CN106304689A - Rolled copper foil, copper-clad laminated board and flexible printed board and electronic equipment - Google Patents
Rolled copper foil, copper-clad laminated board and flexible printed board and electronic equipment Download PDFInfo
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- CN106304689A CN106304689A CN201510301876.4A CN201510301876A CN106304689A CN 106304689 A CN106304689 A CN 106304689A CN 201510301876 A CN201510301876 A CN 201510301876A CN 106304689 A CN106304689 A CN 106304689A
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- copper foil
- copper
- clad laminated
- laminated board
- rolled copper
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
Abstract
Rolled copper foil, copper-clad laminated board and flexible printed board and the electronic equipment of etching and bendability all excellences are provided.[solution] rolled copper foil, it comprises the copper of more than 99.9% in terms of quality rate, after carrying out heat treatment under either condition among 350 DEG C × 1 second, 350 DEG C × 20 minutes or 200 DEG C × 30 minutes, the ratio of the crystal grain that surface and { 102 } exist the differential seat angle within 10 degree is more than 1% and less than 50%.
Description
Technical field
The present invention relates to be suitable for FPC(flexible printed board) etc. rolled copper foil, copper-clad laminated board and flexible printed board and electronic equipment.
Background technology
The method carrying out connecting up as the part to the movable part of electronic equipment, Existential Space restriction, it is possible to use FPC(flexible printed board).As FPC, it is possible to use Copper Foil and resin bed to be carried out the copper-clad laminated board being laminated.
FPC uses after bending in equipment, but along with the miniaturization of equipment, the radius bend of FPC diminishes, it is desirable to improve the bending of FPC.Furthermore, it is contemplated that wearable terminal from now on is universal, FPC is also required the raising of fatigue properties.And then, along with the miniaturization of FPC wiring, also require the etching of Copper Foil when forming circuit.
But, FPC generally uses when Copper Foil has carried out recrystallization.Copper Foil is carried out calendering and adds man-hour, Crystal Rotation and formed calendering set tissue.Further, when carrying out annealing or be machined to that the operation till end article, in other words operation to becoming FPC apply heat after being rolled by rolled copper foil, it may occur that recrystallization.Recrystallization tissue after becoming this rolled copper foil below is referred to as " recrystallization tissue ", will apply the calendering tissue before heat referred to as " calendering tissue ".Affected it should be noted that recrystallization tissue is substantially organized by calendering, by controlling calendering tissue, it is also possible to control recrystallization tissue.
Thus, it is proposed that following technology: make Cube orientation i.e. (200) face ({ 100}) development, the technology (such as, patent documentation 1) of raising bendability as the recrystallization tissue of rolled copper foil.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 11-286760 publication.
Summary of the invention
The problem that invention is to be solved
But, when the Cube of Copper Foil is orientated excessive development, there is etching and reduce this problem.This is considered because: even if Cube set organizational development also will not become monocrystalline, and being in the mixing crystalline form of the little crystal grain that there is other orientation in the big crystal grain of Cube orientation, etching speed changes because of the crystal grain of each orientation.Especially, the L/S width of circuit becomes the shortest (micro-spacing), the problem that the most more there will be etching.During it addition, Cube is orientated excessive development, Copper Foil becomes excessively soft sometimes, operability is poor.
Accordingly, it is intended that, improve the technology of bendability with not making Cube orientation development.It should be noted that Cube orientation is the recrystallization set orientation of fine copper system.
Therefore, it is an object of the invention to, it is provided that rolled copper foil, copper-clad laminated board and the flexible printed board of etching and bendability all excellences and electronic equipment.
Means for solving the above
The present inventor etc. are conceived to the method that { 102 } of rolled copper foil are used as improving bendability with not making Cube orientation development.When making { 102 } to develop on plate face, it can be ensured that the etching equal with the existing electrolytic copper foil that Cube orientation does not develops, and also bendability and bending can be improved.The reason that bendability and bending improve can be made as { 102 }, it is believed that though the degree of not up to Cube orientation, but its orientation that to be Young's modulus low.It should be noted that { 100 } refer to (100) face or (100) orientation.
