WO2003004715A1 - Thin alloy sheet of low thermal expansion and shadow mask using the same - Google Patents
Thin alloy sheet of low thermal expansion and shadow mask using the same Download PDFInfo
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- WO2003004715A1 WO2003004715A1 PCT/JP2002/006785 JP0206785W WO03004715A1 WO 2003004715 A1 WO2003004715 A1 WO 2003004715A1 JP 0206785 W JP0206785 W JP 0206785W WO 03004715 A1 WO03004715 A1 WO 03004715A1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
- H01J29/06—Screens for shielding; Masks interposed in the electron stream
- H01J29/07—Shadow masks for colour television tubes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2229/00—Details of cathode ray tubes or electron beam tubes
- H01J2229/07—Shadow masks
- H01J2229/0727—Aperture plate
- H01J2229/0733—Aperture plate characterised by the material
Definitions
- the present invention is a low thermal expansion alloy sheet, in particular, be used in the CRT of the shadow mask or the like, 1.0 X 10- 6 IK excellent in productivity and etching property
- the present invention relates to a low-thermal-expansion alloy sheet having an average thermal expansion coefficient of 20 to 100 ° C. and a shadow mask using the same. Background art
- Fe-Ni alloys containing approximately 36% Ni have an extremely low coefficient of thermal expansion near room temperature, so they can be used in precision equipment, pi-metals, shadow masks for computer and television bran tubes, etc. Widely used.
- Japanese Patent No. 2694864 discloses that the content of Ni is 34% or more, Mn is 0.1% or less, C is less than 0.009%, the balance is Fe and unavoidable impurities, and the average thermal expansion from around room temperature to 100 ° C. coefficient lower low thermal ⁇ nickel alloy full 1 X 10- 6 I has been proposed for the shadow mask.
- FIG. 1 is a diagram showing the relationship between Mn + Si + Al and the average thermal expansion coefficient at 20-100 ° C.
- Embodiment the present inventors of the implementation of the invention the cracking and breakage during production, or no flaw occurred, stable 1.0 average thermal expansion coefficient of the X 10- 6 / K or less of 20-100 is obtained and, The following findings were obtained as a result of a study on low thermal expansion alloy sheets that provide good etching properties and dimensional accuracy during shadow mask production.
- Ni is an essential element for obtaining a low coefficient of thermal expansion. 20-100 The average thermal expansion coefficient of ° C to less 1.0 X 10- 6 / K is the amount and 35.0-37.0%.
- Mn, Si, A1 break in hot rolling and cold rolling, cracks, and prevent the occurrence of flaws, the Netsu ⁇ Choritsu below 1.0 X 10- 6 / K, the defective etching and dimensional accuracy defect of the shadow mask
- fine oxides are formed on the surface of the thin plate during heat treatment in the manufacturing process to deteriorate the etching properties, and to prevent electron beam scattering and increase heat dissipation as in the case of shadow masks. In some cases, the formation of a dense and high-black film is hindered, and the coefficient of thermal expansion is further increased.
- the respective amounts of Mn and Si must be 0.09%, 0.04% or less, and 0.04% or less. Further, as shown in FIG. 1, in order to stably obtain a coefficient of thermal expansion of 1.0 ⁇ 10 ′′ 6 / K or less, it is necessary to set Mn + Si + A1 ⁇ 0.15%.
- Mn is a strong sulfide-forming element, and fixes S, which causes grain boundary embrittlement during hot working, as a sulfide to improve hot workability and cracks in bulk rolling, forging, hot rolling, etc. And work to prevent breakage.
- Mn I S needs to be 20 or more.
- Mn / S exceeds 300, the Mn amount becomes excessive even if Mn is 0.09% or less, causing the above-mentioned problem.
- 0 0 is not only a cause of cracking during hot rolling, flaws during cold rolling, and poor etching during the formation of oxidized products, but also inhibits the growth of crystal grains during heat treatment and leads to the formation of fiber bundles. Since it may have an effect and it may be difficult to stably secure a low coefficient of thermal expansion, the content is preferably set to 0.005% or less.
- S Since S causes grain boundary embrittlement during hot working, it causes cracks and fractures in spreading, forging, and hot rolling, and segregation occurs when S that cannot be completely fixed by Mn increases. Since the hot workability and the etching property are greatly reduced in a strong portion, the content is preferably 0.002% or less.
- the low-thermal-expansion alloy sheet of the present invention can be produced by melting, sintering, hot rolling, It can be manufactured by cold rolling and annealing.
- a slab having a thickness of 100 to 400 mm is produced by melting an alloy having the above-mentioned composition and forming it by a continuous forming method or an ingot forming method.
- hot rolling is performed at 800 ° C or higher to obtain a sheet having a thickness of 2 to 4 mm, and cold rolling and annealing are performed once or more times to obtain a desired thin sheet.
