經濟部智慧財產局員工消費合作社印製 593692 A7 _____ B7____ 五、發明說明（/ ) 〔發明所屬之技術領域〕 本發明係關於蝕刻穿孔性優異之Fe - Ni系合金蔭罩用 素材，特別是關於蝕刻穿孔時的孔徑均一性優異之Fe-Ni 系合金蔭罩用素材。本發明另關於一 Fe-Ni系合金蔭罩用 素材，其具備將異常孔所造成之開口部的直徑偏差加以改 善之電子線透過孔。 〔先前技術〕 以往，彩色布朗管用蔭罩方面一般是使用軟鋼。然而 ，若連續的使用布朗管，因照射電子線而使蔭罩之溫度上 昇，基於熱膨脹會使螢光體和電子線的照射位置變得不一 致而產生色差。亦即，在彩色顯像管動作時，通過蔭罩的 開孔部之電子束僅全體的1/3以下，由於其他電子束會衝 撞蔭罩，而造成蔭罩的溫度上昇。 於是，近年來，在彩色布朗管用蔭罩之領域上，基於 防止色差的觀點係使用低膨脹係數之稱作「36合金」之Fe -Ni系合金。 在製造Fe-Ni系合金蔭罩用素材時，係將既定成分之 Fe - Ni系合金例如藉VIM爐之真空熔解或LF之爐外精煉 來進行熔製後，鑄造成鑄錠(ignot)，藉鍛造或初軋來得出 板坯(slab)。之後，實施熱軋，除去表面之氧化鱗皮後，反 覆實施冷軋和退火，實施最終冷軋以使薄板厚度成爲 0.3mm以下。之後，切割成既定板寬之蔭罩用素材。蔭罩 用素材在脫脂後，在兩面塗佈光阻劑，燒上圖案並加以顯 像後，用蝕刻液實施穿孔加工，再切斷成各個平面蔭罩。 4 本尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) ----------_裝--------訂------- (請先閱讀背面之注音？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 593692 ΚΙ _Β7_ 五、發明說明（二） 將平面蔭罩在非氧化性環境氣氛中退火以賦予衝壓加工性 後(預退火法則對蝕刻前的最終軋製材來進行退火），藉衝 壓來球面成形爲蔭罩形態。最後，將球面成形後之蔭罩脫 脂後，在水蒸氣或燃燒氣體周圍環境中退火，以在蔭罩表 面形成黑化氧化膜。如此般來製作出蔭罩。 本發明中，係將包含最終退火後之蔭罩用素材、及平 面蔭罩之供作爲賦予衝壓成形性的退火之材料總稱爲蔭罩 用素材。 這種蔭罩用素材，一般係藉由使用氯化鐵水溶液之周 知的蝕刻加工技術，來形成電子線的通過孔。蝕刻加工的 進行，係運用光微影技術，來形成耐蝕罩(在合金帶的一表 面具有多數個例如直徑80//m的正圓形開口部、在另一表 面之相對位置具有例如直徑180/zm的正圓形開口部)後， 吹附噴霧狀的氯化鐵溶液。 藉由該蝕刻加工，雖能得出緻密且整齊排列著微小開 口部之蔭罩，但起因於蝕刻條件之局部偏差等，會使開口 部的直徑產生偏差。若該偏差變大，在布朗管內組裝蔭罩 時將產生色差而成爲不合格的製品。以往，該開口部直徑 的偏差，會使蔭罩蝕刻加工時之良率降低，而造成成本增 大的主要原因。 關於抑制開口部直徑之偏差方面，過去已作過各檢討 ，就材料方面，例如日本專利特開平05 - 086441及特開平 10- 111614號公報中提案出，藉由控制集合組織來防止偏 差之方法。這些是藉由控制集合組織來謀求蝕刻之均一性 5 本I張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐)賴 · ~ -----------裝--------- 訂·！-------- (請先閱讀背面之注意事項再填寫本頁) 593692 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（3 ) 〇 然而，近年來已開始明白，有上述公知技術所無法防 止之孔徑偏差現象的存在。圖1係顯示新發現出之構成孔 徑偏差原因的異常孔例的SEM像和正常孔的對比。該異常 孔的特徵在於，孔壁面比正常孔來得粗糙，孔輪廓部受到 異常的侵蝕而顯示鋸齒狀的形態，同時孔徑有比目標直徑 爲大之傾向。如此般異常孔的特徵，會按照蝕刻條件等的 不同而有程度上的變化，有時壁面沒有粗糙的情形，或有 時有無法淸楚觀察到鋸齒現象的情形。該異常孔發生所造 成之孔徑偏差，係前述控制集合組織的技術所無法防止者 〇 作爲防止這種異常孔的手段，本發明人於日本專利特 願2〇00 - 117788號中提案出，在Fe-Ni素材中，讓直徑 50〜lOOOnm的MnS夾雜物以1500個/mm2以上的頻度來分 散之方法。其乃基於，藉由以下的機構，微小的MnS將能 防止異常孔所引起之開口部直徑偏差。本發明人同時提出 相關之申請案特願2000 - 117766號。 蔭罩用Fe-Ni系合金，一般是使用氯化鐵水溶液來對 蔭罩作蝕刻加工。這時，係在材料上塗佈耐蝕膜而將不須 開口的部分被覆住，以僅使得須開口的部分接觸氯化鐵水 溶液。若在該開口部有微細MnS的存在，該MnS將成爲 腐蝕的起點而促進基質的蝕刻。若所有的開口部都沒有 MnS的存在，每個開口部都會成爲同樣的蝕刻狀態而不致 產生孔徑偏差。然而，在現實的工業生產上，要完全沒有 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------"訂 L-------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 593692 A7 _____B7____ 五、發明說明（，）Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593692 A7 _____ B7____ V. Description of the Invention (/) [Technical Field to which the Invention belongs] This invention relates to materials for etching masks of Fe-Ni series alloys with excellent perforation properties, particularly Material for Fe-Ni based alloy shadow masks with excellent uniformity of pore diameter during etching. The present invention also relates to a material for a Fe-Ni alloy shadow mask, which is provided with an electron beam transmission hole for improving a diameter deviation of an opening portion caused by an abnormal hole. [Prior Art] Conventionally, soft steel is generally used for shadow masks for color brown tubes. However, if a Brown tube is continuously used, the temperature of the shadow mask rises due to the irradiation of electron beams, and the thermal expansion will cause the phosphors and the electron beams to irradiate different positions and cause chromatic aberration. That is, during the operation of the color picture tube, the electron beam passing through the opening portion of the shadow mask is only 1/3 or less of the whole, and the temperature of the shadow mask rises because other electron beams collide with the shadow mask. Therefore, in recent years, in the field of shadow masks for color brown tubes, from the viewpoint of preventing chromatic aberration, a Fe-Ni-based alloy called "36 alloy" with a low expansion coefficient has been used. When manufacturing a material for an Fe-Ni-based alloy shadow mask, a predetermined composition of the Fe-Ni-based alloy is melted by, for example, vacuum melting in a VIM furnace or refining outside the LF, and then cast into an ingot. Slabs are obtained by forging or preliminary rolling. After that, hot rolling is performed to remove the oxidized scale on the surface, and then cold rolling and annealing are repeatedly performed, and finally cold rolling is performed so that the thickness of the sheet becomes 0.3 mm or less. After that, it is cut into a mask material having a predetermined plate width. Shadow mask After the material is degreased, a photoresist is coated on both sides, a pattern is burned and developed, and then a perforation process is performed with an etching solution, and then cut into individual flat shadow masks. 4 This standard applies to China National Standard (CNS) A4 specifications (210 X 297 mm) ----------_ installation -------- order ------- (please first Read the phonetic on the back? Matters need to fill in this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593692 ΚΒ_Β7_ V. Description of the invention (II) After annealing the flat shadow mask in a non-oxidizing environment to give stamping workability ( The pre-annealing method anneals the final rolled material before etching), and the spherical surface is formed into a shadow mask shape by stamping. Finally, the mask after the spherical surface is degreased is annealed in the surrounding environment of water vapor or combustion gas to form a black oxide film on the surface of the shadow mask. This is how to make a shadow mask. In the present invention, a material including a mask material after final annealing and a flat mask as an annealing material for imparting press formability is collectively referred to as a material for a shadow mask. Such a material for a shadow mask is generally formed by a well-known etching process technique using an aqueous solution of ferric chloride to form a through hole for an electron beam. The etching process is performed using a photolithography technique to form a corrosion-resistant cover (the surface of the alloy