CN1035778C - An alloy sheet having high etching performance - Google Patents
An alloy sheet having high etching performance Download PDFInfo
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- CN1035778C CN1035778C CN93120826A CN93120826A CN1035778C CN 1035778 C CN1035778 C CN 1035778C CN 93120826 A CN93120826 A CN 93120826A CN 93120826 A CN93120826 A CN 93120826A CN 1035778 C CN1035778 C CN 1035778C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
An alloy sheet having a pierced hole face and providing a desirable etching performance, comprising {331}, {210}, and {211} planes on the surface; the gathering degree of the {311} plane being 14% or less, the gathering degree of the {210} plane being 14% or less, and the gathering degree of the {211} plane being 14% or less; and the ratio of the gathering degrees expressed by the equation {210}/({331}+{211}) being 0.2 to 1.
Description
The present invention relates to a kind of electronics that is used for and have the high etching performance latten, particularly a kind of latten material that is applicable to shadow mask for color cathode-ray tube and unicircuit (IC) lead frame.
The Fe-Ni alloy has been used as the shadow mask on the color cathode ray tube and the material of leads of IC frame.The Fe-Ni alloy is compared with the soft steel that is used as electronic material usually, has lower thermal expansivity significantly.For this reason, for example, even heat with electron beam, the shadow mask of producing with the Fe-Ni alloy sheets also can occur moving problem owing to the colour pase that thermal expansion causes hardly.
The Fe-Ni latten that is used for shadow mask and leads of IC frame need carry out photoetching treatment.Yet common Fe-Ni latten exists the shortcoming that etching performance is lower than soft steel.Specifically, the Fe-Ni alloy demonstrates quite low corrodibility to etching liquid.Compare and have a very big grain fineness number with soft steel.Therefore, provide when perforation when the Fe-Ni latten is etched with, the distribution of penetration hole diameter and perforation shape is dispersion state.Owing to there is an above-mentioned shortcoming, because during the pore that etching produces, certainly will on shadow mask, produce unsharp edge as the Fe-Ni latten of shadow mask when light transmission.In addition, the brightness of light transmission shadow mask is also a little less than the brightness than the shadow mask that makes with soft steel.Particularly, the high definition shadow mask with little spacing and pore that requires day by day for the electronic market causes reducing significantly the problems referred to above of color cathode ray tube quality probably.In addition, the window of tube of new type colorful cathode tube strong request high brightness, and the shadow mask of low-light level can reduce the competitiveness of product.About being used for the material of leads of IC frame, the unicircuit (IC) that trends towards high-density (highly integrated) requires the arrangement lead-in wire of fine and closely woven spacing on lead frame.Because there is above-mentioned variety of issue in common Fe-Ni alloy, they can not satisfy the requirement that fine and closely woven spacing is arranged lead-in wire.Except the problems referred to above, also there is the shortcoming of plating properties difference in common Fe-Ni alloy after etching.
Some kinds of technology of relevant Fe-Ni alloy etch performance issue have been proposed to solve.It is spared and comprises following method.
(1) the patent announcement communique No.2-9655 that examined of Japan discloses and has a kind ofly had that { 100} crystal face concentration class is 35% or higher latten, and it can be used as a kind of Invar alloy thin plate that can obtain high precision and uniform etching on plate surface.
(2) Japanese uncensored patent disclosure communique No.62-243782 discloses a kind of method that can improve etching speed and reduce the Fe-Ni Invar alloy of perforation sharp edge that is used to produce, this alloy has in its surface that { 100} crystal face and surface roughness Ra scope are 0.2-0.7 μ m, and 100 μ m or thinner metal sheet (Sm) and 8.0 or bigger grain size number.
(3) Japanese uncensored patent disclosure communique No.2-270941 discloses and has been used to produce a kind of method with the Fe-Ni Invar alloy that improves etching speed, this alloy in its surface { 200} crystal face concentration class is 50% or bigger.This alloy contains 0.007% (weight) or C still less, the S of 0.005% (weight) or P still less and 0.005% (weight), and 0.10% (weight) or other impurity still less.
Yet technology (1) can not prevent from the shadow mask that makes to produce unintelligible edge, and the brightness of shadow mask is lower than the common shadow mask brightness made from soft steel, although this technology has improved etched accuracy and homogeneity.The shadow mask brightness that technology (2) makes also is lower than the brightness of the common shadow mask made from soft steel, although improved etching speed and improved the unintelligible edge that perforation produces.
The etched problem in too much edge has appearred in technology (3) on the leads of IC frame that makes, and the inferior problem of lead frame working accuracy.
All there is the inferior problem of plating properties through the leads of IC frame of etch processes in these three kinds of technology.For example, when the leads of IC frame of producing by technology (3) carries out the scolder plating, the misgrowth of the needle-like crystal of " whisker " has taken place to be referred to as, this is a kind of quality problems.
The purpose of this invention is to provide a kind of latten with fabulous etching performance and plating properties.
To achieve these goals, the invention provides a kind of latten with fabulous perforated surface, this latten has following performance:
Described latten has { 331}, { 210} and { 211} crystal face in its surface;
{ 311} crystal face concentration class is 14% or littler, and { 210} crystal face concentration class is 14% or littler, and { 211} crystal face concentration class is 14% or littler; With
Concentration class ratio is 0.2-1, and { 210}/({ 331}+{211}) provides this ratio by formula.
In addition, the present invention also provides a kind of latten with perforated surface of fabulous etching performance, and this latten has following performance:
Described latten has { 111}, { 100}, { 110}, { 311}, { 331}, { 210} and { each crystal face of 211};
Described each crystal face has following concentration class:
{ the concentration class S of 111} crystal face
1: 1-10%,
{ the concentration class S of 100} crystal face
2: 50-94%,
{ the concentration class S of 110} crystal face
3: 1-24%,
{ the concentration class S of 311} crystal face
4: 1-14%,
{ the concentration class S of 331} crystal face
5: 1-14%,
{ the concentration class S of 210} crystal face
6: 1-14%,
{ the concentration class S of 211} crystal face
7: 1-14%; With
The ratio of concentration class is 0.8-20, and this ratio is by formula (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) provide.
Fig. 1 is the curve that concerns between the surface roughness Ra of expression optimum implementation-1 shadow mask transmittance and perforated surface;
Fig. 2 is { 331}, { 210} and { each crystal face concentration class ratio of 211} { curve that concerns between the unintelligible edge that perforation produces on 210}/({ 331}+{211}), etching coefficient and the planar mask on expression optimum implementation-1 alloy surface;
Fig. 3 is expression optimum implementation-1 alloy sheets { 331}, { 210} and { { 210}/({ 331}+{211}) is to the curve of etching coefficient influence for each crystal face concentration class ratio of 211} on the mean grain size and alloy surface on the thickness direction;
Fig. 4 is when { 210}/({ 331}+{211}) represented the mean grain size on the latten thickness direction and the curve of the relation between the etching coefficient when value is 0.25;
Fig. 5 is the graphical representation of expression etching coefficient and the definition of perforation outside surface;
Fig. 6 is the curve that concerns between the surfaceness of expression optimum implementation-2 planar mask transmittance and perforated surface;
Fig. 7 is expression optimum implementation-2 each crystal face concentration class ratio ({ 100}+{311}+{210})/({ 100}+{111}+{311}+{211}), the curve that concerns between the unintelligible edge that etching coefficient and perforation produce;
Fig. 8 is that expression optimum implementation-2 is used the curve that concerns between each crystal face concentration class ratio of parameter ({ 100}+{311}+{210})/({ 100}+{111}+{311}+{211}) and the etching coefficient as a supplement in the grain fineness number on the latten thickness direction; With
Fig. 9 is the curve that expression optimum implementation-2 concerns between grain fineness number on the latten thickness direction and etching coefficient.
Optimum implementation-1
Have same apertures and identical shaped etch-hole in order to produce in the whole surface range of Fe-Ni alloy sheets, the present inventor finds, should keep constant etching speed and on whole material surface scope, sufficiently high ratio should be arranged, important thing provides high etching coefficient (defining) in Fig. 5, by the ratio of the upper particular crystal plane concentration class of control etched surfaces (alloy surface) and the grain size on the control latten thickness direction, can effectively improve to a great extent etching coefficient. In addition, the present inventor finds, surface roughness on the perforated surface (Ra) is controlled at prescribed level or lower, be very important to the plating properties after the etching and shadow mask brightness preservation in excellent level, can obtain the surface roughness of the perforated surface of above-mentioned requirements by the concentration class of control particular crystal plane.
It mainly is the component of Fe and Ni that various latten of the present invention contains, or mainly is the component of Fe, Ni and Co and/or Cr. Preferred content and the reason of above-mentioned key component element below are described.
Now narration is used for the latten of material for shadow mask.
