (SH3)) is used, and single crystal is used. The diamond tool is subjected to a cutting process in which a plurality of depths of 20 μm and a width of 20 μm are V-grooves in a range of 100 mm in the longitudinal direction and 100 mm in the lateral direction of the surface of the electroplated nickel-phosphorus alloy plating film.
此外，雖未被限定，但電性鎳-磷合金鍍覆被膜之厚度可設為20μm至10mm。 Further, although not limited, the thickness of the electroplated nickel-phosphorus alloy plating film may be set to 20 μm to 10 mm.
在此，被膜中之磷含量係藉由能量分散型X線分光法進行定量分析。此外，氫含量係以惰性氣體中之石墨坩堝對被膜之-部分進行通電熔融，從所產生之氣體抽出氫，且以熱傳導測定式氣相層析儀(gas chromatograph)進行定量分析。 Here, the phosphorus content in the film was quantitatively analyzed by energy dispersive X-ray spectroscopy. Further, the hydrogen content is obtained by electrically melting a portion of the film by graphite crucible in an inert gas, extracting hydrogen from the generated gas, and performing quantitative analysis by a gas chromatograph.
如前所述，在施行高精密度彫刻加工之電性鎳-磷合金鍍覆被膜表面，使用標準之沙井特(Sargent)浴(鉻酸250g/公升、硫酸2.5g/公升)，在溫度50℃、電流密度40A/dm2之條件下，獲得將膜厚1.0μm之Cr鍍覆被膜予以被覆而成之本發明之試驗片1的射出成型用模具。再者，在氫93mol%、甲烷7mol%之電漿環境下，獲得在已施行高精密度彫刻加工之電性鎳-磷合金鍍覆被膜表面被覆膜厚0.5μm之DLC而成之本發明之試驗片2的射出成型用模具。再者，藉由電弧離子鍍覆法，在偏壓50V之條件下，獲得在已施行高精密度彫刻加工之電性鎳-磷合金鍍覆被膜表面被覆膜厚1.2μm之TiN而成之本發明之試驗片3的射出成型用模具。再者，將在已施行高精密度彫刻加工之電性鎳-磷合金鍍覆被膜表面未施加被覆層之射出成型用模具作為比較例。 As mentioned above, the standard Sargent bath (chromic acid 250g/liter, sulfuric acid 2.5g/liter) is used at a temperature of 50 on the surface of an electro-nickel-phosphorus alloy coated film that is subjected to high-precision engraving. Under the conditions of a current density of 40 A/dm 2 , a mold for injection molding of the test piece 1 of the present invention obtained by coating a Cr plating film having a film thickness of 1.0 μm was obtained. Further, in the plasma environment of 93 mol% of hydrogen and 7 mol% of methane, the present invention is obtained by coating DLC having a thickness of 0.5 μm on the surface of an electro-nickel-phosphorus alloy plating film which has been subjected to high-precision engraving processing. The injection molding die of the test piece 2. Further, by the arc ion plating method, under the condition of a bias voltage of 50 V, TiN having a thickness of 1.2 μm coated on the surface of the electroless nickel-phosphorus alloy plating film which has been subjected to high-precision engraving processing is obtained. The mold for injection molding of the test piece 3 of the present invention. In addition, a mold for injection molding in which a coating layer is not applied to the surface of the electroplated nickel-phosphorus alloy plating film which has been subjected to high-precision engraving is used as a comparative example.