I.e., the rolled copper foil of the present invention comprises the copper of more than 99.9% in terms of quality rate, after carrying out heat treatment under either condition among 350 DEG C × 1 second, 350 DEG C × 20 minutes or 200 DEG C × 30 minutes, the ratio of the crystal grain that surface and { 102 } exist the differential seat angle within 10 degree is more than 1% and less than 50%.
Preferably, one kind or two or more with add up to 10 ~ 300 mass ppm to contain in Ag, Sn, Zn, Ni, Ti and Zr, surplus is made up of the rolled copper foil of the present invention Cu and inevitable impurity.
The copper-clad laminated board of the present invention is that aforementioned rolled copper foil is layered in the two-sided of resin bed or one side, and in the aforementioned rolled copper foil of at least one, the ratio of the crystal grain that surface and { 102 } exist the differential seat angle within 10 degree is more than 1% and less than 50%.
The flexible printed board of the present invention uses aforementioned copper-clad laminated board and forms circuit on aforementioned rolled copper foil and form.
The electronic equipment of the present invention uses foregoing soft printed base plate to form.
Invention effect
In accordance with the invention it is possible to obtain etching and the rolled copper foil of bendability all excellences.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the test method of 180 ° of closely sealed bendings.
Fig. 2 is the schematic diagram of bend test method.
Detailed description of the invention
Hereinafter, illustrate for the rolled copper foil described in embodiments of the present invention.It should be noted that in the present invention, % is to represent quality % under conditions of being not particularly limited.Rolled copper foil described in embodiments of the present invention makes the purposes of FPC for utilizing etching to remove after itself and laminated resin are made copper-clad laminated board beyond circuit part be useful.
<composition>
Rolled copper foil comprises the copper of more than 99.9% in terms of quality rate.As this composition, JIS-H3510(C1011 can be listed) or JIS-H3100 (C1020) in regulation oxygen-free copper, JIS-H3100(C1100) in regulation tough pitch copper or JIS-
The phosphorized copper of regulation in H3100 (C1201 and C1220).It should be noted that the upper limit of the oxygen content comprised in copper is not particularly limited, in general it is below 500 mass ppm and then usually below 320 mass ppm.
And then, the one kind or two or more element in Ag, Sn, Zn, Ni, Ti and Zr containing 10 ~ 300 mass ppm can be added up to.In order to make { 102 } to develop, need to make { 112 } to develop in the intermediate annealing (final cold rolling before annealing) of rolled copper foil, when adding these elements, broaden for the condition and range being made by intermediate annealing { 112 } to develop, can more reliably make { 102 } to develop, and easily manufacture.When the total amount of above-mentioned element is less than 10 mass ppm, the effect utilizing intermediate annealing to make { 112 } to develop is few, during more than 300 mass ppm, conductivity reduces and recrystallization temperature rises sometimes, it is difficult to suppresses the surface oxidation of Copper Foil and makes its recrystallization in the annealing after final calendering.
<thickness>
The thickness of Copper Foil is preferably 4 ~ 100 μm, more preferably 5 ~ 70 μm.When thickness is less than 4 μm, the operability of Copper Foil is poor sometimes, and when thickness is more than 100 μm, the bendability of Copper Foil is poor sometimes.
<{ 102 } of copper foil surface>
After carrying out heat treatment with the either condition among 350 DEG C × 1 second, 350 DEG C × 20 minutes or 200 DEG C × 30 minutes, the ratio of the crystal grain that the surface of rolled copper foil and { 102 } exist the differential seat angle within 10 degree is more than 1% and less than 50%.It should be noted that " surface " of rolled copper foil refers to, with electrolytic polishing, outmost surface carries out the surface after 0.5 ~ 2 μm is ground.
Herein, etching (the softest etching) is affected by the planar orientation of the crystal grain of copper foil surface.It addition, bendability and bending are also copper foil surface to be applied maximum strain and produces.Thus, it is stipulated that the development degree of { 102 } of copper foil surface (calendering face).But, when copper foil surface exists oxide layer, antirust coat etc. and needs to remove them, the surface after removing regards as copper foil surface.During generally it can be thought that the thickness of copper foil surface is removed below 1 μm, it is possible to measure planar orientation, there is no difference before and after being oriented in removal.
