CN1420196A - Fe-Ni and Fe-Ni-Co alloy strip for shadow mask plate - Google Patents

Fe-Ni and Fe-Ni-Co alloy strip for shadow mask plate Download PDF

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Publication number
CN1420196A
CN1420196A CN02152729A CN02152729A CN1420196A CN 1420196 A CN1420196 A CN 1420196A CN 02152729 A CN02152729 A CN 02152729A CN 02152729 A CN02152729 A CN 02152729A CN 1420196 A CN1420196 A CN 1420196A
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Prior art keywords
quality
integrated level
shadow mask
thickness
slab
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CN02152729A
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CN1173064C (en
Inventor
近藤祐幸
深町一彦
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Nippon Mining Holdings Inc
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Nippon Mining and Metals Co Ltd
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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
    • 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
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Cathode-Ray Tubes (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

To provide a high-strength Fe-Ni-based and Fe-Ni-Co-based alloy bars with high strength for a shadow mask capable of effectively preventing the occurrence of mask unevenness. In the Fe-Ni-based and Fe-Ni-Co-based alloys which contain Ni of 34-38 mass%, Mn of 0.1-1.0 mass%, C of 0.10 mass% or less and Al of 0.05 mass% or less, the average value [alpha]AVE of the {100} integration degree distribution in the plate thickness direction on a plate surface is 60% or less and the {100} integration degree [alpha]<SB>c</SB>on the plate surface after removing up to 50% of the plate thickness by etching is larger than the {100} integration degree [alpha]<SB>s</SB>on the plate surface.

