200304953 玖、發明說明 【發明所屬之技術領域】 本發明係關於使用於布朗管之蔭罩（S h a d 〇 w m a s k ) 等之F e - N i系低熱膨脹合金薄板及其製造方法。 【先前技術】 布朗管之蔭罩，係對素材的合金薄板，進行蝕刻加工 以穿孔作成用以使電子束通過的孔，並進行衝壓前退火 以使成形容易，依布朗管的形狀進行成形而製作後，再 行組裝到布朗管中。 向來，作爲布朗管的蔭罩的素材，習知者爲F e - N i系 合金薄板。此合金，由於熱膨脹係數較軟鋼低，不易因 於發生拱起（doming)(亦即，經由電子束而加熱、熱膨 脹所產生的蔭罩的變形）、致通過蔭罩的孔之電子束未 打到螢光面的既定位置而產生色偏移之現象。實際上， 本發明者等，經確認得知：F e - N i系合金薄板於2 0〜1 0 0 t之平均熱膨脹係數只要是 1 . 2 X 1 6 / t以下，則不 易發生拱起的情形，再者，若爲0 . 9 X 1 0 _ 6 / °C以下， 則幾乎不會發生拱起的情形。 然而，習知的F e - N i系合金薄板，因於布朗管移送之 時的振動等之衝擊而容易發生蔭罩面的凹陷與其因於磁 遮蔽性不充分所導致之電子束的偏移等之顏色偏差的問 題。因此，衝壓前軟化退火後之耐衝擊性的改善與磁特 性的提高受到殷切的企求。 又，本發明者預先就衝壓前軟化退火後的耐衝極性與 312/發明說明書(補件)/92-06/92106480 200304953 磁特性加以檢討之下，得知：衝壓前軟化退火後的Q . 2 % 耐力若爲2 7 0 Μ P a以上，於蔭罩成形後的衝擊試驗中凹 陷的發生率會格外地小，以及 ◦ · 2 %耐力若超過 ：3 2 0 Μ P a，貝IJ蔭罩的成形本身會變得困難。又，最大透磁 係數只要爲8 0 0 0以上，則蝕刻加工後的磁遮蔽性試驗 中之侵入磁束會格外地小。 爲了謀求耐衝擊性的改善（強度的改善），於日本專利 第3 1 5 0 8 3 1號公報中，揭示出對F e - N i系合金添加Nb 使楊氏係數提高之低熱膨脹合金薄板。具體而言，係由 ^ ^ C:0. 003-0. 02% 、 N : 0 . 0 1 % ΙίΑ Τ 、200304953 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a F e-Ni-based low thermal expansion alloy sheet and a method for manufacturing the same, which are used in a brown tube shadow mask (S h a d o w m a s k). [Prior art] The shadow mask of the brown tube is an alloy sheet of material, which is etched to make holes for the electron beam to pass through, and annealed before pressing to make it easy to form. According to the shape of the brown tube, After fabrication, they are assembled into a Brown tube. Conventionally, as a material for a shadow mask of a Brown tube, a known person is a F e-Ni-based alloy thin plate. Since this alloy has a lower thermal expansion coefficient than soft steel, it is not easy to cause doming (that is, deformation of the shadow mask caused by heating and thermal expansion via an electron beam), and the electron beam passing through the holes of the shadow mask is not hit. The color shift occurs when the light reaches a predetermined position on the fluorescent surface. In fact, the present inventors confirmed that the average thermal expansion coefficient of the F e-Ni alloy sheet from 20 to 100 t is less than 1.2 X 1 6 / t, so that arching is unlikely to occur. In addition, if it is below 0.9 X 1 0 _ 6 / ° C, arching will hardly occur. However, the conventional F e-N i series alloy sheet is prone to the depression of the shadow mask surface due to the shock of vibration and the like during the transfer of the Brown tube, and the deviation of the electron beam due to insufficient magnetic shielding properties. The problem of color deviation. Therefore, improvement of impact resistance and improvement of magnetic properties after soft annealing before pressing are earnestly sought. In addition, the inventors reviewed the impact resistance before softening and annealing before stamping and the magnetic properties of 312 / Invention Specification (Supplements) / 92-06 / 92106480 200304953 under review, and learned that Q after softening and annealing before stamping. If the 2% endurance is more than 270 MPa, the incidence of sags in the impact test after the shadow mask is formed will be extremely small, and if the 2% endurance exceeds: 320 MPa, the IJ shade Forming the hood itself becomes difficult. In addition, as long as the maximum magnetic permeability coefficient is 8000 or more, the intruding magnetic flux in the magnetic shielding property test after the etching process is extremely small. In order to improve the impact resistance (improvement of strength), Japanese Patent No. 3 15 0 8 31 discloses a low thermal expansion alloy sheet in which Nb is added to the F e-Ni alloy to increase the Young's coefficient. . Specifically, ^ ^ C: 0. 003-0. 02%, N: 0.01% ΙίΑ Τ,
Si:0.01 〜2.0% 、 Μη :0.01 〜3.0% 、 Ni:25 〜45% 、Si: 0.01 to 2.0%, Μη: 0.01 to 3.0%, Ni: 25 to 45%,
