EP0627494B1 - Legierung für Schattenmaske und Verfahren zu dessen Herstellung - Google Patents

Legierung für Schattenmaske und Verfahren zu dessen Herstellung Download PDF

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Publication number
EP0627494B1
EP0627494B1 EP19930120232 EP93120232A EP0627494B1 EP 0627494 B1 EP0627494 B1 EP 0627494B1 EP 19930120232 EP19930120232 EP 19930120232 EP 93120232 A EP93120232 A EP 93120232A EP 0627494 B1 EP0627494 B1 EP 0627494B1
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European Patent Office
Prior art keywords
cold
rolling
annealing
forming
press
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EP19930120232
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English (en)
French (fr)
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EP0627494A1 (de
Inventor
Tadashi C/O Intellectual Prop. Dept. Inoue
Kiyoshi C/O Intellectual Prop. Dept. Tsuru
Michihito C/O Intellectual Prop. Dept. Hiasa
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JFE Engineering Corp
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NKK Corp
Nippon Kokan Ltd
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Priority claimed from JP15288593A external-priority patent/JP3367147B2/ja
Priority claimed from JP18493893A external-priority patent/JP3367153B2/ja
Application filed by NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Priority to EP96101338A priority Critical patent/EP0739992B1/de
Publication of EP0627494A1 publication Critical patent/EP0627494A1/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/14—Manufacture of electrodes or electrode systems of non-emitting electrodes
    • H01J9/142—Manufacture of electrodes or electrode systems of non-emitting electrodes of shadow-masks for colour television tubes
    • 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
    • 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
    • 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
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • 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
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • 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
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0268—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment between cold rolling steps
    • 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
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • 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 relates to an alloy sheet for making a shadow mask having high press-formability and a method of manufacturing the same.
  • a recent trend of up-grading color television to high definition TV has employed Fe-Ni alloy containing 34 to 38wt.% Ni as the alloy for making a shadow mask to suppress color-phase shift.
  • Fe-Ni alloy containing 34 to 38wt.% Ni as the alloy for making a shadow mask to suppress color-phase shift.
  • conventional Fe-Ni alloy has a considerably lower thermal expansion coefficient. Accordingly, a shadow mask made of conventional Fe-Ni alloy raises no problem of color-phase shift coming from the thermal expansion of the shadow mask even when an electron beam heats the shadow mask.
  • An alloy ingot is prepared by a continuous casting process or ingot-making process.
  • the alloy ingot is subjected to slabbing, hot-rolling, cold-rolling, and annealing to form an alloy sheet.
  • the alloy sheet for the shadow mask is then usually processed in the following steps to form a shadow mask.
  • the alloy sheet is photo-etched to form passage-holes for the electron beam on the alloy sheet for the shadow mask.
  • a thin alloy sheet for a shadow mask which has been perforated by etching is hereinafter referred to as a "flat mask”.
  • the flat mask is subjected to annealing.
  • the annealed flat mask is pressed into the curved shape of a cathode ray tube.
  • the press-formed flat mask is assembled to form a shadow mask, which is then subjected to blackening treatment.
  • a shadow mask which is prepared by cold-rolling, recrystallization annealing, or by further slight finishing rolling after recrystallization annealing, has greater strength than conventional low carbon steel. Accordingly, such a conventional Fe-Ni alloy is subjected to softening-annealing (annealing before press-forming) at a temperature of 800°C or more before press-forming to make the grains of which it is composed coarse. After the softening-annealing, a warm-press is applied to carry out spheroidal forming. A temperature of 800°C or more is, however, in the high temperature region.
  • JP-A-H3-267320 the term JP-A- referred to herein signifies an unexamined Japanese patent publication .
  • This prior art employs cold-rolling, recrystallization annealing, finish cold-rolling and softening annealing. The finish cold-rolling is conducted at a reduction ratio of 5 to 20%.
  • the temperature of the softening annealing is below 800°C, more specifically at 730°C for 60 min.
  • This prior art produces a sheet having sufficiently low strength to give good press-forming performance with a 0.2% proof stress of 9.5 kgf/mm 2 (10 kgf/mm 2 or less) at 200°C.
  • Shadow masks prepared by the prior art were found to gall the die and to exhibit cracks generated at the edge of the shadow masks.
  • the object of the present invention is to provide an alloy sheet for making a shadow mask having high press-formability and a method of manufacturing the same.