It addition, the crystal grain that there is the differential seat angle within 10 degree with { 102 } can be regarded as the planar orientation near { 102 }, specify the most in this wise.During with the differential seat angle of { 102 } more than 10 degree, become big with the difference of { 102 }.
It addition, rolled copper foil generally with the state shipment of " calendering tissue ", manufacture copper-clad laminated board time, occur recrystallization to form recrystallization set tissue when fitting with resin bed.Therefore, in order to evaluate the bendability of copper-clad laminated board, bending, etching, need " the recrystallization tissue " of rolled copper foil as object.On the other hand, recrystallization tissue depends not only on calendering tissue, also significantly can change because of temperature conditions during recrystallization.
Thus, in the representative preparation method of copper-clad laminated board, the thermal history suffered by rolled copper foil either condition Imitating ground in 350 DEG C × 1 second, 350 DEG C × 20 minutes or 200 DEG C × 30 minutes is reappeared, represents the state of the Copper Foil of recrystallization in copper-clad laminated board.
Therefore, heat treatment self is only carrying out under the conditions of any one among 3 conditions, carries out the heat treatment of 350 DEG C × 20 minutes after not being by the heat treatment of 350 DEG C × 1 second for the 2nd time for same sample.Wherein, such as when carrying out the heat treatment of 350 DEG C × 1 second and when carrying out the heat treatment of 350 DEG C × 20 minutes, the ratio of above-mentioned crystal grain all reaches more than 1% and less than 50%.
Further, the planar orientation of copper foil surface with { 102 } be in the crystal grain ratio of the differential seat angle within 10 degree be more than 1% time, { 102 } can be developed, the bendability of copper-clad laminated board and bending improve.On the other hand, the ratio making above-mentioned crystal grain industrially it is difficult to more than 50%.
The planar orientation of copper foil surface utilizes EBSD(electronics backscattering diffraction: electron backscatter diffraction) measure.EBSD can measure the crystal orientation near specimen surface with the resolution capability of the nm order of magnitude, it is possible to calculated the change (local orientation is poor) of localised crystal's orientation by determination data.Further, these data the ratio of the crystal grain that there is differential seat angle within 10 degree with { 102 } is calculated.
It should be noted that about EBSD, when increasing mensuration area, measuring interval broadens and becomes rough data, thus the most preferred.During it addition, { 100 } are developed on calendering face, particle diameter can increase to about 100 μm, even if in this case, also mensuration area is set to 4mm2So that measure region internal memory at sufficient amount of crystal grain.It addition, the interval of measuring point is set to below 1 μm.Now, it is difficult to by once measuring 4mm2All areas, therefore the position randomly drawed repeatedly is measured and make mensuration area amount up to 4mm2?.
The rolled copper foil of the present invention generally can repeat repeatedly after hot rolling dough-making powder is cut that (usually about 2 times) cold rolling and annealing, after then carrying out final full annealed, carries out the most cold rolling and to be manufactured into desired paper tinsel thick.And then, after this Copper Foil is carried out defat, in order to ensure its adaptation with resin bed, one side (with the face of resin bed stacking) can be carried out roughening treatment, so carry out antirust treatment and for copper-clad laminated board.
" final full annealed " refers to the last annealing among final cold rolling front annealing.
Herein, in order to make { 102 } of copper foil surface to develop as described above, adjust annealing conditions so that represent " final full annealed " afterwards and final cold rolling before integrated diffraction intensity ratio (the I(200)/I of X-ray diffraction of the crystal development degree that plate face is { 100 }0(200) scope of 2 ~ 10) it is in.Intensity (I/I0) be the intensity (I(200) of the integrated diffraction intensity utilizing the X-ray diffraction in calendering face to obtain) integrated diffraction intensity (I in (200) face that obtains with the X-ray diffraction utilizing micropowder copper0(200) ratio), represents the development degree of cube (cube set) tissue.