- Fe-Ni alloy No. 1-21 with the component composition shown in Table 1 was melted, formed into a hot rolled sheet by slab rolling and hot rolling, pickled, cold rolled and annealed, if necessary Tension leveler treatment and strain relief annealing were performed to produce 0.1 mm and 0.2 mm thin sheets.
- “ ⁇ ” indicates that it could be manufactured without any problem
- “X” indicates that it had a fracture or a flaw.
- the thin plate thus obtained was subjected to a heat treatment at 850 ° C for 15 min, and then the average thermal expansion coefficient at 20-100 ° C was measured by an optical interference thermal dilatometer.
- the determining the maximum value, as the difference between the maximum value and the minimum value is more than 0.5 X 10- 6 / K is the lack of stability of the preparation X as measured by 10 for each alloy did. Furthermore, a resist film having a large number of circular holes with an opening diameter of 90 m is formed on the surface of the obtained thin plate, and a ferric chloride solution having a solution temperature of 40 ° C or more and a concentration of 40% or more is applied at 30 to 50 MPa.
- a hole with a diameter of 100-200 m was drilled in the thin plate by etching at a pressure of, and the presence or absence of abnormalities in the hole shape of 100 holes, and the dimensional accuracy with respect to the average diameter, that is, the variation of the hole diameter were investigated.
- a hole having a high roundness and a dimensional accuracy of ⁇ 3% or less was indicated by “ ⁇ ”, and a hole having a low roundness and a dimensional accuracy exceeding ⁇ 3% was indicated by “X”.
- Alloy Nos. 1-10 of the present invention exhibited good manufacturability without cracking or breakage in hot rolling or cold rolling.
- the etching property was good and an extremely low coefficient of thermal expansion was obtained.
- alloy No. 11-21 of the comparative example was inferior in either property. That is, in No.ll, the value of Mn + Si + A1 is out of the range of the present invention, so that a low coefficient of thermal expansion cannot be obtained. In No. 12, a low coefficient of thermal expansion cannot be obtained because the amount of Mn, the amount of Si, the value of Mn + Si + Al, and the value of Mn / S are out of the range of the present invention. In the case of N0.13, the values of Mn amount and Mn / S are out of the range of the present invention, so that they are cracked or broken by hot rolling, resulting in poor productivity.
Abstract
A thin alloy sheet having a low thermal expansion which has a substantial chemical composition in mass %: Ni: 35.0 to 37.0 %, Mn: 0.01 to 0.09 %, Si: 0.01 to 0.04 %, Al: 0.01 to 0.04 % and balance: Fe, with the proviso that Mn/S is 20 to 300 and Mn + Si + Al ≤ 0.15 %, and has an average thermal expansion coefficient in the range of 20 to 100˚C of 1.0 X 10-6/K or less. The thin alloy sheet is free from the occurrence of a crack, a fracture or a flaw and exhibits good etching characteristics and dimensional precision in the manufacture of a shadow mask.
Description
明細書 低熱膨張合金薄板およびそれを用いたシャドウマスク ， 技術分野 本発明は、 低熱膨張合金薄板、 特に、 ブラウン管のシャドウマスク等に使用され、 製造性およびエッチング性に優れた 1.0 X 10—6 I K以下の 20-100 °cの平均熱膨張係 数を有する低熱膨張合金薄板およびそれを用いたシャドウマスクに関する。 背景技術 Specification low thermal expansion alloy sheet and a shadow mask using the same, TECHNICAL FIELD The present invention is a low thermal expansion alloy sheet, in particular, be used in the CRT of the shadow mask or the like, 1.0 X 10- 6 IK excellent in productivity and etching property The present invention relates to a low-thermal-expansion alloy sheet having an average thermal expansion coefficient of 20 to 100 ° C. and a shadow mask using the same. Background art
Niを約 36 %含む Fe-Ni合金は、 室温付近で極めて低い熱膨張率を有するため、 温 度変動による寸法変化を嫌う精密機器、 パイメタル、 コンピュータやテレビのブラ ゥン管のシャドウマスク等に幅広く使用されている。 Fe-Ni alloys containing approximately 36% Ni have an extremely low coefficient of thermal expansion near room temperature, so they can be used in precision equipment, pi-metals, shadow masks for computer and television bran tubes, etc. Widely used.
その多くは、 室温から 100 °Cの温度範囲において約 1.2-2.0 X lCr6 / K程度の平均 熱膨張係数を有しているが、 近年、 高輝度化と高画質化の要望が強いブラウン管の シャドウマスクには、 より低い熱膨張率を有する材料が求められている。 Most of them have an average coefficient of thermal expansion of about 1.2-2.0 X lCr 6 / K in the temperature range from room temperature to 100 ° C. In recent years, there has been a strong demand for high brightness and high image quality CRTs. A material having a lower coefficient of thermal expansion is required for the shadow mask.