  • the present invention provides an alloy sheet for making a shadow mask consisting of 34 to 38 wt.% of Ni, 0.001-0.07 wt.% of Si, 0.002 wt.% or less of B, 0.002 wt.% or less of O, 0.0001-0.002 wt.% of N, 0-1 wt.% of Co, optionally 0.0001-0.005 wt.% of C, optionally 0.001-0.35 wt.% of Mn, optionally 0.001-0.05 wt.% of Cr, and a balance of Fe and inevitable impurities;
  • the present invention also provides an alloy sheet for making a shadow mask consisting of 28 to 38 wt.% of Ni, 0.001-0.07 wt.% of Si, 0.002 wt.% or less of B, 0.002 wt.% or less of O, 0.0001-0.002 wt.% of N, over 1 to 7 wt.% of Co, optionally 0.0001-0.005 wt.% of C, optionally 0.001-0.35 wt.% of Mn, optionally 0.001-0.05 wt.% of Cr, and a balance of Fe and inevitable impurities;
  • the present invention also provides a method for manufacturing an alloy sheet for a shadow mask comprising the steps of:
  • vorable press-formability means having excellent shape freezing performance, having a good fit with dies (free of galling of dies), and generating no cracks in materials during press-forming.
  • the present invention asks for a specific range of yield strengths in order to improve shape fixability during hot press-forming and to suppress crack generation in alloy sheet.
  • Yield strength is represented by 0.2% proof stress of 28.0 kgf/mm 2 at room temperature after softening annealing before press-forming (hereinafter referred to as "annealing before press-forming"). 0.2% proof stress of 28.0 kgf/mm 2 or less further improves the shape fixability.
  • the gist of the present invention is as follows.
  • Fe-Ni alloy sheet for shadow masks has to have an upper limit to average thermal expansion coefficient of approximately 2.0 x 10 -6 / °C in the temperature range of 30 to 100°C.
  • the average thermal expansion coefficient depends on the content of Ni in the alloy sheet.
  • the Ni content which satisfies the above limitation of average thermal expansion coefficient is in a range of 34 to 38wt.%. Consequently, the preferred Ni content is in a range of 34 to 38wt.%. More preferably, the Ni content which further decreases average thermal expansion coefficient is in a range of 35 to 37wt.%, and most preferably in a range of 35.5 to 36.5 wt.%.
  • Fe-Ni alloy includes Co as one of the inevitable impurities.
  • Co of 1 wt.% or less does not affect the characteristics. Ni content which satisfies the above described range is also employed. On the contrary, when over 1 wt.% to 7 wt.% Co is included, the Ni content which satisfies the above limitation of average thermal expansion coefficient is in a range of 28 to 38 wt.%. Consequently, the Ni content is specified as 28 to 38 wt.% when over 1 wt.% to 7 wt.% Co is included. Co and Ni content to further improve the characteristics is in a range of 3 to 6 and 30 to 33 wt.%, respectively. As Co of over 7 wt.% increases the thermal expansion coefficient, the upper limit of Co content is defined as 7 wt.%.
  • Oxygen is one of the inevitable impurities.
  • non-metallic oxide inclusion increases in the alloy.
  • Non-metallic inclusion suppresses the growth of crystal grains during annealing before press-forming, particularly under conditions of 720 to 790°C and 40min or less annealing time, which are the conditions before press-forming specified in this invention. If the content of O exceeds 0.002%, the growth of crystal grains is suppressed and 0.2% proof stress after annealing before press-forming exceeds 28.0 kgf/mm 2 .
  • the lower limit of O content is not specially limited, but it is selected to be 0.001% from the economy of ingot-making processes.
  • Boron enhances the hot-workability of the alloy.
  • An excess amount of B induces the segregation of B at boundaries of recrystallized grains formed during annealing before press-forming, which inhibits the free migration of grain boundaries and results in the suppression of grain growth and the 0.2% proof stress after annealing before press-forming limit to be exceeded.
  • the suppression of grain growth is strong and the does not uniformly affect all grains, so a severely mixed grain structure is accompanied by irregular elongation of material during press-forming.
  • Boron also increases the gathering degree of ⁇ 211 ⁇ planes after annealing, which causes cracks on the skirt of the material.
  • Silicon is used as the deoxidizer during ingot-making of the alloy.
  • Si content exceeds 0.07wt.%, an oxide film of Si is formed on the surface of the alloy during annealing before press-forming. The oxide film degrades the fit between die and alloy sheet during press-forming and results in the galling of the die by the alloy sheet. Consequently, the upper limit of Si content is specified as 0.07wt.%. Less Si content improves the fit of die and alloy sheet. The lower practical limit of Si content is 0.001wt.% or more from the economy of ingot-making processes.