Cr:1.0% 以下、Nb:0.01 〜 1.0%、 B : 0 . 0 1 % "f 、 S:0.Q1%以下，其餘爲 Fe及不可避免的雜質所構成， 且爲（C + N)S - 0.008Nb + 0.023 之 Fe-Ni 系合金薄板。 另一方面，爲了提高磁特性，於日本專利特開平 1 0 - 1 9 9 7 1 9號公報中，揭示出將 N減低並添加 B之 F e - N i系合金薄板。其詳細係爲：將N定爲5 Q p p m以下， 並以使B成爲5〜50ppm的範圍內、使B [原子％]/N [原 子％]成爲0.8以上的方式添加B，如此作成的30~85%Ni 的F e - N i系合金薄板。該公報中指出，此合金薄板，若 使A1作成爲40〇ppm以下、使0作成爲50ppm以下， 則可得到優異的磁特性，且Cr、Mn、Cu、S i等之添加 於磁特性的改善上是有效的。 然而，日本專利第3 1 5 Q 8 3 1號公報中所記述的合金薄 312/發明說明書(補件)/92-06/92106480 200304953 板，雖因於高楊氏係數而可提高蔭罩的剛性，卻無法得 到安定的高透磁係數，於蔭罩的磁遮蔽性並不充分。又， 熱膨脹係數爲1 . 5 1〜2 · 3 2 X 1 6 / °C，無法充分抑制拱 起的情形。 又，如日本專利第3 1 5.0 8 3 1號公報所記述般的Nb添 加型的F e - N i合金，由於再結晶及其後的結晶粒生長不 易進行，故以使用此種合金的薄板用於蔭罩的情況，必 須進行8 5 Q °C以上的衝壓前退火。然而，就製造成本的 觀點考量，以在未滿8 5 0 °C的溫度域亦可軟質化的材料 爲佳。 曰本專利特開平1 0 - 1 9 9 7 1 9號公報中記述的合金薄 板，其N i的成分範圍寬廣，而無法安定地得到符合所 要目的低熱膨脹係數。 【發明內容】 本發明之目的在於提供：可得到充分低的熱膨脹係數 且在8 5 0 °C未滿的溫度下進行衝壓前軟化退火，於蔭罩 成形後可得到優異的耐衝擊性與磁特性之 F e - N i系的 低熱膨脹合金薄板及其製造方法。 此目的，可藉由實質上以質量％計爲 N i : 3 5〜3 7 %、 C: 0.02%以下、Si:0.3%lU"f ' Mn：0.6%]^T ' Ρ ： 0 . 0 1 % 以下、S:0.005%J^T 、 N : 0 . 0 1 % JiA T 、 Α1:0.1% 以下、 Cr：0.08%I^~F 、 Nb:0.05 〜1%、 V:0.01 〜1%、及其餘 分爲F e所構成，且（N b + V ) g 1 · 0 %的低熱膨脹合金薄板 來達成。 312/發明說明書(補件)/92-06/92106480 200304953 此等低熱膨脹合金薄板，可藉由具有下述步驟之低熱 膨脹合金薄板的製造方法而實現。所述步驟爲：對具有 上述成分之熱軋製板至少反覆進行1次以上之冷軋製與 再結晶退火的步驟，與於最終再結晶退火之後，再以1 5 % 以上的冷軋延率進行最終冷軋製的步驟；與於最終冷軋 製後，於8 0 ot以下進行去除變形退火之步驟。 【實施方式】 本發明者等，就F e - N i系合金薄板的衝壓前軟化退火 後的耐衝擊性與磁特性及衝壓前軟化退火時的軟化特性 做了檢討。其結果得知：經由Nb與V之複合添加可改 善耐衝擊性與磁特性，進而，經由添加B與S b可改善 磁特性，蔭罩成形後的衝擊試驗之凹陷的發生率相當依 存於衝壓前軟化退火後之 Q . 2 %耐力等。茲就其其詳細 情形說明如下： (1 ·成分） N i : N i爲欲得到低熱膨脹特性之必要的元素。若未滿 3 5 %或超過3 7 %則熱膨脹係數無法充分的低，故將N i定 爲 3 5〜3 7 % ° C :由於 C會使蝕刻性與低熱膨脹性變差，故定爲 0.02%以下，而以0.005%以下爲佳，尤以0.003%未滿 更佳。 S i :由於 S i會使低熱膨脹性與蔭罩的黑化處理性變 差，故定爲0.3%以下，而以0.09%以下更佳。 Μ η :由於Μ η會使低熱膨脹性變差，故定爲◦. 6 %以下， 312/發明說明書(補件)/92-06/92106480 200304953 而以◦· 1 %以下爲佳。又，由於Μ η爲合金的脫氧 工性方面之有效元素，故以〇·01%以上爲佳。 Ρ :由於ρ會使蝕刻性變差，故定爲ο . ο 1 %以Τ S :由於S作爲硫化物析出會使合金的熱加工性 故定爲〇 · 0 0 s %以下。 Ν:Ν若與Al、Nb、ν等元素一起含有，則會作 物析出使而使蝕刻性變差，並且使合金的熱加 差’故定爲〇·〇1%以下。 A 1 : A 1作舄氮化物、氧化物等之析出物而析出 特I主與低熱‘脹性變差，並使合金的熱加工性變 疋爲〇·1%以下，而以Q.Q4%以下爲佳。又，A1 熔製時具有減低合金中的介在物的效果，故 ◦ . 0 Q 5 %以上爲佳。 C r : C r作爲碳化物、氮化物析出會使磁特性變 定爲Q . 0 8 %以下。又，C r亦會使低熱膨脹性變差 儘可能降低爲佳。Cr: 1.0% or less, Nb: 0.01 to 1.0%, B: 0. 0 1% " f, S: 0.Q1% or less, the rest is composed of Fe and unavoidable impurities, and is (C + N) S-0.008Nb + 0.023 Fe-Ni based alloy sheet. On the other hand, in order to improve the magnetic characteristics, Japanese Patent Laid-Open No. 10-1 9 9 7 1 9 discloses a F e-Ni-based alloy sheet in which N is reduced and B is added. The details are as follows: N is set to 5 Q ppm or less, B is added in a range of 5 to 50 ppm, and B [atomic%] / N [atomic%] is 0.8 or more, and 30 is thus prepared. ~ 85% Ni F e-N i series alloy sheet. The publication states that if this alloy sheet is made A1 to be 40 ppm or less and 0 is made to 50 ppm or less, excellent magnetic properties can be obtained, and Cr, Mn, Cu, Si, and the like are added to the magnetic properties. Improvement is effective. However, the alloy thin 312 / Invention Specification (Supplement) / 92-06 / 92106480 200304953 described in Japanese Patent No. 3 1 5 Q 8 3 1 can improve the shadow mask due to its high Young's coefficient. It is rigid, but cannot obtain a stable high magnetic permeability coefficient, and the magnetic shielding property of the shadow mask is insufficient. In addition, the thermal expansion coefficient was 1.5 1 to 2 · 3 2 X 1 6 / ° C, and it was impossible to sufficiently suppress arching. In addition, as described in Japanese Patent No. 3 1 5.0 8 31, an Nb-added Fe-Ni alloy as described in Japanese Patent No. 3 1 5.0 8 31 is not easy to undergo recrystallization and subsequent crystal grain growth. Therefore, a thin plate using such an alloy is used. In the case of shadow masks, it is necessary to perform annealing before stamping above 8 5 Q ° C. However, from the viewpoint of manufacturing cost, a material that can be softened in a temperature range of less than 850 ° C is preferred. The alloy thin plate described in Japanese Patent Laid-Open No. 10-1 9 9 7 1 9 has a wide range of Ni components, and cannot stably obtain a low thermal expansion coefficient that meets the intended purpose. [Summary of the Invention] The object of the present invention is to provide: a sufficiently low thermal expansion coefficient can be obtained and softened and annealed before pressing at a temperature of less than 850 ° C, and excellent impact resistance and magnetic properties can be obtained after the shadow mask is formed. F e-Ni-based low thermal expansion alloy sheet with special characteristics and its manufacturing method. For this purpose, Ni: 35 to 37%, C: 0.02% or less, Si: 0.3% lU " f'Mn: 0.6%] ^ T'P: 0. 