In order to prevent that colour pase from moving, the Fe-Ni latten that is used for shadow mask needs to have 2.0 * (1/10 in 30-100 ℃ of temperature range6)/℃ the upper limit as mean thermal expansion coefficients. Thermal coefficient of expansion depends on the Ni content of alloy, and the scope that provides the Ni content of above-mentioned thermal coefficient of expansion is 34-38% (weight). In order to obtain being lower than the thermal coefficient of expansion of afore mentioned rules numerical value, Ni content is preferably limited in 35-37% (weight) scope, preferably is limited in 35.5-36.5% (weight) scope. Usually, the Co that is present in the Fe-Ni alloy is inevitable impurity to a certain extent. The impact Ni content very slight, in the afore mentioned rules scope of 1% (weight) or lower cobalt content alloy characteristic is gratifying, but when alloy contains greater than 1% (weight) until when 7% (weight) or lower Co, the Ni content that satisfies above-mentioned thermal coefficient of expansion specified value is in 28-38% (weight) scope. So, when alloy contains greater than 1% (weight) until when 7% (weight) or lower Co, Ni content is preferably in 28-38% (weight) scope. In addition, the Ni of the Co of 3-6% (weight) and 30-33% (weight) can provide lower thermal coefficient of expansion, and when Co content surpassed 7% (weight), thermal coefficient of expansion can increase. Therefore, the upper limit of Co content is preferably due to 7% (weight).
About being used for the latten situation of leads of IC frame, the Ni content of the average coefficient of expansion condition that the satisfied Fe-Ni latten that is used for the leads of IC frame requires is in 38-52% (weight) scope. Ni content is lower than 38% (weight) or is higher than 52% (weight) and will cause the mean thermal expansion coefficients value excessive, and this will cause the compatibility of same semiconductor, glass and pottery inferior. Therefore, Ni content is preferably limited in 38-52% (weight) scope. As mentioned above, the Co that is present in the Fe-Ni alloy is inevitable impurity in certain program, and the impact of 1% (weight) or lower Co alloy characteristic is very slight. So acceptable Ni content is in above-mentioned scope.
On the other hand, by adding the Co of 1-20% (weight), can strengthen the compatibility for the same semiconductor element of the latten of leads of IC frame, glass and pottery. 1% (weight) or lower or can not get above-mentioned effect greater than the Co content of 20% (weight). When alloy contained the Co of 1-20% (weight), the Ni content range that satisfies the mean thermal expansion coefficients condition that is used for the leads of IC frame material was 27-32% (weight). Be lower than 27% (weight) or be higher than 32% (weight)NiContent will make thermal coefficient of expansion increase. Therefore, when alloy contained the Co of 1-20% (weight), preferred Ni content was 27-32% (weight).
Chromium is a kind of element that improves mechanical performance, and Cr also is a kind of element that reduces thermal coefficient of expansion. For the Cr upper content limit of the thermal expansion character that obtains requirement of the present invention is 3.0% (weight). Therefore, allow to contain the Cr that is limited to 3.0% (weight).
Collateral security is used for the viewpoint of leads of IC characteristic that frame material requires, except above-mentioned essential element, preferably other element is done following restriction, i.e. 0.0050% (weight) or lower C, 0.50% (weight) or lower Mn, 0.20% (weight) or lower Si, 0.0050% (weight) or lower N, 0.0050% (weight) or lower O and 0.0050% (weight) or lower B.
Secondly, the lip-deep crystal face concentration class of latten will be described, the mean grain size on concentration class ratio and the latten thickness direction, they are the most outstanding features of the present invention.
The present inventor finds, the latten that will have a mentioned component lip-deep { 311}, { 210} and { ratio of 211} crystal face concentration class and these crystal face concentration class is controlled in the prescribed limit and can effectively improves etching coefficient, simultaneously, reduce the surface roughness (Ra) of the perforated surface shown in Fig. 5 symbol, improve shadow mask brightness and the plating properties after the etching is brought up to fabulous level.
Fig. 1 shows the relation between the surface roughness Ra of the light transmittance of planar mask and perforated surface. By { 311}, { 210} is with { Fe-Ni latten, Fe-Ni-Co latten, Fe-Ni-Cr latten and the Fe-Ni-Co-Cr latten of the different concentration class of each crystal face of 211} carry out photoetching, produce the planar mask that can be used for the etching latten that shadow mask bored a hole to having in its surface. By measuring the light transmission capacity of planar mask, its value is determined the light transmittance of planar mask divided by having the light transmission capacity of same size by the planar mask of mild steel manufacturing. By determining in the method described in each embodiment the surface roughness of perforated surface later on.
Each X-ray diffraction intensity with (111), (200), (220), (311), (331), (420) and (422) diffraction surfaces is determined the concentration class of each crystal face, and this diffracted intensity is again to determine by the X-ray diffraction method of latten. For example, relevant X-ray diffraction intensity by (311) diffraction surfaces comes definite { concentration class of 331} crystal face than the summation divided by the relevant X-ray diffraction intensity ratio of (111), (200), (220), (311), (331), (420) and (422) each diffraction surfaces. { the 210} crystal face is with { concentration class of 211} crystal face is also determined by similar approach. Relevant X-ray diffraction intensity is worth resulting numerical value than being defined as the X-ray diffraction intensity that each diffraction surfaces records divided by corresponding diffraction surfaces X ray strength theory. For example, by with the X-ray diffraction intensity of (111) diffraction surfaces divided by (111) diffraction surfaces X-ray diffraction intensity theoretical value, determine the X-ray diffraction intensity ratio of (111) diffraction surfaces.
The relevant X ray diffraction intensity of (420) diffraction surfaces by having same orientation with those corresponding crystal faces is than { 111} is to { summation of 422}7 the relevant X-ray diffraction intensity ratio of crystal face is come definite { concentration class of 210} crystal face divided by above-mentioned. Equally, also be by { the relevant X-ray diffraction intensity of 422} diffraction surfaces is than { 111} is to { summation of 422}7 the relevant X ray diffraction intensity ratio of crystal face is come definite { concentration class of 211} crystal face divided by above-mentioned.
In the curve of Fig. 1, white round dot is corresponding to { 331}, { 210} and { 211} each crystal face 14 % or lower concentration class, and bullet is corresponding to { 331}, { 210} and { arbitrary crystal face all surpasses 14% concentration class in each crystal face of 211}.
According to Fig. 1, as { 331}, { 210} and { concentration class of each crystal face of 211} is 14% or when lower, the surface roughness Ra of perforated surface is that 0.90 μ m or the lower light transmittance of planar mask that makes bring up to 1.0 or larger, and this will cause the brightness of planar mask greater than the brightness of mild steel ordinary flat shadow mask. With regard to the plating properties of leads of IC frame alloy sheets after the etching, the test that the present inventor carries out confirms, by will { 331}, { 210} and { concentration class of each crystal face of 211} is controlled at 14% or lower, make surface roughness Ra become 0.90 μ m or lower, this will provide fabulous scolder plating properties.
If { 331}, { 210} and { concentration class of arbitrary crystal face exceeds the scope of afore mentioned rules among the 211}, and then perforated surface roughness Ra will so just can not obtain above-mentioned characteristic above 0.90 μ m.The microscopic examination of above-mentioned latten perforated surface shows, has occurred pitting (irregularity) on whole surface range.Therefore, this class pitting estimates it may is to cause the surface roughness Ra of perforated surface to be increased to 0.90 μ m or higher major cause.After deliberation the influence that concerns between the surface roughness Ra of other parameter to shadow mask brightness and perforated surface.Among various indexs, center line average surface roughness (Ra) has the strongest dependency to above-mentioned relation.
Therefore, in order to obtain the plating properties condition after fabulous shadow mask brightness and the fabulous etching, the present invention will { 331}, { 210} and { each crystal face concentration class of 211} is defined as 14% or lower.
In order to improve etching coefficient effectively, { 331}, { 210} and the { ratio of each crystal face concentration class of 211} on the essential control latten surface.Fig. 2 shows { 331}, { 210} and { ratio of each crystal face concentration class of 211} and the relation between the etching coefficient, and the relation between the unintelligible edge that perforated surface produces on concentration class ratio and the planar mask on the latten.This latten is carried out photoetching, and they are Fe-Ni lattens, Fe-Ni-Co latten, Fe-Ni-Cr latten and Fe-Ni-Co-Cr latten.The concentration class of this latten within the scope of the present invention, and ratio with various concentration class, { 211}/({ 210}+{211}) provides this ratio by formula.
The present invention is defined as etching coefficient 1.8 or the higher value that can not produce any practical problems.Determine { 311}, { 210} and { concentration class of each crystal face of 211} is determined etching coefficient by same procedure described in each embodiment that will provide later on by above-mentioned X-ray diffraction method.Determine the unintelligible edge that perforation produces according to the following judgement criteria that provides by visual inspection.
A: do not observe the unintelligible edge that perforation produces.
B: find the slight unintelligible edge that perforation produces, but can not produce any problem fully in actual applications.
C: find that perforation has produced unintelligible edge to a certain degree.But can not have problems in actual applications.
D: the unintelligible edge that perforation produces occurred, this will cause problem in actual applications.
E: the tangible sharp edge that perforation produces occurred, problem has taken place in actual applications.
A can not have problems in actual applications to the C grade.
