CN1120246C - Fe-Ni alloy for shadow mask, observational method of inpurities and discriminating method of aperature uniformity - Google Patents

Fe-Ni alloy for shadow mask, observational method of inpurities and discriminating method of aperature uniformity Download PDF

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Publication number
CN1120246C
CN1120246C CN01111269A CN01111269A CN1120246C CN 1120246 C CN1120246 C CN 1120246C CN 01111269 A CN01111269 A CN 01111269A CN 01111269 A CN01111269 A CN 01111269A CN 1120246 C CN1120246 C CN 1120246C
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hole
etching
alloy
inclusion
diameter
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CN1318651A (en
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喜多芳久
波多野隆绍
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Nippon Mining Holdings Inc
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Nippon Mining and Metals Co Ltd
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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
    • 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
    • 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
    • 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
    • H01J2229/075—Beam passing apertures, e.g. geometrical arrangements

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • ing And Chemical Polishing (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Electrodes For Cathode-Ray Tubes (AREA)

Abstract

In the stock for shadow mask excellent in the uniformity of opening diameter at the formation of electron beam transmission holes by etching, etching pits of 0.5-10 &mu m diameter are produced with >=2,000 pieces/mm2 frequency when the surface of an Fe-Ni alloy stock having a composition consisting of 34-38% Ni, <=0.5% Mn and the balance Fe with inevitable impurities or accompanying elements (where C, Si, Al, S and P are made to <=0.10% C, <=0.30% Si, <=0.30% Al, <=0.005% S and <=0.005% P) is mirror polished and immersed in a 3% nitric acid-ethyl alcohol solution at 20 deg.C for 30 s. In addition, a simple method for observing the existence of fine inclusions or precipitates in the Fe-Ni alloy stock and a method for discriminating the uniformity of hole diameter when electron beam transmission holes are pierced by etching are also provided.

Description

The electronics line sees through the Fe-Ni alloy shadow-mask starting material of aperture, hole excellent in uniform
The present invention relates to be used for Fe-Ni alloy for shadow mask starting material, particularly relate to etching and processing and wear the electronics line when seeing through the hole, can get the Fe-Ni alloy shadow-mask starting material that the uniform electronics line in aperture sees through the hole with fine etching and processing perforation.The present invention also relates to simple and easy observational technique that in the Fe-Ni alloy raw material small inclusion or precipitate exist and Fe-Ni alloy shadow-mask with raw-material, wear the aperture inhomogeneity in advance method of discrimination of the electronics line of electronics line when seeing through the hole with etching and processing through the hole.
Always, the shadow mask of colorful cathode ray tube generally uses mild steel.Yet if use cathode tube continuously, because the irradiation of electronics line, the temperature of shadow mask rises, because thermal expansion, fluor and electron beam irradiation position become inconsistent, and it is inaccurate to produce chromatography.Also promptly, make colour picture tube when operation, the electron beam by shadow mask hole is below 1/3 of whole electron beams, and remaining electron beam then bombards on shadow mask, rises so cause the temperature of shadow mask.
Therefore, in the shadow mask field of colorful cathode ray tube,, use Fe-Ni alloy low thermal coefficient of expansion, that be called as " 36 alloy " from the inaccurate viewpoint of chromatography.
As the Fe-Ni alloy shadow-mask be with raw-material manufacture method: with the regulation the Fe-Ni alloy after for example founding with the vacuum metling of VIM stove or with the external refining of LF, be cast as ingot, forge the back hot rolling, remove the oxide skin on slab surface, carry out cold rolling repeatedly and annealing (recrystallization annealing), behind the final annealing, carry out finally cold rollingly, make that to be finish-machined to the following pre-stator of thick 0.3mm thick.Subsequently, rip cutting it, obtain the wide shadow mask starting material of regulation plate.After the degreasing, coating photoresist material in two sides bakes after figure makes video picture subsequently, with etching solution perforation processing, through with every cut-out, obtains the plane screen cover.Plane screen is covered in the non-oxidizing atmosphere gas annealing make it have (in this A Nier method of Prey, this annealing is implemented final stocking) after the punch process before etching, be shaped to the punching press sphere and shield hood-shaped attitude.At last, after the screen cover degreasing with the sphere moulding, in water vapor or combustion gas atmosphere gas, carry out melanism and handle, be formed on lip-deep melanism oxide film.Made shadow mask like this.