Description

Shadow mask board is an alloy bar with iron-nickel system and iron-nickel-cobalt
Technical field
The present invention relates to the bar that the shadow mask board on the color selective electrode in a kind of cathode tube that is used to be provided in the used High Resolution Display of colour television set or home computer is used.
Background technology
The bar that is used on the shadow mask board is made as described below, promptly, the steel ingot that adopts dissolving and casting technique to make is carried out after heat forged and the hot rolling, carries out cold rolling repeatedly and annealing, carries out final cold rolling processing then.The bar that this shadow mask board is used carries out degreasing in etching manufactory, whole surface is handled after, on two surfaces, apply photoresists, then dry and the shadow mask pattern that develops, afterwards, by atomizer, spray ferric chloride Solution from the two sides and bore a hole, be made into shadow mask board thus.
In recent years, along with home computer's indicating meter to high definition development and the thin spaceization in the hole that forms, the bar that the strong request shadow mask board is used has and can suppress shadow mask board and produce uneven high etching pierceability, high strength and low thermal expansion character etc.Take place inhomogeneous and carry out the perforation of thin space ground in order to suppress shadow mask board, must be with the reduced thickness of material, still, thickness one attenuate, rigidity just weaken, with regard to problems such as shock-resistance weakens after having distortion of when processing and cathode tube to pack into.Therefore, wish that the blank that shadow mask board is used has good etching pierceability and intensity.
An index estimating etching and punching is etching factor (below, be referred to as EF).So-called EF is meant the ratio of etch depth with respect to side etching amount (radius in the hole after the etching deducts the size of resist opening radius), and this value is big more, etching and punching is just good more.As everyone knows, in order to improve the EF value, essential improve on the plate face { integrated level of 100} direction (below, be called { 100} integrated level) is particularly when { the 100} integrated level can obtain very good etching and punching 60% when above.But, on the plate face, obtain more than 60% { the 100} integrated level must be suppressed to final processing stage when cold rolling lower.Therefore, just be in such state, promptly, owing to limited the degree of work hardening and can not realize corresponding with high strength.
Summary of the invention
The inventor is to { integrated level of 100} direction is studied in the distribution of thickness of slab direction and the relation of etching and punching with respect to the plate face, found that: in order to suppress the inhomogeneous of shadow mask board, form on the only thickness of slab direction { integrated level of 100} direction distributes, can more effectively improve the section form in hole than improving the etching factor.
The iron that shadow mask board of the present invention is used-nickel system alloy bar is to make on the basis of above-mentioned discovery, it is characterized in that, contains nickel: 34～38 quality %, manganese: 0.1～1.0 quality %; Have by carbon: following, the silicon of 0.10 quality %: 0.1 quality % is following, aluminium: what impurity that 0.05 quality % is following, can not exempt from and the remainder that comes down to iron constituted forms; { the mean value α that the 100} integrated level distributes in the thickness of slab direction on the plate face AVEBe below 60%, and at { the 100} integrated level α that with etch process thickness of slab is removed on the face that goes to after 50% c{ 100} integrated level α than plate face surface sAlso big.
As mentioned above, according to the present invention, because { the mean value α that the 100} integrated level distributes in the thickness of slab direction on the plate face AVEBe below 60%, and at { the 100} integrated level α that with etch process thickness of slab is removed on the face that goes to after 50% c{ 100} integrated level α than plate face surface sAlso big, thereby can obtain high strength and can prevent the effect of the inhomogeneous generation of shadow mask board effectively.
Description of drawings
Fig. 1 is the synoptic diagram of expression with the section form in the hole of etch process perforation.
Fig. 2 is the synoptic diagram of expression with the planeform in the hole of etch process perforation.
Fig. 3 is the expression { synoptic diagram that the 100} integrated level distributes of the present invention.
Fig. 4 is { the mean value α that the 100} integrated level distributes in the thickness of slab direction that represents to obtain approx on the plate face AVEThe graphic representation of method.
Embodiment
Fig. 1 is the synoptic diagram that is used to illustrate effect of the present invention, the section in the hole that expression is bored a hole by etch process.Fig. 1 (A) be illustrated on the plate face of bar { the mean value α that the 100} integrated level distributes in the thickness of slab direction is the section form in 60% hole when following; Fig. 1 (B) be illustrated on the plate face of bar { the mean value α that the 100} integrated level distributes in the thickness of slab direction surpasses the section form in 60% o'clock hole.The EF of, Fig. 1 (B) visible from these accompanying drawings is than the EF height of Fig. 1 (A).And under the occasion of lower Fig. 1 of EF (A), the interface on the inner peripheral surface in hole and surface divide to form sharp-pointed section form, and shown in Fig. 2 (A), the shape in hole just is not correct circle, forms oblate shape.It is inhomogeneous that shadow mask board just takes place its result easily.