According to Fig. 2, can find out that { increase of 210}/({ 331}+{211}) ratio can improve etching coefficient, and when this ratio is 0.2 or when higher, etching coefficient will be 1.8 or higher numerical value.On the other hand, when { 210}/when ({ 331}+{211}) ratio surpassed 1.0, the unintelligible edge degradation that perforation produces also went wrong in actual applications.Therefore, the present invention will { 210}/({ 331}+{211}) ratio be defined in the 0.2-1.0 scope, so that reduce the unintelligible edge that perforation produces and obtain high etching coefficient, this is a purpose of the present invention.The scope of this ratio is 0.25-0.6 more preferably, because the unintelligible edge that the ratio in this scope can not occur boring a hole and produce.
Therefore, the ratio of particular crystal plane concentration class will improve etching coefficient effectively on the control latten surface.However, in order further to improve etching coefficient, the mean grain size on the restriction latten thickness direction also is effective.The uncensored patent disclosure communique 2-243782 of Japan (above-mentioned prior art (2)) is defined as No.8.0 with grain fineness number or than the granularity of large size.Yet, be No.10.0 only in the grain size number minimum described in this patent application specification, be 11 μ m (from (grain size number) calculating=16.6439-6.6439log ((mean grain size/1.125.)).In contrast, the latten of controlling with the ratio of the concentration class of each particular crystal plane and concentration class of the present invention, because further improved etching coefficient to 10 μ m or littler (10.3 or than the grain fineness number of large size) with the mean grain size on the latten thickness direction is low, above-mentioned mean grain size is less than the granularity of aforementioned prior art.
Fig. 3 shows that { 210}/({ 331}+{211}) ratio and given mean grain size are to the influence of Fe-Ni latten, Fe-Ni-Co latten, Fe-Ni-Cr latten and Fe-Ni-Co-Cr latten etching coefficient, above-mentioned each latten all passes through photoetching in advance, { 331}, { 210} and { concentration class of each crystal face of 211} all is 14% or lower, and on the latten thickness direction, has different mean grain sizes, according to Fig. 3, even identical { under 210}/({ 331}+{211}) ratio, the more little etching coefficient of mean grain size is big more.When mean grain size surpasses 10 μ m, in that { 210}/({ 331}+{211}) ratio is that 0.2 o'clock etching coefficient is reduced to 1.8 or lower.Yet, when mean grain size remains on 10 μ m or more hour, even { 210}/({ 331}+{211}) ratio is 0.2, and etching coefficient also surpasses 1.8.Therefore, in order further to improve etching coefficient, preferably mean grain size is limited in 10 μ m or littler.If mean grain size is 6 μ m or more hour, etching coefficient will further be improved in this scope.
Fig. 4 show 210}/({ 331}+{211}) ratio be 0.25 o'clock on the latten thickness direction mean grain size and the relation between the etching coefficient.
In order to obtain { the 331}, { 210} and { the concentration class value of each crystal face of 211} needs control to produce the condition of latten so that can not cause the formation of above-mentioned each crystal face of the present invention regulation.For example, in following situation, i.e. the hot-rolled sheet that obtains with breaking down slab or continuous casting slab; Or the cast panel that obtains of direct pouring alloy; Or its hot rolling obtained that hot-rolled sheet is annealed to the finished product after the hot rolling when producing latten of the present invention as starting material and annealing temperature is controlled in about 910-990 ℃ the scope, this all is in order to suppress the formation of above-mentioned each crystal face.
In order to obtain { 331}, { 210} and the { numerical value of the ratio of each crystal face concentration class of 211} in specialized range of the present invention, corresponding to { 331}, { 210} and { each the crystal face concentration class of 211} after the above-mentioned hot-rolled finished product annealing, in the series of processes of the cold rolling-recrystallization annealing after hot-roll annealing-cold finish rolling process, it is effective making the constrained optimization of cold rolling rate, recrystallization annealing (annealing temperature, time and heating rate).
Concentration class numerical value for each crystal face of obtaining the present invention regulation had better not carry out homogenizing thermal treatment to the slab that makes by breaking down or continuous casting in the latten production process.For example, when at 1200 ℃ or higher temperature carried out 10 hours or during the homogenizing thermal treatment of longer time, { 331}, { 210} and { at least a concentration class is not in the scope of the present invention's regulation in the 211} crystal face.Therefore, should avoid above-mentioned homogenizing thermal treatment.
Except aforesaid method, reach rapid solidification or crystallization control tissue by the recrystallize during the control hot-work, also can obtain each crystal face concentration class of the present invention's regulation.
Embodiment
Produce by refining in hot metal ladle and to have in table 1 and the table 3 listed A to the various alloy pigs of C, J and L composition.Carry out the cogging breaking down after this ingot cleaning, surface finish and hot rolling (1100 ℃, 3 hours) are to produce hot-rolled sheet.Melt having the alloy of table 1 to the interior listed D of table 3 to I and K composition, external refining and direct pouring are to produce cast panel.Carry out hot rolling at 1350-1000 ℃ of draught subsequently with 30%, then 750 ℃ around volume to produce hot-rolled sheet.
At 910-990 ℃ resulting hot-rolled sheet is annealed, and then carry out cold rolling, recrystallization annealing and cold finish rolling, to produce No.1 with the mean grain size on table 4 and listed crystal face concentration class of table 3 and the thickness direction latten to No.31.Determine { 331}, { 210} and the { concentration class of each crystal face of 211} by above-mentioned X-ray diffraction method.
On the latten that respectively makes, d shown in Figure 5 is estimated and measured to the photoresist figure
1Etching coefficient during=135 μ m.In Fig. 5, illustrate the etching coefficient method for measuring.In 40 ℃, the ferric chloride Solution groove of 45Baunes degree with 2.5kg/cm
2Spraying pressure spray to come latten is carried out etching in 50 seconds, measure etching coefficient then.Use formula E
f=2H/ (d
2-d
1) represent etching coefficient.
To No.1 to the latten material of No.24, No.29 to No.31 by the optical graving plate shadow mask of making even, and measure the light transmission capacity of this shadow mask.The light transmission capacity of surveying divided by the light transmission capacity of the soft steel planar mask of same size.This calculated value is processed into the transmittance of planar mask.Measure the surfaceness of each the planar mask perforated surface that has made with the non-contact laser roughmeter.For 0.02mm, remove tapered zone on the perforated surface that becomes fluctuating factor by (cut-off) value, utilize this roughness curve to measure center line mean roughness (Ra) to draw roughness curve.Measure the unintelligible edge that each planar mask perforation produces according to the used identical standard of Fig. 2 by visual inspection.
Measure the surfaceness of the perforated surface of No.25 after the photoetching of No.28 latten material with above-mentioned identical method.These material samples are carried out soldering and its scolder plating properties is estimated.
Shown in table 3 and table 4, have { 331}, { 210} and { each crystal face concentration class of 211} and { material of No.6 to No.27, No.29 to No.31 of 210}/({ 331}+{211}) ratio demonstrates in the specialized range of the present invention, the surface roughness Ra of perforated surface is 0.90 μ m or littler, and is 1.0 or bigger as the transmittance of the planar mask of material for shadow mask.Therefore, obtained to be higher than the brightness of the soft steel planar mask brightness of prior art.These materials have also provided the fabulous scolder plating properties as the leads of IC frame material.The etching coefficient of these materials is 1.8 or higher.To the planar mask of No.24 material manufacturing in fact the problem that perforated surface produces aspect, unintelligible edge does not appear with No.6.
No.6, No.9 demonstrate to No.14 latten material that { 210}/({ 331}+{211}) ratio is in the 0.25-0.26 scope.Yet No.9 has 10 μ m or littler mean grain size to the latten of No.14 on thickness direction, so that demonstrates than the higher etching coefficient of No.6 with 11.1 μ m mean grain sizes, and this shows that above-mentioned materials has fabulous etching performance.In the latten material of No.14, the latten that has less mean grain size on thickness direction has provided bigger etching coefficient at No.9, and therefore, the mean grain size on the reduction thickness direction can improve effectively loses coefficient.
Opposite with above sample of the present invention, the No.1 material is that a kind of { 331} crystal face concentration class surpasses the control sample of the upper limit of the present invention.The No.2 material is that a kind of { 210} crystal face concentration class surpasses the control sample of the upper limit of the present invention.The No.3 material is that a kind of { 211} crystal face concentration class surpasses the control sample of the upper limit of the present invention.These three kinds of samples have provided the surface roughness Ra of 0.90 μ m or bigger perforated surface, and have provided and be lower than 1.0 planar mask transmittance, compare with sample of the present invention, and they have reduced the brightness of shadow mask.The No.4 material is that a kind of { 210}/({ 331}+{211}) ratio surpasses the upper limit of the present invention, and the unintelligible edge that perforation produces is inferior to the control sample of sample of the present invention.The No.5 material be a kind of 210}/331}+{211}) ratio is lower than lower limit of the present invention, and etching coefficient is lower than 1.80 control sample, this can not provide the etching performance of requirement of the present invention.The No.28 material is a kind of { 210} and { concentration class of 211} crystal face all surpasses the upper limit of the present invention, and the surface roughness Ra of perforated surface is greater than the control sample of 0.90 μ m, and this has reduced the scolder plating properties after the etching.