In the present invention, see through pitting and carve material processed and always be referred to as the shadow mask starting material supplying with last electronics line after cold rolling.
Such shadow mask generally uses iron(ic) chloride to form the hole that sees through of electronics line by well-known etching and processing.Etching and processing is to use the positive round hole portion that has most for example diameter 80 μ m on the side surface that photoetching technique is formed on the alloy band and behind the mask that forms the positive round hole portion with diameter 180 μ m for example on the relative position on opposite side surface, with the vaporific spraying of ferric chloride in aqueous solution.
Obtain having densification and the shadow mask of the small aperture portion of marshalling by this etching and processing, but owing to partial irregular the irregular of aperture portion diameter that produce of etching condition.This is irregular as become big, when then shadow mask being assembled into cathode tube, will become the inaccurate product of chromatography and inapplicable.Always, decrease in yield when this aperture portion diameter irregular is the etching and processing shadow mask, the major cause that cost increases.
About the irregular inhibition problem of aperture portion diameter, past attempts was done various researchs, aspect material, for example specially opened flat 05-08 No. 6441 and specially opened flat 10-111614 number proposition and set up the method that prevents that this is irregular of knitting jointly by control sets.These method attempts reach the homogeneity of etching and processing by the set Microstructure Control.
Yet by the inventor's research with keen determination, the result understands fully: useful such known technology the electronics line that can not prevent see through the existence of the irregular phenomenon in aperture in hole.Accompanying drawing 1 illustrates, see through " the normal hole " in hole and the SEM photo of " abnormal hole " example (the only shape in comparative observation hole when the side surface etching) with the formed electronics line of etching and processing, this " abnormal hole " be newfound through the present invention, become the irregular reason in aperture.The feature of this abnormal hole is that wall surface of the hole is compared coarse with normal hole; The hole profile portion is corroded unusually, demonstrates the sawtooth form; Simultaneously, the aperture ratio preset aperture has the tendency that becomes big.The feature of this abnormal hole is owing to the difference of etching condition etc. has variation on the degree, and wall is not coarse yet sometimes yet, can not observe spination expressly.Because the aperture deviation can not prevent with technology always due to the generation of this abnormal hole.
Problem of the present invention provides: when forming the electronics line through the hole with etching and processing, even the local etching condition has deviation that irregular Fe-Ni alloy shadow-mask starting material also do not take place on the aperture portion diameter.
The inventor is in order to finish above-mentioned problem, from the brand-new viewpoint that is not always had, with regard to metal structure and as the aperture portion diameter of above-mentioned abnormal hole cause the relation between irregular carried out research with keen determination.Found that: with the Fe-Ni alloy shadow-mask with raw-material surface mirror mirror polish, in 3% nitric acid-ethanolic soln under 20 ℃, after flooding for 30 seconds, the Fe-Ni alloy shadow-mask that has many etch-holes on its erosional surface with starting material on, see through pitting at electronics line thereafter and carve to add and be difficult to produce the irregular of aperture portion diameter man-hour.Distinguished already in the case: exist frequency at 2000/mm as the etch-hole of 0.5 μ m～10 μ m 2More than, show that then the electronics line is seen through pitting to be carved and add the irregular inhibition effect of aperture portion diameter in man-hour.Here, when measuring the etch-hole of erosional surface, in ethanol (the JIS K8101 superfine) 100ml of purity 〉=99.5%, sneak into the nitric acid (JIS K8541) of concentration 60%, be deployed into corrosive fluid.Use opticmicroscope again, under the multiplying power of dark-field picture * 400 that make erosional surface, photograph, on this photo, measure the etch-hole of diameter 0.5 μ m～10 μ m.Again with image analysis apparatus with regard to 0.2mm 2Area calculate the mensuration etch-hole.
The inside of nearly all usefulness 3% nitric acid-ethanolic soln etch-hole all exists inclusion or precipitate particle, and to the result that these particle compositions are identified, they are Al 2O 3, SiO 2, MnO, MgO, CaO, MnS, CaS, AlN, BN etc.