1% or less, S: 0.005% J ^ T, N: 0.01% JiA T, Α1: 0.1% or less, Cr: 0.08% I ^ ~ F, Nb: 0.05 ~ 1%, V: 0.01 ~ 1% , And the rest are divided into F e and (N b + V) g 1 · 0% low thermal expansion alloy sheet. 312 / Description of the Invention (Supplement) / 92-06 / 92106480 200304953 These low thermal expansion alloy sheets can be realized by a method for manufacturing a low thermal expansion alloy sheet having the following steps. The steps are: a step of cold rolling and recrystallization annealing of the hot rolled sheet having the above composition at least once, and after the final recrystallization annealing, a cold rolling reduction of 15% or more Perform the final cold rolling step; and after the final cold rolling, perform the step of removing the deformation annealing below 80 ot. [Embodiment] The present inventors reviewed the impact resistance and magnetic characteristics after softening annealing before pressing and softening characteristics of softening annealing before pressing for F e-Ni alloy sheet. As a result, it was learned that the combined addition of Nb and V can improve the impact resistance and magnetic properties, and further that the addition of B and S b can improve the magnetic properties. The incidence of dents in the impact test after the shadow mask formation is quite dependent on stamping. Q. 2% endurance after pre-softening annealing. The details are described below: (1. Composition) N i: N i is an element necessary to obtain low thermal expansion characteristics. If it is less than 35% or more than 37%, the thermal expansion coefficient cannot be sufficiently low, so Ni is set to 35 to 37% ° C: Since C deteriorates the etchability and low thermal expansion, it is determined as 0.02% or less, preferably 0.005% or less, and more preferably 0.003% or less. S i: Since S i deteriorates the low thermal expansion property and the blackening property of the shadow mask, it is set to 0.3% or less, and more preferably 0.09% or less. Μ η: Since Μ η deteriorates low thermal expansion, it is determined to be 6% or less, 312 / Invention Specification (Supplement) / 92-06 / 92106480 200304953, and preferably ≦ 1% or less. In addition, since M η is an effective element for deoxidizing workability of the alloy, it is preferably 0.01% or more. Ρ: Because ρ deteriorates the etching properties, it is determined as ο. Ο 1% with T S: Because S precipitates as a sulfide, the hot workability of the alloy is set to 0. 0 0 s% or less. If N: N is contained together with elements such as Al, Nb, and ν, it will be precipitated to deteriorate the etchability, and the thermal difference of the alloy 'is therefore set to 0.001% or less. A 1: A 1 is precipitated as hafnium nitrides, oxides, etc. and precipitates special I main and low thermal expansion properties, and makes the hot workability of the alloy less than 0.1%, and Q.Q4 % Is preferred. In addition, A1 has the effect of reducing the intervening substances in the alloy during melting, so it is better that 0 Q 5% or more. C r: C r is precipitated as carbides and nitrides, and the magnetic properties are changed to Q. 0.8% or less. In addition, C r also deteriorates the low thermal expansion property as much as possible.
Nb:Nb爲本發明中最重要的元素，與次要的v 添加’則可改善衝壓前軟化退火後的耐衝擊性 性。爲此目的，N b必須爲0 5 %以上，惟，多量 會使低熱膨脹性變差，故定爲1 %以下，而以〇 · 爲佳。 V :如上述般，與Nb作複合添加可改善衝壓前 火後的耐衝擊性與磁特性。因此，V必須有0 · 0 1 多量的添加，會使低熱膨脹性變差，故定爲1 %以 312/發明說明書(補件)/92-06/92106480 與熱加 :變差， 爲氮化 工性變 會使磁 差，故 由於在 以疋爲 差，故 ，故以 作複合 與磁特 的添加 6 %以下 軟化退 %，惟， 下，而 10 200304953 以0.6%以下爲佳。 再者，Nb及V若多量複合添加，則衝壓前軟 的0 · 2 %耐力會超過3 2 0 Μ P a致衝壓成形困難， 必須定爲1 . 〇 %以下，而以〇 . 6 %以下爲佳。 又，其餘部分實質上爲F e。亦即，在不妨礙 效果的範圍內亦可含有其他的元素。 如此般，藉由實質上由Ni:35〜37%、C:0.' Si：0.3%]^T>Mn：0.6%J^T'P：〇.〇l%J^T'i DX T 、 Ν ： 0 . 0 1 % JiA Τ' > A 1 : 0 . 1 % Τ 、 C r : 0 . ι Nb:〇.05~l%、V:0.01~l%、 ：¾¾ 倉余音 β# 胃 F € 且（N b + V ) g 1 · 0 %，可得到不易發生拱起的情 X 1 0 _ 6 / t：以下的熱膨脹係數。再者，藉 C:0.005%J^ T 、 Si:0.09%]^ T 、 Μ η : 0 . 0 ] Α1··〇·0〇5 〜0.04%、 Nb :0.05 〜0.6%、 V ： 0 . 0 且（Nb + V)S0.6%，可得到幾乎不會發生拱起 〇· 9 X 1 0 — 6 / °C以下的熱膨脹係數。 於上述的成分中，進一步使其含有具有使結 化之作用的 B與 Sb中之至少 1種，於 B 0 . 0 Q 0 5 %以上，於S b的情況爲0 . 0 0 1 5 %以上 壓前軟化退火後可得到更大的最大透磁係數。 了不使蔭罩的黑化處理性變差，必須將B定焉 以下，將 Sb定爲 0.010%以下，且將（2B- 〇.〇01〜 0.01〇％c (2 ·製法） 312/發明說明書(補件)/92-06/92106480 :化退火後 故（Nb + V) :本發明之 〇2 %以下、 3:0.0 0 5 % 3 8 %以下、 >所構成， 形之 1 . 2 由作成爲 〜0 · 1 % 、 1-0.6%， 的情形之 晶粒均一 的情況爲 ，則於衝 此時，爲 0.0 0 3 % Sb )定爲 11 200304953 本發明ΐ低熱膨張合金薄板，可藉由具有下述步驟 ζ製造方7去製造。