そのため、 例えば特許第 2694864号公報には、 Niを 34 %以上、 Mnを 0.1 %以下、 C を 0.009 %未満含み、 残部が Feおよび不可避的不純物であり、 室温付近から 100 °C の平均熱膨張係数が 1 X 10—6 I 満のより低い低熱膨鉄ニッケル合金がシャドウ マスク用に提案されている。 Therefore, for example, Japanese Patent No. 2694864 discloses that the content of Ni is 34% or more, Mn is 0.1% or less, C is less than 0.009%, the balance is Fe and unavoidable impurities, and the average thermal expansion from around room temperature to 100 ° C. coefficient lower low thermal膨鉄nickel alloy full 1 X 10- 6 I has been proposed for the shadow mask.
しかしながら、 特許第 2694864号公報に記載された低熱膨張鉄二ッケル合金の薄 板を製造するとき、 分塊圧延、 熱間圧延、 冷間圧延等の圧延工程で割れや破断、 あ るいは疵が発生したり、 目的とする低熱膨張率が安定的に得られないといった問題 がある。 また、 シャドウマスク製造時には、 エッチング不良や寸法精度不良等の問 題も生じる。 '
発明の開示 本発明の目的は、 製造時に割れや破断、 あるいは疵が発生せず、 安定して 1.0 X 10-6 I K以下の 20-100 °Cの平均熱膨張係数が得られ、 かつ、 シャドウマスク製造時 に良好なエッチング性と寸法精度の得られる低熱膨張合金薄板を提供することにあ る。 However, when producing a sheet of low thermal expansion iron nickel alloy described in Japanese Patent No. 2694864, cracks, breaks, or flaws occur in rolling processes such as slab rolling, hot rolling, and cold rolling. And the desired low coefficient of thermal expansion cannot be obtained stably. In the production of a shadow mask, problems such as poor etching and poor dimensional accuracy also occur. ' Disclosure object of the present invention relates to a cracking or fracture, or crack is not generated at the time of manufacture, the average thermal expansion coefficient of the stable 1.0 X 10- 6 IK less 20-100 ° C is obtained and the shadow An object of the present invention is to provide a low-thermal-expansion alloy thin plate that can obtain good etching properties and dimensional accuracy when manufacturing a mask.
上記目的は、 実質的に、 質量％で、 Νί: 35.0-37.0 %、 Mn: 0.01-0.09 %、 Si: 0.01- 0.04 %、 Al: 0.01-0.04 %、 残部： Feからなり、 かつ Mn / S: 20-300および Mn + Si + Al ≤ 0.15 %である 1.0 X If)-6 / K以下の 20-100 °Cの平均熱膨張係数を有する低熱膨張 合金薄板により達成される。 図面の簡単な説明 図 1は、 Mn + Si + Alと 20-100 °Cの平均熱膨張係数との関係を示す図である。 発明の実施の形態 本発明者等は、 製造時に割れや破断、 あるいは疵が発生せず、 安定して 1.0 X 10—6 / K以下の 20-100 の平均熱膨張係数が得られ、 かつ、 シャドウマスク製造時 に良好なエッチング性と寸法精度の得られる低熱膨張合金薄板について検討した結 果、 以下の知見を得た。 The above purpose is, in mass%, substantially: 35.0-37.0%, Mn: 0.01-0.09%, Si: 0.01-0.04%, Al: 0.01-0.04%, balance: Fe, and Mn / S : 20-300 and Mn + Si + Al ≤ 1.0 are 0.15% X If) - is achieved by a low thermal expansion alloy sheet having an average thermal expansion coefficient of 6 / K or less of 20-100 ° C. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the relationship between Mn + Si + Al and the average thermal expansion coefficient at 20-100 ° C. Embodiment the present inventors of the implementation of the invention, the cracking and breakage during production, or no flaw occurred, stable 1.0 average thermal expansion coefficient of the X 10- 6 / K or less of 20-100 is obtained and, The following findings were obtained as a result of a study on low thermal expansion alloy sheets that provide good etching properties and dimensional accuracy during shadow mask production.
1)熱膨張率を低減するために Mn、 Si、 Al量を低減することは有効であるが、 こ れら強力な硫化物形成元素や脱酸元素の量を過度に低減すると、 固溶 Sや酸化物系 介在物が増加し、 熱間圧延時の割れや破断、 冷間圧延時の割れゃ疵、 エッチング不 良を引き起こす。 1) It is effective to reduce the amount of Mn, Si, and Al to reduce the coefficient of thermal expansion.However, if the amount of these strong sulfide-forming elements and deoxidizing elements is excessively reduced, And oxide-based inclusions increase, causing cracks and fractures during hot rolling, cracks and flaws during cold rolling, and poor etching.
2) . これらの元素量を適正範囲に制御しない場合には介在物の量が変動し、 それ が謹形成にも影響を及ぼし 1.0 X 10·6 / Κ以下の熱膨張率が得られない。 2). If the amounts of these elements are not controlled within the appropriate range, the amount of inclusions will fluctuate, which will affect the formation and will not provide a coefficient of thermal expansion of 1.0 X 10 6 / / or less.