The above is clearly pointed out, with { 331}, { 210} and { concentration class of each crystal face of 211} is limited in the scope of the present invention regulation can make the surface roughness Ra optimizing of perforated surface, thereby the transmittance and the scolder plating properties of planar mask are brought up to fabulous level on the latten surface.In addition, will { 210}/({ 331}+{211} concentration class ratio is limited in the limit of the present invention regulation can improve etching coefficient effectively, and reduces the unintelligible edge that perforation produces.And the reduction meeting of the mean grain size on the latten thickness direction further improves etching coefficient.
Table 1
| The alloy code name | Chemical ingredients (weight % is except that H) | ||||||||
| Ni | H (ppm) | Mn | Al | Si | Cr | Ti | O | N | |
| A | 35.9 | 0.8 | 0.34 | 0.020 | 0.01 | 0.04 | 0.01 | 0.0013 | 0.0011 |
| B | 35.7 | 0.4 | 0.25 | 0.005 | 0.002 | 0.01 | ＜0.01 | 0.0009 | 0.0007 |
| C | 36.4 | 1.0 | 0.05 | 0.010 | 0.05 | 0.02 | 0.02 | 0.0025 | 0.0015 |
| D | 36.0 | 0.6 | 0.22 | 0.008 | 0.02 | 0.02 | ＜0.01 | 0.0011 | 0.0011 |
| E | 32.2 | 0.9 | 0.13 | 0.007 | 0.01 | 0.02 | 0.02 | 0.0022 | 0.0013 |
| B | P | S | Mo | W | Nb | V | Cu. | C | Co |
| 0.00005 | 0.002 | 0.0010 | 0.03 | 0.02 | 0.02 | 0.02 | 0.02 | 0.0025 | - |
| 0.0001 | 0.001 | 0.0003 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | 0.0014 | 0.002 |
| 0.0001 | 0.004 | 0.0018 | 0.02 | 0.01 | 0.01 | 0.01 | 0.01 | 0.0047 | 0.03 |
| 0.0001 | 0.003 | 0.0011 | 0.03 | 0.02 | ＜0.01 | ＜0.01 | 0.01 | 0.0031 | 0.700 |
| 0.0001 | 0.004 | 0.0018 | 0.03 | 0.02 | ＜0.01 | ＜0.01 | ＜0.01 | 0.0015 | 4.100 |
Table 2
| The alloy code name | Chemical ingredients (weight % is except that H) | ||||||||
| Ni | H (ppm) | Mn | Al | Si | Cr | Ti | O | N | |
| F | 31.9 | 0.4 | 0.13 | 0.008 | 0.05 | 0.02 | ＜0.01 | 0.0021 | 0.0015 |
| G | 29.5 | 0.8 | 0.35 | 0.010 | 0.01 | 0.03 | ＜0.01 | 0.0016 | 0.0008 |
| H | 41.5 | 1.0 | 0.35 | 0.001 | 0.07 | 0.02 | ＜0.01 | 0.0030 | 0.0011 |
| I | 28.5 | 1.0 | 0.30 | 0.015 | 0.03 | 0.01 | ＜0.01 | 0.0030 | 0.0020 |
| B | P | S | Mo | W | Nb | V | Cu | C | Co |
| 0.0001 | 0.004 | 0.0013 | 0.03 | 0.02 | ＜0.01 | ＜0.01 | 0.02 | 0.0018 | 5.500 |
| 0.0020 | 0.003 | 0.0005 | 0.01 | 0.01 | ＜0.01 | ＜0.01 | 0.01 | 0.0045 | 6.521 |
| 0.0001 | 0.002 | 0.0010 | 0.01 | 0.01 | ＜0.01 | ＜0.01 | 0.02 | 0.0040 | 0.250 |
| 0.0001 | 0.001 | 0.0015 | 0.01 | 0.01 | ＜0.01 | ＜0.01 | 0.01 | 0.0035 | 16.530 |
Table 3
| The alloy code name | Chemical ingredients (weight % is except that H) | ||||||||
| Ni | H (ppm) | Mn | Al | Si | Cr | Ti | O | N | |
| J | 36.5 | 1.9 | 0.37 | 0.005 | 0.01 | 0.95 | ＜0.01 | 0.0025 | 0.0014 |
| K | 35.0 | 2.0 | 0.25 | 0.010 | 0.10 | 1.50 | ＜0.01 | 0.0020 | 0.0018 |
| L | 35.5 | 1.8 | 0.01 | 0.020 | 0.05 | 2.82 | ＜0.01 | 0.0010 | 0.0006 |
| B | P | S | Mo | W | Nb | V | Cu | C | Co |
| 0.0015 | 0.001 | 0.0010 | 0.02 | 0.01 | ＜0.01 | ＜0.01 | 0.01 | 0.0030 | - |
| 0.0001 | 0.002 | 0.0006 | 0.02 | 0.02 | ＜0.0 1 | ＜0.01 | 0.01 | 0.0020 | 0.502 |
| 0.0008 | 0.002 | 0.0008 | 0.01 | 0.01 | ＜0.0 1 | ＜0.01 | 0.01 | 0.0006 | 0.520 |
Table 4
| The alloy code name | Material number | Crystal face concentration class (%) | {210}/({331) +{211}) | Mean grain size on the alloy sheets thickness direction (μ m) | The surface roughness Ra of perforated surface (μ m) | The transmittance of planar mask | The unintelligible edge that perforation produces | Etching coefficient | The scolder plating | ||
| {331} | {210} | {211} | |||||||||
| C | 1 | 13 | 10 | 7 | 0.40 | 13.2 | 1.08 | 0.95 | B | 1.81 | - |
| B | 2 | 13 | 16 | 5 | 0.89 | 11.2 | 0.93 | 0.98 | B | 2.01 | - |
| B | 3 | 12 | 7 | 15 | 0.26 | 8.8 | 1.16 | 0.91 | A | 2.09 | - |
| A | 4 | 2 | 7 | 4 | 1.17 | 11.1 | 0.87 | 1.01 | E | 2.24 | - |
| | 5 | 14 | 3 | 9 | 0.13 | 11.1 | 0.79 | 1.04 | B | 1.76 | - |
| B | 6 | 13 | 4 | 3 | 0.25 | 11.1 | 0.76 | 1.05 | A | 1.82 | - |
| B | 7 | 7 | 6 | 4 | 0.55 | 11.1 | 0.61 | 1.09 | A | 1.96 | - |
| B | 8 | 1 | 5 | 4 | 1.00 | 11.1 | 0.67 | 1.08 | C | 2.17 | - |
| C | 9 | 8 | 3 | 4 | 0.25 | 10.0 | 0.72 | 1.06 | A | 1.92 | - |
| | 10 | 12 | 5 | 7 | 0.26 | 8.3 | 0.53 | 1.13 | A | 2.11 | - |
| C | 11 | 8 | 4 | 6 | 0.25 | 6.9 | 0.40 | 1.17 | A | 2.25 | - |
| C | 12 | 3 | 2 | 5 | 0.25 | 5.3 | 0.39 | 1.16 | A | 2.48 | - |
| C | 13 | 8 | 3 | 4 | 0.25 | 3.5 | 0.30 | 1.20 | A | 2.69 | - |
| C | 14 | 2 | 1 | 2 | 0.25 | 2.0 | 0.21 | 1.22 | A | 2.92 | - |
Table 5
| The alloy code name | The material material | (%) crystal face concentration class | {210}/({331} +{211}) | Mean grain size on the alloy sheets thickness direction (μ m) | The surfaceness of perforated surface, Ra (μ m) | The transmittance of planar mask | The unintelligible edge that perforation produces | Etching coefficient | The scolder plating | ||
| {331} | {210} | {211} | |||||||||
| B | 15 | 3 | 10 | 9 | 0.56 | 8.8 | 0.56 | 1.10 | A | 2.23 | - |
| A | 16 | 11 | 10 | 9 | 0.50 | 8.9 | 0.56 | 1.11 | A | 2.20 | - |
| A | 17 | 3 | 2 | 1 | 0.50 | 7.7 | 0.54 | 1.12 | A | 2.30 | - |
| A | 13 | 0 | 2 | 3 | 0.67 | 3.3 | 0.35 | 1.18 | B | 2.91 | - |
| B | 19 | 1 | 1 | 1 | 0.50 | 5.5 | 0.46 | 1.14 | A | 2.63 | - |
| A | 20 | 1 | 1 | 1 | 0.50 | 7.7 | 0.52 | 1.12 | A | 2.31 | - |
| C | 21 | 3 | 5 | 4 | 0.56 | 7.0 | 0.43 | 1.15 | A | 2.40 | - |
| D | 22 | 6 | 5 | 5 | 0.45 | 8.1 | 0.72 | 1.04 | A | 2.23 | - |
| E | 23 | 6 | 3 | 4 | 0.30 | 8.0 | 0.70 | 1.06 | A | 2.20 | - |
| F | 24 | 5 | 4 | 4 | 0.44 | 8.2 | 0.71 | 1.05 | A | 2.22 | - |
| H | 25 | 5 | 5 | 5 | 0.50 | 10.0 | 0.75 | - | - | 2.10 | Good |
| G | 26 | 6 | 6 | 5 | 0.55 | 9.5 | 0.70 | - | - | 2.13 | Good |
| H | 27 | 11 | 10 | 9 | 0.50 | 9.3 | 0.73 | - | - | 2.15 | Good |
| I | 29 | 3 | 16 | 15 | 0.70 | 9.5 | 1.20 | - | - | 1.80 | Bad |
| J | 29 | 11 | 10 | 10 | 0.48 | 9.0 | 0.55 | 1.11 | A | 2.22 | - |
| K | 30 | 10 | 9 | 9 | 0.47 | 9.1 | 0.56 | 1.11 | A | 2.21 | - |
| L | 31 | 10 | 10 | 10 | 0.50 | 8.9 | 0.54 | 1.12 | A | 2.23 | - |
Optimum implementation-2
The present invention provides Fe-Ni, Fe-Ni-Co, Fe-Ni-Cr or the Fe-Ni-Co-Cr latten with uniform, fine figure by carry out photoetching treatment in the whole surface range of latten.For this reason, importantly on whole surface, keep high speed etching speed and improve etching coefficient.Specifically, require control etched surfaces (alloy surface) to go up the ratio of each particular crystal plane concentration class and the grain fineness number on the control latten thickness direction.