Above-mentioned (I(200)/I0(200) time) less than 2, in the Copper Foil finally given after the most cold rolling, { 200 } can gather, and therefore { 102 } of copper foil surface will not be developed.This is because, (the I/I in final full annealed stage0) hour, the most final cold rolling time (I(200)/I0(200)) change ratio big, { 100 } increases, { 102 } will not be developed.
On the other hand, above-mentioned (I(200)/I0(200), time) more than 10, copper foil surface becomes close orientation randomly, { 102 } will not be developed.This is because, final cold rolling front (I(200)/I0(200) time) more than 10, the most final cold rolling time become close orientation randomly, { 102 } will not be developed.
As by after final full annealed and final cold rolling before (I(200)/I0(200)) management to 2 ~ 10 method, can with the temperature of more than 600 DEG C carry out final full annealed and in this temperature-rise period by 200 ~ 500 DEG C by the time control be 5 ~ 60 seconds.During by deficiency of time 5 seconds, (I(200)/I0(200)) less than 2, during by the time more than 60 seconds, (I(200)/I0(200)) more than 10.It should be noted that the cooling procedure after temporarily heating up and having carried out " final full annealed " does not interferes with the generation of { 102 }.
It addition, in order to make { 102 } of copper foil surface orientation develop, the most cold rolling degree of finish η is managed to 2.8 ~ 3.7.When η is less than 2.8, copper foil surface becomes close orientation randomly, { 102 } will not be developed.When η is more than 3.7, { 100 } gather, { 102 } of copper foil surface will not be developed.
It should be noted that with η=ln(A/B) represent, A, B be respectively cold rolling before, the most cold rolling after sectional area.
The copper-clad laminated board of the present invention is the rolled copper foil the two-sided of resin bed or one side stacking with above-mentioned characteristic.As long as resin bed has and is applicable to the characteristic of printed circuit board (PCB) etc. and is just not particularly limited, such as, can use paper base material phenolic resin, paper base material epoxy resin, synthetic fibers cloth base material epoxy resin, glass cloth paper composite base material epoxy resin, glass cloth glass non-woven fabric composite base material epoxy resin and glass cloth base material epoxy resin etc. in rigidity PWB purposes.It addition, polyester film, polyimide film, liquid crystal polymer (LCP) film, polytetrafluoroethylene (registered trade mark) film, polyethylene terephthalate film, poly (ethylene naphthalate) film etc. can be used in FPC purposes.
Resin bed self can be multilamellar.
During it addition, resin bed low for the thermostabilitys such as polyethylene terephthalate and Copper Foil are fitted, according to thermo-compressed condition during laminating, the Copper Foil of " calendering tissue " state is possible without becoming above-mentioned " recrystallization tissue ".Now, Copper Foil carries out any hot in above-mentioned 350 DEG C × 1 second, 350 DEG C × 20 minutes or 200 DEG C × 30 minutes in advance process and make its recrystallization, the ratio of the crystal grain of the differential seat angle existed with { 102 } within 10 degree is adjusted after more than 10%, fits with resin bed and make copper-clad laminated board.
And then, carry out harsh bending, bending according to the composition of FPC, the most only Copper Foil to the one side of copper-clad laminated board.When this purposes, can be in the two sides laminated copper foil of the resin bed of copper-clad laminated board, and the Copper Foil side applying harsh bending condition wherein uses the Copper Foil of the present invention, at other Copper Foil of another side stacking (the most cheap electrolytic copper foil).
Laminating method about rolled copper foil Yu resin, following method can be listed: prepare to make resin impregnated in base materials such as glass cloth and make resin be cured to the prepreg till semi-cured state, Copper Foil is overlapped in prepreg and makes its method heating pressurization in the case of rigidity PWB purposes.In the case of FPC, by bonding agent bonding Copper Foil on the resin beds such as polyimide film, or can not use bonding agent ground lamination adhesive Copper Foil at high temperature under high pressure to manufacture copper-clad laminated board.It is dried and cured in the case of FPC or after polyimide precursor is coated rolled copper foil, such that it is able to manufacture copper-clad laminated board.