3 さらに、 これらの元素の合計 MMn + Si + A1を 0.15 %以下にすることにより安
定して 1.0 X 10—δ / Κ以下の熱膨張率が得られる。 3 Furthermore, the total MMn + Si + A1 of these elements is reduced to 0.15% or less, The coefficient of thermal expansion of 1.0 X 10— δ / Κ is obtained.
本発明は、 こうした知見に基づいて行われたもので、 以下にその詳細を説明する。 The present invention has been made based on such knowledge, and the details thereof will be described below.
Ni: Niは、 低熱膨張率を得るための必須の元素である。 20-100 °Cの平均熱膨張係 数を 1.0 X 10-6 / K以下とするためには、 その量を 35.0-37.0 %とする。 Ni: Ni is an essential element for obtaining a low coefficient of thermal expansion. 20-100 The average thermal expansion coefficient of ° C to less 1.0 X 10- 6 / K is the amount and 35.0-37.0%.
Mn、 Si、 A1:熱間圧延や冷間圧延における破断、 割れ、 疵の発生を防止し、 熱膨 張率を 1.0 X 10—6 / K以下にし、 シャドウマスクのエッチング不良や寸法精度不良 を防止するためには、 Mn、 Si、 A1のそれぞれを少なくとも 0.01 %添加する必要があ る。 一方、 こうした元素を過剰に添加すると、 製造工程における熱処理時に薄板表 層に微細酸化物が形成されエッチング性を劣化させたり、 シャドウマスクの場合の ように電子線散乱防止や熱放散性増加を目的とした緻密で黒色度の高い被膜形成を 阻害したり、 さらに熱膨張率を増加させる場合がある。 そのため、 Mn、 Si、 の それぞれの量を 0.09 %、 0.04 %以下、 0.04 %以下とする必要がある。 また、 図 1に示 すように、 1.0 X 10"6 / K以下の熱膨張率を安定して得るには、 Mn + Si + A1 ≤ 0.15 %とする必要がある。 Mn, Si, A1: break in hot rolling and cold rolling, cracks, and prevent the occurrence of flaws, the Netsu膨Choritsu below 1.0 X 10- 6 / K, the defective etching and dimensional accuracy defect of the shadow mask To prevent this, it is necessary to add at least 0.01% of each of Mn, Si and A1. On the other hand, if these elements are added excessively, fine oxides are formed on the surface of the thin plate during heat treatment in the manufacturing process to deteriorate the etching properties, and to prevent electron beam scattering and increase heat dissipation as in the case of shadow masks. In some cases, the formation of a dense and high-black film is hindered, and the coefficient of thermal expansion is further increased. Therefore, the respective amounts of Mn and Si must be 0.09%, 0.04% or less, and 0.04% or less. Further, as shown in FIG. 1, in order to stably obtain a coefficient of thermal expansion of 1.0 × 10 ″ 6 / K or less, it is necessary to set Mn + Si + A1 ≦ 0.15%.
Mnは、 強力な硫化物形成元素であり、 熱間加工時に粒界脆化をもたらす Sを硫化 物として固定して熱間加工性を改善し、 分塊圧延、 鍛造、 熱間圧延等における割れ や破断を防止する働きがある。 そのためには、 Mn I Sを 20以上にする必要がある。 また、 Mn / Sが 300を超えると、 たとえ Mnが 0.09 %以下であっても Mn量が過剰にな り上記のような問題を引き起こすので Mn/Sを 300以下にする必要がある。 Mn is a strong sulfide-forming element, and fixes S, which causes grain boundary embrittlement during hot working, as a sulfide to improve hot workability and cracks in bulk rolling, forging, hot rolling, etc. And work to prevent breakage. For that purpose, Mn I S needs to be 20 or more. When Mn / S exceeds 300, the Mn amount becomes excessive even if Mn is 0.09% or less, causing the above-mentioned problem.
0: 0は、 酸ィ匕物を形成して熱間圧延時の割れ、 冷間圧延時の疵、 エッチング不良 の原因になるばかりでなぐ 熱処理時の結晶粒成長を阻害して組纖形成に影響を与 え、 低熱膨張率の安定的確保が困難になる場合があるため、 0.005 %以下にするこ とが好ましい。 0: 0 is not only a cause of cracking during hot rolling, flaws during cold rolling, and poor etching during the formation of oxidized products, but also inhibits the growth of crystal grains during heat treatment and leads to the formation of fiber bundles. Since it may have an effect and it may be difficult to stably secure a low coefficient of thermal expansion, the content is preferably set to 0.005% or less.
S: Sは、 熱間加工時に粒界脆化をもたらすため、 分赃延、 鍛造、 熱間圧延にお いて割れや破断の原因となるとともに、 Mn等で固定しきれない Sが増加すると偏析 の強い部分で熱間加工性やエツチング性が大きく低下する原因にもなるため、 0.002 %以下にすることが好ましい。 S: Since S causes grain boundary embrittlement during hot working, it causes cracks and fractures in spreading, forging, and hot rolling, and segregation occurs when S that cannot be completely fixed by Mn increases. Since the hot workability and the etching property are greatly reduced in a strong portion, the content is preferably 0.002% or less.