所述步驟爲：對具有上述成分之熱 軋製板至少反覆進行1次以卜> 人以上之冷軋製與再結晶退火的 步驟、，與_再結晶退火之後，再以15%以上的冷乳 延率進彳了最終冷軋製的井，·跑 一 欢打步騄，與於最終冷軋製後，於8 〇 〇 。(：以下進行去除變形退火夕井_ ^火之步驟。將最終的冷軋製的冷 軋延率定爲1 5 %以上，將丰除 將去除變形退火的溫度定爲8〇〇 °C以下的理由在於：在苒彳士曰B s t 两日日及晶粒生長不易進行的Nb 添加型的Fe，系合金中’於衝壓前軟化退火中，不須 施行85 (TC以上的高溫退火即可使其軟化之故。 粟整上述者#發明之低熱膨脹合金薄板的製造方法 的流程成爲：「熱軋製板…冷車1製+再結謝）χη(η $ 1 )>最終冷乳製·>去除變形退火」。 熱軋製板，係將上述成分的合金進行熔製，經由造塊 法或連續禱造法作成爲厚板之後，加熱至900t以上進 行熱軋製而可製造。於造塊法中，對鑄造鋼錠於必要時 在1 ο ο 〇 °C以上施行均質化熱處理後，進行分塊軋製， 作成爲厚板。又，於連續鑄造法所製造的厚板，於必要 時可在1 0 0 Q °c以上施行均質化熱處理後進行熱軋製。 熱軋製’可在例如8 5 0〜9 5 0 °c的終軋溫度、6 5 0〜8 0 0。〇 的捲繞溫度下進行。 又，如此製造成的熱軋製板，於經由酸洗或硏磨將表 面的積垢除去後，如上述般反覆進行至少i次的冷軋製 與再結晶退火後，可作成板厚0 · 〇 5〜0 · 5 m m程度的薄板。 12 312/發明說明書(補件)/92·06/92106480 200304953 (實施例1 ) 將表1所示之成分的鋼A ~ r以電爐熔製，造塊後，進 行1 2 0 Q °C以上的均熱處理’施行分塊軋製作成厚板。 鋼A~G皆爲本發明例，爲Nb、V、B、Sb等的成分經適 當地調整的鋼。此中’鋼A ~ C及E爲N ^ - v添加鋼’鋼 D爲N b - V - B添加鋼’鋼F爲N b — V - S b添加鋼、鋼G爲 N b - V - B - S b添加鋼。另一方面’鋼P〜r皆爲比較例， 於鋼p中未添加有Nb、V的任一者，於鋼q中雖添加有 Nb卻未添加V，於鋼r中雖添加有Nb與V惟（Nb + V) 的量係超過1 . 〇 %。 然後，將厚板之表面全體進行硏磨後’加熱至1000 °C以上，於終乳溫度 850〜95QC、捲繞溫度 650~800 t下進行熱軋製，作成熱軋製捲片（C 〇 1 1 ) °然後’將熱 軋製捲片酸洗除去表面的積垢後’反覆進行2次冷軋延 率2 0 ~ S 0 %的冷軋製與7 5 0〜1 1 〇 0 °C的再結晶退火，之 後，以冷軋延率20〜25%進行最終冷乳製，於70(3〜800 °c下施行去除變形退火，製作成板厚◦ ·12 m m的薄板。 自此薄板捲片的寬方向中央部採取J1 s 5號拉伸試驗 片、磁特性評價用環狀試驗片、熱膨脹係數測定用試驗 片，作爲相當於衝壓前軟化退火之熱處理，係於A r環 境中進行800〜900 °C Xl5分鐘之均熱的熱處理’再進 行作爲蔭罩的耐衝擊性、磁特性、熱膨脹係數之評價。 拉伸試驗，係依據J I s z 2 2 4 1之拉伸試驗方法進行’ 求出0 · 2 %耐力。 13 312/發明說明書(補件)/92-06/92106480 200304953 磁特性評價，係依據j I s C 2 5 3 1進行，求出施加磁 場1 0 Ο e時的最大透磁係數。 熱膨脹係數測定，係用光干涉式熱膨脹測定裝置施 行，求出2 0〜1 0 0 °C下的平均熱膨脹係數。 結果示如表2。 又，圖1顯示衝壓前軟化退火後之〇 . 2 %耐力與最大 透磁係數的關係。於此圖中，於同一的鋼顯示有3個結 果，其爲由左起依序對應著衝壓前軟化退火溫度9 0 0、 8 5 0、8 0 0 °C 的結果。 由圖1，於本發明例之鋼A ~ G，得到2 7 0〜3 2 0 Μ P a的 〇 . 2 %耐力與8 0 0 0以上的最大透磁係數。而且，此等的 鋼，亦可滿足就強度-磁特性的均衡的觀點上之較佳的 關 ί系之 〇.2%PS + 6(// max/1000) ^ 340 ° 由表2，於鋼A〜G，可得到 1 · 2 X 1 0 _ 6 / °C以下之低 的熱膨脹係數，尤其是於Mn、Nb、V等較低的鋼A及 E〜G，可得到 0 . 9 X 1 0 _ 6 / °C以下之低的熱膨脹係數。 又，於N b、V之外亦添力□ B或S b的鋼D、F、G，則可 得到更大的最大透磁係數。 另一方面，於比較例之未添加N b、V的鋼p，其強度 與磁特性的均衡差，於任一的退火溫度中，〇 . 2 %耐力均 未達到作爲目標値之2 7 0 Μ P a。於僅添加N b的鋼q中， 與鋼P相比，強度-磁特性的均衡雖得到改善，惟，除 了 9 0 0 °C退火以外，最大透磁係數皆未達到8 0 0 0以上。 又，於（Nb + V)超過1.0%的鋼r，0.2%耐力，除了 900 14 312/發明說明書(補件)/92-06/92106480 200304953 T：退火以外，皆未能成爲3 2 0 Μ P a以下。於鋼q及r， 經由 900 °C退火，可得到 270〜320MPa的 0.2%耐力與 8 0 ◦◦以上的最大透磁係數，惟，9 0 ◦ °C退火，作爲衝壓 前軟化退火，於通常實行的溫度範圍之中是較高的，會 導致製造成本的顯著增高。 15 312/發明說明書(補件)/92-06/92106480 200304953 (％_») 備註 發明例 發明例 發明例 發明例 發明例 發明例 發明例 比較例 比較例 比較例 Λ 0} <0.0003 <0.0003 <0.0003 <0.0003 <0.0003 0.0024 0.0019 <0.0003 <0.0003 <0.0003 PQ <0.0002 <0.0002 <0.0002 0.002 1 <0.0002 <0.0002 0.0011 <0.0002 <0.0002 <0.0002 > .010 .015 .810 .431 .062 .058 .057 • 001 .001 .511 ο ο ο ο ο ο ο ο ο ο JQ S ο Γ0 〇 Η Ch Ο Η γΗ Ο Η Η Ο CM m ο γΗ ΓΟ ο γΗ m ο <0.001 Η ro ο ιη ο 1~1 < 0.030 0.022 0.034 0.031 0.031 0.029 0.028 0.027 0.031 0.029 0.0025 0.0038 0.0034 0.0044 0.0028 0.0029 0.0035 0.0019 — 0.003 9 0.004 1 OD 0.0007 0.0004 0.0004 0.0003 0.0006 0.0006 0.0007 0.0005 0.0008 0.0006 〇4 0.003 0.003 ι_ 0.003 0.003 0.003 0.002 0.002 0.001 0.004 0.003 Μη m ο 03 Ο 寸 ο γΗ η ο 寸 ο 寸 ο ο ΓΟ 寸 ο γΗ ο Ο ο ο ο ο ο ο ο ο •Η CO VD ο OJ Ο CN Ο 03 Ο 寸 ο 寸 ο ΓΟ Ο ΓΟ ο ΓΟ ο 寸 ο ο Ο Ο Ο ο ο ο ο ο ο υ 0.0042 0.0035 0.0029 0.0045 0.0041 0.0031 0.0033 0.0017 0.0044 0.0028 •Η 15 寸 if) m 00 VD ro LD νο ΓΟ Ρ0 KD m 00 LD ΓΟ \ΐ) Γ0 〇 Γ〇 (Μ VD ΓΟ ΓΜ VD ΓΟ γΗ m lag 癖 < PQ υ Q ω cn Ο Λ σ 91 08s2s/90-CN6/ff}}i)_s:CKis微/(Nle 200304953 表2 鋼 衝壓前軟化 退火溫度 (°C ) 0.2% 耐力 (MPa) 最大透磁 係數 (X1000) 平均熱膨脹 係數 (X10-6/ °〇 備註 A 800 300 8.9 - 發明例 850 295 9.5 0.8 900 290 11 . 0 0 . 9 B 800 318 8 . 2 - 發明例 850 314 8 . 7 1.1 900 308 10 . 4 1.2 C 800 284 9.8 - 發明例 850 281 10 . 3 1.2 900 275 11.5 1.1 D 800 284 11.8 - 發明例 850 279 13 . 3 1.0 900 274 14 . 4 1.1 E 800 304 9.8 - 發明例 850 298 10 . 9 0 . 9 900 292 11.6 0.9 F 800 305 10.4 - 發明例 850 300 11.5 0 . 9 900 295 12.0 0 . 9 G 800 304 11.8 - 發明例 850 299 12 . 3 0 . 9 900 294 12 . 9 0 . 9 P 800 26 7 8 . 3 - 比較例 850 264 9.8 1.1 900 259 11.9 1 . 0 q 800 301 6 . 2 - 比較例 850 294 7.8 0.9 900 289 8 . 9 0 . 9 r 800 327 8 . 6 - 比較例 850 321 9.8 0 . 9 900 314 11.5 0 . 9 加底線部分：目標範圍外 17 312/發明說明書(補件)/92-06/92106480 200304953 (實施例2 ) 使用表1中所不的鋼A及p的iff造鋼錠’以與實施例1 同樣的方法製造成板厚〇 · 1 2 m m的薄板。此時，如表3所 示般，係將最終冷軋製的冷軋延率與去除變形退火的溫 度，於鋼A係作成爲5組，於鋼P係作成爲3組而變化。 並對此薄板’進行與實施例1的場合之同樣的試驗。又’ 衝壓前軟化退火’係在A r環境下7 5 〇〜9 0 0 °C X 1 5分鐘 之均熱的條件下進行。 結果示如表3 ° 又，圖2係顯示衝壓前軟化退火溫度與〇 . 