The thickness of resin (layer) is not particularly limited, and generally uses 9 ~ 50 μm left and right thickness persons.It addition, the relatively thick one the most also using resin thickness to be more than 50 μm.The upper thickness limit of resin is not particularly limited, for example, 150 μm.
The copper-clad laminated board of the present invention can be used for various flexible printed board (printed circuit board (PCB) (PWB)).As printed circuit board (PCB), it is not particularly limited, such as, from the viewpoint of the number of plies of conductive pattern, is applicable to more than one side PWB, two-sided PWB, multilamellar PWB(3 layer)；From the viewpoint of the kind of dielectric substrate material, be applicable to rigidity PWB, flexible PWB(FPC), rigid and flexible PWB.
Embodiment
<manufacture of rolled copper foil>
To be added with the tough pitch copper of the element of composition shown in table 1 or oxygen-free copper as raw material, cast thickness is the ingot casting of 100mm, with 800 DEG C of hot rollings carried out above until thickness is as 10mm, the oxide skin on surface is carried out face and cuts.Thereafter, repeat cold rolling and annealing, obtain the calendering board coil that thickness is 0.5mm.After behind cold rolling, the condition of table 1 is utilized to carry out final full annealed.Finally with the degree of finish of table 1 by the most cold rolling be finish-machined to specific thickness (thickness of embodiment 9,6,13 be 9 μm, the thickness of embodiment 7 be the thickness of 18 μm, other embodiments and comparative example 1 ~ 4 be 12 μm).
It should be noted that " OFC+30ppmAg " in the hurdle of table 1 composition is directed to the addition of in the oxygen-free copper OFC of JIS-H3100 (C1020) Ag of 30 mass ppm.It addition, " TPC+200ppmAg " is directed to JIS-H3100(C1100) tough pitch copper (TPC) in the addition of the Ag of 200 mass ppm.The situation of other addition is also same.
< integrated diffraction intensity strength ratio (the I(200)/I of X-ray0(200)) >
For after final full annealed and the surface of final cold rolling front Copper Foil, measure { the X-ray diffraction intensity in 100} face.Further, utilize the same terms to carry out X-ray diffraction, use the value (I of thus obtained fine copper powder0(200): X ray reflection mean intensity) it is standardized.
The condition determination of X-ray diffraction is as follows: incident X-rays source: Cu, accelerating potential: 25kV, tube current: 20mA, divergent slit: 1 degree, scatter slit: 1 degree, by optical slits: 0.3mm, dissipates longitudinal direction and is limited slit: 10mm, monochromatic is set to 0.8mm by optical slits.Fine copper powder employs micropowder copper (325mesh).
<crystal orientation>
After Copper Foil after the most cold rolling is carried out each heat treatment shown in table 1 further, surface being carried out slight electrolytic polishing, the EBSD carrying out surface measures.Measure area to be set to as above add up to 4mm2.Use analysis software (the OIM Analysis of TSL SOLUTIONS LTD) attached in EBSD device, calculate the ratio that the planar orientation on surface and { 102 } exist the crystal grain of differential seat angle within 10 degree.
It should be noted that about the heat treatment of 350 DEG C × 1 second, even if being put in the stove of 350 DEG C 1 second by Copper Foil merely, the time was short and does not regard as having carried out the heat treatment of 350 DEG C × 1 second.Thus, between 2 corrosion resistant plates (SUS410/ thickness 5mm Ra 0.1, Rz 0.6) being heated to 350 DEG C, Copper Foil is clamped 1 second, as the heat treatment of 350 DEG C × 1 second.
It addition, each heat treatment of 350 DEG C × 20 minutes, 200 DEG C × 30 minutes be respectively by Copper Foil 350 DEG C, place the stipulated time in the stove of 200 DEG C and carry out.
<manufacture of copper-clad laminated board>
Relative to each embodiment and the rolled copper foil of comparative example of table 1, utilize the laminating method shown in table 2 that itself and resin bed are carried out stacking, thus manufactured copper-clad laminated board.It should be noted that about the rolled copper foil of table 1, employ the Copper Foil before carrying out the heat treatment of table 1.