  • Nitrogen is an element unavoidably entering into the alloy during ingot-making processes. 0.0020 wt.% or more of nitrogen induces the concentration of N on the surface of the alloy during annealing before press-forming. The concentrated N on the surface of the alloy degrades the fit of the die and alloy sheet to gall the die with the alloy sheet. Consequently, N content is specified to be below 0.0020wt.%. The lower practical limit of N content is 0.0001wt.% or higher from the economy of ingot-making processes.
  • the composition further contains 0.0001 to 0.005 wt.% C, 0.001 to 0.35wt.%Mn, and 0.001 to 0.05wt.% Cr.
  • the control of alloy composition and of 0.2% proof stress after annealing before press-forming specified in this invention suppresses the galling of dies by alloy sheet during press-forming and gives a superior shape fixability.
  • press-forming quality there remains the problem of crack generation in press-formed materials.
  • Fig. 1 shows the relation between crack generation on alloy sheet during press-forming, the gathering degree of ⁇ 211 ⁇ planes, and 0.2% proof stress for an alloy sheet having chemical composition specified in the present invention.
  • the gathering degree of ⁇ 211 ⁇ planes is determined from the relative X-ray intensity ratio of (422) diffraction planes of alloy sheet after annealing before press-forming divided by the sum of the relative X-ray diffraction intensity ratios of (111), (200), (220), (311), (331), and (420) diffraction planes.
  • the relative X-ray diffraction intensity ratio is defined as the value of X-ray diffraction intensity observed on each diffraction plane divided by the theoretical X-ray diffraction intensity of that diffraction plane.
  • the relative X-ray diffraction intensity ratio of the (111) diffraction plane is determined from the X-ray diffraction intensity of the (111) diffraction plane divided by the theoretical X-ray diffraction intensity of the (111) diffraction plane.
  • the measurement of the degree of ⁇ 211 ⁇ planes was carried by measuring the X-ray diffraction intensity of (422) diffraction planes which have equivalent orientation to ⁇ 211 ⁇ planes.
  • Fig. 1 clearly shows that the case where 0.2% proof stress does not exceed 28.0 kgf/mm 2 and where the gathering degree of ⁇ 211 ⁇ planes does not exceed 16% does not induce crack generation in alloy sheet during press-forming, which fact indicates the effect of this invention. Based on this finding, the invention specifies 16% or less for the gathering degree of ⁇ 211 ⁇ planes as the condition to suppress crack generation in the alloy sheet.
  • uniform heat treatment of the slab after slabbing is not preferable.
  • a uniform heat treatment is carried at 1200°C or more for 10 hours or more, the gathering degree of ⁇ 211 ⁇ planes exceeds the range specified in the present invention. Therefore, such heat treatment must be avoided.
  • Fig. 2 shows the trend that a high degree of ⁇ 211 ⁇ planes gives a low elongation perpendicular to the rolling direction. Increased degree of ⁇ 211 ⁇ planes decreases the elongation perpendicular to the rolling direction and lowers the fracture limit, then presumably induces cracks.
  • Hot-rolled alloy strips having the composition above were subjected to annealing (in the temperature range of 910 to 990°C), cold-rolling, recrystallization annealing, finish cold-rolling, and annealing before press-forming (at 750°C for 15min.) to produce alloy sheets.
  • the alloy sheets were tested for tensile strength to determine 0.2% proof stress (the values are shown in parentheses in Fig. 3).
  • Fig. 3 shows the relation between the 0.2% proof stress, reduction ratio of finish cold-rolling and average austenite grain size before finish cold-rolling. In this test, the specified austenite grain size was obtained by varying the temperature of recrystallization annealing before finish cold-rolling.
  • the structure control of the alloy sheet of the present invention is realized by controlling the frequency of nucleation during recrystallization, through the control of the overall structure of the alloy during hot-rolled sheet annealing, and an adequate reduction ratio of finish cold-rolling in response to the grain size before finish cold-rolling.
  • Fig. 3 shows that further reduction of 0.2% proof stress after annealing before press-forming is achieved by optimizing the reduction ratio of finish cold-rolling (R%).
  • the 0.2% proof stress can be 27.5 kgf/mm 2 or less. 21 ⁇ R ⁇ 70 6.38D - 122.6 ⁇ R ⁇ 6.38D - 65.2
  • the 0.2% proof stress can be 27 kgf/mm 2 or less.