The inventor also understands fully in detail: small inclusion or precipitate and under 20 ℃, give birth to the relation between the etch-hole when flooding for 30 seconds in 3% nitric acid-ethanolic soln.Also be, with various Fe-Ni alloy raw material surface mirror mirror polish, seek inclusion that diameter is 0.1 μ m～5 μ m or precipitate, this position of corrosion in 3% nitric acid-ethanolic soln with electron microscope in its surface, when observing this erosional surface under the dark-field at opticmicroscope, can see in the part corresponding to this inclusion or precipitate has etch-hole.Again, this etch-hole diameter is 0.5 μ m～10 μ m.In the etch-hole that corrodes in 3% nitric acid-ethanolic soln conversely speaking, and show diameter being arranged is inclusion or the precipitate existence of 0.1 μ m～5 μ m.
Owing to small inclusion or precipitate that just can not direct viewing without electron microscope be carried out observation by light microscope as etch-hole, therefore, above-mentioned observational technique is the effective ways of small inclusion or the simple and easy observation of precipitate.For example, when industrial production contained the Fe-Ni alloy of small inclusion of phase to some extent or precipitate amount, for the quality of management product, when just checking contained inclusion of product or precipitate etc. in the manufacturing shop, observational technique of the present invention was extremely useful.
Small inclusion or precipitate to since due to the etching and processing electronics line see through the mechanism of the irregular inhibition of hole aperture portion diameter, not clear in detail as yet, but can do following supposition.
Fe-Ni alloy involved in the present invention is generally made etching and processing with iron(ic) chloride to shadow mask.At this moment, will protect mask to coat on the material, not perforate will partly be covered, only on the perforate part, contact ferric chloride in aqueous solution.If have fine inclusion or precipitate (following with inclusion table it) to exist in this aperture portion, then this inclusion just works as the corrosive starting point, promotes the etching of matrix.Do not have inclusion as all aperture portion, then no matter which aperture portion all becomes same etching state, the irregular of aperture just do not taken place.Yet, in the industrial production of reality, make inclusion completely without being difficult, the inclusion that becomes the corrosion starting point in plurality of opening portion exists with some probability.Faster than the etching speed of aperture portion that it does not have starting point all around in the aperture portion that such corrosion starting point is arranged, therefore, the perforate footpath is just bigger.Do not have that the aperture portion of starting point is early to begin etching more and in the aperture portion that starting point is arranged than it all around, therefore, have the aperture portion of starting point to become anode on the electrochemistry, the aperture portion of not having starting point then becomes negative electrode.In the case, the difference of corrosion speed further strengthens, and the aperture difference of opening after etching and processing ends has also become greatly.On the other hand, when containing fine inclusion as starting material more than the frequency with some, also can there be inclusion in which aperture portion equably, and then irregular on the aperture portion diameter just do not taken place yet.
In the starting material of " abnormal hole " in the invention described above takes place, the inclusion that becomes the corrosion starting point only exists below the frequency with certain, therefore, spreads all over all inclusion homogeneities of starting material and has just lost.In the case, though more than half aperture portion contains the inclusion of mean level (ML), taken place: the aperture portion that does not 1. contain inclusion; 2. contain the many aperture portion of inclusion; 3. distribution aperture portion devious of portion's inclusion etc. within it.Its inclusion of this kind contain the state aperture portion different with respect to the aperture portion that contains the mean level (ML) inclusion with mean level (ML), its inclusion creates a difference to etched percentage contribution, therefore, produces difference on etching speed.As a result, at wall surface of the hole, the hole profile portion, the unusual corrosive hole that has the band feature on the aperture etc. is detected under electron microscope.Again, this abnormal hole can be used as the irregular of aperture portion diameter and estimates.
Like this, in the present invention, with always notion is opposite, to import energetically in the Fe-Ni alloy substrate more than the fixed number, therefore, eliminating or attenuating see through the irregular of hole aperture portion diameter by electronics line due to the etching and processing with microinclusions.
Based on above knowledge and investigation, the invention provides with etching and processing and wear the Fe-Ni alloy shadow-mask starting material that the electronics line sees through the aperture excellent in uniform in hole, it is characterized in that: by (following represent) Ni:34～38% with % in quality percentage (%), below the Mn:0.5%, below the C:0.10% of inevitable impurity of surplus Fe and conduct or associated element, below the Si:0.30%, below the Al:0.30%, below the S:0.005%, the following Fe-Ni alloy shadow-mask of forming of P:0.005% is with on the starting material, after this starting material surface mirror polish, in 3% nitric acid-ethanolic soln under 20 ℃, when flooding for 30 seconds, diameter is that the etch-hole of 0.5 μ m～10 μ m is with 2000/mm 2Above frequency shows.