About the thickness of resin bed, embodiment 3 is set to 50 μm；Embodiment 8,12,19 is set to 35 μm；Other embodiments and comparative example 1 ~ 4 are set to 25 μm.Among each resin bed, polyimides and epoxy be Thermocurable, liquid crystal polymer be thermoplastic.It addition, " polyimide/epoxy " represents multi-layer resinous layer polyimide layer and epoxy layer being laminated, as be described hereinafter as shown in laminating method " C ", epoxy layer side carries out bonding as adhesive linkage with Copper Foil.
In table 2, when being laminated for " two-sided " of Copper Foil, represent and be laminated with Copper Foil respectively the two-sided of resin bed.
Additionally, in table 2, laminating method " A " refers to: possesses thermoplastic polyimide film or the liquid crystalline polymer film duplexer overlapping with Copper Foil is placed on and is heated between 2 corrosion resistant plates (SUS410) of 350 DEG C by commercially available, carries out suppressing and keeping the pressure sintering of 1 second.It should be noted that, " possess " thermoplastic polyimide film to refer to: common polyimide film is Thermocurable, also will not be bonding even if applying heat, therefore the substrate surface at polyimide film adds the polyimide film possessing thermoplastic polyimides about 2 μm in advance.
Laminating method " B " is commercially available polyimide precursor varnish to be coated on Copper Foil and made it be dried and solidification.Baking temperature is 200 DEG C × 3 minutes, be cured as 350 DEG C × 30 minutes.
Laminating method " C " be on commercially available polyimide film, be coated with commercially available epoxy adhesive after, be dried and make the solvent in epoxy adhesive evaporate, so laminating Copper Foil after, make bonding agent solidify (cure).Baking temperature is 200 DEG C × 3 minutes, be cured as 200 DEG C × 30 minutes.
For gained copper-clad laminated board, carry out following evaluation.
<crystal orientation>
In the same manner as the situation of above-mentioned rolled copper foil, for the copper-clad surface of copper-clad laminated board, there is the ratio of the crystal grain of the differential seat angle within 10 degree in the planar orientation on mensuration surface and { 102 }.When copper-clad laminated board two-sided is laminated with Copper Foil, arbitrarily arbitrary copper-clad surface is measured.
<bending>
About following bending and bendability, utilize bending to evaluate the sample that the periodicity rupturing to test film is few, utilize bendability to carry out the sample that evaluation cycle number is many.
Repeat 180 ° of closely sealed bendings of copper-clad laminated board, determine the number of times rupturing to Copper Foil.Utilize CCD camera to observe the copper foil surface (crooked outer surface) after bending each time with or without fracture.Even if the sample that also will not rupture for 3 times of bending is denoted as zero, be denoted as by the sample of fracture ×.
180 ° of closely sealed bendings are carried out as shown in Figure 1.First, in the way of the rolling direction by Copper Foil becomes length direction, test film is cut into the short strip shape of 12.7mm × 100mm.This test film S1 is bent to U-shaped at central part in the way of the two ends of length direction coincide with one another, in the way of length direction is up to the standard, it is made laterally down C-shaped, is installed on compression test (the universal testing machine AGS-5kN that Shimadzu Seisakusho Ltd. manufactures) ((a) of Fig. 1) in this condition.Specifically, test film S1 is positioned on the pedestal 12 of compression test, makes the slide block 11 above test film S1 with load-carrying 98kN(10kgf), the speed of 50mm/ minute decline, keep 5 seconds after applying load-carrying, complete crushing test sheet S1.Thereafter, make slide block 11 increase, take out the test film S2 that collapses under pressure of U-shaped portion, by length direction become upper and lower in the way of change direction, as (b) of test film S3(Fig. 1).Test film S2, S3 have the prominent sigmoid portion C that U-shaped portion collapses under pressure.
And, test film S3 is positioned on the pedestal 12 of above-mentioned compression test in the way of upward by bending section C, make the slide block 11 above bending section C decline with load-carrying similar to the above and speed, keep 5 seconds after applying load-carrying, (c), (d) of complete crushing test sheet S3(Fig. 1).Thereafter, make slide block 11 increase, take out bending section C and collapse under pressure and basically reach smooth test film S4, observe the crooked outer surface Sk specifying region centered by bending section C, it is judged that with or without fracture ((e) of Fig. 1).