  • the present invention specifies the reduction ratio of finish cold-rolling R(%) to satisfy equations (2a) and (2b) above, in response to the average austenite grain size D ( ⁇ m) before finish cold-rolling to obtain 0.2% proof stress of 27.5 kgf/mm 2 or less, and specifies the reduction ratio of finish cold-rolling R(%) to satisfy equations (3a) and (3b) above, in response to the average austenite grain size D ( ⁇ m) before finish cold-rolling to obtain 0.2% proof stress of 27.0 kgf/mm 2 or less.
  • the average austenite grain size specified by the relation to reduction ratio of finish cold-rolling, R is obtained by annealing a hot-rolled sheet followed by cold-rolling- and annealing in a temperature range of 860 to 950°C for 0.5 to 2 min.
  • this invention specifies the temperature (T) of annealing before press-forming to be 790°C or less, and the annealing time (t) before press-forming to be 40min. or less and T ⁇ -53.8 log t + 806.
  • the alloy of this invention gives both 0.2% proof stress and gathering degree of ⁇ 211 ⁇ planes specified in this invention.
  • the comparative alloys clearly have problems in their press-formability with 0.2% proof stress exceeding 28.0 kgf/mm 2 even if annealed at 750°C, and with the gathering degree of ⁇ 211 ⁇ planes exceeding the limit specified in the present invention. Accordingly, the present invention emphasizes the alloy composition as well as the specification of manufacturing method.
  • the annealing before press-forming of this invention may be carried before photo-etching. In that case, if the conditions for annealing before press-forming are kept within the ranges specified in this invention, then satisfactory photo-etching quality is secured. As for the alloy of the prior art, annealing before press-forming cannot be conducted before photo-etching because photo-etching after annealing before press-forming following the conditions of this invention results in poor quality photo-etching. On the contrary, the alloy of this invention having specified composition and gathering degree of ⁇ 211 ⁇ planes keeps its favorable quality if photo-etching after annealing before press-forming is conducted.
  • alloys No. 1 through No. 23 having the compositions shown in Table 1 and Table 2.
  • Alloys No. 1 through No. 13 and No. 18 through No. 23 were cast into ingots. These ingots were subjected to adjusting, blooming, scarfing and hot-rolling (at 1100°C for 3 hrs) to provide hot-rolled sheet.
  • Alloys No. 14 through No. 17 were directly cast into thin plates, these plates were hot-rolled at a reduction ratio of 40%, then rolled at 700°C to provide a hot-rolled sheet.
  • hot-rolled sheets were subjected to annealing (at 930°C), cold-rolling, recrystallization annealing, cold-rolling, recrystallization annealing (following the conditions shown in Table 5) and finish cold-rolling (at a reduction ratio of 21%) to provide alloy sheets having a thickness of 0.25 mm.
  • the hot-rolled sheets were fully recrystallized by hot-rolling.
  • the alloy sheets were etched to make flat masks, which flat masks were then treated by annealing before press-forming at 750°C for 20 min. to provide materials No. 1 through No. 23. These were press-formed to inspect the press-formability.
  • Table 1 and Table 2 shows the average austenite grain size before finish cold-rolling of each material
  • Table 3 and Table 4 shows the gathering degree of ⁇ 211 ⁇ planes, tensile properties and press-formability.
  • the tensile properties (0.2% proof stress and elongation perpendicular to the rolling direction) and gathering degree of ⁇ 211 ⁇ planes were inspected after annealing before press-forming. The tensile properties were determined at room temperature. The measurement of the gathering degree of ⁇ 211 ⁇ planes was carried out with the X-ray diffraction method described before.
  • materials No. 1 through No. 13 which have chemical compositions, gathering degrees of ⁇ 211 ⁇ planes, and 0.2% proof stresses within the ranges specified in the present invention, show excellent press-formability. Materials No. 1 through No. 17 of the present invention that include Co also show excellent press-formability.
  • Hot-rolled sheets of alloy Nos. 1, 9 and 14, which were used in Example 1, were employed. Annealing for hot-rolled sheet was applied to these materials under various annealing conditions given in Table 6, and no annealing was applied to one material, which is also given in the table. They were subjected to cold-rolling, recrystallization annealing, cold rolling, recrystallization annealing (at 890°C for 1 min.), finish cold-rolling (at a reduction ratio of 21%) to provide alloy sheet having a thickness of 0.25 mm. The flat masks were then treated by annealing before press-forming at 750°C for 15 min. to give materials No. 24 through No. 28. The flat masks were press-formed and were tested for press-formability. Table 6 shows the annealing temperature, average austenite grain size before finish cold-rolling and gathering degree of ⁇ 211 ⁇ planes. Table 7 shows tensile properties and press-formability. The methods for measuring properties were the same as in Example 1.