Be associated therewith, the present invention also be provided in quality percentage (%) by contain Ni:34～38%, below the Mn:0.5%, surplus Fe and below the C:0.10% as inevitable impurity or associated element, below the Si:0.30%.Simple and easy observational technique and Fe-Ni alloy shadow-mask that small inclusion below the Al:0.30%, in the S:0.005% Fe-Ni alloy raw material following, that form below the P:0.005% or precipitate exist use starting material electronics line to see through the inhomogeneity method of discrimination in advance in aperture, hole:
(1) the simple and easy observational technique that small inclusion or precipitate exist in the Fe-Ni alloy raw material is characterized in that; After should raw-material surface mirror mirror polish in 3% nitric acid-ethanolic soln under 20 ℃, etch-hole observation by light microscope when flooding for 30 seconds, from this observation by light microscope result can observe indirectly without electron microscope with regard to direct viewing less than small inclusion or the existence of precipitate;
(2) the Fe-Ni alloy shadow-mask sees through the inhomogeneity method of discrimination in advance in aperture in hole with starting material electronics line: after this starting material surface mirror polish, in 3% nitric acid-ethanolic soln under 20 ℃, when flooding for 30 seconds, diameter is that the etch-hole of 0.5 μ m～10 μ m is with 2000/mm 2Above frequency is showed, and differentiates with etching and processing as benchmark with this to wear the aperture excellent uniformity that the electronics line of electronics line when seeing through the hole sees through the hole.
Regulation Fe-Ni alloy shadow-mask is 34～38% with raw-material Ni content among the present invention.This is because if Ni content exceeds this scope, and then thermal expansivity increases and can not be used for the cause of shadow mask, and Mn is innoxious and add in order to make the deleterious S of hot workability.Yet Mn is as surpassing 0.5%, the starting material hardening, and its processibility degenerates.Therefore, Mn content on be limited to 0.5%.
In addition, the higher limit of making C, Si, Al and P that impurity or associated element contain in the Fe-Ni alloy is limited in 0.10%, 0.30%, 0.30% and 0.005% respectively, this is because when surpassing this concentration and containing these elements, the infringement etching and punching then can not use as material for shadow mask, and S content is significantly undermined above the hot rolling processibility of 0.005% o'clock material.Therefore, S content on be defined as 0.005%.
Fe-Ni alloy raw material of the present invention below is described in detail in detail with etching characteristic due to 3% nitric acid-ethanolic soln:
(1) number of etch-hole: when with the Fe-Ni alloy surface in 3% nitric acid-ethanolic soln under 20 ℃, the diameter that is taken place when flooding for 30 seconds is that the etch-hole number of 0.5 μ m～10 μ m is at 2000/mm 2When above, the electronics line that can suppress when forming the electronics line and see through the hole with etching and processing sees through the irregular of perforate footpath, hole.Therefore, specified diameter is that the number of etch-hole necessity of 0.5 μ m～10 μ m is at 2000/mm in the object of the invention 2More than.Etch-hole is preferably in 2500～10000/mm 2Scope in disperse.
Moreover the shape of etch-hole is a spheric roughly, when measuring its diameter, be determined at the rolling direction parallel direction on the aperture.
(2) diameter of etch-hole
Little with the irregular inhibition effect in the perforate footpath that sees through the hole less than the electronics line of the corresponding inclusion in the hole of 0.5 μ m when forming the electronics line with etching and processing and see through the hole in 3% nitric acid-ethanolic soln under 20 ℃, in the etch-hole of dipping after 30 seconds; Again, injure the electronics line significantly with the corresponding inclusion in hole that surpasses 10 μ m and see through the shape that pitting adds the aperture portion in man-hour quarter, therefore, the diameter of regulation etch-hole is 0.5 μ m～10 μ m.