In addition, in order further to improve the brightness of planar mask printing opacity, importantly the surfaceness (center line mean roughness) of etching latten is controlled at prescribed value or below the prescribed value with etching and punching.Can make surface roughness Ra be reduced to prescribed value or reach meticulousr level by controlling contiguous concentration class of carrying out the particular crystal plane on etched latten surface.Feature of the present invention concentrates on the aforesaid method.Now the reason that these methods is provided quantity limitation will be described.
Below narration limits the reason of each component concentration with percentage ratio.The Fe-Ni latten that is used for electronics as the present invention should prevent because the colour pase that material heat expansion may cause moves during as material for shadow mask.Therefore, the mean thermal expansion coefficients of alloy must be limited in 2.0 * 10 in 30-100 ℃ of temperature range
-6/ ℃ or littler.The Ni content that satisfies Fe-Ni latten mean thermal expansion coefficients condition is in 34-38% (weight) scope.When the Fe-Ni latten that is used for electronics when the unicircuit wire frame material, for the thermal expansion of balance semi-conductor, glass and pottery, it is above but below 52% (weight) to make Ni content be about 38% (weight).Owing to considering above-mentioned 2 reasons, therefore, Ni content is defined in 34-52% (weight) scope.
In the Fe-Ni-Co latten, when Co content is 20% (weight) or when lower, for the Ni content that satisfies the mean thermal expansion coefficients condition should be in 28-38% (weight) scope.When Co content surpassed 20% (weight), any Ni content all can't satisfy the condition of thermal expansivity.Therefore, the Ni content of Fe-Ni-Co latten is defined in 28-38% (weight) scope, and the Co content of material is defined in 20% (weight) or lower.
Chromium is a kind of element that can improve alloy mechanical performance.Yet, add Cr and certainly will increase mean thermal expansion coefficients.Therefore, in order to obtain above-mentioned mean thermal expansion coefficients, Cr content should be 3% (weight) or lower.So for the Fe-Ni-Cr latten, Ni content is limited in 34-52% (weight) scope, and Cr content is limited in 3% (weight) or lower.For the Fe-Ni-Co latten, restriction Ni content is 28-38% (weight) scope, and Co content is that 20% (weight) or lower and Cr content are 3% (weight) or lower.
Below be the reason that limits each crystal face concentration class, the X-ray diffraction analysis of alloy thin sheet surface provided the X-ray diffraction intensity of (111), (200), (220), (311), (331), (420) and (422) each diffraction surfaces.Measure the concentration class of each high preferred orientation with X-ray diffraction intensity.For example, measure { the concentration class of 111} crystal face with the relevant X-ray diffraction intensity ratio of (111) crystal face divided by the summation of the relevant X-ray diffraction intensity ratio of (111), (200), (220), (311), (331), (420) and (422) each diffraction surfaces.
Measure { 100}, { 110}, { 311}, { 331}, { 210} and the { concentration class of each crystal face of 211} with identical method.Be used in the X-ray diffraction intensity measured on each diffraction crystal face and define relevant X-ray diffraction intensity ratio divided by the X-ray diffraction intensity theoretical value of corresponding diffraction surfaces.For example, penetrate intensity is determined (111) crystal face divided by the X-ray diffraction intensity theoretical value of (111) diffraction surfaces relevant X-ray diffraction intensity ratio with the X ray of (111) crystal face.
Relevant X ray with (200) crystal face with each crystal face same orientation of the same person spreads out strength ratio divided by above-mentioned (111) summation to the relevant X-ray diffraction intensity ratio of (422) 7 diffraction surfaces, measures { the concentration class of 100} crystal face.Also use (220), (420) and the relevant X-ray diffraction intensity of (422) each crystal face recently to measure { 110}, { 210} and the { concentration class of each crystal face of 211}.
Research by each crystal face concentration class of drawing with aforesaid method, the present inventor finds, { 111}, { 100}, { 110} and { each crystal face concentration class of 311} can suppress after the etching thin plate and bend and prevent that perforation from producing unintelligible edge on control Fe-Ni, Fe-Ni-Co, Fe-Ni-Cr or each latten surface of Fe-Ni-Co-Cr.
When { concentration class of 100} crystal face is increased to 50% or when bigger, can suppress the bending after the etching.Yet, when { when the concentration class of 100} crystal face surpasses 94%, the unintelligible edge that perforation produces just occurring.So { concentration class of 100} crystal face is defined as the scope of 50-94%.
On the other hand, { 111}, { 110} and { concentration class of each crystal face of 311} will certainly increase the bending after the etching.When { concentration class of 111} crystal face surpasses 10%, { concentration class of 110} crystal face surpasses 24% with { when the concentration class of 311} crystal face surpassed 14%, the bending after the etching became fairly obvious, and this can reduce the quality of planar mask.
When 111}, 110} and when the concentration class of each crystal face of 311} all is lower than 1%, and can reduce more significantly etching coefficient.So { concentration class of 111} crystal face is defined in the 1-10% scope, and { concentration class of 110} crystal face is defined in the 1-24% scope, and { concentration class of 311} crystal face is defined in the 1-14% scope.
The present inventor also finds, { 331}, { 210} and { concentration class of each crystal face of 211} and { 111}, { 100}, { 110} and { the concentration class ratio of each crystal face of 311} on control Fe-Ni, Fe-Ni-Co, Fe-Ni-Cr and each latten surface of Fe-Ni-Co-Cr, can increase etching coefficient and reduce the surfaceness (Ra of perforated surface, and the printing opacity brightness that improves planar mask the center line mean roughness).
Fig. 6 shows the relation curve of the planar mask transmittance of calculating to the surfaceness of perforated surface.In Fig. 6, white round dot (O) is corresponding to following condition:
{ the concentration class of 111} crystal face: 1-14%
{ the concentration class of 100} crystal face: 50-94%
{ the concentration class of 110} crystal face: 1-24%
{ the concentration class of 311} crystal face: 1-14%
{ the concentration class of 331} crystal face: 1-14%
{ the concentration class of 210} crystal face: 1-14%
{ the concentration class of 211} crystal face: 1-14%; With
Bullet () is corresponding to following condition:
{ the concentration class of 331} crystal face: 1-14%
{ the concentration class of 210} crystal face: 1-14%
{ the concentration class of 211} crystal face: 1-14%
Even { 111}, { 100}, { 110} and { concentration class of each crystal face of 311} is controlled in the scope of afore mentioned rules, if { 331}, { 210} and { concentration class of each crystal face of 211} surpasses 14%, and the surfaceness of perforated surface also can chap so.Show relation between the surfaceness (Ra, μ m) of planar mask transmittance and perforated surface by the relation curve of bullet () expression among Fig. 6.As seen in Fig., the surfaceness chap of perforated surface, the transmittance step-down of planar mask, perhaps the transmittance blackening of planar mask.
On the contrary, as { 331}, { 210} and { concentration class of each crystal face of 211} all is controlled in 14% or when being lower than 14%, the surfaceness of perforated surface attenuates, and the transmittance of planar mask uprises, perhaps the transmittance of planar mask brightens, and has shown this relation by white round dot (O) among Fig. 6.With the light transmission capacity of the planar mask of latten material manufacturing the transmittance that defines planar mask with the resulting numerical value of light transmission capacity of the planar mask of the former same perforations that has divided by the ordinary low-carbon steel manufacturing.When transmittance is 1 or when higher, planar mask of the present invention has provided the brightness higher than common shadow mask.
Therefore, { 331}, { 210} and { concentration class of each crystal face of 211} need remain on 14% or lower, yet when this numerical value was lower than 1%, etching coefficient will reduce.So { concentration class of 331} crystal face is defined in the 1-14% scope, and { concentration class of 210} crystal face is defined in the 1-14% scope, and { concentration class of 211} crystal face also is defined in the 1-14% scope.