2 %耐力的關 係。 鋼A - 1 ~ A - 3，係將去除變形退火的溫度作成爲7 5 〇 °C， 改變最終冷軋製的冷軋延率而進行製造。於任一者的情 況’隨者衝壓則軟化退火溫度的上昇，〇 . 2 %耐力大幅降低 成爲32〇MPa以下。0·2%耐力爲32〇Mpa以下的退火溫 度’於本發明例的鋼A ~ 3爲8 〇 q它，相對於此，比較例的 鋼A - 2爲8 5 0 °C ，鋼 A - 1則爲9 〇 〇艺。由於通常衝壓前軟Nb: Nb is the most important element in the present invention, and the addition of the minor v 'can improve the impact resistance after soft annealing before pressing. For this purpose, N b must be greater than or equal to 0.5%. However, a large amount will degrade low thermal expansion, so it is set to 1% or less, and preferably 0 ·. V: As mentioned above, the compounded addition with Nb can improve the impact resistance and magnetic properties after the fire before pressing. Therefore, V must be added in a large amount of 0 · 0 1, which will deteriorate the low thermal expansion property, so it is set to 1%. 312 / Invention Specification (Supplement) / 92-06 / 92106480 and heat addition: worse, it is nitrogen. Chemical properties change will cause magnetic difference, so because of the difference between 疋, it is added as a composite and magnetic characteristics below 6% softening and regression, but below, and 10 200304953 is preferably 0.6% or less. In addition, if Nb and V are added in a large amount in combination, the soft 0.2% endurance before pressing will exceed 320 MPa, which will make stamping difficult, and it must be set to 1.0% or less, and 0.6% or less. Better. The remaining portion is substantially F e. That is, other elements may be contained as long as the effect is not hindered. In this way, by essentially making Ni: 35 ~ 37%, C: 0. 'Si: 0.3%] ^ T > Mn: 0.6% J ^ T'P: 0.01% J ^ T'i DX T , Ν: 0.01% JiA Τ '> A 1: 0.1% Τ, C r: 0. Ι Nb: 0.05 to 1%, V: 0.01 to 1%,: ¾¾ Warehouse residual tone β # Stomach F € and (N b + V) g 1 · 0%, it is possible to obtain a situation where arching is unlikely to occur X 1 0 _ 6 / t: the following thermal expansion coefficient. Furthermore, C: 0.005% J ^ T, Si: 0.09%] ^ T, Mη: 0.0] Α1 ·· 〇 · 0〇5 ~ 0.04%, Nb: 0.05 ~ 0.6%, V: 0. 0 and (Nb + V) S 0.6%, a thermal expansion coefficient of 0.9 X 1 0-6 / ° C or less can be obtained. Among the above components, it is further contained at least one of B and Sb, which has the effect of forming a structure, in B 0. 0 Q 0 5% or more, and in the case of S b, 0. 0 0 1 5% After the softening and annealing before pressing, a larger maximum magnetic permeability coefficient can be obtained. In order not to deteriorate the blackening properties of the shadow mask, it is necessary to set B or less, Sb to 0.010% or less, and (2B- 〇01.01 ~ 0.01〇% c) (2. Production method) 312 / Invention Instruction (Supplement) / 92-06 / 92106480: After chemical annealing (Nb + V): The present invention is composed of 0.02% or less, 3: 0.0 05% to 8% or less, > 2 From the case of ~ 0.1% and 1-0.6%, when the grains are uniform, then at this time, 0.03% Sb) is set to 11 200304953 The low thermal expansion alloy sheet of the present invention, It can be manufactured by having the following steps ζ manufacturing method 7. The steps are: a step of cold rolling and recrystallization annealing of a hot-rolled sheet having the above-mentioned composition at least once, and after annealing with recrystallization, the temperature is further increased by 15% or more. The cold-elongation ratio entered the final cold-rolled well, and ran for a while, and after the final cold-rolling, at 800. (: The following steps are performed to remove the deformation annealing annealing __fire. The final cold rolling cold rolling elongation is set to 15% or more, and the temperature of the deformation removal annealing is set to 800 ° C or less. The reason is that Nb-added Fe, which is not easy to carry out grain growth for two days at the time of Bst, and the grain growth, is not required to be subjected to high-temperature annealing at 85 (TC or higher) in the softening annealing before stamping in the alloy. The reason for the softening. The process of the method for manufacturing the low thermal expansion alloy sheet invented by the above #invention is: "Hot-rolled sheet ... made by cold car 1 + re-examination) χη (η $ 1) > final cold milk Manufacturing > Deformation Annealing. "Hot rolled sheet is made by melting the alloy with the above