(3) kind of inclusion, precipitate
If in 3% nitric acid-ethanolic soln, under 20 ℃, flooded for 30 seconds after, observe as etch-hole, and though then the oxide compound, nitride, the carbide that constitute of the kind of inclusion, precipitate and which metal all it doesn't matter, Al can be arranged 2O 3, SiO 2, MnO, MgO, CaO, MnS, CaS, AlN, BN etc.
As described in initial, the Fe-Ni alloy shadow-mask with raw-material manufacture method in, with the Fe-Ni alloy of regulation after vacuum metling or the external refining in LF are founded in VIM stove for example, be cast as ingot, forge the back hot rolling, remove the oxide skin on slab surface, carry out cold rolling repeatedly and annealing (recrystallization annealing), carry out finish rolling behind the final annealing and arrive the finally cold rolling of the following pre-determined thickness of thickness 0.3mm.Subsequently, rip cutting it, obtain the wide shadow mask starting material of predetermined plate.With shadow mask with after the starting material degreasings, two sides coating photoresist material, bake the figure video picture after, with etching solution perforation processing, each sheet is cut off, the plane screen cover.Plane screen covered in the non-oxidizing atmosphere gas anneal, give (this annealing is carried out final stocking in this A Nier method of Prey) after the punch process before etching, be shaped to the shadow mask form with the punching press sphere to it.At last, after the screen cover degreasing of sphere moulding, in water vapour or combustion gas atmosphere, carry out melanism and handle, form the melanism oxide film from the teeth outwards.Make shadow mask like this.
In this a succession of operation,, at first, must adjust the concentration of each element (Al, Si, Mn, Mg, Ca, O, S, N etc.) that constitutes inclusion in order to control the content of above-mentioned inclusion.For this reason, following item is important: 1. select melt raw material according to the foreign matter content of melt raw material; Want suitably as its addition of element of interpolations such as reductor during 2. for refining; 3. for adjusting the content of gaseous constituent (O, S, N etc.), the atmosphere gas in the time of paying attention to molten the refining is taked suitable refining condition; 4. because body of heater material and slag are the sources of sneaking into of impurity, so will make their composition suitable etc.
Secondly, if classification then has: a) generation person in molten metal to inclusion by the inclusion generative process; In ingot, crystallize out or the person of separating out when b) molten metal being cast; C) in the process of processing ingot, the person of separating out etc. in forging, hot rolling, recrystallization annealing.
As Al 2O 3, SiO 2, chemically stable inclusion such as MgO, CaO, CaS through a) or b) process and be imported in the ingot, then this inclusion does not have big variation in thermal treatment (forging, hot rolling, recrystallization annealing etc.) thereafter.Therefore, the condition of founding of ingot has material impact to the amount of these inclusiones.But, with forging, hot rolling, cold rolling etc. starting material are added man-hour, inclusion sometimes or cracking or distortion, its form changes.
On the other hand, with regard to chemically unsettled inclusion c such as MnS and BN) process also be important to it.Also promptly, it is big more when temperature is high more for the solubleness of element in the Fe-Ni starting material that constitutes inclusion, and therefore, when when high temperature is heat-treated, inclusion disappears (solid solution), and when low temperature is heat-treated, then has inclusion to generate (separating out) and react.Solid solution is carried out situation and is separated out the boundary temperature of carrying out situation according to the composition of inclusion and constitute the concentration of element and change, but on qualitative, when the speed of cooling of heat-treating at low temperature or heat was slow, inclusion just increased.
As described above, the means of the small inclusion of several importings are arranged, use which means also out of question.
The cold rolling solid solution that does not participate in inclusion/separate out, as be illustrated, then its draught is restricted by following reason.Here, rolling draught (R) is with R (%)=(t 0-t)/t 0* 100 define, wherein, and t 0Be rolling preceding thickness; t 1Be the thickness after rolling.Surpass 85% as the cold roling reduction before the final recrystallization annealing, then (200) set tissue is significantly flourishing, and the roundness in etching and processing hole descends; On the other hand, be lower than 50% as degree of finish, then the prosperity of the set tissue of (200) in the product is spent lowly, and etching speed descends.When final cold rolling degree of finish surpassed 40%, rolling set tissue was extremely flourishing, and etching speed descends; On the other hand, degree of finish is lower than at 10% o'clock, and in the annealing for the punching formation property before giving punch process, the non-recrystallization tissue residue gets off, and punching formation property descends.