<bendability>
After the Copper Foil of copper-clad laminated board being etched and forming the circuit of regulation, utilizing the IPC(U.S. printed circuit industry meeting shown in Fig. 2) bend test device is curved test.In slip bend test, measure the resistance of circuit part, resistance value unbroken and that number of bends is more than 10000 times sample when the initial stage rises 15% is denoted as zero, by resistance value before the initial stage rises 15% or the sample of the moment fracture that rises 15% be denoted as ×.
This IPC bend test device is presented on the structure being combined with conduct vibrations parts 3 on vibratory drive body 4, test film 1 the part of the screw 2 shown in arrow and 3 leading section amount at 4 at be fixed in device.When vibration section about 3 drives, the pars intermedia of test film 1 bends to hairpin with radius of curvature r of regulation.
It should be noted that, experimental condition is as follows: direction taked by test film width: 12.7mm, test film length: 200mm, test film: by the length direction of test film reach with rolling direction parallel in the way of take, radius of curvature r:1.5mm, vibrating stroke: 25mm, vibration velocity: 1500 beats/min
During it addition, Copper Foil is formed at the one side of copper-clad laminated board, Copper Foil is towards the crooked inner surface of radius of curvature r of Fig. 2.It addition, when copper-clad laminated board two-sided is laminated with Copper Foil, the copper-clad surface determining above-mentioned crystal orientation is etched and forms circuit, etching is utilized to remove the Copper Foil of opposing face completely.Further, using this circuit face as the crooked inner surface of radius of curvature r of Fig. 2.
Etching following circuit linearity and half-etching judge.It should be noted that in the case of copper-clad laminated board two-sided is laminated with Copper Foil, the copper-clad surface determining above-mentioned crystal orientation is etched.
About circuit linearity, after the copper foil surface of copper-clad laminated board take width as 50 μm width and length direction mask defines longer short strip shape circuit pattern, the iron chloride of 60 DEG C are etched in copper foil surface by the injection carrying out spraying and define the short strip shape circuit of 50 μm width.This circuit length direction with 5 μm spacing respectively with SEM measure above-mentioned width circuit width.With above-mentioned spacing for the mensuration of 100 points, it is that the situation within ± 2 μm is denoted as zero by 3 σ of the normal distribution of circuit width.
About half-etching, till the thickness utilizing the mixed aqueous solution of sodium peroxydisulfate (40g/L) and sulphuric acid (20g/L) to be etched to Copper Foil reaches the half at initial stage, utilize CP(cross section ion polishing instrument, Cross
Section Polisher) after cutting profile, it is utilized respectively SEM along etching face direction with the spacing of 5 μm and measures the thickness of section.For with above-mentioned spacing for the mensuration of 100 points, be that the situation within ± 2 μm is denoted as zero by 3 σ of the normal distribution of thickness.
About the evaluation of etching, the situation that circuit linearity and half-etching are zero is denoted as overall merit zero, by any one in circuit linearity and half-etching be not zero situation be denoted as overall merit ×.
Acquired results is shown in table 1, table 2.
Can be clear and definite by table 1 ~ table 2: in the case of each embodiment that ratio is more than 1% and less than 50% of the crystal grain that the planar orientation of the copper foil surface in copper-clad laminated board and { 102 } exist the differential seat angle within 10 degree, bending, bendability and etching are the most excellent.
It should be noted that, when Copper Foil before the copper-clad laminated board that will be laminated in each embodiment carries out the heat treatment of 350 DEG C × 1 second, 350 DEG C × 20 minutes or 200 DEG C × 30 minutes, the ratio of the crystal grain that the planar orientation on surface and { 102 } exist the differential seat angle within 10 degree is more than 1% and less than 50%.