  • materials No. 24 and No. 25 having a chemical composition and satisfying the conditions specified in the present invention have excellent press-formability.
  • materials No.26 through No. 28 give a hot-rolled sheet annealing temperature above the limit of this invention, and all of these materials give the gathering degree of ⁇ 211 ⁇ planes above the upper limit of this invention and generate cracks in the alloy sheet during press-forming.
  • material No. 28 gives 0.2% proof stress of more than 28.0 kgf/mm 2 and raises the problem of shape fixability during press-forming.
  • Hot-rolled sheets of alloy Nos. 1, 2, 4, 6, 7, 8, 9, 11, 12, 13 and 14 which were used in Example 1 were employed. These hot-rolled sheets were subjected to a process including annealing (at 930°C), cold-rolling, recrystallization annealing, cold-rolling, recrystallization annealing (at the temperature shown in Table 8 and Table 9 for 1 min.), finish cold-rolling to obtain alloy sheets having a thickness of 0.25mm.
  • the alloy sheets were etched to make flat masks, which flat masks were then subjected to annealing before press-forming at 750°C for 20 min. to obtain materials No. 29 through No. 66. These materials were press-formed to determine the press-formability.
  • Table 8 and Table 9 show the annealing temperature before finish cold-rolling, average austenite grain size before finish cold-rolling, reduction ratio of finish cold rolling and tensile properties.
  • Table 10 and Table 11 show the gathering degree of ⁇ 211 ⁇ planes and press-formability. The methods for measuring properties were the same as in Example 1.
  • Table 8 through Table 11 show that materials No. 30 through No. 35, No. 38, No. 41 through 43 and No. 47 through 66, which have chemical compositions and satisfy the conditions of hot-rolled sheet annealing and annealing before press-forming specified in the present invention and give the relation between average austenite grain size before finish cold-rolling and reduction ratio of finish cold-rolling in a region specified in the present invention, give 16% or less of ⁇ 211 ⁇ planes.
  • materials No. 5 30, No. 35, No. 38, No. 41, No. 47, No. 49, No. 50, No. 54, No. 60, No. 63 and No. 66 employed reduction ratios of finish cold-rolling, R, (in Region I in Fig.
  • the relation among the average austenite grain size before finish cold-rolling, conditions of hot-rolled sheet annealing and reduction ratio of finish cold-rolling of comparative materials No. 29, No. 36, No. 37, No. 39, No. 40, No. 44, and No. 45 failed to satisfy the conditions specified in the present invention even if they satisfied the conditions of chemical composition, hot-rolled sheet annealing and annealing before press-forming specified in the present invention. They are out of the scope of this invention for one of the 0.2% proof stress and the gathering degree of ⁇ 211 ⁇ planes or both, and they raise problems with at least one of the shape fixability and crack generation in alloy sheet during press-forming or both.
  • Material No. 46 was treated by annealing before finish cold-rolling at 850°C for 1 min. Such an annealing condition gives an austenite grain size of 10.0 ⁇ m, so the 0.2% proof stress exceeds 28.0 kgf/mm 2 even if the reduction ratio of finish cold-rolling is selected to be 15%. These figures cannot provide a shape fixability during press-forming to satisfy the specifications of this invention.
  • Hot-rolled sheets of alloy Nos. 1, 4, 9, 10, 12, 14, 21 and 22 which were used in Example 1 were employed. These hot-rolled sheets were subjected to a process including annealing (at 930°C), cold-rolling, recrystallization annealing, cold-rolling, recrystallization annealing (at 890°C for 1 min.), finish cold-rolling (at a reduction ratio of 21%) to obtain alloy sheets having a thickness of 0.25 mm.
  • the alloy sheets were etched to make flat masks, which flat masks were then subjected to annealing before press-forming under the conditions shown in Table 12 to obtain materials No. 67 through No. 84. These materials were press-formed to determine their press-formability.
  • Table 12 shows average austenite grain size before finish cold-rolling, conditions for annealing before press-forming, gathering degree of ⁇ 211 ⁇ planes, tensile properties and press-formability.