strip has a plurality of perfectly circular openings, for example, a diameter of 80 // m, and the opposite position on the other surface has, for example, a diameter of 180 / zm square opening), a sprayed ferric chloride solution was blown. According to this etching process, a dense shadow mask with fine openings arranged neatly can be obtained, but the diameter of the openings varies due to local variations in etching conditions and the like. If this deviation becomes large, a color difference will be generated when the shadow mask is assembled in the Brown tube, and it will become a defective product. Conventionally, this variation in the diameter of the opening portion has reduced the yield rate during the etching process of the shadow mask, and has caused a cost increase. Regarding the suppression of variations in the diameter of the openings, various reviews have been made in the past. In terms of materials, for example, Japanese Patent Laid-Open Nos. 05-08641 and 10-111614 have been proposed to prevent deviations by controlling the collective organization . These are to control the uniformity of the etching to achieve the uniformity of etching. 5 This I-size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). -------- Order! -------- (Please read the precautions on the back before filling out this page) 593692 Printed by A7 B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs V. Invention Description (3) 〇 However, in recent years, it has begun to understand, There is a phenomenon of pore diameter deviation which cannot be prevented by the above-mentioned known techniques. Fig. 1 shows a comparison between an SEM image and a normal pore of an example of an abnormal pore that newly causes the pore diameter deviation. This abnormal hole is characterized in that the hole wall surface is rougher than a normal hole, the hole contour portion is abnormally eroded to show a jagged shape, and the hole diameter tends to be larger than the target diameter. The characteristics of such abnormal holes may vary to some extent depending on the etching conditions, etc. Sometimes the wall surface is not rough, or sometimes the jagged phenomenon cannot be clearly observed. The deviation of the pore diameter caused by the occurrence of the abnormal pores cannot be prevented by the aforementioned technique for controlling the collective structure. As a means to prevent such abnormal pores, the present inventor proposed in Japanese Patent Application No. 2000-117788. A method of dispersing MnS inclusions with a diameter of 50 to 100 nm in Fe-Ni materials at a frequency of 1500 / mm2 or more. This is based on the fact that, with the following mechanism, minute MnS can prevent deviations in the opening diameter caused by abnormal holes. The inventor also filed related applications No. 2000-117766. Fe-Ni alloys for shadow masks are generally etched using an aqueous solution of ferric chloride. At this time, the material is coated with a corrosion-resistant film and the portion that does not need to be opened is covered so that only the portion that needs to be opened comes into contact with the aqueous solution of ferric chloride. If fine MnS is present in the opening, the MnS will be the starting point of corrosion and promote the etching of the substrate. If no MnS is present in all the openings, each opening will be in the same etched state without deviation in the pore diameter. However, in actual industrial production, there are no 6 paper sizes that are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). -" Order L ------- line (please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593692 A7 _____B7____ 5. Description of the invention (,)
MnS等夾雜物的存在很難，在一些開口部上，構成腐蝕起 點之MnS會有一定的存在機率。在這種具有腐蝕起點之開 口部，其蝕刻速度將比其周邊之無腐蝕起點的開口部快， 而使開口徑變大。又，有起點之開口部上，由於比其周邊 之無起點的開口部較早開始蝕刻，故有起點之開口部將成 爲電化學上的陽極，無起點存在之開口部則成爲陰極。這 時，蝕刻速度的差異會變得更大，而使蝕刻終了後之開口 徑差異變大。另一方面，只要使素材含有一定頻度以上的 微細MnS，MnS將均等地存在於每個開口部，而不致產生 開口部直徑的偏差。前述會發生本發明中稱作「異常孔」 的素材，由於構成腐蝕起點的MnS僅以一定頻度以下來存 在，就素材全體而言，將失去MnS分布的均一性。這時， 雖然大部分的開口部是含有平均水準的MnS，但會產生Φ 不含MnS的開口部，②含多量MnS之開口部，③內部之 MnS的分布不均之開口部等。這些MnS的含有狀態和平均 水準不同的開口部，相對於含有平均水準MnS之開口部， MnS對蝕刻的幫助將有程度上的不同，而產生蝕刻速度之 差異。其結果，在電子顯微鏡下將會檢測出腐蝕異常的孔( 在孔壁面、孔輪的孔廓部、孔徑等帶有特徵）。又，能把該 異常孔當作開口部直徑的偏差來評價。 又，特願2000 - 117788號揭示出之製造方法，作爲將 微小MnS導入Fe-Ni系合金素材中之手段，係將Μη及S 濃度分別調整成〇·〇5〜0.5mass及4〜20mass ppm，以將熱軋 及再結晶退火的條件最適化而生成期望量的MnS。 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------φ裝---------訂“-------線Φ (請先閱讀背面之注音？事項再填寫本頁) 593692 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（t) 然而，該製造方法中，爲了生成（析出)MnS，熱壓延 後的材料之漸冷，或使用分批熔爐以低溫長時間的條件來 進行再結晶退火是必要的。又，爲了使一旦析出後的MnS 不致消失（固溶），在進行MnS析出處理後之再結晶退火中 ，必須調整爐內溫度及通板速度以使材料的到達溫度不致 超過900°C。如此般熱處理條件的限制，由於會降低生產 效率，又會增大生產成本，並不符合工業上的需求。 〔發明所要解決之課題〕 於是，藉由使MnS微細析出物分散於素材全體，以在 藉蝕刻加工來形成電子線透過孔時不致產生開口部直徑的 偏差之新技術中，希望能開發出不須上述般熱處理條件的 限制之Fe-Ni系合金素材。 因此，本發明之課題係提供一 Fe-Ni系合金素材，其 在藉蝕刻加工來形成電子線透過孔時不致產生開口部直徑 的偏差，且能以和相同於以往的生產效率及生產成本來製 造出。 〔用以解決課題之手段〕 爲增加Fe-Ni系合金中微細MnS夾雜物個數之最容 易的手段，係增加Fe-Ni系合金中之S濃度。然而，若S 濃度超過20mass ppm，長度超過10/zm之粗大MnS夾雜 物將大量產生，在該粗大夾雜物的位置進行蝕刻來形成電 子線透過孔時，將無法獲得正圓形的孔。又，若S濃度變 高，在鍛造、初軋、熱軋等也會有易產生裂痕之問題。 特願2000 - 117788號中，係將S濃度的上限値限制爲 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------^訂 i*-------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 593692 A7 __B7______ 五、發明說明（6 ) 20mass ppm，以讓素材中的S儘量析出成MnS，又爲防止 一旦析出後的MnS固溶而將熱軋及再結晶退火的條件最佳 化，而成功得出期望數目的MnS。 相對於此，本發明的前提，係藉由將Fe-Ni系合金中 的S濃度設定爲更高的數値，不須以特殊條件來進行熱軋 及再結晶退火，即可獲得期望的MnS。又，針對S濃度提 高時之①粗大MnS的生成②高溫下的加工性降低等2個課 題之解決手段作深入的硏究。其結果發現到，若在Fe-Ni 系合金中添加微量的Cu，就算提高S濃度也不會產生粗大 的 MnS 〇 該認知的發端，係在用透射式電子顯微鏡來分析各種 Fe-Ni系合金中的微細MnS的組成之過程中，確認出微細 MnS中有Cu的存在。之後，本發明人著眼於Cu濃度和 MnS尺寸的關係，反覆的進行實驗(在Fe-Ni系合金中添 加各種濃度的Cu後觀察MnS夾雜物的形態）。