The concentration class of main 7 crystal faces is important for improving etching coefficient on the control latten surface.Fig. 7 is unintelligible edge and the (S that expression etching coefficient, perforation produce
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) curve that concerns between the ratio, this ratio is with { the concentration class S of 100} crystal face
2, { the concentration class S of 311} crystal face
4{ the concentration class S of 210} crystal face
6Summation divided by { the concentration class S of 111} crystal face
1, { the concentration class S of 110} crystal face
3, { the concentration class S of 331} crystal face
5{ the concentration class S of 211} crystal face
7Summation obtain.This graphic representation has comprised the concentration class scope of following each crystal face: { 111} crystal face 1-10%, { 100} crystal face 50-94%; { 110} crystal face 1-24%; { 311} crystal face 1-14%; { 331} crystal face 1-14%; { 210} crystal face 1-14% and { 211} crystal face 1-14%.The grading of measuring the unintelligible edge of perforation generation by visual inspection is: " A " perforation does not produce unintelligible edge; " E " perforation produces serious sharp edge, thereby goes wrong in actual applications; " B " to " D " is between " A " and " E "." A " to " C " grade is defined as " practical application is not had any problem ".
As seen in fig. 7, the etching coefficient value is with (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) ratio increase and increase, as (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) when reducing excessively or increasing, the degree that perforation produces sharp edge certainly will degenerate.Therefore, (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) ratio is defined in the 0.8-20 scope, this numerical range practical problems can not occur.This numerical value is the 1.5-11.5 scope more preferably, because perforation can not produce unintelligible edge in this scope.
Fig. 8 is expression with the (S of parameter as a supplement of the grain fineness number (D) on the sheet gauge direction
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) curve that concerns between ratio and the etching coefficient.This graphic representation has comprised the concentration class scope of following each crystal face: { 111} crystal face 1-10%; { 100} crystal face 50-94%; { 110} crystal face 1-24%; { 311} crystal face 1-14%; { 331} crystal face 1-14%; { 210} crystal face 1-14% and { 211} crystal face 1-14%.Fig. 9 is the curve that concerns between grain fineness number on the expression sheet gauge direction and the etching coefficient.
As shown in Fig. 8 and Fig. 9, the grain fineness number that increases on the sheet gauge direction can reduce etching coefficient.Therefore, the grain fineness number on the thickness of slab direction is defined as 10 μ m or littler of to guarantee that etching coefficient is 2 or bigger, so just practical problems can not occur.If grain fineness number is 6 μ m or less, then can further increase etching coefficient.
The invention provides a kind of fabulous etching performance that has, the latten that can be used for electronics, the present invention has stipulated the lip-deep grain fineness number of latten on the concentration class of each crystal face on the main ingredient, latten surface of Fe-Ni, Fe-Ni-Co, Fe-Ni-Cr or Fe-Ni-Co-Cr alloy and ratio and the thickness direction.Except that above-mentioned main ingredient, latten of the present invention also contains following component: 0.05% (weight) or lower C, 0.60% (weight) or lower Mn, 0.30% (weight) or lower Si, 0.0030% (weight) or lower N and 0.0060% (weight) or lower O.
If the content of cobalt (impurity) is 1% (weight) or lower, it just can not influence etching performance.
Remain on for concentration class in the scope of the present invention's regulation each crystal face on the latten surface, during producing the procedure of processing of latten with molten steel, preferably select to avoid forming the suitable working condition of above-mentioned each crystal face, above-mentioned procedure of processing comprises molten steel solidification, hot rolling, cold rolling and annealing.For example, when the slab with steel ingot or continuous casting carries out breaking down, and with the slab hot rolling of breaking down and the steel band that obtains when being used to produce latten of the present invention, it is gratifying that the hot rolled steel sheet after the hot rolling is annealed.According to the difference of hot rolling draught, annealing temperature preferably is chosen in the 910-990 ℃ of scope.
By making cold roling reduction and annealing conditions (temperature, time and rate of heating) optimizing, can obtain the various characteristics of latten of the present invention corresponding to each each numerical value of crystal face concentration class on the latten surface after the latten annealing.When the hot rolled alloy thin plate before latten annealing fully during recrystallize, annealing is only effective.
For the concentration class of 7 crystal faces obtaining gratifying focal attention of the present invention, had better not after breaking down, carry out homogenizing and handle slab.For example, when at 1200 ℃ or higher temperature carried out 10 fens or the homogenizing of long period when handling, at least one in above-mentioned 7 crystal face concentration class can exceed the scope of the present invention's regulation.Therefore, must avoid this homogenizing to handle.Table 6
(unit: % is except that H)
| The alloy code name | Ni | H(ppm) | Mn | Al | Si | Cr | Ti | O | N | W | Nb | V | Cu | C | B | P | S | Mo | Co |
| A | 35.9 | 0.8 | 0.34 | 0.020 | 0.01 | 0.04 | 0.01 | 0.0013 | 0.0011 | 0.02 | 0.02 | 0.02 | 0.02 | 0.0025 | 0.00005 | 0.002 | 0.0010 | 0.03 | - |
| B | 35.7 | 0.4 | 0.25 | 0.005 | 0.002 | 0.01 | ＜0.01 | 0.0009 | 0.0007 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | 0.0014 | 0.0001 | 0.001 | 0.0003 | ＜0.01 | 0.001 |
| C | 36.4 | 1.0 | 0.05 | 0.010 | 0.05 | 0.02 | 0.02 | 0.0025 | 0.0015 | 0.01 | 0.01 | 0.01 | 0.01 | 0.0047 | 0.0001 | 0.004 | 0.0018 | 0.02 | 0.02 |
| D | 36.1 | 1.7 | 0.22 | 0.011 | 0.03 | 0.01 | ＜0.01 | 0.0015 | 0.0009 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | 0.0011 | 0.0001 | 0.002 | 0.0005 | ＜0.01 | 0.002 |
| E | 36.0 | 0.6 | 0.22 | 0.008 | 0.02 | 0.02 | ＜0.01 | 0.0011 | 0.0011 | 0.025 | ＜0.01 | ＜0.01 | 0.01 | 0.0031 | 0.0001 | 0.003 | 0.0011 | 0.03 | 0.7 |
| F | 32.1 | 1.2 | 0.11 | 0.012 | 0.01 | 0.01 | ＜0.01 | 0.0011 | 0.0011 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | 0.0012 | 0.0001 | 0.001 | 0.0009 | ＜0.01 | 5.1 |
| G | 32.2 | 0.9 | 0.13 | 0.007 | 0.01 | 0.02 | 0.02 | 0.0022 | 0.0013 | 0.02 | ＜0.01 | ＜0.01 | ＜0.01 | 0.0015 | 0.0001 | 0.004 | 0.0018 | 0.03 | 4.1 |
| H | 31.9 | 0.4 | 0.13 | 0.008 | 0.05 | 0.02 | ＜0.01 | 0.0021 | 0.0015 | 0.02 | ＜0.01 | ＜0.01 | 0.02 | 0.0018 | 0.0001 | 0.004 | 0.0013 | 0.03 | 5.7 |
| I | 29.5 | 0.8 | 0.34 | 0.010 | 0.01 | 0.03 | ＜0.01 | 0.0016 | 0.0008 | 0.01 | ＜0.01 | ＜0.01 | 0.01 | 0.0045 | 0.0020 | 0.003 | 0.0005 | 0.01 | 6.52 |
| J | 41.5 | 1.0 | 0.35 | 0.001 | 0.07 | 0.02 | ＜0.01 | 0.0030 | 0.0011 | 0.01 | ＜0.01 | ＜0.01 | 0.02 | 0.0040 | 0.0001 | 0.002 | 0.0010 | 0.01 | 0.250 |
| K | 28.5 | 1.0 | 0.30 | 0.015 | 0.03 | 0.01 | ＜0.01 | 0.0030 | 0.0020 | 0.01 | ＜0.01 | ＜0.01 | 0.01 | 0.0035 | 0.0001 | 0.001 | 0.0015 | 0.01 | 10.530 |
| L | 36.5 | 1.0 | 0.37 | 0.005 | 0.01 | 0.95 | ＜0.01 | 0.0025 | 0.0014 | 0.01 | ＜0.01 | ＜0.01 | 0.01 | 0.0030 | 0.0015 | 0.001 | 0.0010 | 0.02 | - |
| M | 35.0 | 2.0 | 0.25 | 0.010 | 0.10 | 1.50 | ＜0.01 | 0.0020 | 0.0018 | 0.02 | ＜0.01 | ＜0.01 | 0.01 | 0.0020 | 0.0001 | 0.002 | 0.0006 | 0.02 | 0.502 |
| N | 35.5 | 1.8 | 0.01 | 0.020 | 0.05 | 2.82 | ＜0.01 | 0.0010 | 0.0006 | 0.01 | ＜0.01 | ＜0.01 | 0.01 | 0.0006 | 0.0008 | 0.002 | 0.0008 | 0.01 | 0.520 |
Embodiment
At length narrate the present invention with reference to each embodiment, with the hot metal ladle refined molten steel and cast and have the alloy ingot of A shown in 6 to the N composition with production.