  • Table 10 and Table 11 show the gathering degree of ⁇ 211 ⁇ planes and press-formability. The methods used for measuring properties were the same as in Example 1.
  • comparative materials No. 72 and No. 73 were annealed before press-forming at a temperature and for a time above the upper limits of the present invention though they satisfied the conditions of chemical composition, hot-rolled sheet annealing and finish cold-rolling (reduction ratio of finish cold-rolling) specified in the present invention. They gave a gathering degree of ⁇ 211 ⁇ planes of 16% or more and cracking was generated. Comparative material No. 63 was annealed before press-forming at a temperature (T) and for a time (t) not satisfying the equation T ⁇ -53.8 log t + 806. Comparative material No.
  • Materials No. 74 and No. 75 employed comparative alloys. Even if annealing before press-forming was carried out at 750°C for 60 min., their 0.2% proof stress values exceeded 28.0 kgf/mm 2 and they had problems with shape fixability during press-forming. The gathering degree of ⁇ 211 ⁇ planes of these materials exceeded 16%, and cracks were generated in the alloy sheets.
  • Table 13 shows the average austenite grain size, conditions for annealing before press-forming and gathering degree of ⁇ 211 ⁇ planes of each material.
  • Table 14 shows the tensile properties, press-formability and etching performance. Etching performance was determined by visual observation of irregularities appeared on the etched flat masks. The measuring methods for each property were the same as in Example 1.
  • Table 15 shows that materials No. 67, No. 69, No. 70 and No. 76 through No. 84, which satisfy the conditions of chemical composition and hot-rolled sheet annealing, finish cold-rolling (reduction ratio of finish cold rolling), annealing before press-forming (temperature, time) specified in the present invention give a gathering degree of ⁇ 211 ⁇ planes of 16% or less. All of these materials give the 0.2% proof stress aimed for in this invention and show high press-forming quality.
  • Table 16 and Table 17 indicate that materials No. 85 through No. 87 which satisfy the conditions for chemical composition and manufacturing process specified in the present invention give favorable states without irregularities in etching, a degree of ⁇ 211 ⁇ planes of 16% or less, and 0.2% proof stresses within the ranges specified in this invention. All of these materials showed excellent press-form quality.

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Claims (17)

  1. Legierungsblech zur Herstellung einer Schattenmaske, das aus 34 bis 38 Gew.-% Ni, 0,001 bis 0,07 Gew.-% Si, 0,002 Gew.-% oder weniger B, 0,002 Gew.-% oder weniger O, 0,0001 bis 0,002 Gew.-% N, 0 bis 1 Gew.-% Co, fakultativ 0,0001 bis 0,005 Gew.-% C, fakultativ 0,001 bis 0,35 Gew.-% Mn, fakultativ 0,001 bis 0,05 Gew.-% Cr und einem Ausgleich aus Fe und unvermeidlichen Verunreinigungen besteht;
    wobei das Legierungsblech nach einem Glühen und vor einem Preßformen eine 0,2 %-Dehngrenze von 28 kgf/mm2 oder weniger hat; und
    der Sammelgrad der {211}-Ebenen an einer Oberfläche des Legierungsbleches 16 % oder weniger ist.
  2. Legierungsblech nach Anspruch 1, in dem der Ni-Gehalt 35 bis 37 Gew.-% ist.
  3. Legierungsblech nach Anspruch 2, in dem der Ni-Gehalt 35,5 bis 36,5 Gew.-% ist.
  4. Legierungsblech nach Anspruch 1 oder 3, in dem der O-Gehalt 0,001 bis 0,002 Gew.-% ist.
  5. Legierungsblech zur Herstellung einer Schattenmaske, das aus 28 bis 38 Gew.-% Ni, 0,001 bis 0,07 Gew.-% Si, 0,002 Gew.-% oder weniger B, 0,002 Gew.-% oder weniger O, 0,0001 bis 0,002 Gew.-% N, über 1 bis 7 Gew.-% Co, fakultativ 0,0001 bis 0,005 Gew.-% C, fakultativ 0,001 bis 0,35 Gew.-% Mn, fakultativ 0,001 bis 0,05 Gew.-% Cr und einem Ausgleich aus Fe und unvermeidbaren Verunreinigungen besteht;
    wobei das Legierungsblech nach einem Glühen und vor einem Preßformen eine 0,2 %-Dehngrenze von 28 kgf/mm2 oder weniger hat; und
    der Sammelgrad der {211}-Ebenen an einer Oberfläche des Legierungsbleches 16 % oder weniger ist.