因而了解到 ，只要添加20mass ppm以上的Cu，就算S濃度超過The presence of inclusions such as MnS is difficult. In some openings, the MnS that constitutes the origin of corrosion will have a certain probability of existence. In such an opening portion having an etching origin, the etching speed is faster than that of the opening portion having no corrosion origin in its periphery, and the opening diameter becomes larger. Since openings having a starting point are etched earlier than openings having no starting point in the periphery, openings having a starting point become electrochemical anodes, and openings having no starting point become cathodes. At this time, the difference in the etching speed becomes larger, and the difference in the opening diameter after the end of the etching becomes larger. On the other hand, as long as the material contains fine MnS at a certain frequency or more, MnS will be uniformly present in each opening without causing variations in the diameter of the opening. In the aforementioned materials that cause "abnormal pores" in the present invention, since the MnS constituting the origin of corrosion exists only at a certain frequency or less, the uniformity of the MnS distribution will be lost for the entire material. At this time, although most of the openings contain an average level of MnS, Φ does not contain MnS, ② openings containing a large amount of MnS, ③ openings with uneven distribution of MnS inside. These openings with different MnS content states and average levels have different degrees of MnS help in etching than openings with average MnS levels, resulting in differences in etching speed. As a result, holes with abnormal corrosion (with features on the hole wall surface, hole profile, hole diameter, etc. of the hole wheel) will be detected under an electron microscope. The abnormal hole can be evaluated as a deviation in the diameter of the opening. Also, the manufacturing method disclosed in Japanese Patent Application No. 2000-117788, as a means for introducing minute MnS into Fe-Ni-based alloy materials, adjusts the Mn and S concentrations to 0.05 to 0.5 mass and 4 to 20 mass ppm, respectively. In order to optimize the conditions of hot rolling and recrystallization annealing, a desired amount of MnS is generated. 7 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----------- φpack --------- Order "------ -Line Φ (Please read the phonetic on the back? Matters before filling out this page) 593692 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (t) However, in this manufacturing method, in order to generate (precipitate) MnS It is necessary to cool the material after hot rolling, or use a batch furnace to perform recrystallization annealing at low temperature for a long time. In order to prevent MnS from disappearing (solid solution) after precipitation, MnS In the recrystallization annealing after the precipitation treatment, the furnace temperature and the plate speed must be adjusted so that the arrival temperature of the material does not exceed 900 ° C. The limitation of such heat treatment conditions will reduce production efficiency and increase production costs. It does not meet the needs of industry. [Problems to be Solved by the Invention] Therefore, by dispersing fine precipitates of MnS throughout the material, a new method of preventing the deviation of the diameter of the opening portion from being formed when an electron beam transmission hole is formed by etching processing. In the technology, I hope to develop The Fe-Ni-based alloy material that is subject to the above-mentioned heat treatment conditions. Therefore, the problem of the present invention is to provide an Fe-Ni-based alloy material that does not cause a deviation in the diameter of the opening portion when an electron beam transmission hole is formed by etching. It can be manufactured with the same production efficiency and production cost as in the past. [Means to Solve the Problem] The easiest way to increase the number of fine MnS inclusions in Fe-Ni based alloys is to increase Fe-Ni. S concentration in the alloy. However, if the S concentration exceeds 20 mass ppm, a large amount of coarse MnS inclusions with a length exceeding 10 / zm will be generated in large quantities. When the positions of the coarse inclusions are etched to form electron beam transmission holes, it will not be obtained. A perfectly circular hole. If the S concentration becomes high, cracks may easily occur during forging, preliminary rolling, and hot rolling. In Japanese Patent Application No. 2000-117788, the upper limit of the S concentration is limited to 8 This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ----------- installation -------- ^ order i * ------- (Please read the notes on the back before filling out this page) Staff of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative 593692 A7 __B7______ 5. Description of the invention (6) 20mass ppm, in order to precipitate S in the material as much as possible into MnS, and to prevent the solid solution of MnS once precipitated, the conditions for annealing and hot rolling are the best In contrast, the premise of the present invention is to set the S concentration in the Fe-Ni-based alloy to a higher value, and it is not necessary to perform hot rolling under special conditions. And recrystallization annealing can obtain the desired MnS. In addition, in order to investigate the two methods of solving the two problems, such as ① the formation of coarse MnS when the S concentration increases, and the decrease in workability at high temperatures. As a result, it was found that if a small amount of Cu is added to the Fe-Ni-based alloy, even if the S concentration is increased, coarse MnS will not be generated. The origin of this knowledge is to analyze various Fe-Ni-based alloys with a transmission electron microscope. During the composition of the fine MnS, it was confirmed that Cu was present in the fine MnS. Then, the present inventors focused on the relationship between the Cu concentration and the size of MnS, and carried out experiments repeatedly (observing the morphology of MnS inclusions after adding various concentrations of Cu to the Fe-Ni-based alloy). Therefore, I learned that if the Cu concentration exceeds 20 mass ppm, even if the S concentration exceeds