composition, making it into a thick sheet through the agglomeration method or continuous prayer method, and heating it to 900t or more for hot rolling to produce it. In the agglomeration method, the cast steel ingot is subjected to a homogenization heat treatment at a temperature of 1 ο ο ° C or higher as necessary, and then subjected to block rolling to form a thick plate. In addition, the thick plate manufactured by the continuous casting method, If necessary, heat can be applied after homogenizing heat treatment above 100 Q ° c Hot rolling can be performed, for example, at a final rolling temperature of 8500 to 95 ° C and a winding temperature of 6500 to 80.0 °. Furthermore, the hot-rolled sheet manufactured in this way, After removing the scale on the surface by pickling or honing, and then repeating the cold rolling and recrystallization annealing at least i times as described above, a thin plate having a thickness of about 0. 005 to 0. 5 mm can be produced. 12 312 / Invention Specification (Supplement) / 92 · 06/92106480 200304953 (Example 1) Steels A to r with the composition shown in Table 1 were melted in an electric furnace, and after agglomeration, they were subjected to 1 2 0 Q ° C or more. The homogeneous heat treatment is carried out to produce thick plates by block rolling. Steels A to G are all examples of the present invention and are steels whose components such as Nb, V, B, and Sb are appropriately adjusted. Among these, steels A to C and E Add steel for N ^-v 'steel D for N b-V-B add steel' steel F for N b — V-S b add steel, steel G for N b-V-B-S b add steel. Another In terms of 'steel P to r, they are all comparative examples. Nb and V were not added to steel p, although Nb was added to steel q, but V was not added. However, Nb and V were added to steel r. The amount of (Nb + V) is more than 1.0%. Then, the surface of the thick plate is After honing, the whole is 'heated to above 1000 ° C, hot-rolled at a final milk temperature of 850 to 95 QC, and a winding temperature of 650 to 800 t to make a hot-rolled coil (C0 1 1) °' After hot-rolled coil pickling to remove surface fouling, cold rolling with a cold rolling reduction of 20 to S 0% and recrystallization annealing at 7 500 to 1 100 ° C are repeated, and then, The final cold milking is performed at a cold rolling reduction of 20 to 25%, and a deformation annealing is performed at 70 (3 to 800 ° C) to produce a sheet with a thickness of 12 mm. Since then, the central part of the sheet coil in the wide direction has taken J1 s No. 5 tensile test piece, magnetic test ring test piece, and thermal expansion coefficient test piece, which are heat treatments equivalent to softening annealing before pressing, and are attached to A r In the environment, heat treatment is performed at a temperature of 800 to 900 ° C for 15 minutes, and the impact resistance, magnetic characteristics, and thermal expansion coefficient of the shadow mask are evaluated. The tensile test was performed according to the tensile test method of J I s z 2 2 4 1 'to obtain a 0.2% endurance. 13 312 / Invention Specification (Supplement) / 92-06 / 92106480 200304953 The magnetic properties were evaluated according to j I s C 2 5 3 1 to determine the maximum magnetic permeability coefficient when a magnetic field of 10 0 e was applied. The thermal expansion coefficient was measured by an optical interference thermal expansion measuring device, and the average thermal expansion coefficient at 20 to 100 ° C was obtained. The results are shown in Table 2. In addition, FIG. 1 shows the relationship between the 0.2% endurance and the maximum magnetic permeability coefficient after softening annealing before pressing. In this figure, three results are shown for the same steel, which are the results corresponding to the softening and annealing temperatures before stamping at 90 °, 850 °, and 800 ° C in order from the left. From FIG. 1, in the steels A to G of the example of the present invention, a 0.2% endurance and a maximum magnetic permeability coefficient of 8000 or more were obtained. Moreover, these steels can also satisfy the better relationship from the viewpoint of the balance of strength-magnetic characteristics. 