本発明の低熱膨張合金薄板は、 通常実施されている溶製、 , 铸造、 熱間圧延、
冷間圧延、 焼鈍により製造することができる。 例えば、 上記成分組成を有する合金 を溶製し、 連続铸造法または造塊法により、 厚さ 100-400 mmのスラブとする。 こ の際、 铸造塊またはスラブについて 1050 °C以上で十分な均質化熱処理を行うか、 または铸造処理により偏析を低減することが望ましい。 次いで、 800 °C以上で熱間 圧延を行い、 厚さ 2-4 mmの板とし、 さらに冷間圧延および焼鈍を 1回から複数回施 すことにより所望の薄板とする。 実施例 The low-thermal-expansion alloy sheet of the present invention can be produced by melting, sintering, hot rolling, It can be manufactured by cold rolling and annealing. For example, a slab having a thickness of 100 to 400 mm is produced by melting an alloy having the above-mentioned composition and forming it by a continuous forming method or an ingot forming method. At this time, it is desirable to perform a sufficient homogenization heat treatment at 1050 ° C or higher for the ingot or slab, or to reduce segregation by the forging process. Next, hot rolling is performed at 800 ° C or higher to obtain a sheet having a thickness of 2 to 4 mm, and cold rolling and annealing are performed once or more times to obtain a desired thin sheet. Example
表 1に示す成分組成の Fe-Ni合金 No.1-21を溶製し、 分塊圧延、 熱間圧延により熱 延板とし、 酸洗を施した後冷間圧延と焼鈍、 必要に応じてテンションレべラー処理 や歪取焼鈍を行って、 板厚 0.1 mmと 0.2 mmの薄板を作製した。 このとき、 薄板の製 造性について、 問題なく製造できたものについては〇、 破断ゃ疵が生じたものにつ いては Xで表した。 また、 このようにして得られた薄板について、 850 °Cで 15 min の熱処理を施した後、 光干渉式熱膨張計によって 20-100 °Cの平均熱膨張係数を測 定した。 このとき、 各合金について 10個ずつ測定してその最大値を求めるとともに、 最大値と最小値との差が 0.5 X 10—6 / Kを超えるものは製造の安定性に欠けるとし て Xで表した。 さらに、 得られた薄板表面に開孔径 90 mの円型の孔を多数配し たレジスト膜を形成し、 液温 40 °C以上、 濃度 40 %以上の塩化第二鉄液を 30-50 MPa の圧力で噴射して、 薄板に直径 100-200 mの孔をエッチング穿孔し、 100個の孔 について孔形状の異常の有無と、 平均径に対する寸法精度すなわち孔径のパラツキ を調査した。 そして、 孔の真円度が高く、 寸法精度が ±3 %以下のものを〇、 真円 度が低く、 寸法精度が ±3 %を超えるものを Xで表した。 Fe-Ni alloy No. 1-21 with the component composition shown in Table 1 was melted, formed into a hot rolled sheet by slab rolling and hot rolling, pickled, cold rolled and annealed, if necessary Tension leveler treatment and strain relief annealing were performed to produce 0.1 mm and 0.2 mm thin sheets. At this time, regarding the manufacturability of the thin plate, “〇” indicates that it could be manufactured without any problem, and “X” indicates that it had a fracture or a flaw. The thin plate thus obtained was subjected to a heat treatment at 850 ° C for 15 min, and then the average thermal expansion coefficient at 20-100 ° C was measured by an optical interference thermal dilatometer. Table In this time, the determining the maximum value, as the difference between the maximum value and the minimum value is more than 0.5 X 10- 6 / K is the lack of stability of the preparation X as measured by 10 for each alloy did. Furthermore, a resist film having a large number of circular holes with an opening diameter of 90 m is formed on the surface of the obtained thin plate, and a ferric chloride solution having a solution temperature of 40 ° C or more and a concentration of 40% or more is applied at 30 to 50 MPa. A hole with a diameter of 100-200 m was drilled in the thin plate by etching at a pressure of, and the presence or absence of abnormalities in the hole shape of 100 holes, and the dimensional accuracy with respect to the average diameter, that is, the variation of the hole diameter were investigated. A hole having a high roundness and a dimensional accuracy of ± 3% or less was indicated by “〇”, and a hole having a low roundness and a dimensional accuracy exceeding ± 3% was indicated by “X”.
結果を表 2に示す。 Table 2 shows the results.
本発明例の合金 No.1-10では、 いずれも熱間圧延や冷間圧延における割れや破断 の発生がなく製造性が良好であった。 また、 エッチング性も良好であるとともに、 極めて低い熱膨張率が得られた。 Alloy Nos. 1-10 of the present invention exhibited good manufacturability without cracking or breakage in hot rolling or cold rolling. In addition, the etching property was good and an extremely low coefficient of thermal expansion was obtained.