On the other hand, in the temperature-rise period when the final full annealed of Copper Foil, 200 ~ 500 DEG C by the time comparative example 1,2 more than 60 seconds in the case of, (I(200)/I0(200)) more than 10, copper foil surface becomes close orientation randomly, and { 102 } are not developed, and the planar orientation of copper foil surface and { 102 } exist the ratio of the crystal grain of the differential seat angle within 10 degree less than 1%.Therefore, in the case of comparative example 1,2, bending, bendability are poor.
In the case of the most cold rolling degree of finish η of the Copper Foil comparative example 3,4 more than 3.7, X-ray diffraction intensity ratio (the I(200)/I after final full annealed0(200)) less than 2, therefore, in copper foil surface { 100 } set finally given, { 102 } orientation of copper foil surface does not develops, and the planar orientation of copper foil surface and { 102 } exist the ratio of the crystal grain of the differential seat angle within 10 degree less than 1%.Therefore, in the case of comparative example 3,4, bending, bendability are good, but etching is poor.
Claims (5)
1. rolled copper foil, it is the rolled copper foil of the copper comprising more than 99.9% in terms of quality rate,
After carrying out heat treatment under either condition among 350 DEG C × 1 second, 350 DEG C × 20 minutes or 200 DEG C × 30 minutes, the ratio of the crystal grain that surface and { 102 } exist the differential seat angle within 10 degree is more than 1% and less than 50%.
2. the rolled copper foil described in claim 1, wherein, adds up to one kind or two or more in Ag, Sn, Zn, Ni, Ti and Zr containing 10 ~ 300 mass ppm, and surplus is made up of Cu and inevitable impurity.
3. copper-clad laminated board, it is the copper-clad laminated board that the rolled copper foil described in claim 1 or 2 is layered in the two-sided of resin bed or one side,
In the described rolled copper foil of at least one, the ratio of the crystal grain that surface and { 102 } exist the differential seat angle within 10 degree is more than 1% and less than 50%.
4. flexible printed board, it is to use the copper-clad laminated board described in claim 3 and form circuit on described rolled copper foil.
5. electronic equipment, it uses the flexible printed board described in claim 4.
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| CN202010316854.6A CN111526674A (en) | 2015-06-05 | 2015-06-05 | Rolled copper foil, copper-clad laminate, flexible printed board, and electronic device |
| CN201510301876.4A CN106304689A (en) | 2015-06-05 | 2015-06-05 | Rolled copper foil, copper-clad laminated board and flexible printed board and electronic equipment |
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| CN201510301876.4A CN106304689A (en) | 2015-06-05 | 2015-06-05 | Rolled copper foil, copper-clad laminated board and flexible printed board and electronic equipment |
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| CN202010316854.6A Division CN111526674A (en) | 2015-06-05 | 2015-06-05 | Rolled copper foil, copper-clad laminate, flexible printed board, and electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111455312A (en) * | 2017-11-14 | 2020-07-28 | 大日本印刷株式会社 | Metal plate for manufacturing vapor deposition mask, method for manufacturing same, and vapor deposition mask device provided with same |
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| CN103290345A (en) * | 2012-02-28 | 2013-09-11 | Jx日矿日石金属株式会社 | Rolled copper foil |
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| JP2001262296A (en) * | 2000-03-17 | 2001-09-26 | Nippon Mining & Metals Co Ltd | Rolled copper foil and its manufacturing process |
| JP3962291B2 (en) * | 2001-07-17 | 2007-08-22 | 日鉱金属株式会社 | Rolled copper foil for copper clad laminate and method for producing the same |
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| CN101481760A (en) * | 2008-01-08 | 2009-07-15 | 日立电线株式会社 | Rolled copper foil and manufacturing method of rolled copper foil |
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| CN111455312A (en) * | 2017-11-14 | 2020-07-28 | 大日本印刷株式会社 | Metal plate for manufacturing vapor deposition mask, method for manufacturing same, and vapor deposition mask device provided with same |
| CN111455312B (en) * | 2017-11-14 | 2022-12-20 | 大日本印刷株式会社 | Method for manufacturing metal plate, vapor deposition mask, method for manufacturing vapor deposition mask, and vapor deposition mask device |
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| CN111526674A (en) | 2020-08-11 |
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