20mass ppm也幾乎不會產生長度超過10 //m之粗大的MnS 〇 雖藉由添加Cu來減少粗大MnS產生之機構尙不詳， 據推測是因Cu會成爲MnS的析出核之故。亦即，在鑄造 、鍛造、初乳、熱軋等將材料冷卻時，在MnS析出前Cu 會先析出。該Cu析出物極微細，係以高頻度分散於Fe-Ni 系合金中， 而作爲 MnS 的有效析出部位來作用 。其結 果，相較於未添加Cu的情形，MnS的析出部位增加，而 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） " -----------裝-------^訂 “------- (請先閱讀背面之注意事項再填寫本頁) 593692 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（η ) 使MnS的個數增加。由於在MnS總量不變下MnS的個數 增加，故MnS的尺寸變小，而使粗大MnS減少。 其次，針對S濃度增加時熱加工性降低的問題，係了 解到，藉由將Fe-Ni系合金中之Mn濃度調整成比以往爲 高，即可加以改善。又同時了解到，藉由縮小鑄錠的組織 ，可有效的防止裂痕。 另一方面，爲使合金所含的S有效地以MnS的形式來 析出，較佳爲儘可能減低會和S形成化合物之不純物元素 的濃度。在Fe-Ni系合金的情形，特別是必須留意Ca和 Mg的含量。由於這些元素和硫的親和力比Mn爲強，將形 成硫化物之CaS、MgS，而使微細MnS的析出量變少。作 爲Ca和Mg之混入來源，可列舉原料、板坯、耐火物等。 有時在精煉時基於脫氧或脫硫的目的也會添加這些元素。 爲了減少Ca和Mg之混入量，在原料、板坯、耐火物、精 煉時之添加元素等的選擇上必須多加注意。又解明出，Ca 和Mg濃度之限制，設Ca和Mg之mass ppm單位的濃度 分別爲〔ppm Ca〕及〔ppm Mg〕時，能定量化成 〔ppm Ca〕/40+〔 ppm Mg〕/24 $ 1。 在添加Cu來將MnS微細化、並將會阻害MnS析出之 Ca及Mg含量加以限制之Fe-Ni系合金中，若將S濃度 限制在15ppm以上，就算用以往的熱軋條件及再結晶退火 條件來製造合金，也能獲得相當程度的MnS個數，以抑制 蝕刻加工時開口部直徑偏差的產生。本發明之Fe_Ni系合 金蔭罩用素材之特徵在於，含有1500個/mm2以上之直徑 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----II----•裝-------- --------ΜΨ (請先閱讀背面之注音？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 593692 A7 B7 五、發明說明（β) ② 將乙醯纖維素塗佈於電解硏磨面後再進行剝離，以使突 出硏磨面之夾雜物附著於乙醯纖維素。 ③ 在乙醯纖維素之夾雜物附著面上蒸鍍碳後，浸在醋酸乙 酯中來溶去乙醯纖維素。 ④ 針對含有夾雜物之碳薄膜，用透射式電子顯微鏡來觀察 夾雜物的形態，同時用EDS和電子線繞射來鑑定夾雜物的 組成。 (2)鈾刻孔的個數：如特願2000 - 117788號所示般， 將Fe-Ni系合金浸在3%硝酸-乙醇溶液時產生之蝕刻孔 、和透射式電子顯微鏡所測定之MnS頻度間有良好的相關 性。圖3爲其數據，當直徑50〜lOOOnm的MnS以1500個 /mm2以上來存在時，係相當於直徑0.5〜10//m的蝕刻孔以 2000個/mm2以上來存在的情形。MnS個數2000〜7000個 /mm2係相當於蝕刻孔個數2500〜10000個/mm2。 又，在蝕刻孔的觀察方面，將Fe-Ni系合金試料的 表面作鏡面硏磨後，於純度g99.5vol%的乙醇(JIS K8101， 特級）100ml中混合濃度60%的硝酸(JIS K8541)3ml而成之 溶液中，於20°C浸漬30秒。接著，使用光學顯微鏡，將 腐蝕面的暗視野像以X400的倍率來攝影，在其照片上測 定出直徑0.5//m〜10# m之蝕刻孔個數。 蝕刻孔的計測方面，係用圖像解析裝置針對0.2mm2 的面積來進行。蝕刻孔的形狀大致呈球形，在其直徑之測 定上，係測定平行於壓延方向上的孔徑。如特願2000 -Π7766號所述般，該觀察方法是非常有效的MnS簡易測 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝--------：訂-------- 593692 A7 B7 五、發明說明（θ)20mass ppm also hardly produces coarse MnS with a length exceeding 10 // m. Although the mechanism for reducing the production of coarse MnS by adding Cu is unknown, it is presumed that Cu will become the nucleus of MnS precipitation. That is, when the material is cooled by casting, forging, colostrum, hot rolling, etc., Cu is precipitated before MnS is precipitated. This Cu precipitate is extremely fine, and is dispersed in the Fe-Ni-based alloy at a high frequency, and functions as an effective precipitation site of MnS. As a result, compared with the case where Cu is not added, the precipitation sites of MnS are increased, and 9 paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " --------- --Equipment ------- ^ Order "------- (Please read the notes on the back before filling in this page) 593692 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (Η) increases the number of MnS. Since the number of MnS increases under the same total amount of MnS, the size of MnS becomes smaller and the coarse MnS decreases. Second, the problem of hot workability reduction when S concentration increases It is understood that it can be improved by adjusting the Mn concentration in the Fe-Ni-based alloy to be higher than in the past. At the same time, it has been learned that by reducing the structure of the ingot, cracks can be effectively prevented. Another On the other hand, in order to effectively precipitate S contained in the alloy in the form of MnS, it is preferable to reduce the concentration of the impurity element that will form a compound with S as much as possible. In the case of Fe-Ni-based alloys, especially Ca and Ca Mg content. Since the affinity of these elements and sulfur is stronger than that of Mn, Ca will form sulfides. S, MgS to reduce the amount of fine MnS precipitation. As sources of mixing Ca and Mg, raw materials, slabs, refractories, etc. may be added. These elements may be added for the purpose of deoxidation or desulfurization during refining. In order to reduce the mixing amount of Ca and Mg, we must pay more attention to the choice of raw materials, slabs, refractories, and refining elements. It is also clear that the limits of the concentration of Ca and Mg are set in units of mass ppm of Ca and Mg. When the concentrations are [ppm Ca] and [ppm Mg], they can be quantified into [ppm Ca] / 40 + [ppm Mg] / 24 $ 1. When Cu is added to refine MnS, it will prevent the precipitation of MnS. In Fe-Ni based alloys with restricted Ca and Mg contents, if the S concentration is limited to 15 ppm or more, even if the alloy is manufactured using conventional hot rolling conditions and recrystallization annealing conditions, a considerable number of MnS can be obtained. Suppression of the diameter deviation of the opening during the etching process. The material of the Fe_Ni-based alloy shadow mask of the present invention is characterized in that it contains 1500 pieces / mm2 or more and has a diameter of 10. Mm) ---- II ---- Install -------- -------- ΜΨ (Please read the note on the back? Matters before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 593692 A7 B7 V. Invention Description ( β) ② Ethyl cellulose is coated on the electrolytic honing surface and then peeled off, so that the inclusions protruding from the honing surface are adhered to the ethyl cellulose. After carbon, immerse in ethyl acetate to dissolve the ethyl acetate. ④ For carbon thin films containing inclusions, use a transmission electron microscope to observe the morphology of the inclusions, and use EDS and electron beam diffraction to identify the composition of the inclusions. (2) Number of uranium engraved holes: as shown in Japanese Patent Application No. 2000-117788, etched holes produced when Fe-Ni-based alloy is immersed in 3% nitric acid-ethanol solution, and MnS measured by transmission electron microscope There is a good correlation between the frequencies. Figure 3 is its data. When MnS with a diameter of 50 to 100 nm exists at 1500 holes / mm2 or more, it corresponds to the case where etched holes with a diameter of 0.5 to 10 / m exist at 2000 holes / mm2 or more. The number of MnS of 2000 to 7000 / mm2 is equivalent to the number of etched holes of 2500 to 10,000 / mm2. In addition, for observing the etched holes, the surface of the Fe-Ni-based alloy sample was mirror-honed, and 60% nitric acid (JIS K8541) was mixed in 100 ml of ethanol (JIS K8101, special grade) with a purity of g99.5vol%. 