Under such consideration, owing to import the small inclusion that satisfies following condition, when forming the electronics line through the hole with etching and processing, even partial etching condition has deviation, also can not taken place has irregular Fe-Ni alloy shadow-mask starting material based on the aperture portion diameter of above-mentioned abnormal hole.The condition that this small inclusion should satisfy is: create conditions, after the mirror polish of starting material surfaces, in 3% nitric acid-ethanolic soln under 20 ℃, when flooding for 30 seconds, diameter is that the etch-hole of 0.5 μ m～10 μ m is with 2000/mm 2Above frequency shows.
Because these starting material are provided as the etching and processing that formation electronics line sees through the hole, thereby obtain make on most inclusion dispersive matrixes form the electronics line see through the hole, improve based on the diameter of aperture portion due to the abnormal hole irregularly, form the shadow mask starting material that the electronics line sees through the hole.
More and,, surplus Fe following to Ni:34-38%, Mn:0.5% and below the C:0.10% as unavoidable impurities or associated element based on quality percentage (%) (following represent) with % according to the present invention.Below the Si:0.30%, below the Al:0.30%.S:0.005% is following, the following Fe-Ni alloy raw material of forming of P:0.005% provides following two methods:
Simple observational technique to small inclusion or precipitate existence in the Fe-Ni alloy, it is characterized in that: after should raw-material surface mirror mirror polish, in 3% nitric acid-ethanolic soln under 20 ℃, the etch-hole observation by light microscope that occurs when flooding for 30 seconds, from the result of this observation by light microscope, observe indirectly just can not direct viewing without electron microscope small inclusion or the existence of precipitate;
The raw-material electronics line of Fe-Ni alloy for shadow mask sees through the inhomogeneity method of discrimination in advance in aperture in hole: after this starting material surface mirror polish, in 3% nitric acid-ethanolic soln under 20 ℃, when flooding for 30 seconds, diameter is that the etch-hole of 0.5 μ m～10 μ m is with 2000/mm 2Above frequency shows that as benchmark, the electronics line when differentiation wears the electronics line through the hole with etching and processing sees through the hole excellent in uniform with this.
Above-mentioned observational technique and method of discrimination are as the etch-hole observation by light microscope with small inclusion that just can not direct viewing without electron microscope or precipitate.Therefore, being that simple and easy observation is small is mingled with or the effective ways of precipitate; Also be the effective ways of the aperture excellent in uniform when in advance differentiating etching and punching processing electronics line through the hole.For example, when industrial production contains the Fe-Ni alloy of small inclusion of phase to some extent or precipitate amount, when the management product quality, for being extremely useful at contained inclusion of manufacturing shop spot inspection product or precipitate etc.
Embodiment
The concentration of Ni concentration and impurity (associated element) is adjusted to Ni:35.8～36.5%, Mn:0.2～0.5%, Si:0.02～0.3%, S:0.0005～0.005%, Al:0.01～0.3%, C:0.001～0.1%, P:0.001～0.003 scope, secondly, with the alloy pig heat forged, hot rolling, carry out cold rolling repeatedly and annealing after then removing surface scale, remake finally cold rolling, make the thick alloy band of 0.13mm (with cold rolling be worked into thick in 0.6mm, carry out recrystallization annealing, be 75% to be cold rolled to the thick 0.15mm of being with draught again, after the recrystallization annealing, be cold rolled to 0.1mm with draught 33% at last).Moreover, cooling conditions, heat treating method after the melting method of alloy pig and the hot rolling are subsequently changed in the above described manner, make the quantitative changeization of inclusion or precipitate.
About final each test portion when rolling, the surface mirror mirror polish that will get from ten places of different positions, dipping is 30 seconds in 3% nitric acid-ethanolic soln, observes under the dark-field of opticmicroscope, and measuring diameter is the number of the etch-hole of 0.5 μ m～10 μ m.
Here in the gained alloy band, the embodiment of essential condition of the present invention is satisfied in test portion No.1～7th, and No.8～12 item are comparative examples.