  6. Legierungsblech nach Anspruch 5, in dem der Ni-Gehalt 30 bis 33 Gew.-% ist.
  7. Legierungsblech nach Anspruch 5 oder 6, in dem der Co-Gehalt 3 bis 6 Gew.-% ist.
  8. Legierungsblech nach einem der Ansprüche 5 bis 7, in dem der O-Gehalt 0,001 bis 0,002 Gew.-% ist.
  9. Legierungsblech nach Anspruch 1 oder Anspruch 5, in dem die 0,2 %-Dehngrenze 27,5 kgf/mm2 oder weniger ist.
  10. Legierungsblech nach Anspruch 9, in dem die 0,2 %-Dehngrenze 27 kgf/mm2 oder weniger ist.
  11. Verfahren zur Herstellung eines Legierungsbleches für eine Schattenmaske, das die folgenden Schritte umfaßt:
    (a) Herstellen eines heißgewalzten Blechs, das Fe, Ni und Co enthält;
    (b) Glühen des heißgewalzten Blechs in einem Temperaturbereich von 910 bis 990°C;
    (c) ein erster Kaltwalzschritt durch Kaltwalzen des geglühten heißgewalzten Blechs unter Herstellung eines kaltgewalzten Blechs;
    (d) erster Rekristallisationsglühschritt eines Glühens des kaltgewalzten Blechs, das dem ersten Kaltwalzen unterzogen worden war;
    (e) ein zweiter Kaltwalzschritt durch Kaltwalzen des kaltgewalzten Blechs, das dem Kristallisationsglühen unterzogen worden war;
    (f) Schritt eines abschließenden Rekristallisationsglühens des kaltgewalzten Blechs, das dem zweiten Kaltwalzen unterzogen worden war;
    (g) ein Fertigkaltwalzschritt durch Kaltwalzen des kaltgewalzten Blechs, das dem abschließenden Rekristallisationsglühen unterzogen worden war, mit einem Reduzierungsverhältnis in Abhängigkeit von der durchschnittlichen Austenit-Korngröße D (µm), die aus dem abschließenden Rekristallisationsglühen resultiert, wobei das Reduzierungsverhältnis des abschließenden Kaltwalzens den folgenden Gleichungen entspricht: 16≤R≤75,
    Figure imgb0039
     6,38D-133,9≤R≤6,38D-51,0
    Figure imgb0040
    (h) Schritt eines Weichglühens durch Glühen des kaltgewalzten Blechs, das dem Fertigkaltwalzen unterzogen worden war, in einem Temperaturbereich von 720 bis 790°C für 2 bis 40 min vor einem Preßformen und bei Bedingungen, die der folgenden Gleichung entsprechen: T≥-53,8 log t + 806,
    Figure imgb0041
    wobei T (°C) die Temperatur und t (min) die Zeit des Glühens ist.
  12. Verfahren nach Anspruch 11, wobei das heißgewalzte Blech aus 34 bis 38 Gew.-% Ni, 0,001 bis 0,07 Gew.-% Si, 0,002 Gew.-% oder weniger B, 0,002 Gew.-% oder weniger O, 0,0001 bis 0,002 Gew.-% N, 0,001 bis 1 Gew.-% Co, fakultativ 0,0001 bis 0,005 Gew.-% C, fakultativ 0,001 bis 0,35 Gew.-% Mn, fakultativ 0,001 bis 0,05 Gew.-% Cr und einem Ausgleich aus Fe und unvermeidbaren Verunreinigungen besteht.
  13. Verfahren nach Anspruch 11, wobei das heißgewalzte Blech aus 28 bis 38 Gew.-% Ni, 0,001 bis 0,07 Gew.-% Si, 0,002 Gew.-% oder weniger B, 0,002 Gew.-% oder weniger O, 0,0001 bis 0,002 Gew.-% N, über 1 bis 7 Gew.-% Co, fakultativ 0,0001 bis 0,005 Gew.-% C, fakultativ 0,001 bis 0,35 Gew.-% Mn, fakultativ 0,001 bis 0,05 Gew.-% Cr und einem Ausgleich aus Fe und unvermeidbaren Verunreinigungen besteht.