0.2% PS + 6 (// max / 1000) ^ 340 ° From Table 2, in For steels A to G, a low thermal expansion coefficient of 1 · 2 X 1 0 -6 / ° C or lower can be obtained, especially for steels A and E to G, such as Mn, Nb, and V, which are relatively low. 0.9 X Low coefficient of thermal expansion below 0 _ 6 / ° C. In addition, steels D, F, and G that add forces □ B or S b in addition to N b and V can obtain a larger maximum magnetic permeability coefficient. On the other hand, in the comparative example, steel P without adding Nb and V had a poor balance between strength and magnetic properties. At any annealing temperature, the 0.2% endurance did not reach the target value of 2 7 0. M Pa. In steel q with only Nb added, compared with steel P, the strength-magnetic property balance is improved, but the maximum magnetic permeability coefficient does not reach more than 8000 except for annealing at 900 ° C. In addition, for steels (Nb + V) exceeding 1.0%, 0.2% resistance, except for 900 14 312 / Invention Specification (Supplement) / 92-06 / 92106480 200304953 T: Annealing, all failed to become 3 2 0 Μ P a or less. For steels q and r, after annealing at 900 ° C, a 0.2% endurance of 270 to 320 MPa and a maximum magnetic permeability coefficient above 80 ◦◦ can be obtained; however, 90 ◦ ° C annealing is used as softening annealing before stamping. The temperature range in which it is implemented is higher, which can lead to a significant increase in manufacturing costs. 15 312 / Invention Specification (Supplement) / 92-06 / 92106480 200304953 (% _ ») Remarks Invention Example Invention Example Invention Example Invention Example Invention Example Invention Example Comparative Example Comparative Example Λ 0} < 0.0003 < 0.0003 < 0.0003 < 0.0003 < 0.0003 0.0024 0.0019 < 0.0003 < 0.0003 < 0.0003 PQ < 0.0002 < 0.0002 < 0.0002 0.002 1 < 0.0002 < 0.0002 0.0011 < 0.0002 < 0.0002 < 0.0002 > .010 .015 .810 .431 .062 .058 .057 • 001 .001 .511 ο ο ο ο ο ο ο ο ο ο JQ S ο Γ0 〇0 Ch Ο Η γΗ Ο Η Η Ο CM m ο γΗ ΓΟ ο γΗ m ο < 0.001 Η ro ο ιη ο 1 ~ 1 < 0.030 0.022 0.034 0.031 0.031 0.029 0.028 0.027 0.027 0.031 0.029 0.0025 0.0038 0.0034 0.0044 0.0028 0.0029 0.0035 0.0019 — 0.003 9 0.004 1 OD 0.0007 0.0004 0.0004 0.0003 0.0006 0.0006 0.0007 0.0005 0.0008 0.0008 0.0006 〇4 0.003 0.003 ι_ 0.003 0.003 0.003 0.002 0.002 0.001 0.004 0.003 Μη m ο 03 Ο inch ο γΗ η ο inch ο ο ο Γο inch ο γΗ ο Ο ο ο ο ο ο ο ο ο • Η CO VD ο OJ OO CN 03 Ο inch ο inch ΓΟ Ο ΓΟ ο ΓΟ ο inch ο ο Ο Ο Ο ο ο ο ο ο ο 0.0042 0.0035 0.0029 0.0045 0.0041 0.0031 0.0031 0.0033 0.0017 0.0044 0.0028 • Η 15 inch if) m 00 VD ro LD νο ΓΟ Ρ0 KD m 00 LD ΓΟ \ ΐ) Γ0 〇Γ〇 (Μ VD ΓΟ ΓΜ VD ΓΟ γΗ m lag habit < PQ υ Q ω cn Ο Λ σ 91 08s2s / 90-CN6 / ff)} i) _s: CKis micro / ( Nle 200304953 Table 2 Softening annealing temperature (° C) before steel stamping 0.2% Endurance (MPa) Maximum magnetic permeability coefficient (X1000) Average thermal expansion coefficient (X10-6 / °) Remark A 800 300 8.9-Invention Example 850 295 9.5 0.8 900 290 11. 0 0. 9 B 800 318 8. 2-Invention Example 850 314 8. 7 1.1 900 308 10.. 4 1.2 C 800 284 9.8-Invention Example 850 281 10. 3 1.2 900 275 11.5 1.1 D 800 284 11.8- Inventive Example 850 279 13. 3 1.0 900 274 14.. 4 1.1 E 800 304 9.8-Inventive Example 850 298 10. 9 0. 9 900 292 11.6 0.9 F 800 305 10.4-Inventive Example 850 300 11.5 0. 9 900 295 12.0 0 9 G 800 304 11.8-Invention Example 850 299 12. 3 0. 9 900 294 12. 9 0. 9 P 800 26 7 8. 3-Comparative Example 850 264 9.8 1.1 900 259 11.9 1. 0 q 800 301 6. 2-Comparative Example 850 294 7.8 0.9 900 289 8. 9 0. 9 r 800 327 8. 6-Comparative Example 850 321 9.8 0. 9 900 314 11.5 0. 9 Bottom line part: outside the target range 17 312 / Invention Specification (Supplement) / 92-06 / 92106480 200304953 (Example 2) The iff steel ingots of steels A and p shown in Table 1 are used to match Example 1 A thin plate having a plate thickness of 0.12 mm was manufactured in the same method. At this time, as shown in Table 3, the cold rolling elongation and the temperature at which the deformation is removed and annealed at the final cold rolling are changed into five groups in the steel A system and three groups in the steel P system. The same test was performed on this sheet plate as in the case of Example 1. The "softening annealing before pressing" was performed under the