3 ml of the solution was immersed at 20 ° C for 30 seconds. Next, the dark field image of the corroded surface was photographed at a magnification of X400 using an optical microscope, and the number of etched holes having a diameter of 0.5 // m to 10 # m was measured on the photograph. The measurement of the etched holes was performed using an image analysis device for an area of 0.2 mm 2. The shape of the etched hole is approximately spherical. The diameter of the etched hole is measured parallel to the rolling direction. As described in TB2000-Π7766, this observation method is a very effective simple measurement of MnS. 13 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). (Please read the precautions on the back before (Fill in this page) Install --------: Order -------- 593692 A7 B7 V. Description of the invention (θ)
Ca及Mg濃度爲： 〔ppm Ca〕/40+〔 ppm Mg〕/24 $ 0.5 ° (請先閱讀背面之注意事項再填寫本頁) 如上所述般，將Cu、Mg及Ca濃度調整後之Fe - Ni 系合金中，只要含有15mass ppm以上之S，就算以通常的 熱軋條件及再結晶退火條件來製造Fe-Ni系合金，也能獲 得上述之MnS個數或蝕刻孔個數。另一方面，若S濃度超 過40mass ppm，就算在Cu的存在下，仍會大量產生長度 超過l〇/zm之粗大MnS，且其頻度會超過0.5個/mm2。於 是，將S濃度定爲15〜40mass ppm。 爲獲得上述MnS個數或蝕刻孔個數，且爲彌補提高S 濃度所造成之熱加工性降低，Μη濃度必須爲0.2mass%以 上。另一方面，若Μη濃度超過0.5mass%，素材會變硬而 使冷加工性降低。於是將Μη濃度定爲0.2〜0.5mass%。 經濟部智慧財產局員工消費合作社印製 (5)製程：工業上在製造蔭罩用合金時，首先將既定成 分之Fe - Ni系合金例如藉VIM爐之真空熔解或LF之爐外 精煉來進行熔製後，鑄造成鑄錠，藉鍛造或初軋來得出板 坯。之後，實施熱軋來加工成厚2〜6mm之板後，除去表面 之氧化鱗皮。接著反覆實施冷軋和退火，經最終再結晶退 火後，實施最終冷軋以精加工成厚度〇.3mm以下之蔭罩用 素材。The concentration of Ca and Mg is: [ppm Ca] / 40 + [ppm Mg] / 24 $ 0.5 ° (Please read the precautions on the back before filling this page) As described above, adjust the Cu, Mg and Ca concentrations As long as the Fe-Ni-based alloy contains S of 15 mass ppm or more, even if the Fe-Ni-based alloy is produced under normal hot rolling conditions and recrystallization annealing conditions, the above-mentioned number of MnS or etched holes can be obtained. On the other hand, if the S concentration exceeds 40 mass ppm, even in the presence of Cu, a large amount of coarse MnS with a length exceeding 10 / zm will still be produced, and its frequency will exceed 0.5 pieces / mm2. Therefore, the S concentration was set to 15 to 40 mass ppm. In order to obtain the number of MnS or the number of etched holes, and to compensate for the decrease in hot workability caused by increasing the S concentration, the Mη concentration must be 0.2 mass% or more. On the other hand, if the Mη concentration exceeds 0.5 mass%, the material becomes hard and the cold workability is reduced. Therefore, the Mη concentration was set to 0.2 to 0.5 mass%. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (5) Process: When manufacturing alloys for shadow masks in industry, firstly Fe-Ni alloys of a predetermined composition are made by, for example, vacuum melting of a VIM furnace or refining outside the LF. After melting, it is cast into ingots and slabs are obtained by forging or preliminary rolling. After that, hot rolling was performed to form a plate having a thickness of 2 to 6 mm, and then the scale on the surface was removed. Next, cold rolling and annealing are repeatedly performed, and after the final recrystallization and annealing, the final cold rolling is performed to finish the shadow mask material having a thickness of 0.3 mm or less.
在這一連串的步驟中，有助於MnS之生成(析出)和消 失（固溶）之主要步驟爲熱軋及再結晶退火。此乃基於，固 溶Μη(〔Μη〕）和固溶S(〔S〕）之溶解度積（〔％Mn〕X〔 %S〕），在進行Fe-Ni系合金合金的熱處理之600〜1200°C 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 593692 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（β) 的溫度範圍內，當溫度降低時會急劇減低之故。亦即，在 高溫側，MnS會固溶於Fe - Ni系合金中，在低溫側，MnS 會析出於Fe-Ni系合金中。例如，若將熱軋後的板實施漸 冷，在冷卻中母材中之Μη及S將以MnS的形式來析出。 又’若在高溫·短時間的條件下進行再結晶退火，有時 MnS會固溶；若在低溫·長時間的條件下進行再結晶退火 ，有時MnS會析出。 本發明之Fe-Ni系合金的特徵在於，只要在通常的 條件下進行熱軋及再結晶退火，即可獲得上述的MnS個數 或蝕刻孔個數。在此之通常的條件爲： Φ熱軋：以1200°C以下的溫度進行熱軋，熱軋後不須進行 特殊的急冷處理(噴水冷卻的情形等除外） ②再結晶退火：使用連續退火爐時，加熱爐中的材料之最 高到達溫度不致超過1100°C。 另一方面，基於MnS個數以外的觀點，本發明之Fe -Ni系合金的製造條件係受到以下的限制。 ①冷軋加工度 a) 最終再結晶退火前之壓延加工度：較佳爲設定在50〜85% 的範圍。若超過85%，（200)集合組織會顯著的發展，而使 蝕刻孔之真圓度降低。另一方面，若低於50%，製品的 (200)集合組織之發展度過低，而使蝕刻速度變低。在此之 壓延加工度(R)，當壓延前之厚度爲t〇，壓延後之厚度爲t 時，係以R(%)=(t〇 - t)/t〇X 100的式子來定義。 b) 最終壓延加工度：較佳爲設定在1〇〜40%的範圍。若超過 16 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------·裝---------訂 --------線· (請先閱讀背面之注意事項再填寫本頁) 593692 經濟部智慧財產局員工消費合作社印制衣 A7 B7 五、發明說明（崢） 40%，壓延集合組織會極度發展，而使蝕刻速度降低。另 一方面，若低於10%，在剛要衝壓加工前之退火中，將殘 留未再結晶組織而使衝壓成形性變低。 ②再結晶退火：爲防止材料表面的氧化，必須將加熱爐的 內部用氫氣、含氫之非活性氣體等來充滿。又較佳爲，將 退火後之再結晶粒之平均直徑調整爲5〜30/zm。若最終退 火後的結晶粒徑超過30//m，蝕刻穿孔後之透過孔的壁面 會變粗糙，又會產生蝕刻速度變慢之問題。又，當中間退 火之結晶粒徑超過30//m時，最終退火後的組織變得不均 一（混雜有大結晶粒和小結晶粒之狀態），透過孔的孔壁會 變粗糙，同時蝕刻速度變得不均一。另一方面，若結晶粒 徑比5//m小，要將材料內的結晶粒徑控制成均一會變得 困難，而會產生接下來的冷乳之加工性變差等的問題。 藉此，可獲得含有1500個/mm2以上的直徑 50〜lOOOnm之MnS夾雜物之Fe-Ni系合金蔭罩用素材， 該素材能用來簡便地評價出蝕刻孔的出現頻度，亦即將該 素材的壓延面施以鏡面硏磨後，於3%硝酸-乙醇溶液中在 20°C浸漬30秒時，直徑0.5//m〜10//m之蝕刻孔將會以 2000個/mm2以上的頻度來出現。該素材能形成異常孔所造 成之開口部的直徑偏差經改善之電子線透過孔，而提供出 藉蝕刻加工所形成之電子線透過孔具有均一孔徑之蔭罩用 素材。 〔實施例〕 接著，藉實施例及比較例來更具體的說明本發明。 17 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------^訂--------- (請先閱讀背面之注意事項再填寫本頁) 593692 A7 B7 五、發明說明（A) ，對形成有直徑80//m的孔之表面，測定100個孔的直徑( 取各孔之最大直徑値）。 表1係顯示各材料之Ni、S、Mn、Cu、Ca及Mg濃 度、再加上代表性的不純物（伴隨元素）之濃度。又，表2 顯示浸漬於硝酸-乙醇溶液後之直徑0.5〜10//m的蝕刻孔 頻度、長度超過l〇//m之夾雜物個數及電子線透過孔的直 徑。透過孔直徑的測定結果，係將透過孔分類成直徑未達 78//m、78〜82//m及超過82#m者，並顯示各類的個數( 全測定個數爲100個）。 -----------裝--------：訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 19 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 593692 A7 _B7 五、發明說明（) [表1】 經濟部智慧財產局員工消費合作社印製 表Ί No. ΓΠΘ55 % 半位· ΓΤ1Θ55 ppm T* Ni Μη s Cu Ga Mg Si Al C 0 P N Cr 1 35.6 0.41 16 28 3 1 85 2 27 50 18 4 96 0.12 2 37.0 0.32 18 130 <1 < 1 320 87 16 18 49 14 120 0.00 3 37.2 0.40 17 180 1 7 93 55 14 44 45 20 260 0.32 4 35.9 0.24 15 230 2 3 210 120 34 41 .29 n 120 0.18 5 36.7 0.44 15 280 4 2 65 7 26 30 23 14 120 0.1 S 6 35.3 0.33 20 20 2 < 1 340 150 20 30 18 16 250 0.05 7 36.2 028 22 32 7 5 77 5 25 34 24 M 220 0.38 8 34.9 0.2S 24 75 2 1 49 4 45 40 9 5 74 0.09 9 36.3 0.28 23 150 12 12 78 6 15 31 29 15 210 0.80 10 36,1 0.25 21 200 3 5 55 2 35 39 8 5 95 0.28 11 35.8 0.21 22 220 7 <1 Θ7 5 23 32 13 S 78 0.18 12 36.0 0.20 22 270 10 3 84 8 38 3$ 22 8 79 0.38 13 34,5 0.24 20 410 < 1 7 63 3 45 42 19 5 88 0.29 14 36.2 0,2$ 26 43 5 1 43 10 $3 37 9 n 85 0.17 15 35.2 0.26 2t 120 7 12 150 340 IS ,33 30 20 180 0.68 16 35,$ 0.42 25 «0 10 <1 83 250 16 43 22 23 54 0.25 17 36.2 0.31 28 310 2 72 310 U 29 35 n 95 0.38 18 35.3 0.30 29 3S0 <1 < 1 270 250 14 24 18 15 150 0.00 19 36,3 0.33 26 63 3 5 70 5 26 29 25 4 103 0.28 20 35.7 〇.2a 32 39 1 5 270 200 8. 39 36 3 240 0.23 21 36.5 .0.27 _ 30. SO <1 6 50 3 22 4S 10 7 74 0.25 22 35.9 0.28 33 61 1 <1 77 6 35 37 12 6 90 0.03 23 36.1 0.21 31 98 12 <1 80 260 12 19 49 10 100 0.30 24 34.8 0,36 33 190 4 5 210 140 23 31 27 18 270 0.35 25 35.9 0.33 35 240 12 6 200 190 30 17 32 10 180 O.SS 26 35.1 0.43 37 v〇 7 1 310 320 27 21 33 19 230 0.22 27 35.2 0.26 '38 310 14 14 190 190 14 50 22 8 68 0.93 28 36.7 Q.29 33 250 8 2 • 250 180 23 31 48 6 130 0.28 29 37.0 0.30 39 ； 460 11 < I 51 150 33 35 18 40 160 0.28 30 35.8 0.41 12 260 1 3 240 290 37 45 38 6 240 0.15 31 35.0 0.29 43 360 3 5 370 220 44 28 22 18 230 0.28 32 36.2 0.14 25 83 < 1 <1 310 310 11 52 24 23 57 0.00 33 35.7 0.28 17 1$ 4 2 300 270 18 36 )7 22 310 0.18 34 36.0 0.25 35 <1 <1 2 1070 190 27 42 43 10 150 0.08 35 37.1 0.40 17 550 2 6 103 52 18 49 38 W 260 0.30 36 35.1 0.22 25 no 24 21 310 250 23 55 48 20 69 1.48 ^ T = C ppm Cj ] / 40 + [ ppm ] / 20 (請先閱讀背面之注咅？事項再填寫本頁) 裝----- 訂--------· 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） 經濟部智慧財產局員工消費合作社印製 593692 Α7 Β7 五、發明說明（（？） 試料Νο·1〜29爲滿足本發明的要件之實施例，試料 No.30〜36爲比較例。 本發明之試料No.l〜29，由於直徑〇·5〜之蝕刻 孔以個數2000個/mm2來存在，故触刻加工後之透過孔的 開口徑不致產生偏差，而顯示均一的蝕刻穿孔性。又，由 於長度超過之夾雜物爲0.5個/mm2以下，故看不出 有起因於粗大夾雜物之孔形狀的異常。 另一方面，由於試料Νο·3〇中之S濃度未達15mass ppm，試料Νο·32中之Μη未達0.2mass%，試料Ν〇·36中 之Ca和Mg濃度過高而成爲〔ppm Ca〕/40+〔 ppm Mg〕 /24>1，故直徑0.5〜l〇//m之蝕刻孔個數會少於2〇〇〇個 /mm2 〇 又，Μη含量少之Ν〇·32，在熱軋時之材料邊緣會產生 裂痕，將其裂痕硏削後加工成厚度0.1mm。又，Ca和Mg 濃度過高之Νο·36，長度超過10//m之夾雜物會變多。 由於試料Ν〇·31中之S濃度超過40ppm，長度超過10 #ηι之夾雜物將以超過0.5個/mm2的頻度來出現。 試料Νο·33及34爲Cu濃度未達20mass ppm的例子 ，Νο·33中之S濃度比No.34爲低。S濃度低之No.33，直 徑0.5〜10# m之蝕刻孔個數係少於2000個/mm2。又，崃 度超過10//m之夾雜物雖進入本發明的規定範圍內，但其 個數爲0.4個/mm2而呈稍多。另一方面，高S濃度之 Νο·34，其長度超過10/zm之夾雜物個數超過0.5個/mm2。 又，直徑0.5〜10//m之蝕刻孔個數，雖進入本發明之規定 22 丨丨— i丨丨丨丨丨丨·丨丨丨丨丨訂-------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 593692 A7 ___B7__ 五、發明說明（/ ) 範圍內，但若考慮到S濃度，則其個數稍嫌少。 試料Νο·35之Cu濃度雖超過500mass ppm，相較於 其他成分相同但Cu濃度爲180mass ppm之Νο·3，直徑 0.5〜10//m之蝕刻孔個數並沒有多很多。該Νο·35在熱軋 時會產生裂痕，故將該裂痕硏削後才加工成厚度O.lmrn。 比較例中，直徑0.5〜10//m之蝕刻孔個數少於2000 個/mm2之Νο·30、32、33，當蝕刻加工後會觀察到直徑超 出80±2//m範圍外之透過孔。又觀察到的長度超過10/zm 之夾雜物比0.5個/mm2更多。No.31、34在蝕刻加工後會 產生邊緣有缺陷的透過孔。又，這種形狀異常的孔並不屬 於直徑測定的對象。 〔發明效果〕 依據本發明，不須特殊條件的熱處理就以低成本來提 供出蝕刻穿孔出的電子線透過孔徑的均一性優異之Fe - Ni 系合金素材。 只要是藉蝕刻加工來穿孔出電子線透過孔之蔭罩用素 材，對於蝕刻加工後不須進行衝壓成形加工、而藉賦予張 力來保持平坦狀之蔭罩等，本發明亦屬有效。又，電子線 透過孔的形狀不一定要是正圓形，對於爲穿孔出橢圓形、 短柵形等的透過孔之蔭罩，本發明亦屬有效。又，本發明 也能適用於將導線架材等施以微細蝕刻加工之蔭罩以外的 用途。 〔圖式之簡單說明〕 圖1係顯示藉蝕刻加工來實施電子線透過孔之穿孔時 23 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂---------. 593692 A7 _B7 五、發明說明（ >丨） 之「正常孔」、以及和本發明有關之構成孔徑偏差原因之 「異常孔」的一例之SEM像。 圖2係顯示MnS析出物的形狀爲橢圓狀、棒狀、線狀 等的情形，代表MnS析出物的直徑之短軸徑L1和長軸徑 L2的說明圖。 圖3係顯示將Fe-Ni系合金浸漬於3%硝酸-乙醇溶 液時所產生之蝕刻孔、和透射式電子顯微鏡所測定出之 MnS夾雜物的頻度間之相關圖。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 24 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）In this series of steps, the main steps contributing to the generation (precipitation) and elimination (solid solution) of MnS are hot rolling and recrystallization annealing. This is based on the solubility product ([% Mn] X [% S]) of solid solution Mn ([Μη]) and solid solution S ([S]), which is subjected to a heat treatment of Fe-Ni-based alloy alloy at 600 to 1200. ° C 15 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 593692 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. In the temperature range of the invention description (β), when the temperature decreases It will decrease sharply. That is, on the high temperature side, MnS is dissolved in the Fe-Ni-based alloy, and on the low temperature side, MnS is precipitated in the Fe-Ni-based alloy. For example, if the hot-rolled sheet is gradually cooled, Mη and S in the base material will be precipitated as MnS during cooling. Also, if recrystallization annealing is performed under high temperature and short time conditions, MnS may be solid-dissolved; if recrystallization annealing is performed under low temperature and long time conditions, MnS may be precipitated. The Fe-Ni-based alloy of the present invention is characterized in that the number of MnS or the number of etched holes can be obtained by performing hot rolling and recrystallization annealing under normal conditions. The usual conditions here are: ΦHot rolling: Hot rolling is performed at a temperature below 1200 ° C, and no special quenching treatment is required after hot rolling (except for the case of water spray cooling, etc.) ② Recrystallization annealing: using a continuous annealing furnace The maximum temperature of the material in the heating furnace should not exceed 1100 ° C. On the other hand, from the viewpoints other than the number of MnS, the manufacturing conditions of the Fe-Ni-based alloy of the present invention are subject to the following restrictions. ① Cold rolling workability a) Rolling workability before final recrystallization annealing: It is preferably set in the range of 50 to 85%. If it exceeds 85%, the (200) aggregate structure will develop significantly, and the true roundness of the etched holes will be reduced. On the