Behind the above-mentioned alloy ingot of cleaning surface, carry out the cogging breaking down to produce slab.This slab further carries out surface-conditioning, and 1100 ℃ stove internal heating 3 hours, carries out hot rolling subsequently to produce latten.At the latten of external refining No.N alloy, direct pouring subsequently becomes slab, carries out hot rolling at the 1350-1000 ℃ of draught with 30% then and handles to produce steel sheet.
At 910-990 ℃ the gained hot rolled steel sheet is annealed, carry out cold rolling subsequently and annealing, change rolling condition and annealing conditions simultaneously.Gained latten No.A is to the No.N alloy.Table 7,8 and 9 has been listed gained No1 to the No.52 properties of materials, and this characteristic comprises the concentration class S of 7 crystal faces of latten
1-S
7(%), (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) grain fineness number (μ m) on ratio and the latten thickness direction.
Table 7
Table 8
Table 9
On each latten of gained, formed the photoetching resist pattern, at d shown in Figure 5
1Etching coefficient is measured at=135 μ m places.By in 40 ℃, the ferric chloride Solution groove of 45Baume degree, with 2.5kg/cm
2Spraying pressure spray and to measure etching coefficient with the etching latten with above-mentioned formula (1) in 50 seconds.
The latten that makes with the same terms carries out photoetching and produces planar mask.Planar mask is placed its sinuousness of measurement on the horizontal stand.With the light transmission capacity of radiant light measurement planar mask, this light transmission capacity is divided by the light transmission capacity that approaches the planar mask of same perforations with alloy that has with the ordinary low-carbon steel manufacturing, to measure transmittance.
Measure the lip-deep surfaceness of alloy thin flat plate perforated shadow mask with the non-contact laser roughmeter.For 0.02mm, remove tapered section on the perforated surface that becomes fluctuating factor by (cut-off) value to draw roughness curve, with this curve determination center line mean roughness (Ra).
Measure the unintelligible edge that perforation produces by visual inspection.
Table 10,11 and 12 shows No.1 to the No.52 properties of materials, this characteristic comprises sinuousness (mm), the surfaceness on the perforated surface (center line average roughness Ra (μ m), unintelligible edge (as defined above) and the etching coefficient that the transmittance of planar mask (as defined above), perforation produce after the etching.
Use the latten of No.46, measure the surfaceness of photoetching perforated surface with aforesaid method to the No.49 material.With scolder plating above-mentioned materials to estimate the scolder plating properties.
Table 10
| The alloy code name | Material No | Sinuousness after the etching (mm) | Surfaceness on the perforated surface (Ra, μ m) | The transmittance of planar mask | The unintelligible edge that perforation produces | Etching coefficient |
| A A A A C C C B B B C A B B B A A B A C | 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 | 10 7 3 15 12 3 3 3 4 3 2 3 3 3 2 2 1 1 2 2 | 0.90 0.77 0.86 0.60 0.64 0.95 1.11 1.27 0.86 0.88 0.84 0.80 0.79 0.89 0.83 0.73 0.70 0.71 0.72 0.69 | 1.00 1.05 1.01 1.10 1.08 0.98 0.92 0.88 1.02 1.01 1.02 1.03 1.03 1.01 1.03 1.05 1.07 1.06 1.05 1.07 | B B E B B B B B B B B B B E A A A A A A | 2.02 2.00 1.93 2.03 2.01 2.02 2.02 2.03 1.97 1.95 1.97 1.96 1.99 2.84 2.06 2.19 2.92 2.04 2.35 2.22 |
Table 11
| The alloy code name | Material No | Sinuousness after the etching (mm) | Perforated surface roughness (Ra, μ m) | The transmittance of planar mask | The unintelligible edge that perforation produces | Etching coefficient |
| C B A B C B A C A B A B B C A A C A B C | 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 | 1 1 1 2 2 2 1 2 1 2 2 2 1 1 1 1 1 2 1 1 | 0.65 0.72 0.70 0.43 0.24 0.31 0.49 0.50 0.84 0.80 0.85 0.54 0.52 0.68 0.65 0.35 0.67 0.69 0.53 0.55 | 1.08 1.06 1.07 1.15 1.20 1.20 1.13 1.13 1.02 1.04 1.02 1.11 1.12 1.08 1.08 1.17 1.07 1.08 1.13 1.12 | A A A A A A A A A A A A A A A A A A B C | 2.27 2.11 2.41 2.40 2.52 2.31 2.59 2.41 2.79 2.65 2.74 2.46 2.18 3.17 2.49 2.55 2.17 2.33 2.53 2.81 |
Table 12
| The alloy code name | Material No. | Sinuousness after the etching (mm) | The surfaceness of perforated surface (Ra, μ m) | The transmittance of planar mask | The unintelligible edge that perforation produces | Etching coefficient | The welding plating |
| I | 46 | 1 | 0.55 | - | - | 3.10 | Excellent |
| J | 47 | 1 | 0.54 | - | - | 2.95 | 〃 |
| K | 48 | 1 | 0.52 | - | - | 3.12 | 〃 |
| J | 49 | 2 | 1.21 | - | - | 2.50 | Bad |
| L | 50 | 1 | 0.63 | 1.07 | A | 2.30 | - |
| M | 51 | 1 | 0.65 | 1.06 | A | 2.35 | - |
| N | 52 | 1 | 0.60 | 1.07 | A | 2.31 | - |
Corresponding to { 111}, { 100}, { 110}, { 311}, { 331}, { 210} and { the concentration class value S of each crystal face of 211}
1, S
2, S
3, S
4, S
5, S
6And S
7And (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) No.15 of ratio in specialized range of the present invention be 2mm or littler to each material of No.48 and No.50 to the sinuousness of each material of No.52 after etching, this sinuousness is less than later described comparative example's sinuousness.Surface roughness Ra on their perforated surfaces all is 0.09 μ m or littler, and the transmittance of its planar mask is 1.0 or higher, and this shows that the printing opacity brightness of gained planar mask is higher than the brightness of ordinary low-carbon steel planar mask.
The etching coefficient of above-mentioned each material be 2.0 or the bigger unintelligible edge degree that produces of boring a hole can not go wrong in actual applications.
Opposite with these materials of the present invention, the No.1 material provides { the concentration class S of 111} crystal face
1Greater than the upper limit of the present invention.The No.2 material provides that { the concentration class S2 of 100} crystal face is less than lower limit of the present invention.The No.3 material provides { the concentration class S of 100} crystal face
2Greater than the upper limit of the present invention.The No.4 material has provided { the concentration class S of 110} crystal face
3Greater than the upper limit of the present invention.The No.5 material provides { the concentration class S of 311} crystal face
4Greater than the upper limit of the present invention.Therefore, the sinuousness after their etchings is 7mm or bigger, and this numerical value is greater than the sinuousness of various embodiments of the present invention.
The No.6 material provides that { the concentration class S5 of 331} crystal face is greater than the upper limit of the present invention.The No.7 material provides { the concentration class S of 210} crystal face
6Greater than the upper limit of the present invention.The No.8 material provides the { S of 211} crystal face
7Greater than the upper limit of the present invention.Therefore, the surface roughness Ra on their perforated surfaces surpasses 0.9 μ m, and the transmittance of planar mask is lower than the planar mask transmittance of various embodiments of the present invention below 1.0.
The No.9 material provides { the concentration class S of 211} crystal face
7Less than lower limit of the present invention.The No.10 material provides { the concentration class S of 210} crystal face
6Less than lower limit of the present invention.The No.11 material provides { the concentration class S of 331} crystal face
5Less than lower limit of the present invention, the No.12 material provides { the concentration class S of 110} crystal face
3, { the concentration class S of 311} crystal face
4All less than lower limit of the present invention.The No.13 material provides (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) ratio is less than lower limit of the present invention.Therefore, these materials provide the etching coefficient less than 2.0, and this numerical value is lower than numerical value of the present invention.
The No.14 material provides (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) ratio is greater than the upper limit of the present invention, so these materials are compared with various embodiments of the present invention, increased the unintelligible edge that the planar mask hole produces.
The No.49 material provides { the concentration class S of 210} crystal face
6{ the concentration class S of 211} crystal face
7All greater than the upper limit of the present invention.Therefore, the surface roughness Ra of the perforated surface that these materials provide is 1.21, and this numerical value is coarser than the surfaceness of various embodiments of the present invention.
The No.3 material provides { the concentration class S of 311} crystal face
4{ the concentration class S6 of 210} crystal face is less than lower limit of the present invention.So the etching coefficient of this material is less than 2.0, this numerical value is inferior to the etching coefficient of various embodiments of the present invention.
As mentioned above, will be corresponding to { 111}, { 100}, { 110}, { 311}, { 331}, { 210} and { the corresponding concentration class S of each crystal face of 211}
1, S
2, S
3, S
4, S
5, S
6And S
7And (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7) ratio is controlled in the scope of the present invention regulation, can reduce sinuousness after the etching, reduce the perforated surface surface roughness Ra, improve planar mask transmittance, increase etching coefficient and reduce the unintelligible degree at the unintelligible edge that perforation produces.