conditions of a soaking temperature of 750 to 900 ° C X 15 minutes in an Ar environment. The results are shown in Table 3 °. Fig. 2 shows the relationship between the softening annealing temperature before pressing and the 0.2% endurance. Steels A-1 to A-3 were manufactured by changing the temperature of the annealing to remove deformation to 750 ° C and changing the cold rolling elongation of the final cold rolling. In the case of either case, the soft annealing temperature rises with the subsequent stamping, and the 0.2% endurance decreases significantly to 32 MPa or less. The annealing temperature at which the 0.2% endurance is 32 MPa or less is '80 MPa 'for the steels A to 3 of the example of the present invention, while the steel A-2 of the comparative example is 8 5 0 ° C and the steel A- 1 is 900 arts. As usually soft before stamping
特性。 製的冷 的軟化characteristic. Softening
8 5 0 °C。因而，鋼A - 3及 3 ] 2/發明說明書(補件)/92-06/92106480 18 200304953 A - 4，與鋼A - 5相比，具有良好的軟化特性。 由上述的結果可知：於添加有Nb的情況，爲了確保衝 壓前軟化退火中的軟化特性，必須將最終冷軋製的冷軋延 率及去除變形退火的溫度控制於特定範圍中。 另一方面，於未添加N b的比較例的鋼p - 1及p - 5，於 去除變形退火溫度 8 0 0 t：以上，0 . 2 %耐力成爲未滿 270MPa，偏離於較佳的範圍之 270~320MPa之外。又， 於鋼P - 3，於衝壓前軟化退火溫度7 5 0 °C下，〇 · 2 %耐力雖 成爲2 7 8 Μ P a，惟，施行與實施例1同樣的試驗進行磁特 性的評價之下，最大透磁係數並未達8 Q 0 0。8 5 0 ° C. Therefore, Steel A-3 and 3] 2 / Invention Specification (Supplement) / 92-06 / 92106480 18 200304953 A-4 has better softening characteristics than Steel A-5. From the results described above, in the case where Nb is added, in order to ensure the softening characteristics during soft annealing before pressing, it is necessary to control the cold rolling elongation of the final cold rolling and the temperature of the deformation removing annealing to a specific range. On the other hand, in the steels p-1 and p-5 of the comparative example to which Nb was not added, the annealing temperature at which the deformation was removed was 8 0 t: above, the 0.2% endurance became less than 270 MPa, which deviated from the preferred range. Beyond 270 ~ 320MPa. In addition, for steel P-3, at a softening annealing temperature of 750 ° C before pressing, although the 0.2% endurance was 278 M Pa, the same tests as in Example 1 were performed to evaluate the magnetic properties. Below, the maximum magnetic permeability does not reach 8 Q 0 0.
C 312/發明說明書(補件)/92-06/92106480 19 200304953 表3 鋼 最終冷軋製 的冷軋延率 (%) 去除變形退火 的溫度 (〇C ) 衝壓前軟化 退火溫度 (°C ) 〇 ·2%耐力 (MPa) 備註 A-1 1_ 750 7 50 43 0 比較例 800 408 850 3Ί9 900 271 A-2 14 750 750 434 比較例 800 399 850 284 900 279 A-3 25 7 50 750 468 發明例 800 300 850 295 900 290 A-4 25 800 7 50 452 發明例 800 294 850 288 900 281 A-5 25 850 750 443 比較例 800 38 7 850 2 79 900 2 73 p-1 2 750 750 335 比較例 800 265 850 263 900 25 7 p-3 25 750 750 2 78 比較例 800 26 7 850 264 900 259 p _ 5 25 850 750 322 比較例 800 262 850 260 900 255 加底線部分：發明（目標）範圍外 20 312/發明說明書(補件)/92-06/92106480 200304953 【圖式簡單說明】 圖1爲顯示衝壓前軟化退火後的〇 · 2 %耐力（0 . 2 % P S )與 最大透磁係數（# m a X )的關係之圖。 圖2爲顯示衝壓前軟化退火溫度與0.2%耐力（0.2%PS) 的關係之圖。 21 312/發明說明書(補件)/92-06/92106480C 312 / Invention Specification (Supplement) / 92-06 / 92106480 19 200304953 Table 3 Cold rolling elongation (%) of final cold rolling of steel Temperature for removing annealing after deformation (° C) Softening annealing temperature before pressing (° C) 0.2% endurance (MPa) Remark A-1 1_ 750 7 50 43 0 Comparative example 800 408 850 3Ί9 900 271 A-2 14 750 750 434 Comparative example 800 399 850 284 900 279 A-3 25 7 50 750 468 Invention Example 800 300 850 295 900 290 A-4 25 800 7 50 452 Invention example 800 294 850 288 900 281 A-5 25 850 750 443 Comparative example 800 38 7 850 2 79 900 2 73 p-1 2 750 750 335 Comparative example 800 265 850 263 900 25 7 p-3 25 750 750 2 78 Comparative example 800 26 7 850 264 900 259 p _ 5 25 850 750 322 Comparative example 800 262 850 260 900 255 Underlined part: outside the scope of the invention (target) 20 312 / Invention Manual (Supplement) / 92-06 / 92106480 200304953 [Simplified description of the figure] Figure 1 shows the 0.2% endurance (0.2% PS) and the maximum magnetic permeability coefficient (# ma X). FIG. 2 is a graph showing the relationship between the softening annealing temperature before the stamping and the 0.2% endurance (0.2% PS). 21 312 / Invention Specification (Supplement) / 92-06 / 92106480