other hand, if it is less than 50%, the development degree of the (200) aggregate structure of the product is too low, and the etching rate becomes low. The rolling processing degree (R) here is defined by the formula of R (%) = (t〇- t) / t〇X 100 when the thickness before rolling is t0 and the thickness after rolling is t. . b) Final calendering degree: It is preferably set in the range of 10 to 40%. If it exceeds 16 paper sizes, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable. ----------- · Installation --------- Order ----- --- Line · (Please read the precautions on the back before filling in this page) 593692 Printed clothing A7 B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (峥) 40%, the rolling collection organization will develop extremely, and Reduce the etching speed. On the other hand, if it is less than 10%, the unrecrystallized structure is left in the annealing immediately before the press working, and the press formability is lowered. ② Recrystallization annealing: In order to prevent oxidation of the surface of the material, the inside of the heating furnace must be filled with hydrogen, an inert gas containing hydrogen, and the like. Still more preferably, the average diameter of the recrystallized grains after annealing is adjusted to 5 to 30 / zm. If the crystal grain size after the final annealing exceeds 30 // m, the wall surface of the perforated hole after etching and perforation will become rough, and the problem of slow etching rate will occur. In addition, when the grain size of the intermediate annealing exceeds 30 // m, the structure after the final annealing becomes non-uniform (a state in which large crystal grains and small crystal grains are mixed), and the hole wall of the through hole becomes rough and etched at the same time. The speed becomes uneven. On the other hand, if the crystal particle diameter is smaller than 5 // m, it becomes difficult to control the crystal particle diameter in the material to be uniform, and problems such as the subsequent deterioration of cold milk processability may occur. Thereby, a material for an Fe-Ni-based alloy shadow mask containing 1500 / mm2 or more MnS inclusions having a diameter of 50 to 100 nm can be obtained. This material can be used to easily evaluate the frequency of occurrence of etching holes, that is, the material After the rolled surface is mirror-polished and immersed in a 3% nitric acid-ethanol solution at 20 ° C for 30 seconds, the etched holes with a diameter of 0.5 // m to 10 // m will be at a frequency of more than 2000 / mm2 To appear. This material can form an electron wire transmission hole with an improved diameter deviation of the opening portion caused by the abnormal hole, and provides a material for a shadow mask having a uniform hole diameter in the electron wire transmission hole formed by the etching process. [Examples] Next, the present invention will be described more specifically with reference to examples and comparative examples. 17 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----------- installation -------- ^ order -------- -(Please read the precautions on the back before filling this page) 593692 A7 B7 V. Description of the invention (A), for the surface with holes with a diameter of 80 // m, measure the diameter of 100 holes (take the maximum of each hole) Diameter 値). Table 1 shows the concentrations of Ni, S, Mn, Cu, Ca, and Mg for each material, plus the concentrations of typical impurities (associated elements). In addition, Table 2 shows the frequency of etched holes having a diameter of 0.5 to 10 // m after being immersed in a nitric acid-ethanol solution, the number of inclusions having a length exceeding 10 // m, and the diameter of the electron beam transmission hole. The measurement results of the diameter of the perforation hole are classified into those with a diameter of less than 78 // m, 78 ~ 82 // m, and more than 82 # m, and the number of each type is displayed (the total number of measurements is 100) . ----------- install --------: order --------- line (please read the precautions on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by employee consumer cooperatives 19 This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 public love) 593692 A7 _B7 V. Description of invention () [Table 1] Printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic AffairsΊ No. ΓΠΘ55% half position ΓΤ1Θ55 ppm T * Ni Μηs Cu Ga Mg Si Al C 0 PN Cr 1 35.6 0.41 16 28 3 1 85 2 27 50 18 4 96 0.12 2 37.0 0.32 18 130 < 1 < 1 320 87 16 18 49 14 120 0.00 3 37.20 0.40 17 180 1 7 93 55 14 44 45 20 260 0.32 4 35.9 0.24 15 230 2 3 210 120 34 41 .29 n 120 0.18 5 36.7 0.44 15 280 4 2 65 7 26 30 23 14 120 0.1 S 6 35.3 0.33 20 20 2 < 1 340 150 20 30 18 16 250 0.05 7 36.2 028 22 32 7 5 77 5 25 34 24 M 220 0.38 8 34.9 0.2S 24 75 2 1 49 4 45 40 9 5 74 0.09 9 36.3 0.28 23 150 12 12 78 6 15 31 29 15 210 0.80 10 36,1 0.25 21 200 3 5 55 2 35 39 8 5 95 0.28 11 35.8 0.21 22 220 7 < 1 Θ7 5 23 32 13 S 78 0.18 12 36.0 0.20 22 270 10 3 84 8 38 3 $ 22 8 79 0.38 13 34,5 0.24 20 410 < 1 7 63 3 45 42 19 5 88 0.29 14 36.2 0,2 $ 26 43 5 1 43 10 $ 3 37 9 n 85 0.17 15 35.2 0.26 2t 120 7 12 150 340 IS, 33 30 20 180 0.68 16 35, $ 0.42 25 «0 10 < 1 83 250 16 43 22 23 54 0.25 17 36.2 0.31 28 310 2 72 310 U 29 35 n 95 0.38 18 35.3 0.30 29 3S0 < 1 < 1 270 250 14 24 18 15 150 0.00 19 36,3 0.33 26 63 3 5 70 5 26 29 25 4 103 0.28 20 35.7 0.2a 32 39 1 5 270 200 8. 