これに対して、 比較例の合金 No.11-21では、 いずれかの特性が劣っていた。 すな わち、 No.llでは、 Mn + Si + A1の値が本発明範囲外のため低熱膨率が得られない。
No.12では、 Mn量、 Si量、 Mn + Si + Alの値、 Mn / Sの値が本発明範囲外のため低熱 膨率が得られない。 N0.13では、 Mn量、 Mn / Sの値が本発明範囲外のため熱間圧延 で割れ、 破断が発生し、 製造性に劣る。 No.14では、 Mn量、 Mn + Si + A1の値が本 発明範囲外のため、 No.15では、 Si量、 Mn + Si + A1の値が本発明範囲外のため、 レ ずれも低熱膨張率が得られない。 No.16では、 Si量、 A1量が本発明範囲外であり、 熱間圧延で割れ、 破断が発生し、 製造性に劣る。 No.17では、 Si量、 A1量が本発明 範囲外のため、 No.18では、 A1量が本発明範囲外のため、 いずれも冷間圧延で疵が 発生し、 製造性に劣る。 また、 熱膨張係数やエッチングの孔径のバラツキも大きい。 No.19では、 A1量が本発明範囲外のため、 低熱膨張率が得られず、 エッチング性に 劣る。 No.20では、 Ni量が本発明範囲外のため、 N0.21では、 Ni量、 Si量が本発明範 囲外のため、 いずれも低熱膨張率が得られない。
On the other hand, alloy No. 11-21 of the comparative example was inferior in either property. That is, in No.ll, the value of Mn + Si + A1 is out of the range of the present invention, so that a low coefficient of thermal expansion cannot be obtained. In No. 12, a low coefficient of thermal expansion cannot be obtained because the amount of Mn, the amount of Si, the value of Mn + Si + Al, and the value of Mn / S are out of the range of the present invention. In the case of N0.13, the values of Mn amount and Mn / S are out of the range of the present invention, so that they are cracked or broken by hot rolling, resulting in poor productivity. In No.14, the Mn content and Mn + Si + A1 values were out of the range of the present invention, and in No.15, the Si content and Mn + Si + A1 values were out of the range of the present invention, so the deviation was low. The expansion rate cannot be obtained. In No. 16, the amounts of Si and A1 are outside the range of the present invention, and cracks and breaks occur during hot rolling, resulting in poor manufacturability. In No. 17, since the amount of Si and A1 were out of the range of the present invention, and in No. 18, the amount of A1 was out of the range of the present invention. Also, there are large variations in the coefficient of thermal expansion and the hole diameter of etching. In No. 19, since the amount of A1 is out of the range of the present invention, a low coefficient of thermal expansion cannot be obtained, and the etching property is poor. In No. 20, the amount of Ni is out of the range of the present invention, and in N0.21, both the amount of Ni and the amount of Si are out of the range of the present invention.
合金 成分（mass%) Mn/S Mn+Si+AI 備考Alloy composition (mass%) Mn / S Mn + Si + AI Remarks
No. Ni Mn Si Al 0 S (mass%) No. Ni Mn Si Al 0 S (mass%)
1 36.3 0.028 0.020 0.020 0.0030 0.0007 40 0.07 本発明例 1 36.3 0.028 0.020 0.020 0.0030 0.0007 40 0.07 Example of the present invention
2 36.1 0.080 0.026 0.019 0.0012 0.0016 50 0.13 本発明例2 36.1 0.080 0.026 0.019 0.0012 0.0016 50 0.13 Example of the present invention
3 35.9 0.012 0.014 0.017 0.0034 0.0002 60 0.04 本発明例3 35.9 0.012 0.014 0.017 0.0034 0.0002 60 0.04 Example of the present invention
4 36.1 0.025 0.010 0.028 0.0009 0.0007 36 0.06 本発明例4 36.1 0.025 0.010 0.028 0.0009 0.0007 36 0.06 Example of the present invention
5 36.0 0.018 0.040 0.020 0.0019 0.0007 26 0.08 本発明例5 36.0 0.018 0.040 0.020 0.0019 0.0007 26 0.08 Example of the present invention
6 36.0 0.044 0.010 0.01 1 0.0046 0.0020 22 0.07 本発明例6 36.0 0.044 0.010 0.01 1 0.0046 0.0020 22 0.07 Example of the present invention
7 36.1 0.049 0.020 0.020 0.0015 0.0002 245 0.09 本発明例7 36.1 0.049 0.020 0.020 0.0015 0.0002 245 0.09 Example of the present invention