  14. Verfahren nach Anspruch 11, wobei das Fertigkaltwalzen bei einem Kaltwalz-Reduzierungsverhältnis in Abhängigkeit von der durchschnittlichen Austenit-Korngröße D (µm), die aus dem abschließenden Rekristallisationsglühen resultiert, durchgeführt wird, wobei das Kaltwalz-Reduzierungsverhältnis R (%) den folgenden Gleichungen entspricht: 21 ≤ R ≤ 70,
    Figure imgb0042
     6,38 D - 122,6 ≤ R ≤ 6,38 D - 65,2.
    Figure imgb0043
  15. Verfahren nach Anspruch 14, wobei das Fertigkaltwalzen bei einem Kaltwalz-Reduzierungsverhältnis in Abhängigkeit von der durchschnittlichen Austenit-Korngröße D (µm), die aus dem abschließenden Rekristallisationsglühen resultiert, durchgeführt wird, wobei das Kaltwalz-Reduzierungsverhältnis R (%) den folgenden Gleichungen entspricht: 26 ≤ R ≤ 63,
    Figure imgb0044
     6,38 D - 108,0 ≤ R ≤ 6,38 D - 79,3.
    Figure imgb0045
  16. Verfahren nach Anspruch 11, wobei das abschließende Rekristallisationsglühen im Temperaturbereich von 860 bis 950°C für 0,5 bis 2 min durchgeführt wird.
EP19930120232 1993-05-31 1993-12-15 Legierung für Schattenmaske und Verfahren zu dessen Herstellung Expired - Lifetime EP0627494B1 (de)

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JP152885/93 1993-05-31
JP184938/93 1993-07-27
JP18493893A JP3367153B2 (ja) 1993-07-27 1993-07-27 プレス成形性に優れたシャドウマスク用Ｆｅ−Ｎｉ−Ｃｒ系合金薄板及びＦｅ−Ｎｉ−Ｃｏ−Ｃｒ系合金薄板、並びにその製造方法

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FR2727131B1 (fr) * 1994-11-23 1996-12-13 Imphy Sa Alliage fer-nickel a faible coefficient de dilatation
FR2728724B1 (fr) * 1994-12-27 1997-01-24 Imphy Sa Procede de fabrication d'un masque d'ombre en alliage fer-nickel
JP2001131709A (ja) * 1999-11-09 2001-05-15 Nippon Mining & Metals Co Ltd セミテンションマスク用低熱膨張Ｆｅ−Ｎｉ系合金並びにそれを用いたセミテンションマスク及びカラーブラウン管
JP2002038239A (ja) * 2000-07-24 2002-02-06 Yamaha Metanikusu Kk 磁気歪制御型合金板及びこれを用いたカラーブラウン管用部品並びに磁気歪制御型合金板の製造方法
DE10146301C1 (de) * 2001-09-19 2002-07-18 Krupp Vdm Gmbh Verfahren zur Herstellung eines Metallbandes aus einer Eisen-Nickel-Legierung für gespannte Schattenmasken
CN103205630B (zh) * 2012-01-16 2016-04-27 昆山允升吉光电科技有限公司 一种镍铁合金材料及其制备方法
CN102716906B (zh) * 2012-07-10 2015-04-01 冶科金属有限公司 一种高板形ic引线框架用铁镍带材的生产方法
CN106623419B (zh) * 2016-12-14 2018-07-27 无锡华生精密材料股份有限公司 定膨胀合金带材的冷轧生产方法

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JPS61113746A (ja) * 1984-11-07 1986-05-31 Nippon Mining Co Ltd シヤドウマスク材
JPS61113747A (ja) * 1984-11-07 1986-05-31 Nippon Mining Co Ltd シヤドウマスク材
DE3545354A1 (de) * 1984-12-28 1986-07-03 Nippon Mining Co., Ltd., Tokio/Tokyo Schattenmaske und verfahren zur herstellung von schattenmasken
DE3636815A1 (de) * 1985-11-12 1987-05-14 Nippon Mining Co Schattenmaske und verfahren zur herstellung von schattenmasken
JPS6314841A (ja) * 1986-07-04 1988-01-22 Nippon Mining Co Ltd シヤドウマスク材及びシヤドウマスク
JPS63259054A (ja) * 1987-04-16 1988-10-26 Nippon Mining Co Ltd シヤドウマスク
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US5308723A (en) * 1992-01-24 1994-05-03 Nkk Corporation Thin metallic sheet for shadow mask
EP0561120B1 (de) * 1992-01-24 1996-06-12 Nkk Corporation Dünnes Blech aus Fe-Ni-Legierung für Schattenmaske und Verfahren zu dessen Herstellung

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