Secondly, the photoetching technique of application of known on these alloy bands forms the mask of just justifying aperture portion with most diameter 80 μ m on alloy band one side surface; And on the relative position of opposite side surface, form after the mask of the just round aperture portion with diameter 180 μ m, with the ferric chloride in aqueous solution spraying, form the etching and processing hole.Measure formed 100 electronics lines and see through the Kongzui major diameter.All holes that enter 80 ± 2 μ m are evaluated as " very ", contain maximum diameter and are evaluated as " bad " less than 78 μ m with above above person among 82 μ m (maximum diameter value in each hole) person.
Illustrate from result shown in the table 1, the diameter 0.5 μ m of the relevant test portion No.1 of the present invention～7～10 μ m etch-hole numbers have 2000/mm 2More than, therefore, seeing through pitting at the electronics line and carve and add man-hour, the perforate footpath that the electronics line sees through the hole does not take place irregular, shows uniform etching and punching.
In contrast, the 2000/mm of etching hole count less than of test portion No.8～12 2With the perforate footpath overshoot value of etching and processing gained electronics line through the hole, etching and punching is bad.
In a word, as known to from The above results, owing to satisfy important document of the present invention, carve to add and do not take place irregularly at the electronics line through the aperture that etches open in hole man-hour so see through pitting at the electronics line, just may make the shadow mask of Fe-Ni alloy have good etching and punching with starting material.
As described above, the present invention is with regard to Fe-Ni alloy shadow-mask starting material, to because the irregular problem of aperture portion diameter due to the abnormal hole during etching and processing, find out from whole viewpoints of always not had: it is irregular to be difficult to produce such aperture portion diameter the many Fe-Ni alloy raw materials more than a fixed number of small inclusion, because energetically with in the small inclusion transfer material integral body, when wearing the electronics line with etching and processing when seeing through the hole, it seems the hole that sees through that also may obtain having uniform pore size from the viewpoint of microcosmic.Can be simple and easy and differentiate the Fe-Ni alloy shadow-mask starting material quality of coming out easily in advance, thus the qualification rate of raising shadow mask product.
To see through the shadow mask in hole effective with starting material to wear the electronics line with etching and processing in the present invention, and only additional tension does not make the shadow mask that keeps even shape etc. effective yet for not needing impact briquetting processing after the etching and processing.Again, the present invention's shape that the electronics line is seen through the hole does not need positive circular and wear ellipse, rectangle etc. to see through the shadow mask in hole also effective.Also may be applied to except that shadow mask, apply the purposes of fine etching and processing as lead frame etc.
The simple declaration of accompanying drawing
Fig. 1
When wearing the electronics line through the hole with etching and processing." normal hole " the SEM photo of newfound with the present invention, as to become the irregular reason in aperture " abnormal hole " example.
Table 1

Claims (1)

1. the electronics line when wearing the electronics line through the hole with etching and processing sees through the Fe-Ni alloy shadow-mask starting material of the aperture excellent in uniform in hole, this material is by containing Ni:34～38% in quality percentage (%), below the Mn:0.5%, surplus Fe and as unavoidable impurities or associated element: below the C:0.10%, below the Si:0.30%, below the Al:0.30%, below the S:0.005%, the following Fe-Ni that is formed of P:0.005% is the alloy shadow-mask starting material, it is characterized in that: after described raw-material surface finish, in 3% nitric acid-ethanolic soln, under 20 ℃, when flooding for 30 seconds, the etch-hole of diameter 0.5 μ m～10 μ m is with 2000/mm 2Above frequency occurs.
CN01111269A 2000-04-19 2001-03-15 Fe-Ni alloy for shadow mask, observational method of inpurities and discriminating method of aperature uniformity Expired - Fee Related CN1120246C (en)

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JP2000117766A JP2001303198A (en) 2000-04-19 2000-04-19 Fe-Ni ALLOY STOCK FOR SHADOW MASK, EXCELLENT IN PROPERTY OF PIERCING BY ETCHING, SIMPLE METHOD FOR INCLUSION OBSERVATION, AND METHOD FOR DISCRIMINATING UNIFORMITY OF ELECTRON BEAM TRANSMISSION HOLE

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KR950006912A (en) * 1993-08-02 1995-03-21 이헌조 Shadow Mask Material for Color CRT
JP3080301B2 (en) * 1997-04-22 2000-08-28 日立金属株式会社 Fe-Ni alloy thin plate with excellent surface properties and etching properties
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