On the other hand, { the 100} integrated level must be as mentioned above, final cold rolling processing stage is reduced, and can not realize corresponding with high strength in order to improve.The present invention is because with { the 100} integrated level is got into below 60% at the mean value α that the thickness of slab direction distributes, thereby can obtain the hole shown in Fig. 1 (B) and Fig. 2 (B).Promptly, use in iron-nickel system alloy bar at shadow mask board of the present invention, since make the thickness of slab skin section { the 100} integrated level is than inner low (make EF less), thereby near the direction of the top layer, with respect to atomizer, spraying, the etching speed to horizontal direction is increased, thereby can be shown in Fig. 1 (B), obtain the smoother section form in edge in hole; Can be as Fig. 2 (B) shown in, obtain hole near correct circle.Like this, spraying with atomizer under the occasion bore a hole, on the thickness of slab direction { in the 100} integrated level distribution mode, near less the sort of top layer, inner higher distribution can obtain good pore cross section shape.And in the inboard of thickness of slab direction, because { the 100} integrated level is higher, EF is higher, thereby can obtain good etching and punching.
In the present invention, because { the mean value α that the 100} integrated level distributes in the thickness of slab direction on the plate face AVEBe below 60%, thus higher by final cold rolling work hardening capacity, like this, just can improve intensity.It is wherein, so-called that { the 100} integrated level is calculated by following several 1.And, the integrated intensity I (hk1) of each crystal plane be by X ray diffraction (below, be called XRD), from each orientation peak (2 θ) ± integrated intensity 3 ° of scopes deducts the intensity of background.
[several 1]
100} integrated level (%) α=
I(200)/{I(111)+I(200)+I(220)+I(311)}×100
And, { the mean value α that the 100} integrated level distributes in the thickness of slab direction on the plate face AVEBe with following several 2 definition.And Fig. 3 represents the { synoptic diagram that the 100} integrated level distributes of the present invention.
[several 2] &alpha; AVE = &Integral; 0 t &alpha; ( t ) &CenterDot; dt t
In fact, mean value α AVECan obtain approx as shown in Figure 4.Remove on the surface of each alloy with the atomizer etching, from a side on the face of 12 μ m (be equivalent to thickness of slab 10%), 36 μ m (be equivalent to thickness of slab 30%), 60 μ m (be equivalent to thickness of slab 50%), measure with XRD.
In order to obtain aforesaid effect of the present invention, effect really, best, thickness of slab is removed { 100} integrated level α on the face that goes to after 50% with etch process c{ 100} integrated level α with respect to plate face surface sRatio be more than 1.2.
And, the iron that above-mentioned shadow mask board is used-nickel system alloy bar is the category that belongs to the invar alloy, be lower than the thermal expansion of iron-nickel system alloy bar and iron-nickel-cobalt is the thermal expansion of alloy bar, and intensity is also higher, can be used for shadow mask board well, this is one of feature of the present invention.Promptly, the iron-nickel-cobalt used of shadow mask board of the present invention is alloy bar, it is characterized in that containing nickel: 28～34 quality %, cobalt: 2～7 quality %, manganese: 0.1～1.0 quality %; Have by carbon: following, the silicon of 0.10 quality %: 0.1 quality % is following, aluminium: what impurity that 0.05 quality % is following, can not exempt from and the remainder that comes down to iron constituted forms; { the mean value α that the 100} integrated level distributes in the thickness of slab direction on the plate face AVEBe below 60%, and thickness of slab removed { the 100} integrated level α that goes to after 50% with etch process c{ 100} integrated level α than plate face surface sAlso big.Owing to added the cobalt that has with the nickel similar effect in the above-mentioned alloy bar, thereby the content of nickel be reduced to 28～34 quality %.
The alloy bar that this shadow mask board is used also can obtain effect and the effect identical with above-mentioned alloy bar.And, in order to obtain such effect of the invention described above and effect really, best, thickness of slab is removed { 100} integrated level α on the face after 50% with etch process c{ 100} integrated level α with respect to plate face surface sRatio be more than 1.2.
And the iron that above-mentioned shadow mask board is used-nickel system alloy bar and iron-nickel-cobalt are in the alloy bar, and so-called " coming down to the remainder of iron " be meant except iron, also can contain the element that the characteristic that can not make alloy bar of the present invention changes.
In the heat treatment process after etching, in order to prevent shadow mask board bonding each other (sintering), on the rolling surface of the bar that is used for shadow mask board, apply the concavo-convex apperance that is called the hair side hole.The concavo-convex apperance in this hair side hole for example can be rolling and obtain by the Rolling roller (below, be referred to as dull roll) that has applied suitable concavo-convex processing through methods such as overbump processing on the surface.In rolling processing, poor along with processing stage increases, skin section and inside just produce deflection, particularly compare, because the frictional force of dull roll and material surface is higher, thereby above-mentioned tendency is remarkable with plain roller.With such dull roll, by the final rolling processing stage of control and the diameter of dull roll, can obtain on the alloy bar that shadow mask board of the present invention is used with skin section { the 100} integrated level is controlled to that lower optimal { the 100} integrated level distributes.