8 36.5 0.015 0.013 0.010 0.001 7 0.0003 50 0.04 本発明例8 36.5 0.015 0.013 0.010 0.001 7 0.0003 50 0.04 Example of the present invention
9 36.0 0.030 0.040 0.012 0.0030 0.0007 43 0.08 本発明例9 36.0 0.030 0.040 0.012 0.0030 0.0007 43 0.08 Example of the present invention
10 36.2 0.040 0.020 0.020 0.0010 0.0007 57 0.08 本発明例10 36.2 0.040 0.020 0.020 0.0010 0.0007 57 0.08 Example of the present invention
1 1 36.1 0.090 0.040 0.039 0.0022 0.0009 100 0.17 比較例1 1 36.1 0.090 0.040 0.039 0.0022 0.0009 100 0.17 Comparative example
12 35.8 0.380 0.050 0.010 0.0030 0.0012 317 0.44 比較例12 35.8 0.380 0.050 0.010 0.0030 0.0012 317 0.44 Comparative example
13 36.0 0.004 0.010 0.013 0.0050 0.0014 3 0.03 比較例13 36.0 0.004 0.010 0.013 0.0050 0.0014 3 0.03 Comparative example
14 35.7 0.240 0.035 0.015 0.0020 0.0015 160 0.29 比較例14 35.7 0.240 0.035 0.015 0.0020 0.0015 160 0.29 Comparative example
15 35.8 0.090 0.084 0.014 0.0010 0.0009 100 0.19 比較例15 35.8 0.090 0.084 0.014 0.0010 0.0009 100 0.19 Comparative example
16 36.1 0.054 0.009 0.009 0.0049 0.0027 20 0.07 比較例16 36.1 0.054 0.009 0.009 0.0049 0.0027 20 0.07 Comparative example
17 35.6 0.051 0.004 0.009 0.0074 0.0010 51 0.06 比較例17 35.6 0.051 0.004 0.009 0.0074 0.0010 51 0.06 Comparative example
18 36.0 0.042 0.031 0.004 0.0069 0.0009 47 0.08 比較例18 36.0 0.042 0.031 0.004 0.0069 0.0009 47 0.08 Comparative example
19 36.4 0.039 0.035 0.080 0.0007 0.0009 43 0.15 比較例19 36.4 0.039 0.035 0.080 0.0007 0.0009 43 0.15 Comparative example
20 37.5 0.019 0.010 0.010 0.0030 0.0006 32 0.04 比較例20 37.5 0.019 0.010 0.010 0.0030 0.0006 32 0.04 Comparative example
21 34.3 0.050 0.044 0.008 0.0019 0.0007 71 0.10 比較例
21 34.3 0.050 0.044 0.008 0.0019 0.0007 71 0.10 Comparative example
20-100 C平均 20-100 C average
ム 丁、"■= &、 tt Mu Ding, "■ = &, tt
丄ツナノノ Ι 去 No. I U /i\ 丄 Tsunano 去 Previous No. I U / i \
1 1 074 Γ\ **f^ To 4Π 1クリ 1 1 074 Γ \ ** f ^ To 4Π 1
0 0
U.O / Λ rid 1クリ リ n 79 リ 太 *^P* Λ 4n偏 Iv'J U.O / Λ rid 1 click n 79 thick * ^ P * Λ 4n bias Iv'J
A o Π 7 /Πリ - 太、御 7t *>11クリ| ς U.O" リ 太 ^Ρ* Λ日 v 83佝 | 'J| u - n An 太 日 B佝 1A o Π 7 / Π--thick, your 7t *> 11 clear | ς U.O "ri thick ^ Ρ * Λ day v 83 | | 'J | u-n An day B´ 1
7 n U ? 太 7ti ΒΠ日 17'J7 n U? Thick 7ti ΒΠ day 17'J
Q o - u. / u 太九日 B掘グリQ o-u./u
Q Q
U.O 太" ¾SB日 ·Μ i 1n u U.O thick "" SB date · 日 i 1n u
11 o 107 o 比 例 11 o 107 o ratio example
12 〇 1.25 〇 比較例12 〇 1.25 〇 Comparative example
13 x(熱間圧延で割れ、破断) 0.70 〇 比較例13 x (cracked and broken by hot rolling) 0.70 〇 Comparative example
14 〇 1.13 O 比較例14 〇 1.13 O Comparative example
15 〇 1.08 〇 比較例15 〇 1.08 比較 Comparative example
16 χ(熱間圧延で割れ、破断) 0.79 〇 比較例16 χ (cracked and broken by hot rolling) 0.79 比較 Comparative example
17 χ(冷間圧延で疵発生） X X 比較例17 χ (scratched by cold rolling) X X Comparative example
18 χ(冷間圧延で疵発生） X X 比較例18 χ (scratched by cold rolling) X X Comparative example
19 〇 1.05 X 比較例19 〇 1.05 X Comparative example
20 〇 1.72 〇 比較例20 〇 1.72 比較 Comparative example
21 〇 1.61 〇 比較例
21 〇 1.61 〇 Comparative example
Claims
1.実質的に、 質量％で、 Ni: 35.0-37.0 %、 Mn: 0.01-0.09 %、 Si: 0.01-0.04 %、 Al: 0.01- 0.04 %、 残部： Feからなり、 かつ Mn / S: 20-300および Mn + Si + A1 ≤ 0.15 %である 1.0 X 10 /K以下の 20-100。Cの平均熱膨張係数を有する低熱膨張合金薄板。 1.Substantially in mass%, Ni: 35.0-37.0%, Mn: 0.01-0.09%, Si: 0.01-0.04%, Al: 0.01-0.04%, balance: Fe, and Mn / S: 20 20-100 up to 1.0 X 10 / K with -300 and Mn + Si + A1 ≤ 0.15%. Low thermal expansion alloy sheet having an average thermal expansion coefficient of C.