39 36 3 240 0.23 21 36.5 .0.27 _ 30. SO < 1 6 50 3 22 4S 10 7 74 0.25 22 35.9 0.28 33 61 1 < 1 77 6 35 37 12 6 90 0.03 23 36.1 0.21 31 98 12 < 1 80 260 12 19 49 10 100 0.30 24 34.8 0, 36 33 190 4 5 210 140 23 31 27 18 270 0.35 25 35.9 0.33 35 240 12 6 200 190 30 17 32 10 180 O.SS 26 35.1 0.43 37 v〇7 1 310 320 27 21 33 19 230 0.22 27 35.2 0.26 '38 310 14 14 190 190 14 50 22 8 68 0.93 28 36.7 Q. 29 33 250 8 2 • 250 180 23 31 48 6 130 0.28 29 37.0 0.30 39; 460 11 < I 51 150 33 35 18 40 160 0.28 30 35.8 0.41 12 260 1 3 240 290 37 45 38 6 240 0.15 31 35.0 0.29 43 360 3 5 370 220 44 28 22 18 230 0.28 32 36.2 0.14 25 83 < 1 < 1 310 310 11 52 24 23 57 0.00 33 35.7 0.28 17 1 $ 4 2 300 270 18 36) 7 22 310 0.18 34 36.0 0.25 35 < 1 < 1 2 1070 190 27 42 43 10 150 0.08 35 37.1 0.40 17 550 2 6 103 52 18 49 38 W 260 0.30 36 35.1 0.22 25 no 24 21 310 250 23 55 48 20 69 1.48 ^ T = C ppm Cj] / 40 + [ppm] / 20 (Please read the note on the back first? Please fill in this page for more details) Packing ----- Order -------- · This paper size is applicable to China National Standard (CNS) A4 (210 χ 297 mm) Printed by the Employees' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs System 593692 Α7 Β7 V. Description of the invention ((?) Samples No. · 1 to 29 are examples satisfying the requirements of the present invention, and sample Nos. 30 to 36 are comparative examples. Samples No. 1 to 29 of the present invention are due to the diameter The number of etched holes of 0 · 5 ～ is 2000 / mm2, so the opening diameter of the perforated hole after the touch processing does not cause deviation, and it shows uniform etching perforation. In addition, the length of inclusions exceeding 0.5 is 0.5 No more than / mm2, so there is no abnormality caused by the shape of the pores of the coarse inclusions. On the other hand, because the S concentration in the sample No. · 30 does not reach 15 mass ppm, the Mn in the sample No. · 32 does not reach 0.2. mass%, the concentration of Ca and Mg in sample No. 36 is too high to become [ppm Ca] / 40 + [ppm Mg] / 24> 1, so the number of etched holes with a diameter of 0.5 to 10 // m will be small At 2000 / mm2, and NO.32 with a small Mη content, cracks will be generated at the edges of the material during hot rolling. After cutting, it is processed to a thickness of 0.1 mm. In addition, No. 36 with a high Ca and Mg concentration will increase the number of inclusions with a length exceeding 10 // m. Since the S concentration in the sample No. 31 exceeds 40 ppm, the length exceeds 10 Inclusions of # ηι will appear at a frequency of more than 0.5 / mm2. Samples No. 33 and 34 are examples where the Cu concentration is less than 20 mass ppm, and the S concentration in No 33 is lower than No. 34. The S concentration is lower No.33, the number of etched holes with a diameter of 0.5 to 10 # m is less than 2000 / mm2. In addition, the number of inclusions with a 超过 degree exceeding 10 // m falls within the scope of the present invention, but the number is It is slightly more than 0.4 / mm2. On the other hand, the number of inclusions with a high S concentration of No.34 exceeding 10 / zm exceeds 0.5 / mm2. In addition, etched holes with a diameter of 0.5 to 10 // m The number, although entering the provisions of the present invention 22 丨 丨 — i 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 Order -------- (Please read the precautions on the back before filling this page) This paper Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 593692 A7 ___B7__ V. Within the scope of the invention description (/), but Considering the concentration of S, the number is a little too small. Although the Cu concentration of the sample No. 35 exceeds 500 mass ppm, compared with No. 3 with the same Cu concentration of 180 mass ppm, the diameter is 0.5 to 10 // m. The number of etched holes is not much larger. The Νο · 35 has cracks during hot rolling. Therefore, the cracks are machined to a thickness of 0.1 mmrn after being milled. In the comparative example, the number of etched holes with a diameter of 0.5 to 10 // m is less than 2000 / mm 2 of No. 30, 32, and 33. After the etching process, transmission beyond the range of 80 ± 2 // m is observed. hole. It was observed that more inclusions with a length exceeding 10 / zm were than 0.5 / mm2. In Nos. 31 and 34, perforated holes with defective edges are formed after the etching process. In addition, such abnormally shaped holes are not subject to diameter measurement. [Effects of the Invention] According to the present invention, an Fe-Ni-based alloy material having excellent uniformity of the transmission aperture diameter of the electron wire etched and punched out can be provided at a low cost without requiring special heat treatment. The present invention is also effective as long as it is a mask material for perforating an electron wire through hole by etching, and does not need to be press-formed after the etching process, and is kept flat by applying tension. In addition, the shape of the transmission hole of the electron wire does not necessarily have to be perfectly circular, and the present invention is also effective for a shadow mask that has a through hole such as an ellipse or a short grid. The present invention can also be applied to applications other than a shadow mask in which a lead frame or the like is subjected to fine etching. [Brief description of the drawing] Figure 1 shows the implementation of the perforation of the through-holes of electronic wires by etching. 23 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first) Please fill in this page for more information) -------- Order ---------. 593692 A7 _B7 V. The "normal hole" of the invention description (> 丨) and the composition related to the invention SEM image of an example of "abnormal pores" due to pore diameter deviation. Fig. 2 is an explanatory view showing a case where the shape of the MnS precipitate is elliptical, rod-shaped, linear, etc., and the short-axis diameter L1 and the long-axis diameter L2 representing the diameter of the MnS precipitate. Fig. 3 is a graph showing the correlation between etched holes generated when a Fe-Ni-based alloy is immersed in a 3% nitric acid-ethanol solution and the frequency of MnS inclusions measured by a transmission electron microscope. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 24 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)