The present invention has stipulated composition as described above, and still, the element that is added is not limited to above-mentioned these compositions, can contain any composition that can not damage functions such as nickel or manganese.Though above-mentioned scheme 1 is iron-nickel system alloy,, along with the interpolation of nickel, also contain the trace (below 0.02%) cobalt.Therefore, under cobalt contained occasion below 0.02%, it also was included in the category of iron-nickel system alloy.
Embodiment
Below, with embodiment the present invention is described in more detail.
With the alloy A, the B that form shown in the molten tabulation 1 of vacuum dissolution process; Then, steel ingot is carried out heat forged and hot rolling.Under this occasion, alloy A is made up of claim 1,2 regulations; Alloy B is made up of claim 3,4 regulations.Then, after the oxide skin on surface is removed, carry out cold rolling repeatedly and annealing, carry out final cold rolling processing then, make the alloy bar of 0.12mm thickness.The processing stage of the cold rolling processing that table 2 expression is final and in this cold rolling processing the diameter of used dull roll.And, measured 0.2% endurance of each alloy bar, its result also remembers in table 2.Also remove on the face of 12 μ m (be equivalent to thickness of slab 10%), 36 μ m (be equivalent to thickness of slab 30%), 60 μ m (be equivalent to thickness of slab 50%), measure with XRD at each alloy surface and with the atomizer etch process, from a side.
[table 1]
Nickel Cobalt Manganese Aluminium Carbon Sulphur Silicon Nitrogen Iron
Alloy A ????36.1 ????0.01 ????0.25 ????0.002 ????0.002 ????0.001 ????0.02 ????0.002 Balance
Alloy B ????32.1 ????5.1 ????0.26 ????0.002 ????0.003 ????0.002 ????0.01 ????0.002 Balance
Resulting integrated level is recorded in the table 2.And, by these integrated levels, as shown in Figure 4, be that the ratio of the 0-50% degree of depth is obtained the mean value that the thickness of slab direction distributes approx with thickness of slab, as mean value α AVEAnd be recorded in the table 2.Also obtain thickness of slab center { 100} integrated level α c{ 100} integrated level α with respect to the surface sRatio, its result also is recorded in the table 2.
[table 2]
Figure A0215272900071
*)Surface (0%): surface { the integrated level measurement result of 100}
12 μ m (10%): { the 100} integrated level measurement result after 12 μ m (thickness of slab the 10%) etching
36 μ m (30%): { the 100} integrated level measurement result after 36 μ m (thickness of slab the 30%) etching
60 μ m (50%): { the 100} integrated level measurement result after 60 μ m (thickness of slab the 50%) etching
Then, use known photoetching method, at the two sides of these alloy bars coating photoresist material, video picture goes out after the pattern drying, and bores a hole from two sides injection ferric chloride Solution, is made into shadow mask board thus.In the darkroom, with transmitted light or reflected light, the shadow mask board that makes is observed, confirm to have or not shadow mask board inhomogeneous.The uneven occasion of shadow mask board will take place to be expressed as " * ", will not to take place that the uneven occasion of shadow mask board is expressed as " zero ", that shadow mask board will take place will be inhomogeneous and use to go up no problem occasion and be expressed as " △ " and be recorded in the table 2.Also shadow mask board intensity is estimated, the inadequate occasion of shadow mask board intensity is expressed as " * ", the sufficient occasion of shadow mask board intensity is expressed as " zero " and is recorded in the table 2 from 0.2% endurance of measuring.
By table 2 as seen, in an embodiment, owing to carried out 40% final processing, thereby the work hardening of alloy bar can fully carry out, and can obtain sufficient shadow mask board intensity.Because processing stage height, thereby { the mean value α that the 100} integrated level distributes in the thickness of slab direction AVEJust become below 60%.Because having used diameter in an embodiment is the dull roll of 50～60mm, thereby the processing strain of the surface element of alloy bar is bigger, { the 100} integrated level α on surface sLess, make α c/ α sGreater than 1.Diameter is among the embodiment 5～6 of 60mm, there have the inhomogeneous generation of shadow mask board to use to be no problem; Diameter is among the embodiment 1～4 of 50mm, do not have the inhomogeneous generation of shadow mask board.And the intensity of any shadow mask board all is sufficient.
Relative therewith, in comparative example 7～10, because final processing stage is lowered into 30%, { distribution of 100} integrated level α surpasses 60% to the thickness of slab direction, thereby that shadow mask board does not irrespectively take place is inhomogeneous with roller diameter.But because final processing stage is lower, thereby shadow mask board intensity is inadequate.The height of the embodiment 1,2 of the shadow mask board strength ratio A alloy of the comparative example 8,10 of B alloy still, still be inadequate as the B alloy that high shadow mask board requirement of strength is arranged with it.
On the other hand, in the comparative example 11,12 that final processing stage has increased, though shadow mask board intensity is fully, because roller diameter is bigger, thereby it is inhomogeneous that shadow mask board has taken place.When used dull roll diameter was big in final processing, processing compressive strain layer was darker, thereby makes α c/ α sDiminish, it is inhomogeneous that shadow mask board just takes place its result.