使用具有被覆層之本發明之試驗片1至3的射出成型用模具、及未具有被覆層之比較例的射出成型用模具，實施聚碳酸酯樹脂(日本三菱工學塑膠公司製，商品名「HL-4000」)之射出成型試驗，以評估離型性。就射出成型機而言，係使用日本FANUC公司製之射出成型機(商品名「Roboshot2000i 100B」)，射出條件係設為成形溫度310℃、模具溫度105℃、充填時間0.7秒、保壓時間2.0秒、冷卻時間20秒、夾持力1000kN。離型性之評估係針對藉由射出成型所得之樹脂製品表面的凹凸形狀，每500射以雷射顯微鏡測量尺寸及形狀，當發現深度為20μm且寬度為20μm之斷面呈V槽形狀的深度及/或寬度之尺寸為超過±2μm之異常時，判斷已達到壽命。其結果顯示在以下之第1表。 The injection molding die of the test pieces 1 to 3 of the present invention having a coating layer and the injection molding die of the comparative example having no coating layer were used to carry out polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name " Injection molding test of HL-4000") to evaluate the release property. In the injection molding machine, an injection molding machine (trade name "Roboshot 2000i 100B" manufactured by FANUC Co., Ltd.) was used, and the injection conditions were set to a molding temperature of 310 ° C, a mold temperature of 105 ° C, a filling time of 0.7 seconds, and a holding time of 2.0. Second, cooling time 20 seconds, clamping force 1000kN. The evaluation of the release property is for the uneven shape of the surface of the resin article obtained by injection molding, and the size and shape are measured every 500 shots by a laser microscope, and when the depth is 20 μm and the width is 20 μm, the cross section has a depth of a V-groove shape. When the size of the width and/or the width is more than ±2 μm, it is judged that the life has been reached. The results are shown in the first table below.
如第1表所示，比較例係在1500射時發現在V槽底有樹脂之熔接，且尺寸精密度悪化，因此判斷已達到壽命。另一方面，本發明之試驗片1至3係與比較例 相比顯現出長壽命。 As shown in the first table, in the comparative example, it was found that the resin was welded at the bottom of the V-groove at the time of 1500 shot, and the dimensional precision was deteriorated, so that it was judged that the life was reached. On the other hand, the test pieces 1 to 3 of the present invention and comparative examples Compared to the long life.
本發明之模具、成形輥及剝離電鑄品，係適用於以使用在聚光型太陽光發電之菲涅爾透鏡用模具、光學用微透鏡用模具、液晶用偏光濾鏡加工用成形輥等為首之各種超精密加工模具等、及必須進行高精密彫刻加工之超微細加工的用途。 The mold, the forming roll, and the peeling electroforming product of the present invention are suitable for use in a Fresnel lens mold for concentrating solar power generation, a mold for optical microlenses, a forming roll for processing a polarizing filter for liquid crystal, and the like. The first ultra-precision machining molds and other ultra-fine machining operations that require high-precision engraving.
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| US10056541B2 (en) | 2014-04-30 | 2018-08-21 | Apple Inc. | Metallic glass meshes, actuators, sensors, and methods for constructing the same |
| US10161025B2 (en) | 2014-04-30 | 2018-12-25 | Apple Inc. | Methods for constructing parts with improved properties using metallic glass alloys |
| US10000837B2 (en) * | 2014-07-28 | 2018-06-19 | Apple Inc. | Methods and apparatus for forming bulk metallic glass parts using an amorphous coated mold to reduce crystallization |
| WO2019181085A1 (en) * | 2018-03-19 | 2019-09-26 | 株式会社野村鍍金 | Corrugating roll and manufacturing method therefor |
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| JPS5950190A (en) * | 1982-09-17 | 1984-03-23 | Seiko Epson Corp | Nickel-phosphorus alloy electroplating bath |
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| US20040047899A1 (en) * | 2001-08-21 | 2004-03-11 | Wataru Urushihara | Member excellent in antibacterial and/or antialgae effects and process for producing the same |
| JP2008246714A (en) * | 2007-03-29 | 2008-10-16 | Nippon Zeon Co Ltd | Mold part manufacturing method and mold part |
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| JPS5950190A (en) * | 1982-09-17 | 1984-03-23 | Seiko Epson Corp | Nickel-phosphorus alloy electroplating bath |
| JPH11269587A (en) * | 1998-03-24 | 1999-10-05 | Toru Yamazaki | Alloy by electrolytic deposition, and micro-arry connector using the same |
| JP2002079522A (en) * | 2000-06-23 | 2002-03-19 | Hitachi Maxell Ltd | Die for molding disk substrate and die for molding resin |
| US20040047899A1 (en) * | 2001-08-21 | 2004-03-11 | Wataru Urushihara | Member excellent in antibacterial and/or antialgae effects and process for producing the same |
| JP2008246714A (en) * | 2007-03-29 | 2008-10-16 | Nippon Zeon Co Ltd | Mold part manufacturing method and mold part |
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