2. さらに、 質量％で、 0≤ 0.005 %である請求の範囲 1の低熱膨張合金薄板。 2. The low thermal expansion alloy sheet according to claim 1, wherein the mass% is 0≤0.005%.
3. さらに、 質量％で、 S≤ 0.002 %である請求の範囲 1の低熱膨張合金薄板。 3. The low-thermal-expansion alloy sheet according to claim 1, wherein, in mass%, S≤0.002%.
4. さらに、 質量％で、 S ≤ 0.002 %である請求の範囲 2の低熱膨張合金薄板。 4. The low thermal expansion alloy sheet according to claim 2, wherein S ≤ 0.002% in mass%.
5.請求の範囲 1-4の低熱膨張合金薄板で製造されたシャドウマスク。
5. A shadow mask made of the low thermal expansion alloy sheet according to claim 1-4.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-7002951A KR100519615B1 (en) | 2001-07-05 | 2002-07-04 | Thin Alloy Sheet of Low Thermal Expansion and Shadow Mask Using the Same |
| EP02745824A EP1403393A4 (en) | 2001-07-05 | 2002-07-04 | Thin alloy sheet of low thermal expansion and shadow mask using the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001204212 | 2001-07-05 | ||
| JP2001-204212 | 2001-07-05 |
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|---|---|
| WO2003004715A1 true WO2003004715A1 (en) | 2003-01-16 |
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|---|---|---|---|
| PCT/JP2002/006785 WO2003004715A1 (en) | 2001-07-05 | 2002-07-04 | Thin alloy sheet of low thermal expansion and shadow mask using the same |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1403393A4 (en) |
| KR (1) | KR100519615B1 (en) |
| CN (1) | CN1200130C (en) |
| WO (1) | WO2003004715A1 (en) |
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| JP3854121B2 (en) * | 2001-10-22 | 2006-12-06 | 日本冶金工業株式会社 | Fe-Ni alloy for shadow mask material with excellent corrosion resistance and shadow mask material |
| CN105648323A (en) * | 2016-01-13 | 2016-06-08 | 铜陵百荣新型材料铸件有限公司 | Ferronickel material and preparation technique thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4402684A1 (en) * | 1993-05-27 | 1994-12-01 | Krupp Vdm Gmbh | Low-expansion iron-nickel alloy |
| JPH09176797A (en) * | 1995-12-27 | 1997-07-08 | Nikko Kinzoku Kk | Fe-ni-cr alloy stock for shadow mask, and shadow mask produced therefrom |
| JP2001192775A (en) * | 2000-01-05 | 2001-07-17 | Nisshin Steel Co Ltd | Fe-Ni ALLOY THIN SHEET FOR SHADOW MASK OF EXTENSION SYSTEM |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19920144C1 (en) * | 1999-05-03 | 2000-08-03 | Krupp Vdm Gmbh | Iron-nickel alloy is used for shadow masks and frame parts of screens, passive components of thermo-bimetals, in the production, storage and transport of liquefied gases or for components of laser technology |
-
2002
- 2002-07-04 EP EP02745824A patent/EP1403393A4/en not_active Withdrawn
- 2002-07-04 WO PCT/JP2002/006785 patent/WO2003004715A1/en not_active Application Discontinuation
- 2002-07-04 CN CNB028022955A patent/CN1200130C/en not_active Expired - Fee Related
- 2002-07-04 KR KR10-2003-7002951A patent/KR100519615B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4402684A1 (en) * | 1993-05-27 | 1994-12-01 | Krupp Vdm Gmbh | Low-expansion iron-nickel alloy |
| JPH09176797A (en) * | 1995-12-27 | 1997-07-08 | Nikko Kinzoku Kk | Fe-ni-cr alloy stock for shadow mask, and shadow mask produced therefrom |
| JP2001192775A (en) * | 2000-01-05 | 2001-07-17 | Nisshin Steel Co Ltd | Fe-Ni ALLOY THIN SHEET FOR SHADOW MASK OF EXTENSION SYSTEM |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP1403393A4 * |
Also Published As
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| EP1403393A1 (en) | 2004-03-31 |
| EP1403393A4 (en) | 2005-01-05 |
| CN1200130C (en) | 2005-05-04 |
| CN1464915A (en) | 2003-12-31 |
| KR100519615B1 (en) | 2005-10-07 |
| KR20030024922A (en) | 2003-03-26 |
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