In addition, the grain fineness number on the latten thickness direction being controlled at can further increase etching coefficient in the specialized range of the present invention.
More than detailed description of the present invention carry out as an example with planar mask.However, the application of latten of the present invention is not limited to planar mask, and it can also be applied to carry out etched various electronics.
Claims (7)
1. Fe-Ni latten that provides fabulous etching performance with perforated surface, it comprises:
The Fe-Ni latten contains Ni when as shadow mask be 34～38% (weight), contains Ni38-52% (weight) when as the leads of IC frame;
Described Fe-Ni latten has { 331}, { 210} and { 211} crystal face in its surface;
{ concentration class of 331} crystal face is 14% or lower, and { concentration class of 210} crystal face is 14% or lower, and { concentration class of 211} crystal face is 14% or lower; With
The concentration class ratio of crystal face, promptly { 210}/{ 331}+{211} is 0.2-1.0;
The surface roughness Ra of described Fe-Ni latten is 0.90 μ m or littler.
The mean grain size of described Fe-Ni latten on its thickness direction is 10 μ m or littler.
2. Fe-Ni-Co latten that provides fabulous etching performance with perforated surface, it comprises:
The Fe-Ni-Co latten contains Ni when the effect shadow mask be 28～38% (weight), and containing Co is 1～7% (weight), and containing Ni when as the leads of IC frame is 27～32% (weight), and containing Co is 1～20% (weight);
Described Fe-Ni-Co latten has { 331}, { 210} and { 211} crystal face in its surface;
{ concentration class of 331} crystal face is 14% or lower, and { concentration class of 210} crystal face is 14% or lower, and { concentration class of 211} crystal face is 14% or lower; With
The concentration class ratio of crystal face, promptly 210}/(331}+{211}) be 0.2-1.0;
The surface roughness Ra of described Fe-Ni-Co latten is 0.90 μ m or littler.
The mean grain size of described Fe-Ni-Co latten on its thickness direction is 10 μ m or littler.
3. Fe-Ni-Cr latten that provides fabulous etching performance with perforated surface, it comprises:
The Fe-Ni-Cr latten contains Cr3% (weight) or still less;
Described latten has { 331}, { 210} and { 211} crystal face in its surface;
{ concentration class of 331} crystal face is 14% or lower, and { concentration class of 210} crystal face is 14% or lower, and { concentration class of 211} crystal face is 14% or lower; With
The concentration class ratio of crystal face, promptly 210}/(331}+{211}) be 0.2-1.0;
The surface roughness Ra of described Fe-Ni-Cr latten is 0.90 μ m or littler.
The mean grain size of described Fe-Ni-Cr latten on its thickness direction is 10 μ m or littler.
4. Fe-Ni latten that provides fabulous etching performance with perforated surface, it comprises:
It is 34～52% (weight) that the Fe-Ni latten contains Ni
Described latten has { 111}, { 100}, { 110}, { 311}, { 331}, { 210} and { 211} crystal face;
Described each crystal face has following each concentration class:
{ the concentration class S of 111} crystal face
1: 1-10%
{ the concentration class S of 100} crystal face
2: 50-94%
{ the concentration class S of 110} crystal face
3: 1-24%
{ the concentration class S of 311} crystal face
4: 1-14%
{ the concentration class S of 331} crystal face
5: 1-14%
{ concentration class of 210} crystal face is S
6: 1-14%
{ the concentration class S of 211} crystal face
7: 1-14%
The concentration class ratio of crystal face, i.e. (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7), be 0.8-20;
The mean grain size of described latten on its thickness direction is 10 μ m or littler.
5. Fe-Ni-Co latten that provides fabulous etching performance with perforated surface, it comprises:
It is 28～38% (weight) that the Fe-Ni-Co latten contains Ni, contains Co 20% (weight) or lower;
Described latten has { 111}, { 100}, { 110}, { 311}, { 331}, { 210} and { 211} crystal face;
Described each crystal face has following each concentration class:
{ the concentration class S of 111} crystal face
1: 1-10%
{ the concentration class S of 100} crystal face
2: 50-94%
{ the concentration class S of 110} crystal face
3: 1-24%
{ the concentration class S of 311} crystal face
4: 1-14%
{ the concentration class S of 331} crystal face
5: 1-14%
{ concentration class of 210} crystal face is S
6: 1-14%
{ the concentration class S of 211} crystal face
7: 1-14%
Concentration class ratio, i.e. (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7), be 0.8-20;
The mean grain size of described latten on its thickness direction is 10 μ m or littler.
6. Fe-Ni-Cr latten that provides fabulous etching performance with perforated surface, it comprises:
It is 34～52% (weight) that the Fe-Ni-Cr latten contains Ni, contains Cr 3.0% (weight) or lower;
Described latten has { 111}, { 100}, { 110}, { 311}, { 331}, { 210} and { 211} crystal face;
Described each crystal face has following each concentration class:
{ the concentration class S of 111} crystal face
1: 1-10%
{ the concentration class S of 100} crystal face
2: 50-94%
{ the concentration class S of 110} crystal face
3: 1-24%
{ the concentration class S of 311} crystal face
4: 1-14%
{ the concentration class S of 331} crystal face
5: 1-14%
{ concentration class of 210} crystal face is S
6: 1-14%
{ the concentration class S of 211} crystal face
7: 1-14%; With
Concentration class ratio, i.e. (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7), be 0.8-20;
The mean grain size of described latten on its thickness direction is 10 μ m or littler.
7. Fe-Ni-Co-Cr latten that provides fabulous etching performance with perforated surface, it comprises:
It is 28～38% (weight) that the Fe-Ni-Co-Cr latten contains Ni, contains Co 20% (weight) or lower, and containing Cr is 3% (weight) or lower;
Described latten has { 111}, { 100}, { 110}, { 311}, { 331}, { 210} and { 211} crystal face;
Described each crystal face has following each concentration class:
{ the concentration class S of 111} crystal face
1: 1-10%
{ the concentration class S of 100} crystal face
2: 50-94%
{ the concentration class S of 110} crystal face
3: 1-24%
{ the concentration class S of 311} crystal face
4: 1-14%
{ the concentration class S of 331} crystal face
5: 1-14%
{ concentration class of 210} crystal face is S
6: 1-14%
{ the concentration class S of 211} crystal face
7: 1-14%; With
Concentration class ratio, i.e. (S
2+ S
4+ S
6)/(S
1+ S
3+ S
5+ S
7), be 0.8-20;
The mean grain size of described latten on its thickness direction is 10 μ m or littler.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP201879/93 | 1993-07-22 | ||
| JP20187993A JP3336691B2 (en) | 1993-07-22 | 1993-07-22 | Alloy thin sheet for electronics with excellent etching processability |
| JP206628/93 | 1993-08-20 | ||
| JP5206628A JPH0762495A (en) | 1993-08-20 | 1993-08-20 | Thin alloy sheet for electronic instrument having excellent etching workability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1097812A CN1097812A (en) | 1995-01-25 |
| CN1035778C true CN1035778C (en) | 1997-09-03 |
Family
ID=26513052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93120826A Expired - Fee Related CN1035778C (en) | 1993-07-22 | 1993-12-15 | An alloy sheet having high etching performance |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR960008889B1 (en) |
| CN (1) | CN1035778C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3740105B2 (en) * | 2001-11-20 | 2006-02-01 | 日鉱金属加工株式会社 | Fe-Ni and Fe-Ni-Co alloy strips for shadow mask |
| CN105803333A (en) * | 2015-01-20 | 2016-07-27 | 日立金属株式会社 | Manufacturing method for Fe-Ni alloy sheet metal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH029655A (en) * | 1988-06-29 | 1990-01-12 | Matsushita Electric Ind Co Ltd | Printing controller of page printer |
| JPH02270941A (en) * | 1989-04-13 | 1990-11-06 | Hitachi Metals Ltd | Fe-ni alloy excellent in etching workability and its production |
| WO1991012345A1 (en) * | 1990-02-15 | 1991-08-22 | Nkk Corporation | Thin sheet of iron-nickel alloy for shadow mask and production thereof |
-
1993
- 1993-12-15 CN CN93120826A patent/CN1035778C/en not_active Expired - Fee Related
- 1993-12-17 KR KR1019930028313A patent/KR960008889B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH029655A (en) * | 1988-06-29 | 1990-01-12 | Matsushita Electric Ind Co Ltd | Printing controller of page printer |
| JPH02270941A (en) * | 1989-04-13 | 1990-11-06 | Hitachi Metals Ltd | Fe-ni alloy excellent in etching workability and its production |
| WO1991012345A1 (en) * | 1990-02-15 | 1991-08-22 | Nkk Corporation | Thin sheet of iron-nickel alloy for shadow mask and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960008889B1 (en) | 1996-07-05 |
| CN1097812A (en) | 1995-01-25 |
| KR950003466A (en) | 1995-02-16 |
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