Claims (4)

1. a shadow mask board is with iron-nickel system alloy bar, it is characterized in that, contain nickel: 34～38 quality %, manganese: 0.1～1.0 quality % has by carbon: following, the silicon of 0.10 quality %: 0.1 quality % is following, aluminium: what impurity that 0.05 quality % is following, can not exempt from and the remainder that comes down to iron constituted forms; { the mean value α that the 100} integrated level distributes in the thickness of slab direction on the plate face AVEBe below 60%, and at { the 100} integrated level α that with etch process thickness of slab is removed on the face that goes to after 50% c{ 100} integrated level α than plate face surface sAlso big.
2. a shadow mask board is with iron-nickel system alloy bar, it is characterized in that, contain nickel: 34～38 quality %, manganese: 0.1～1.0 quality % has by carbon: following, the silicon of 0.10 quality %: 0.1 quality % is following, aluminium: what impurity that 0.05 quality % is following, can not exempt from and the remainder that comes down to iron constituted forms; { the mean value α that the 100} integrated level distributes in the thickness of slab direction on the plate face AVEBe below 60%, and at { the 100} integrated level α that with etch process thickness of slab is removed on the face that goes to after 50% c{ 100} integrated level α with respect to plate face surface sRatio be more than 1.2.
3. a shadow mask board is an alloy bar with iron-nickel-cobalt, it is characterized in that, contains nickel: 28～34 quality %, cobalt: 2～7 quality %, manganese: 0.1～1.0 quality %; Have by carbon: following, the silicon of 0.10 quality %: 0.1 quality % is following, aluminium: what impurity that 0.05 quality % is following, can not exempt from and the remainder that comes down to iron constituted forms; { the mean value α that the 100} integrated level distributes in the thickness of slab direction on the plate face AVEBe below 60%, and thickness of slab removed { the 100} integrated level α that goes to after 50% with etch process c{ 100} integrated level α than plate face surface sAlso big.
4. a shadow mask board is an alloy bar with iron-nickel-cobalt, it is characterized in that, contains nickel: 28～34 quality %, cobalt: 2～7 quality %, manganese: 0.1～1.0 quality %; Have by carbon: following, the silicon of 0.10 quality %: 0.1 quality % is following, aluminium: what impurity that 0.05 quality % is following, can not exempt from and the remainder that comes down to iron constituted forms; { the mean value α that the 100} integrated level distributes in the thickness of slab direction on the plate face AVEBe below 60%, and thickness of slab removed { the 100} integrated level α that goes to after 50% with etch process c{ 100} integrated level α with respect to plate face surface sRatio be more than 1.2.
CNB021527296A 2001-11-20 2002-11-20 Fe-Ni and Fe-Ni-Co alloy strip for shadow mask plate Expired - Fee Related CN1173064C (en)

Applications Claiming Priority (4)

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JP2001354603 2001-11-20
JP354603/2001 2001-11-20
JP2002237093A JP3740105B2 (en) 2001-11-20 2002-08-15 Fe-Ni and Fe-Ni-Co alloy strips for shadow mask
JP237093/2002 2002-08-15

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JP6177299B2 (en) * 2015-11-04 2017-08-09 Ｊｘ金属株式会社 Metal mask material and metal mask
TWI765121B (en) 2017-11-14 2022-05-21 日商大日本印刷股份有限公司 Metal plate for manufacturing vapor deposition cover, inspection method of metal plate, manufacturing method of metal plate, vapor deposition cover, vapor deposition cover device, and manufacturing method of vapor deposition cover

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JPS6314841A (en) * 1986-07-04 1988-01-22 Nippon Mining Co Ltd Shadow mask material and shadow mask
JP2929881B2 (en) * 1992-01-31 1999-08-03 日本鋼管株式会社 Metal sheet for shadow mask with excellent etching processability
CN1035778C (en) * 1993-07-22 1997-09-03 日本钢管株式会社 An alloy sheet having high etching performance
JPH08273433A (en) * 1995-03-29 1996-10-18 Nikko Kinzoku Kk Raw material for fe-ni alloy lead frame
MY123398A (en) * 1997-05-09 2006-05-31 Toyo Kohan Co Ltd Invar alloy steel sheet for shadow mask, method for producing same, shadow mask, and color picture tube

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CN1173064C (en) 2004-10-27

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Granted publication date: 20041027